T.L. Brunton Edin. University Session 1861-2 Lecture notes Of lectures on Organic Chemistry by Professor Lyon Playfair [illegible] Contents [Inorganic] Table of Contents Table of organic substances wh may be formed from their elements without vital agency 1 Difference between organic & inorganic substances 4 Definitions of organic chemistry 6 Preparation of a higher from a lower alcohol 7 Empirical & rational formulas 8 Homologous series 10 Heterologous class 11 Qualitative examination of organic bodies 12 Quantitative analysis 15 Example of organic analysis 31 Olifines Ethylene series, Olefiant gas, Propylene, Butylene, Amylene, Hesylene &c 19 Marsh gas series, Hydricles of ethylene series 26 Alcohol radicals. Preparation 29 Table. Transformation of organic compounds by different ferments 32 Reduction of other series to olifines 33 Definition of radical 35 Ethers. 36 Substitution products of methylic ether 37 Haloid compounds of ether 41 Ethers as a class 42 Alcohols 44 Wines & spirits 48 Fermentation 51 Theory of the action of ferments 53 Brewing 55 Composition of malt liquors. Table 56 Homologues of the alcohols 57 General properties of alcohols 58 Compound ethers 59 Biatomic ethers & alcohols 62 Aldehyds 65 Ketones 68&74 Anhydrides or acids 69 Hydrated acids. Relation of these to alcohol & ether 71 Relation between the alcohols, aldehyds, & ketones 74 Acetates 76 Acids homologous to acetic acid 79 Fatty acids 82 Candles 84 Saponification 86 Candles from coal 88 Acids produced from bratomic alcohols 91 Oxalates 96 Negative radicals. Acetoyl. Allyl. Angelyl 98 Oxidized radicals of allyl 100 Table. Homologues of acrlylic acid 101 Glycerine 102 Glycerides on common fats 104 Soap 105 Chief fats 107 Aromatic series 109 Phenyl 109 & 117 Benzyl 115 Distillation of coal. Naphtha 118 Coal tar colours 122 Malic Tumaric, Tartaric, Racemic & Kainic Acids 127-132 Trebasic acids Citric, gallic, tanine &c 132 Tanning 137 Compound haloid radicals 139 Cyanogen 140 Hydrocyanic acid 142 Cyanides 145 Haloid ethers of cyanogen 146 Nitriles 147 Preparation of higher acids from nitriles 147 Double electronegative cyanides 148 Ferrocyanogen 148 Ferridcyanogen 152 Nitroferrocyanides or nitroprussides 153 Cyanates 155 Sulphocyanogen 156 Sulphocyanates & sulphocyanides 157 Bicyanogen 157 Fulminates 158 Tricyanogen 159 Characters of cyanogen 160 Organic bases representative of alkalis & metallic oxides in organic chemistry 160 Amines 161 Monameries 161 Production of these compound ammonias 162 Organic bases coal tar 164 Diamines. Urea. 164 Triamines 166 Organic alkaloids 166 alkaloids from hemlock, broom, tobacco, opium, chinchona bark, strychnine family, solinacia family. tea &c. 168-182 Hydrates of Carbon Action of dilute acids & oxidizing agents on them 182 Views of their chemical constitution 183 Cellulose-gum cotton-vegetable parchment 183 Starch. Starch in vegetables 186 British gum. Manufacture of starch 188 Special starches 189 Starch in the animal kingdom 190 Inulin Lichenin 190 Glycogen. Dextrin 191 Gums 193 Quantities of cellulose & gum in different vegetable substances 193 Arabin. Cerasine. Bassorin. Pectin 194 Sugars 195 Grape sugar or glucose 196 Test for diabetic sugar 197 Caramel. Saccharides. Glucic acid 198 Action of yeast & of nitrogenous ferments on grape sugar. mucic acid 199 Fruit sugar on fructose 200 Cane sugar or sucrose 200 Barley sugar. Caramel. Conversion of sucrose into glucose. Saccharides 201 Fermentation of sucrose 202 Manufacture of sugar 202 Refining of sugar 205 Sweetness & uses of sugar 206 Relation of H+O in sugar 207 Milk sugar 208 Lacto-carmel. Lactose 209 Trehulose. Megatose. Mellitose 210 Non fermentible sugars. Inosite 210 Seyllite. Sorbite 211 Glucosides. Salicin 212 Action of amulcin & acids on salicin 212 Saligenin. Populin. Quercitrin Convolvulin 213 Colouring matters 214 Isolation of colouring matters 214 Dyeing. Mordants. Printing 215 Madder. Ruberithric acid 218 Aliyacin. Lakes. Resemblance to 219 naphthalin. Production of Chloralizarin from naphthalin Purpurine. Rubiacine 219 Logwood Hematoxylin. Brazilwood 221 yellow dyes 221 Indigo 222 Topical dyeing 223 Colouring matters of lichens 224 Cochineal. Carminic acid 225 Volatile oils, resins & caoutchouc Essential oils 226 Stereoptines 227 Preparation of essential oils 227 Classification of these oils. Central formula 228 Essences isomeric with camphine 229 Turpentine 229 Essences not isomeric with camphine 231 Oxygenized essences Camphors 231 Resins, Copal. Mastic. Sandarac. Lac. 232 Sealing wan Lacquers 234 Guayacum. Jalaps. Amber 235 Caoutchouc. Gutta-percha 236 Asphalt & bitumen 238 Ozokerite. Sheerite. Fichtilite. Hartite Idualite 239 Animal chemistry Vital agency 240 Histogenetic substances 241 Existence of some both in animals & vegetables 242 Soluble & insoluble states Action of acids & alkalis on them 243 Putrefaction 244 Test for any of these nitrogenous bodies 245 Protein 245 Albumen albumen of blood 246 Insoluble albumen 248 Fibrin 248 Syntonine 249 Casein Vitellin 250 Globulin 252 Hemato crystalline 253 Derivatives from the albumenous group 253 Ossein Glutin 254 Glue confectionary gelatine 256 Theory of the formation of nitrogenous substances occuring as derivatives in the animal body 257 Kreatin. Kreatinine Sarkosine 258 Methyluramine. Sarkin. Guanine 260 Kanthin Cystin 261 Allantoin Tyrosine 262 Alloxan Parabanic acid 263 Thyanicric acid Alloxantin. Cerebrin. 264 Amide acids. Taurin. Leucin 265 Uric acid. Action of peroxide of Plouit. 267 Urates 268 Derivatives of uric acid 269 Murexide. Guanocolours. Purpuric acid. 270 Compounds from uric acid 271 Cyanuric acid. Inosic acid 272 Acids of bile 272 Glycocholic acid 273 Taurocholic acid 274 Cholic acid 275 Hyoglycholic acid 276 Hyocholic acid. Hyotaurcholic acid 276 Lithofellinic acid 276 Action of acids on cholic acid. Cholordic acid 277 Cholosterin 277 Solid constituents of animals. Bones 278 Teeth. Dentin. 279 Muscular Tissues Composition 280 Sapid constituents of flesh 281 To make strong soup. To boil meat 281 & 2 Extract of flesh 283 Relative values of meat 283 Salting of meat 283 Components of the brain 284 Cerebric acid, Oleophosphoric acid 285 Glands & their juices 286 Digestive fluids Saliva, Ptyalin, Froth, Tartar 287 Functions of saliva 289 Pancreatic fluid 290 Gastric juice, Pepsin. 291 Intestinal juice. Bile. 294 Excrement 296 Intestinal gases 297 Blood 298 Blood corpuscles. Lymph corpuscles 299 Composition of blood 300 Composition of blood corpuscles & liquor sanguinis 301 Hematin, Hematocrystallin 301 Gases in blood 302 Coagulum. Serum 303 Relation of dropsy to the quantity of albumen in serum 304 Chyle 305 Lymph 306 Fluids of generation & developement. 307 Milk 308 Urine 310 Urea 312 Uric acid 314 Hippuric acid 315 Extractive matter, what it is. 315 Mineral ingredients 316 Abnormal ingredients 318 Urine of animals 320 Urinary sediments 321 Urinary calculi 324 Respiration 325 Difference in volume between air inspired & expired 326 Cause of difference in colour between venous & arterial blood 326 N1 NH3 & CO2 in air expired 327 Effects of air richer or poorer in O than usual on respiration 329 Effect of air containing CO2 on respiration. Cause of CO2 acting as a poison 330 Differences in the expiration of CO2 331 Effect of fasting on the quantity of CO2 332 Influence of sex & age 332 Effect of exercise. Influence of food 333 Respiratory equivalents 333 Exciters & nonexciters of respiration 334 Cause of sleep 335 Sleep of hybernating animals 336 Conditions in wh we are most prone to sleep 337 Respiration of the lower animals 337 Origin of the co2 338 General conclusions 339 Animal nutrition 340 Classes of food. Flesh formers & heat givers 341 Flesh formers 342 Use of gelatine 344 Non-nitrogenous substances or heat givers 345 Varying quantity of respiratory food. 347 Formation of fat. 350 Use of fat to hybernating animals 351 Proportion between flesh formers & heat givers in various foods 352 Mineral matter in food 353 Amount of several kinds of food required. Manner of finding uses 354 Pauper & prison diets 357 Action of alcoholic beverages 360 Cost of 1 oz of alcohol in different beverages 360 Relation between character of men & their food 361 Balance between animal & vegetable life 362 Functions of animals 365 Mutual relation of plants & animals 367 [illegible] 13 1 Organic Chemistry Table of the most of important bodies capable of being formed from their elements without vital agency. Cyanogen (C2 N)=Cy Hydrocyanic acid CyH. Ferrocyanide of Fe2 Cy6 Potassium 4k+6HO. Ferricyanide of K. Fe2 Cy6 3K. Urea NH3 CyO } Ho } Marsh gas C2 H4 Oxalic acid C2 O3 HO } C2 O3 HO } Formic acid C2 HO3 } HO } Chloroform C2 H Cl3 Acetic acid C4 H3 O3 } HO } Alcohol C4 H5 O } HO } 2 Ether C4 H5 O } C4 H5 O } Olefiant gas C4 H4 Acetic Ether C4 H5 O } C4 H3 O3 } Oil of garlic C6 H5 S } C6 H5 S } Oil of mustard C6 H5 S } Cy S } Glycerine C6 H8 O6 Butyric acid C8 H7 O3 } HO } Oil of pine apples C4 H5 O } C8 H7 O3 } Oil of pears C10 H11 O } C4 H3 O } Oil of apples C10 H11 O } C10 H9 O3 } Valerianic acid C10 H9 O3 } HO } Grape sugar C12 H12 O12 Lactic acid C12 H12 O12 3 Caproic acid C12 H11 O3 } HO } Benzole C12 H6 Nitrobenzol C12 H5 NO4 C12 H5 O } HO } Picric acid C12 H2 (NO4)3 O } HO } Salicylate of methyl C14 H5 O5 } Oil of Wintergreen C2 H3 O } Naphth C20 H8 4 Organic chemistry is that part of the science wh relates to living bodies. Organic substances are either those with build up living bodies or are produced by living bodies or by submitting these products to different processes in the laboratory. If you compare alcohol an organic base with KO an inorganic base you perceive a great difference between them. Place alcohol in contact with an acid & it does not combine with it while KO does forming a salt. If you add chloroform an organic substance rich in Cl to acetate of Pb you get no precipitate of Pb.Cl. while if you add NaCl an inorganic substance containing Cl. you get a precipitate 5 precipitate If you take a solution of a salt & try reactions with it to-day & then try the same reactions with it to-morrow you will get the same result. If you can do this with an organic compound you may very probably get a different result. If you break up an organic compound you get C, O, H, & N but if you put these together in a flask you cannot make them combine. If you place Na, O & P together you will get NaOPO5 Place C, H & O together & you will not get an organic body. It was supposed at the beginning of the century that there were two different sciences. 6 It was sought to give a definition & in order to do this it was sought whether there was not some element common to organic chemistry & peculiar to it. It was proposed to call it the chemistry of carbon. But CO2, cyanogen & cyanide of K can be made without vital agency. There are bodies not organic wh contain carbon. Liebig defined it as the chemistry of compound radicals you deal in it, not with elements but with little systems. We have however as much right to consider SO2 as a compound 7 compound radical as many of the organic. The last definition was, In organic chemistry combination is ternary or quaternary in inorganic chemistry it is binary. A chemical definition could not be got. It was shown that many products of vital action could be obtained in the laboratory Wöhler made urea & acetic acid artificially. Any alcohol, can be made from a lower one by making a cyanide of an alcohol radical & from this a compound ammonium by acting on it by nascent H The alcohol can be made from this. 8 We see then that the laws of transformation are the same & why then is it necessary to break up the science? The division is empirical. The compounds of C have been farther investigated than the compounds of any other element. These compounds of C occur in living beings & for this reason we call it organic chemistry. The compounds of C are particularly complex. It is important to distinguish between empirical or rational formulæ. The empirical formula is merely the translation of the analysis. Some chemists believe that the rational formula expresses the mode in wh the atoms 9 are arranged. The chemists who hold this doctrine seldom come to an agreement regarding the rational formula of a body. The empirical formula is a fact, the rational is a conjecture. When two chemists were arguing about the formula, it resolved itself into an enumeration of what could be got from the body ; & when one chemist was hard pressed he said "although you show that a certain body" can be taken from this body you cannot show that it exists in the body. Gerhardt proposed that you should make the formula indicate the transformations wh a body could undergo. 10 Thus alcohol C4 H5 } O2 H } Meaning that H & O could be replaced by other substances & that ethers could be got from it in wh C4 H5 exists. The importance of rational formulae is apparent when we consider isomeric bodies Acetate of methyl C4 H3 O2 } O2 = C6 H6 O4 C2 H3 } Formiate of ethyl C2 HO2 } O2 = C6 H6 O4 C4 H5 } These bodies have the same empirical formula but different properties. In organic chemistry the notion of homologous series is important. A homologous series is a series of bodies differing from one 11 another by n times C2 H2. The members represent one another in function, if you apply the same reagents you get the same result. C4 H6 O2 act on it by C4 H5 I C6 H8 O2 C6 H7 I C10 H12 O2 C10 H11 I Heterologous Class. If you compare the bodies you derive from common alcohol you get bodies said to be heterologous. Alcohol C4 H6 O2 C6 H8 O2 Ether C4 H5 O C6 H7 O Aldehyd C4 H4 O2 C6 H6 O2 In the horizontal line the bodies are heterologous & in the vertical lines homologous The boiling pt of alcohol uses 19 degrees Centigrade for every addition of C2 H2. 12 The qualitative examination of organic bodies is peculiar. Examination of bodies for C. When you heat a body rich in C decomposition takes place CO2 being given off & some residual C deposited Organic bodies when heated, as a rule deposit C. Heat sugar in a tube Organic matter when heated either deposits carbonaceous matter or gives off a peculiar smell due to empyreumatic oils. This is the test for C. We seldom test for it. Organic bodies frequently contain N. the testing for which is very important. When a body containing N is burned a peculiar smell is given off. Burns a feather. 13 When a body containing N is heated to redness with a mixture of soda & lime called soda-lime NH3 on a compound NH4 is given off. Another method. When you heat an organic body to redness with Na. you can get the N transformed into Cy or NaCy. Dissolve the residue in HO & add a mixture of per & proto salts of Fe & HCl, if N be present you get prussian blue. The detection of Br. S. & c in organic bodies is attended with difficulty. When organic bodies contain Cl & the like the properties of the Cl are masked & you must heat to redness or with some strongly oxidizing body. Cause the organic body to come 14 into contact with red hot NaOCO2 the Cl combines with the Na & you get Na Cl from which you may calculate the Cl. In place of heating to redness you may heat it to 150°C with strong No5. If you seal up an organic body containing Cl with NO5 & Ag O No5. you get the Cl as AgCl. Detection of S. Not to miss the S you must effect complete destruction of the body. 15 Quantitative Analysis. When organic bodies are heated to redness with great excess of O all the C becomes CO2 & all the H becomes HO. This is universally true. Organic analysis is founded on this fact As certain how much CO2 & HO a given weight of the substance will yield. Several methods may be employed. Bring the body into contact with red hot Cu O. The apparatus consists of 2 parts the combustion & absorption parts. Previously to using the Cu O must be heated red hot since anything exposed to the air takes up dust wh is often organic. You may conveniently heat the Cuo in a Cu crucible. [illustration] The absorption part consists of a 16 Ca Cl Tube + KO bulls. The solution of the KO is made by dissolving 1 part of stick caustic KO in 2 1/2 parts HO. The connections must be light. To test this warm the bulbs so as to expel some air & if the liquid keeps its level afterward for 2 or 3 minutes the joints are tight. In place of CuO, PbO CrO3 is often used. It fuses at a red heat & buries the substance to be burned. Oils are burned by PbO CrO3 O must be passed thro' the tube at the end of the operation, either from a gas holder or from some KO Cl O5 in the tube. When a substance contains N a little alteration is necessary in this arrangement. When a body containing N is heated to redness with CuO, the 17 C Becomes CO2 & the Hi HO, the N appears partly as N & partly as NO2. The NO2 would interfere with the CO2. To remedy this you introduce clean Cu turnings NO2 when slowly passed over Cu turnings is decomposed. Cu turnings prevent NO2 from becoming NO. When a substance contains Cl it is essential to make the combustion with PbOCrO3. If it contains I you must place a long layer of Cu turnings in the front of the tube, these at a red heat absorb the I. To make combustion of liquids make a small glass bulb & seal one end [illustration], weigh it, fill it with liquid by warming it, seal it & weigh again. 18 The difference of the wts is the wt of the liquid taken up. You allow the liquid to distil very slowly over the CuO. When gas ceases to escape the operation is finished. Then pass o over it. Determination of N. Most organic bodies when heated to redness with a caustic alkali yield NH3, the HO of the caustic alkali being decomposed, the C taking the O & forming CO2 & the N taking H & forming NH3 thus– { CN } = NH3 { C1/2 } { O H } { O H } CO2 = { O H } Will & Varrenhapp's method. [illustration] In this case you use a mixture of NaO + CaO for combustion The N is converted into NH3 & absorbed 19 by the HCl with wh the bulbs are filled If you were to operate on KoNo5 you would get no NH3 You would only get traces if you were working with indigo. Where the N is present in the oxidized or nitrous state you get no NH3. Mix a body with CuO, heat to redness, cause the products to pass over Cu turnings & collect the gas in a mercurial trough All the C is got as CO2 the H as HO & you measure the N. General formula of Olefines C2n H2n. Olefiant gas was described in the inorganic part of the course Olefiant gas or Ethylene C4 H4 atomic wt 28 S.G. 9784 20 When HOSO3 is heated with alcohol C4 H6 is produced. [illustration] Alcohol C4 H6 O2 C4 H6 O2 = C4 H6 & H2 O2 taken by HOSO3 . C6 H4 is a colourless gas, has a faint smell, is poisonous, produces headache if much gets into the atmosphere, burns with a very luminous flame. It is contained in a small quantity in common illuminating gas. The name of the gas is got from the fact that when it brought into contact with Cl an oily liquid is formed. [illustration] B is a gas holder containing C4 H4 & C a bottle containing Cl. Pass the C46H4 into C & an oily liquid is seen on the sides C4 H4 readily unites with Br [illustration] 21 C is a glass stopcock fitting tightly into the mouth of the vessel B, into wh some Br is put, C4 H4 is then passed thru it & B is gently heated, & afterwards the liquid formed is poured out of B The Brome liquid is not miscible with HO. C6 H4 takes up 2 equivalents of Cl, Br or I forming Dutch liquid C4 H4 Cl2 C6 H4 Br2 C6 H6 I2 C6 H4 unites with hydracids C4 H4 + HCl = C4 H4 Chloride of ethyl C4 H4 + HBr = Bromide C4 H4 + HI = Iodide C4 H4 unites with HOSO3 C4 H4 HOSO3 sulphurinic acid. HOSO3 These reactions require time To get the reaction with HOSO3 22 Seal up C4 H4 with HOSO3 & Hg & shake up. Berthelot the discoverer of the process shook it 5000 times. If Cl be made to act on C4 H4 Cl2 substitution products are obtained. Act in the sunshine on C4 H4 Cl2. by Cl & you may get C4 Cl4 Cl2. Dutch liquid is not attacked by aqueous caustic KO but when digested for some time with an alcoholic solution of KO it yields C4 H3 Cl + HCl wh the alcohol takes away. Monochloride of ethylene is acted on by Cl yielding C4 H3 Cl, Cl2 . If you act on this by a solution of caustic KO in alcohol you get C4 H3 Cl2 + H CL. 23 Ethylene C4 H6 C4 H3 Cl2 C4 H2 Cl2 C4 H Cl3 C4 Cl4 C4 H4 Cl2 C4 H3 Cl Cl2 C4 H2 Cl2 Cl2 C4 H Cl3 Cl2 C4 Cl4 Cl2 A similar set of reactions can be got with every [oliferic] Propylene. C6 H6 A gas having a very disagreeable smell, very noxious C6 H5 I + 2Hg + HCl = C6 H6 + HgI + HgCl C6 H6 exists in many mixtures it represents C4 H4 exactly. It combines with Br I & hydracids With HCl it forms chloride of propyl. HI - iodide HoSo3 Butylene C8 H8. 24 C8 H8 occurs in small quantity in coral gas, it is colourless. slightly soluble in HO, soluble in alcohol, combines with Br & I. Amylene C10 H10. A A colourless liquid, boils at a temp. very little above the ordinary one of the atmosphere has a disagreeable smell, very volatile. Distil potato spirit with Zn Cl Potato spirit = C10 H12 O2 C10 H12 O2 + Zn Cl = C10 H10 It is a liquid heavier than HO. Readily combines with Cl & Br producing much heat. [illustration] Pours some Br from a pipette into some C10 H10 in a flask. Violent action takes place. Combines with hydracids. With H CL it forms chloride of amyl. 25 Unites with NO4 forming a beautiful crystalline compound. C10 H10 (NO4)2 The higher olifines are very little known Hexylene C12 H12 Distil oleic acid. May be got pure from mannite It is a colourless liquid boils at 60°C . resembles amylene. Unites with Cl violently with Br. C14 H14 Caprylene C16 H16 Elaene C18 H18 Paramylene C20 H20 Cetylene C32 H32 got from spermaceti The composition of olifines above C12 H12 is little known 26 Marsh gas C2 H4 = 16.S.G.5596 Marsh gas is derived from C2 H2 by adding 2 equivalents. Add H2 to any olifine & you get corresponding member of the marsh gas family C2 H4 occurs native, bubbles up in marshy places, exists in considerable quantity in coal mines, & in common gas Prep. Heat acetate of KO with HO KO Acetate of KO = C2 O2 C2 H3 K/O2 HOKO=H/K/O2 C2 O2 C2 H3 K/O2 + H K / O2 = C2 O2 K K/O4 + H C2 H3 Marsh gas = hydride of ethyl Zinc ethyl is a colourless liquid of enimense energy, as great as that of K. It unites with great energy with Ho. ZN C2 H3 + Ho = ZnO + C2 H3 H. 27 [illustration] Break the end off a small bulb of Zn methyl under HO. You may collect & measure the gas produced. Break the end of a glass bulb & the liquid will take fire depositing ZnO & metallic Zn C2 H4 burns without much smoke, it is inert, Br does not act on it Expose C2 H4 + CL to sunlight & you get action Members of the olifine family may be absorbed by fuming HOSO3. You may make this by adding anhydrous SO3 to HOSO3 There are not many members of the marsh gas family well known. C2 H4 Marsh gas C4 H6 hydride of Ethyl. C6 H8 } exist but not C8 H10 } well examined 28 C10 H12 hydride of amyl C12 H16 - hexyl. Hydride of Ethyl atomic wt 30 S.G. Place Zn Ethyl in HO. Take propionate of KO + HOKO heat together & you get hydride of ethyl. It is a colourless gas. It closely resembles hydride of methyl in its properties Hydride of Amyl. Boils at about 30°c, has a smell like chloroform [illustration] Iodide of amyl Zn + HO are sealed up in a table & heated in the water bath for some time Zn amyl forms first & then acts on the HO. It is very light, the lightest liquid known, has a pleasant smell. 29 Hydride of Hexyl C6 H14 May be got from mannite Colourless, very light boils at 60°C. It is very probable that it is the H representative of the sugar family. Very little certain is known of the higher families Family of alcohol radicals. Methyl C2 H3 C2 H3 Ethyl C4 H5 Propyl Butyl Amyl C10 H11 C10 H11 Amyl boils at a very high temp. is a colourless mobile liquid with a peculiar smell 30 When an iodide of an alcohol radical is heated strongly with Zn you get Zn I & the radical. C4 H5 } I } C4 H5 } I } + Zn2 = Zn } I } Zn } I } + C4 H5 C4 H5 Alcohol radicals may be got from fatty acids If you electrolyse acetic acid you get CO2 & methyl. Acetic acid = C2 O2 C2 H3 } H } O2 C2 O2 C2 H3 } H } O2 + O = C2 O2 O2 + HO + C2 H3 Take any other fatty acid of the series & you get an alcohol radical having C2 less than the acid is an extremely indifferent body The alcohols have not yet been 31 got from alcohol radicals Example of organic analysis Analysis of mannite. .3532 grams mannite gave .5069 - CO2 diff. of wt of KO bulb .2505 - HO - of CaCl tube Since 22 grams of CO2 contain 6C you multiply the co2 by 3 & divide by 11. .5069 x 3 = 1.5207 ÷ 11 = .1382 C To find the H divide the HO by 9 .2505 ÷ 9 = .0277 .3512 : .1382 :: 100 : 39.13 Percentage of C .3512 : .0277 :: 100 : 7.8 - H The diff between the wts of C + H & of the mannite is 0. 39.1C ÷ 6 = 6.5C = 65 7.8H ÷ 1 = 7.8H = 78 53.1O ÷ 8 = 6.60 = 66 100. To find the formula divide the percentage by the equivalents 32 of the bodies. The percentage of C should not be 2/10 ° below the theoretical quantity of the percentage of H 1/10 above it. Transformation of organic compounds by different ferments. Diatase Starch { C12 H10 O10 + 4HO = Grape sugar { C12 H14 O14 2 yeast Grape sugar { C12 H14 O14 = alcohol { 2C4 H6 O2 + 4CO2 + 2HO 3 Casein Milk sugar { C24 H24 O24 = Lactic acid { 2(C12 H10 O10, 2HO) Lactic acid { C12 H12 O12 = Butyric acid { C8 H8 O4 + 4CO2 + 4H 33 4 Synaptase Amygdalin { C40 H27 NO22 = Hydrocyanic acid { HC2 N + Oil of bitter almonds { 2C14 H6 O2 + Formic acid 2C2 H4 O6+3HO + Grape sugar { C12 H14 O14 /2 Salicin C26 H18 O14 + 4HO = Salicenin { C14 HO + Grape sugar We have considered the olifines the homologues of marsh gas & the alcohol radicals. We can reduce nearly all the others to the olifines Methyline C2 H2 supposed to exist in wood spirit, not known in a separate state. Ethylene C4 H4 Propylene C6 H6 Butylene C8 H8 Amylene C10 H10 These are distinctly radicals in themselves they unite 34 with Cl. They are biatomic. This is expressed by two dots thus C6 H6,, They unite with 2 atoms Cl, Br &c. Homologous of marsh gas These are olifines having their biatomicity gratified by 2 atoms, H. C2 H4 C4 H6 &c There are some instances where the biatomicity is not fully gratified having only 1 atom of H & 1 atom to be filled up by something else. These are the alcohol radicals. C2 H2 , H = C2 H3 methyl C4 H4 , H = C4 H5 ethyl C6 H6 , H = C6 H7 propyl C8 H8 , H = C8 H9 butyl C10 H10 , H = C10 H11 amyl. These are olifines stepping towards 35 the gratification of their biatomicity Suppose you add 1 atom Cl to C2 H3 you get chloride of methyl C2 H3 Cl or to C4 H5 you get chloride of ethyl C4 H4 HCl = C4 H5 Cl Suppose instead of Cl you substitute O, thus, C4 H6 HO You get ethers, of wh common ether is the type General formula of ethers Cn Hn HO corresponding to marsh gas Cn Hn HH. A radical is merely a body wh moves about Act on PbO by HCl. PbO + HCl = PbCl + H O. What is the radical ? The body you can move about viz., Pb. In the same way C4 H4 H O + H Cl = C4 H5 CL + HO. Instead of C4 H4 H you write 36 C4 H5. the radical because you move it about. What are the ethers wood spirit n methylic common propylic butylic amylic Methylic ether C2 H3 O = 23. Or when free it is doubled, as instead of C4 H5 to get a four volume formula you have C8 H10 (C4 H4 ) H this is lob sided having H on one pole & not on the other H (C4 H4) (C4 H4) H When doubled it is symmetrical. Why does ether double itself. O(C4 H4) H. The symmetry is not quite complete, tho' it is thus when in combination H O H (C4 H4) (C4 H4) H H O When free it doubles its combining vol. 37 wh is 2 Methylic ether vap. density Prep. Heat wood spirit with 4 parts HOSO3 & pass thro HOKO. It is a colourless etherial gas not condensible at 60°C, burn, with a pale blue flame, very soluble in HO to the extent of soluble in alcohol. Combines readily with HOSO3 & HCl. Act on KO by HCl. KO + HCl = KCl + HO. - C2 H3 O - C2 H3 O + HCl = C2 H3 Cl + HO. You may get chloride, iodide & bromide of methyl. Substitution products of Chloride of methyl, C2 H3 Cl. Chloroform. Two equivalents of H are substituted by Cl. (C2 H Cl2) Cl. The arbitrary formula is C2 H Cl3. 38 s.g of liquid chloroform 1.48 boils at 60.8°C Put 20 lbs Ca Cl in 120 lbs HO place in a Cu retort 1/3 full add 4 lbs alcohol. Heat quickly to 80°c & then withdraw the fire. You get 2 fluids the heavier is chloroform, wash with It is a colourless liquid, of an etherial sweet odour, sharp & sweetish taste. It is inflamed with difficulty. Place some on cotton wool it burns & gives off HCl. It falls thro' HO without dissolving. It is a good solvent of india rubber, P. Vinic ether, C4 H5 0 combining formula. & C8 H10 O2 its free formula. 39 formula. s.g of liquid .03736 at 0°C & .0724 at 16°C or 257. Boils at 35.5°C or 957. Vap. den. 2.586 Prep. Act on common alcohol with HOSO3 [illustration] C4 H6 O2 common alcohol HO - C4 H5 O = ether. you may suppose alcohol to be the hydrate of ether. There have been many treatises on this reaction. The HOSO3 has an affinity for HO & takes it away. Seal up anhydrous MgOSO3 & alcohol in a tube, the MgOSO3 takes away the HO & you get ether. There is no difficulty 40 in this case. But in distilling alcohol & HOSO3 , the HOSO3 does not combine with the HO. In the receiver you get HO & ether equal in bulk to the alcohol. There are many like instances in catalyses. The HOSO3 takes the HO but the heat drives it off. There are other theories. One is that a body called sulphorinic acid is formed. first. There is reason to suppose that HOSO3 is S2 O6 = HO/ HO/ S2 O6 Ho | C4 H5 O | S2 O6 sulphorinic acid KO | C4 H5 O | S2 O6 sulphorinate of Ko. They say that the sulphorinic 41 sulphorinic acid is decomposed, Haloid compounds of ether. Hydrochloric ether, C4 H5 Cl Pass HCl thro' ether or better thro' alcohol, you get C4 H5 Cl, chloride of ethyl. S.g of liquid 0.874 boils at 11°C A colourless, very volatile liquid & has a penetrating etherial odour. Slightly soluble in HO, soluble in alcohol. Analogous to an oxide KO + HCl = KCl + HO C4 H5 O + HCl = C4 H5 Cl+ HO. Iodide of ethyl. C4 H5 I. s.g boils at 72°C Colourless of an etherial smell. Much used to get radicals Act on hydrochloric ether by Cl & you get chlorinated ether. Act on it with Cl in sunlight 42 sunlight & you get Dichlorinated ether. Act with Cl by sunlight & heat & you get Trichlorinated ether. Ethers as a class. They represent the protoxides of metals Ko when free is probably not KO but KKO2 or K2 02. Ether when separate is not C4 H4 O but C8 H10 O2. Two atoms of radical united with 2 of O. What happens to KO when it is hydrated? KH/O2 = KO1 HO. one atom k going out & one of H going in. Take 1 atom of radical from ether & add 1 of H. (C4 H5) O2 alcohol is one of the H radicals of the double 43 ether taken out & 1 atom H put in its place. That the ethers are really duplicated in their separate state follows from the fact that you are able to substi- tute one radical by another C4 H5 } C4 H5 } O2 C4 H5 } C2 H3 } O2 C2 H3 } C2 H3 } O2 C2 H3 } C4 H5 } O2 When not in a free state they halve themselves & unite with a base. KO + NO5 = KONO5 C4 H5 O + NO5 = C4 H5 O NO5 you can form a whole set of ethers. The ethers are to be considered as the protoxides of the metals & the alcohols as the 44 hydrates of the protoxides KO (C4 H5 O) HO KO. (C4 H5 O) HO. Alcohols = 4 vols. S.G liquid vap. Boiling point Wood spirit C2 H4 O2 0.798 1.12 150° Spirit of wine C4 H6 O2 0.796 1.61 173 Propylic alcohol C6 H8 O2 - 2.02 206 Butylic C8 H10 O2 0.803 2.59 233 Amylic C10 H12 02 0.818 3.14 270 Caproic C12 H16 O2 0.830 3.53 304 Caprylic C16 H18 02 0.820 4.5 356 Lauric C24 H26 O2 Cetylic C32 H34 O2 Cerylic C54 H56 O2 Melissic C60 H62 O2 Aldehydes. Formic aldehyd Acetic Propionic Butyric 45 Valerianic aldehyd Caproic Oenauthylic Capric Euodic Ethers form a homologous series corresponding to the alcohols. The general formula of an alcohol is that of an ether + 1HO Ether = Cn Hn,, Ho1 + HO = Cn Hn an alcohol. The alcohols belong to a different class from the ethers, as a hydrate does not represent a protoxide but a peroxide. O | O | K2 O | O | (CnHn)2 | O | | O | K O | HO | K O | HO | C4 H5 O | NO5 | K O | NO5 | C4 H5 Alcohol is a hydrate of ether & is a salt. 46 Wood spirit on methylic alcohol C2 H6 O2 = O| HO | C2 H3. equals 32. s.g of liquid 0.818 at 32°, at 65° 0.798 vap. density 1.12 boils at 150° F Prep Distil wood, acetic acid & wood spirit are given off it is purified by lime & distilled from Ca Cl. When pure, it is colourless has the odour of acetic ether is a good solvent for resins when oxidized it forms formic acid. Vinic alcohol or spirit of wine. C4 H6 O2. O| HO| C4 H5 = 46. s.g when free at 60° is 0.794 vap. den. 1.613 boils at 173°F or 78°C. Alcohol has been made synthetically. We believe it contains C4 H4 47 add 2 atoms HO & you alcohol. C4 H4 " H2 O2 - C4 H6 O2 Pass C4 H4 into HOSO3 add HO & distil, alcohol comes over. [illustration] Prep. Distil from fermented add KOCO2 wh has been heated & the KOCO2 takes the HO & falls to the bottom. you distil again from Ca Cl or dried CuO. It is a colourless, volatile mobile liquid of an aromatic smell & burning taste It has a strong affinity for HO, & the mixture contracts. burns without smoke. It has never been solidified by cold, at -166° F it becomes viscid, is a good solvent for Br, I, S, Na & bodies containing H. In using it as a fuel it is 48 completely burnt. C4 H6 O2 + 120 = 4CO2 + 6HO. It unites with salts as HO does & forms alcoates instead of hydrates. Wines & spirits. Proof spirit 50.76 P.C. alcohol & 49.74 HO [illustration] Proof used to be -set some gunpowder on a tile pour spirit over it. & set the spirit on fire. If the spirit be above proof the gunpowder should go off when the spirit is burned. if under proof the HO it contains wets the powder so that it does not go off. Distilled spirits. Brandy contains 55 P.C. alcohol in its ordinary state it is coloured with burnt sugar 49 & peach kernels are added during distillation to flavour it. gin is got from fermented grain & flavoured by juniper berries. Whisky is distilled from grain & has a slightly smoky taste. Rum is got from sugar Arrack from fermented rice betel nuts or palm juice Potato brandy is get by converting potato starch into glucose & distilling it. Wines are the fermented fluid without distilling. When all the sugar is converted into alcohol they are called dry. when much sugar remains they are called fruity. The bouquet is due 1st,, to the completion or 50 non completion of these actions 2nd to the deposition of cream of tartar 3d to the formation of fragrant ethers by the action of vegetable acids on the strength of wines Port or Madeira 15-20 P.C alcohol Sherry 15-17 Lisbon 16 Malmsey 13 Champagne 12 French clarets 9-10 Rhenish wines 10-12 Cider 4-8 Perry 6-8 Ale 6-8 Porter 5 Small beer 1 1/2 The market value of wines depends on their flavour 51 One imperial pint of the following wines contains HO oz alcohol oz sugar grs Tartaric acid grs. Port 16 4 1-2 80 Brown sherry 4 1/2 360 90 Claret 2 none 161 Burgundy 12 1/2 2 1/2 160 Fermentation It is the process by wh sugar is converted into alcohol. Grape sugar in honey C12 H12 O12 Act by yeast = 4Co2 + 2(C4 H6 O2) Yeast does not appear in the final product Conditions for fermentation The temperature must be 50°-60° F HO must be present to keep the sugar in solution Air must be present to make the yeast live & effect the transformation Nitrogenized substances 52 must be present & a body capable of fermenting. There is spontaneous fermentation as in crushed grapes the air acts on the nitrogenous matter in the cells. When we add a ferment to sugar, & the ferment disappears or forms a heavy substance wh falls to bottom. The yeast is a vegetable growing body, & consists of cells wh when placed in a warm saccharine fluid increase, one cell giving off many others, about 1/250th of an inch in diameter. They finally cease to produce gas. 53 Composition Before fermentation after C 47.71 p.c 48.31 H 6.7 7.33 N 10.15 5.07 O 35.44 39.29 SoP Traces Traces. The N is only one half of what it was when the operation commenced. When yeast is active it is acid if you add an alkali to it, it stops its action & the fermentation. Weak acids favour fermentation, strong acids destroy it. Some poisons destroy it others do not. Theory of action of ferments Liebig's view is that the ferment is in a state of internal change & that it communicates this change to the other body 54 wh is in a state of statical equilibrium. Pasteur considers that it is an action not correlative with the death of the plant but with its life. He burnt yeast & added the ashes & an ammonia salt to sugar. The NH3 disappeared from the solution. The result of fermentation is complex. Glycerin & butylic acid are produced as well as alcohol & CO2. Suppose you put a piece of putrid cheese or casein into sugar, you get a different action & lactic acid is produced If the cheese is very putrid the lactic acid becomes butyric 55 acid. C12 H12 O12 The brewing of beer is a reproductive fermentation A certain quantity of yeast is added to the fermenting liquid & grows so much that much more yeast is obtained. Malting is the germination of barley. When the young sprout is about 1/2 inch in length & begins to bifurcate, its life is destroyed by roasting. The barley in malting contains diastase. Diastase can convert starch into dextrin, it then changes the dextrin into grape sugar. One part diastase can convert 4000 parts of starch into sugar malt contains 1/500th of its weight of diastase, so there is enough 56 diastase left to An infusion of the malt is made & 4 or 5 parts of fresh barley added It converts the barley into sugar you then add say 1 part yeast wh produces 2 parts of alcohol 4CO2 + 2HO In the barley there is gluten a body of the same composition as the muscle of our bodies. The yeast acts on the gluten & it receives so much food from the gluten that it grows with great rapidity & produces much new yeast. Composition of 1 imperial pint HO oz ale oz sugar grs acetic acid grs London stout 18 1/2 1 1/2 281 54 - porter 19 1/4 3/4 267 45 pale ale 17 1/2 2 1/2 240 40 mild - 18 3/4 1 1/4 280 38 strong - 18 2 2.136 54 57 Homologues of the alcohols. Propylic alcohol. C6 H8 O2. Found in the product of the fermentation of grape skins. It is a colourless liquid with an agreeable fruity smell, lighter than HO. Prepared by synthesis from propylene. Propylene is passed into HOSO3 HO is added & it is distilled. Butylic alcohol C8 H10 O2 Found in small quantity in fusel oil. It is a colourless liquid, smelling like fusel oil & wine, soluble in HO but separates on the addition of salt. Amylic alcohol. C10 H12 O2 S.G of the liquid 0.818 vap. density 3.147 boils at 58 Has a higher boiling pt than the previous ones. Brandy contains a little fusel oil & whiskey a good deal. Test pour some of the spirit thought to contain it on your hand & allow it to evaporate you can then smell the fusel oil. It is though a colourless, mobile liquid, of a disagreeable odour burning taste, slightly soluble in HO, soluble in alcohol & ether when strong it is poisonous & produces a cough & spasm of the glottis Caproic alcohol. Formed in the fermentation of grape skins, Refracts light strongly: insoluble in HO General properties of alcohols. The chemical reactions of alcohols 59 alcohols are nearly all the same. If we act on them by acids you get ethers. C4 H5 O HO + NO5 = C4 H5 O NO5 + HO KO HO + NO5 = KONO5 + HO. The compound ethers are on the same type as alcohols, but acids replacing the HO. Boiling pts Vinic alcohol 78°C } difference Propylic 96C } 18°C Butylic 112° } 16°C Amylic 132 } 20°C Caproic 150°} 18°C Compound ethers are derived from the alcohols, & are salts of the ethers, the HO of the alcohol being replaced by acid. Sulphuric ether, not that of shops wh is common ether but that of chemists C4 H5 OSO3 Prep. Act on ether by anhydrous 60 anhydrous SO3 in the cold, Colourless, aromatic liquid not miscible with HO. Nitric ether. C6 H5 ONO5. Used in pharmacy. S.G of liquid 1.11 boils at 85°C. Distil HONO5 with alcohol & a little urea. When pure it is a colourless aromatic liquid, with a faint smell of apples, explodes when quickly heated. Nitrous ether C4 H5 ONO3 s.g of liq boils at 16.4°C Distil spirit of wine with HONO5 It is yellow, inflammible insoluble in HO soluble in alcohol. Decomposed in heating with the evolution of N. Even the feeble acids have 61 been made to unite with ether. C4 H5 O CO2 C4 H5 O Sc O2 a proposition was made for covering the houses of Parliament with a coating of silica by means of C4 H5 OSiO2. Sulphovenates, are salts of ether in wh one of the equivalents of HO in HOSO3 viewed as a bibasic acid is replaced by ether. HO | HO | S2 O6 HO | C4 H5 O | S2 O6 add KO KO | C4 H5 O | S2 O6 Sulphovenate of Ko It is not HOSO3 alone wh acts in this way, PO5 does it also HO | HO | HO | PO5 HO | HO | C4 H5 O | PO5 Phosphovenic acid As every ether has its alcohol & every alcohol can form a compound ether you might 62 go on in the series but when you know the properties of one in a series the others much resemble it. Nitrite of amyl. It is amylic alcohol with HO displaced & NO3 added C10 H11 O HO C10 H11 O NO3 It has properties the very reverse of chloroform. It increases the action of the heart, & produces acute headache. In cases of long suspended syncope it might be useful. Biatomic ethers & alcohols. An ether is monoatomic when it unites with 1 atom acid or with of HO to form alcohol. C4 H4 " HH. marsh gas. C4 H4 ClCl C4 H4 HO ether. 63 C4 H4 O O Cn Hn" O O biatomic ether Cn Hn OO + 2HO - alcohol Why should those be biatomic? KOHO it has one of O in the base KONO5 Sn O2, 2HO it has 2 of O in the base Sn O2, 2NO5 The same with biatomic alcohol. Ethylene ether C4 H4 O2 corresponding to dutch liquid Has been imperfectly studied. 2b hydrate or ethylene alcohol C4 H4 O2 + 2HO generally called glycol is better known. Empirical formula C4 H6 O4 Obtained by the action of HOKO on acetate of ethylene. C4 H4 O2, 2C4 H3 O3 + 2KO HO = 2(KOC4 H3 O3) + C4 H4 O2 + 2HO. A clear thick sweet liquid 15 64 Soluble in HO & alcohol, the vapour burn & is converted into acid by oxidation. Acetate of ethylene. Act on Bromide of ethylene a dutch liquid by acetate of KO. C4 H4 I2 + 2KOC4 H3 O3 = 2 KI + C4 H4 O2, 2C4 H3 O3 Acetic ether is a colourless liquid, at a high temp. it smells feebly of acetic acid. We can produce the homologues of glycol thro the whole series. C4 H4 HO common ether C6 H6 OO biatomic - . C4 H4 HO + HO common alcohol. C4 H4 OO + 2HO biatomic - Cn Hn HO + HO common Cn Hn OO + 2HO biatomic Cn Hn OO, 2HO Cn Hn OO, 2A C6 H6 OO 2(C4 H3 O3) binacetate of ether of olifine 65 Every homologous olifine has an ether & alcohol belonging to it. We now consider a stepping stone between the alcohols & acids, the aldehydes. Alcohol Aldehyde Acids of alcohols. Cn Hn + 1. +1 means that there is 1 atom of H more than the number of C. alcohol Cn Hn +1 O, HO = HO + ether General way of forming aldehydes from alcohols. Cn Hn +1 HO - 2H = aldehyde. It is simply by oxidation that you do this. [illustration] Put a heated Pt wire into a glass in wh is a little ether. Aldehyde vapours form round the Pt. You are forcing the H to combine with the O by the action 66 of the Pt. [illustration] Distil alcohol, HOSO3 & Mn O2 in a capacious retort & aldehyde is produced. Add 2 atoms of H to an aldehyde & you get an alcohol. Vinic or acetic aldehyde C4 H6 O2. s.g of liq 0.79. vapour density 1.53 4 volume formula boils at 21°C. Distil in a capacious retort 6 parts HOSO3, 4 alcohol of 85 P.C.. 4HOO 6 MnO2. The loss is considerable. you get a colourless liquid of an irritating pungent odour, burns with a white flame, with alkaline bisulphides it forms a white solid compounds. It is singularly unstable, if you seal it up in a tube it changes after a time to porcelain 67 like substance, it is then probably C12 H12 O6 There are several of these varieties. General process to get aldehydes. Suppose you wish acetic aldehyde. Distil acetate of lime with one equivalent of formiate of lime acetic aldehyde. Ca O C4 H3 O3 + Ca O C2 HO3 = 2Ca O CO2 + C6 H4 O2 General view of the constitution of aldehydes There are several views. Gerhardt thinks they are constituted on the type of H. H = H } H } C4 H3 O2 } H } = acetic aldehyde. That one H is replaced by C4 H3 O2 a radical he calls acetyle. Liebig thinks that they are alcohols of unknown radicals 68 & that the radicals are negative or are Cn Hn -1 having 1 atom less H than C. C4 H3 O HO = aldehyde = hydrate of oxide of acetyle. He calls C4 H3 O acetyle. In our view we view aldehyde as the alcohols of oxidized olifines C4 H4 " HO common ether C4 H3 O, " HO aldehyde 1 H being replaced by O. Every alcohol has its ether - aldehyde - ketone. If you take the acid salt of any as Acetate of Pt + distil you get a tarry liquid wh when purified is a acetone the ketone of the ketone the aldehyde in wh 1 H is substituted by the alcohol radical below it in the series 69 C2 H3 methyl is the radical below C4 H5 ethyl in the series. C4 H5 O, HO substitute the H by methyl C4 H5 O (C2 H3) O. Ketone of the series. Acetone C6 H8 O2 = C4 H5 O2 C2 H3/ C6 H8 O2 Heat chloride of acetyle with Zn methyl. It is a clear colourless liquid of an etherial smell, soluble in HO but separates readily on the addition of salt, readily soluble in alcohol & ether. Absorbs H Cl readily & polymerizes Anhydrides or acids. When monoatomic alcohols homologous with methylic are fully oxidized they are changed into aldehydes & then into 70 acids. All the acids are derived from corresponding alcohols by oxidation It was long supposed that there was no anhydrous acid in the organic series. KOSO3 = KSO4 There is a great disposition among chemists to reduce to the binary type. They have got anhydrous acids mode. General reaction. By acting on a salt such as an acetate with a body wh is oxichloride of P, P Cl3 O2. Example. To get anhydrous acetic acid. Take acetate of KO. C4 H3 O3, HO, From chloride of P. you can get chloride of acetyle C4 H3 O2 Cl, = anhydrous acetic 71 acid in wh 1 of O is replaced by Cl. C4 H3 O3 KO + C4 H3 O2 Cl = 2(C4 H3 O3)+ KCl. Anhydrous acetic acid. Its formula is doubled C8 H6 O6 liquid s.g 1.073 vapour density 3.47 boils at 140°C. It is a colourless mobile, highly refracting liquid. It sinks thro HO like oil but gradually unites with it & forms vinegar All other anhydrous acids could be prepared. Hydrated acids Relation of these acids to alcohol & ether. Ether C4 H6 " HO Ethylene ether C4 H6 " OO - Alcohol or glyeds C4H4 OO HO HO Oxydized series Aldehyde C4 H3 O " HO Anhydride C4 H3 O " OO Acetic acid C4 H3 O OO/HO 72 Formic Acid. empirical formula C2 H2 O4 s.g of liquid 1.235 vapour density 1.554. Occurrence. Called formic acid because it occurs in the red ant Formica rufa: occurs in the stinging nettle urtica urens & in various animal secretions. Obtained by synthesis. By passing CO over HO KO KO HO + 2CO = KOC2 H3 O3. Distil starch with HOSO3 + MnO2 This is not the best way. Mix syrupy glycerine with oxalic acid & heat. It was formerly got by crushing & distilling ants. It forms many salts wh crystallize readily & form definite & permanent compounds. Acetic acid. HO C4 H3 O3 or C4 H4 O4 s.g of liquid 1.063 vapour density 73 2.08 boils at 119°C. Occurs as acetates in various vegetable juices in the perspiration of animals, in the juice of flesh Prepared by synthesis. By the action of CO2 on Zn methyl. C2 H3 Na + C2 O4 = Na C6 H3 O3. you get acetate of Na Commercially. Distil wood & you get pyroligneous acid & pyroxylic spirit. The ash, oak & beech are preferred. Add lime & you get acetate of lime, distil over & you get glacial acetic acid, it is so called because it becomes solid when exposed to cold. If you pass alcohol over spongy Pt in presence of air you get acetic acid Oxidize alcohol. A large cask is 74 taken, wh allows air to pass thro it, & filled with beech wood shavings & alcohol [illustration] poured over it, it is done two or three times & in its passage is oxidized to acetic acid. 1 part alcohol + 6 HO + 1/1000 th part of honey are taken. Relation between the alcohols aldehydes & ketones. alcohol C4 H4 H1 O1 HO double ether C4 H4 " H1 O1 (C2 H3)O Aldehyd C4 H3 O " H1 O. Acetone C4 H3 O " (C2 H3)O. is not a common alcohol in wh the H is replaced by the radical neat lower in the series it is the aldehyd in wh the H is replaced by the radical 1 below it in the series. Thus, Butyrone, C8 H7 O " (C6 H7)O. 75 16 [illustration] Prep of acetone C is a Cu retort in wh Acetic acid. C4 H4 O2 At 55° it is solid & crystalline melts at 62°, has a pungent peculiar smell, burning taste, acid taste, miscible with HO, ether & alcohol, it dissolves camphor & essential oils, the strongest acetic acid forms aromatic vinegar & is generally flavoured with essence of camphor or bergamot. It is used in medicine as a rubefacient, when too strong it blisters the skin. Most acetates are soluble. Vinegar is dilute acetic acid is is made from bad wine The temp necessary to produce oxidation is 70-80°F. Malt vinegar is now largely 76 used, it contains about 5 P.C of acetic acid. Acetic acid may be acted on by Cl & forms a very complete substitution acid. KO C4 H3 O3 acetate of KO. KO C4 Cl3 O3 chloracetate of KO. Acetates. Acetate of KO. KO C4 H3 O3 Prep. Dissolve KO CO2 in acetic acid Prep. Anhydrous. foliated, deliquescent. Acetate of NaO. NaOC6 H3 O3 + 6HO. Colourless transparent effloresent cooling taste. Acetate of ammonia. NH4 OC6 H3 O3. White crystalline easily solube decomposes when heated. distilled. Nh4 OC6 H3 O3 = 4HO + C4 H3 N = C2 H3 C2 N or cyanide of methyl. The cyanide of the radical below that from wh acid is derived. 77 another example propionate of ammonia. NH4 OC6 H5 O3 = 4HOC6 H5 N = C6 H5 C2 N NH4 OC2 H3 O3 is used in medicine as a refrigerent & to act on the kidneys Acetate of PG. PGOC4 H3 O3 + 3HO this is neutral acetate. Prep. Dissolve PGO in acetic acid & crystallize. It is often called sugar of PG. It crystallizes in transparent rhombic prisms, has a sweet taste, soluble in twice its wt of HO & alcohol, it is used as a lotion is poisonous. There are some subacetates. 3PbO, 1C4 H3 O3 6PbO 1 C4 H3 O3. Acetates of Cu. There are several. Neutral acetate 1 CuO 5 acetic acid 78 & 5HO. There are various insoluble subacetates. Verdigris. Expose sheets of Cu in alternate layers with fermented grape skins. The crust is scraped off & made into a paste with vinegar & made into moulds. Glycocol is connected with acetic acid. Occurs in the transformation of many animal substances in the decomposition of hippuric acid &c. It is crystalline sweet, fusible at 78°C soluble in HO & hydrated alcohol, insoluble in ether & absolute alcohol. It is a very weak acid acting partly as an acid & partly as a base. 79 It is acetic acid in wh 1 atom H ionical is substituted by amidoger NH2 . Acetic acid (C4 H2 HO)"OO Glycolic -- (C4 H2 OO)"OO Glycocol C4 H2 (NH2)O) OO NH3 thought to be (NH2) H hydride of amidogen Acids homologous to acetic acid Propionic acid. HOC6 H5 O3 liquid s.g 0.991 boils at 140°C Its synthesis has been effected by Na ethyl . C4 H5 Na + C2 O4 = NaOC6 H5 O3 proprionate of NaO. Butyric acid C8 H8 O4 = HOC8 H7 O3 liquid s.g 0.978 Occurs ready formed in certain fruits, in sourkrout. In the animal organism it is found sometimes in sweat, in gastric juice, in 80 certain diseases in wh the expectorations have a bad smell. In the bad smelling juices of certain animals. In the oxidation of casein & fibrin By fermenting sugar by poor cheese or curd in presence of chalk. you get butyrate of lime, lactate of lime is first formed. Add HCl & distil & you get butyric acid. It is a colourless liquid, with a very disgusting odour. Crystallized by intense cold. Slightly soluble in HO. Butyrates crystallize & have no disagreeable smell when dry, tho when wet the CO2 of the air liberates some 81 butyric acid & causes a smell. They have more the character of soaps than any salts we have yet dealt with. Butyrate of lime. It is much more soluble in than Butyric ether C4 H5 OC8 H7 O3. liquid s.g .901 boils at 119°C, a clear, mobile, liquid, & fragrant ether It occurs in the pineapple, melon strawberry & other fruits Some fragrant ethers are got from acids having an abominable smell A strong alcoholic solution of butyric ether is sold under the name of essence of pineapples, & more diluted as essence of strawberries. Amylic or valeric acid C10 H10 O6 = HO1 C10 H9 O3 82 liquid s.g 0.937 vapour density 3.66 boiling point 347° Occurs in valerian & angelica root, in putrid cheese in train & sperm oil Prep. Distil valerian root with HO. Or Distil fusel oil with HOSO3 + KO2CrO3 It is limpid, has an odour like cheese floats on HO. Forms valeriates wh are soapy substances. Fatty acids Rutic is the first true fatty acid or oil when melted. It occurs in the fat of goats. Palmitic acid C32 H32 O4 or Ho C32 H31 O3 Melts at 62°C. All the fats vegetable & animal are compound ethers, the ether they contain is that of Glycerin united with a fatty acid Palmitic acid in combination 83 with glycerin is in almost all fats especially human & pigs It is obtained by saponification Fat = Glycerin } Fatty acid } + KO = KO } fatty acid } = soap. Act on soap by alcohol & you get the acid in a free state. Prep. Tasteless white fat crystallizes in tufts insoluble in HO soluble in alcohol & ether. Palmitates are soaps insoluble when the bases are earths, soluble when they are fats. Stearic acid C36 H36 O4 melts at 69.2°C occurs in combination with glycerine in most fats, in all animal fats the richer the fat in stearic acid the harder it is. It is got from stearate of KO by HCl insoluble in HO. 84 When distilled it is converted into palmitic acid. Stearates of alkalis are soluble Neutral stearates are decomposed by HO into alkalis & Lamps were used before candles were introduced. Torches were the first candles & were probably used with lanterns. Pling alludes to candles wh were probably of wax. The only cheap candles in this country were the fats themselves. They had a low fusing point & ran & the wick did not burn away and required snuffing. [illustration] Palmers candlestick was meant to remedy this. The candle was kept at the level of the candlestick by a spiral spring & the 85 wick wh was double turned outwards so that the end was always exposed to the air & thus burned away. Improvements in candles. It was discovered that tallow consisted of stearine & oleine & that by heating tallow to the fusing pt of oleine but not to that of stearine the oleine might be pressed out & stearine left. Tallow melts at 102° Stearine 144 Stearic acid 15° Candles of stearic acid would thus be better than those of stearine The stearine was saponified & the soap acted on by HCl. There were many objections to the use of stearic acid candles The wick got clogged up. This was found to be owing to the wick 86 leaving alkaline ashes & forming a soap with the stearic acid This was remedied by dipping the wick in HOSO3. C6 H5 O3"' Glycerine ether (C6 H5 O3"') 3HO Glycerine (C6 H5 O3"') 3A A fat. Tallow is a mixture of fats, as, oleine. palmitine & stearine glycerine itself is not combustible. In the stearic acid candles, the oleine & glycerine are both removed. Stearic acid candles so called, are generally palmitic acid & are got from palm oil. The improvements in candle making depend chiefly on Chevreuls researches on fats. Saponification. The fat is boiled with lime, & HOSO3 added. 87 to the lime salt of the fatty acid thus obtained. the acid is then got in free state (C6 H5 O3"') 3a + CaO = lime salt 3HO = glycerine 3SO3 Another difficulty in the use of stearic acid candles is that it has a tendency to crystallize. The crystalline flakes often broke off the candles. By putting a little arsenic into the acid the crystallization was stopped, but fumes of as were given off while the candle was burning & hurt the health of those who used it. This nearly put a stop to the manufacture but after some time it was found that a small percentage of wax served the same purpose as the As. The saponification was next 58 effected by HOSO3 instead of lime. Mix the fat with HOSO3 & heat by blowing steam thro' them C6 H5 O3"' 3A + 6HOSO3 = C6 H5 O3"', 3SO3 + 3A,3S03. Pass superheated steam at about 600° thro' the fat. it splits it up into the acid & the ether. C6 H5 O3"' | 3A. The glycerin & acid both distil, separately. Candles from Coal. Coal when distilled produces various gases. among others olefiant gas C4 H4 & other higher homologues. C8 H8 C10 H10 Cn Hn 89 If you distil at a low temperature Cn Hn comes over chiefly in a solid state. if at a higer temp. you get liquid products; & higer still gaseous products Boghead coal is distilled at as low a temp. as possible & an oil comes over. wh. is called paraffin because it possesses almost no affinities This when cooled from 40° to 32° deposits solid paraffine. In 1852 L. Playfair thought that paraffine could be got from the oil, but the maker of the oil would not try it, so Playfair obtained a quantity from him & by experimenting succeeded in getting it. Paraffine contains the conditions of illumination in the highest degree. The illuminant in coal gas is C4 H4 & its homologues 90 Paraffine is C4 H4 in a condensed state. All the paraffine is burned. It is not fat wh burns in a candle it is gas. The pores of the carbonized part of the wick act as so many retorts. Acids heterologous Melissic HOC62 H59 O3 Cerotic HOC34 H53 O3 Arachidic Stearic Palmitic Myristic Lauric Rutic Pelargonic Caprylic Ænanpylic Caproic Valeric 91 Butyric Propionic Acetic Formic Acids produced from biatomic alcohols. C4 H4 " HOHO monoatomic alcohol. C4 H4 "OO2HO bi -. In examining the oxidation of monoatomic alcohols we found that aldehydes were first produced & then acids.. C4 H4 "HO C4 H4 O"HO C4 H3 O"OO. Products of the oxidation of Glycol. We find two acids result. In the first 2 atoms of H in C4 H4 are replaced by O. In the second all the H is replaced by O. 92 Glycol ether C4 H4 "OO glycolic acid C4 H2 O2"OO Oxalic - C4 O4 "OO. What would be the acid for methylene C2 H2 if it were fully oxidized? C2 O2 OO = C2 O4 = 2CO2 . Formic acid C2 HO"OO Carbonic C2 O2 "OO Acetic C4 H3 O"OO Glycolic C4 H2 O3 "OO Glycolic acid. Got by the slow oxidation of glycol. It is a syrupy acid liquid The anhydride is got by distilling tartaric acid Lactic acid C6 H6 O6 = 2HOC6 H4 O4 Occurrence. It is extensively distributed in the animal kingdom it is found free in the gastric juice, found in muscle, in 93 the pancreas, in milk, in the brain & lungs & abnormally in urine blood & saliva. It is supposed to be the acid wh dissolves out the mineral matter in bones & produces rickets. It stands in the same relation to propylic wh the latter bears the glycol. Glycol or ethylene alcohol C4 H6 O41 - 2H + 2O = C4 H4 O6 Glycolic acid. Propylene alcohol C6 H8 O4 - 2H + 2O = C6 H6 O6 Lactic acid. Prep. 8 parts of sugar are dissolved in 50 parts HO, 1 part of poor cheese & 8 of chalk are added, & fermented at 80°. Lactate of lime is thus got & by adding HOSO3 you get the acid. It is a transparent, uncrystalline liquid, of a sharp taste It is not volatile & can displace volatile acids, when heated it 94 loses HO & becomes lactic anhydride. Lactates of alkalies do not crystallize - earths & metallic oxides do. Lactate of Zn unites with 3HO. Flesh juice lactates all contain 1 equivalent less of HO than those of that got by fermenting sugar. Fully oxidized olifine acids in wh the H is substituted by O. Formic acid C2 HO"OO Carbonic C2 OO"OO Carbonic oxide C2 O2 is a radical. Sulphocarbonic C2 O2 S2 acid Chloro - C2 O2 Cl2 Oxalic C4 H2 O8 C6 H4 O8 Succinic C8 H6 O8 Lupinic C10 H8 O8 Sebacic C20 H18 O8 Oxalic acid 2HOC4 O6 Occurs in vegetable juices, as acid 95 oxalates, in common sorrel, in lichens in rhubarb, sometimes free. Rarely in the animal kingdom as oxalates of lime in calculi & in urine in an abnormal state. Prep. Heat starch gently with HONO5. It has been obtained by another method. Heat sawdust with caustic Ko & NaO. The H is removed & the O goes You get a mixture of oxalates of NaO & KO. Add CaO & you get insoluble oxalate of lime. Add HOSO3 & you get oxalic acid free. 2Nao, C4 O6 + 2CaO = 2CaOC4 O6 2CaO, C4 O6 + 2SO3 = 2CaOSO3 + C4 O6. It is a crystalline acid crystallizes in colourless transparent like Epsom salts, for wh 96 it is sometimes mistaken. The remedy is chalk, CaOCO2 or magnesia It forms a numerous class of salts, the oxalates, the principal are those of KO & NH3 . Oxalate of KO. 2KO1 C4 O6 + 2HO. Soluble in HO. crystallizes in There is a bin- & quadroxalate wh is is found in sorrel & cress. Neutral Ko| Ko| C4O6 Binoxalate Ho| Ko| C4O6 Quadroxalate Ho| Ko| C4O6 + Ho| Ho| C4O6 + 4HO. Oxalate of ammonia . Prep. Saturate oxalic acid with NH3 & crystallize. It is largely used for testing, as for salts of lime, with wh it gives a white precipitate of 97 neutral oxalate of lime. Oxalate of lime Occurs native in the animal & vegetable kingdoms. Succinic acid 2HOC8 H4 O6 It is homologous with acetic acid It occurs in amber in various fossil resins. in turpentine in the animal kingdom, in the spleen of oxen. It is formed by the oxidation of some organic substances, by the putrefaction of plants of the asparagus kind & by the fermentation of malate of lime. Prop. It is a white brilliant, crystalline acid, crystallizes in rhombic prisms, not easily soluble in cold alcohol, soluble in hot alcohol soluble in HO. From 175 to 180° C it sublimes 98 It is a fixed acid not easily acted on by reagents. Like most bilasic acids it forms neutral & acid succinates. Negative radicals. We have been considering positive radicals. the radicals of the alcohols, the general formula for wh is Cn Hn +1 as for example ethyl C4 H5 = C4 H4 + H The general formula of negative radicals is Cn Hn -1 as for example Acetoyl C4 H3 Allyl C6 H5 Angelyl C10 H9 How can we consider these as olifines? C has a great tendency to unite with itself. Allyl C6 H5 ={(C4 {(C2 H4)"H. C2 having united with the C in the olifine. & the biatonicty of the radical thus formed not being fully 99 gratified by uniting with 1 of H as ethyl C4 H5 = C4 H4 H. It is not mere speculation that C unites with itself. It may be so in the case of allyl but it is known in the case of naphthalene C20 H8 a body wh chokes up gas pipes & wh has all the characters of an olifine. Allyl C6 H5 or in the separate state C12 H10. liquid s.g 0.58 boils at 59ºC. It has the synonym acryl. It has been got in a separate state. Got by the action of Na on iodide of allyl. It is a volatile ethereal liquid burns with an illuminating flame unites with Br & I & forms compounds. Sulphide of allyl or oil of garlic C6 H5 S. boils at 140ºC. 100 occurs in garlic & may be distilled from it & then forms sulpo of allyl. Oil of mustard is the sulphocyanide of allyl. Oil of garlic C6 H5 S. - mustard C6 H5 CyS. It may be got artificially. Act on iodide of allyl by KS. C6 H5 I + KS Allyl ether C6 H5. - alcohol C6 H5 OHO. When oxidized it forms an acid corresponding to acetic, acrylic acid, Oxidized radicals of allyl. Alcohol C4 H6 O2 - 2H = C4 H4 O2 aldehyde. - C4 H6 O2 - 2H + 2O = C4 H4 O4 acetic acid Allyl alcohol C6 H6 O2 - 2H = C6 H4 O4 acryl aldehyd - C6 H6 O2 - 2H + 2O = C6 H4 O4 acrylic acid. Allyl or acryl aldehyde synonym acrolene. It is the nasty smell you perceive when you blow out a candle 101 candle In this case it is got from glycerin wh is distilled in the red hot part of the wick. It has a frightful smell, extremely pungent. attacks the eyes, & if concentrated burns the skin. Oxidized allyl alcohol. Homologues of acrylic acid (with 2C added Acrylic acid C6 H4 O4 same as acetic acid series Angelic C10 H8 O4 from angelica root Damaluric C14 H12 O4 in urine of cows Hypogaic C32 H30 O4 in earth nuts Oleic C36 H34 O6 in most fats C38 H36 O4 C in mustard seed Oleic acid C36 H34 O4 = HOC36 H33 O3 Occurs in most oils & fats as a glyceride. May be got from almond oil by saponifying & converting it 102 into a lead soap & acting on this by HCl. It is tasteless has no smell, does not act on vegetable colours It is solid below 14° C, is insoluble in HO. soluble in alcohol & ether. With NO4 it forms a solid substance. Pass NO4 thro castor oil wh contains much oleic acid Glycerine. The basis of fats. It appears to contain the same radical as allyl. C6 H5 OHO allyl alcohol C6 H5 O3 3HO Glycerin The atoms cannot be arranged in the same way (C4 H4") (C2 ) HO (C4 H4) (C2 O2) HO in Glycerine ether. Glycerin C6 H8 O6 liquid s.g 1.97. 103 Prep. Distil fats with super- heated steam. It is a colourless, syrupy, liquid does not crystallize, has no smell, sugary sweet taste, not volatile except in the vapour of steam. When distilled by itself it is decomposed. When acted on by yeast it yields propionic, acetic & formic acid When heated with KO C6 H8 O6 + 2KO = Acetate of KO KOC4 H3 O3 + Formeate of KO KOC2 HO3 + 4H Made by synthesis. Make iodide of allyl C6 H5 I. Act on it by 3Br. C6 H5 I + 3Br = C6 H5 Br3 + I. C6 H5 "'Br3 + 3KOC4 H3 O3 = 3KBr + C6 H5 O3 , 3C4 H3 O3 Decompose with HOKO or HOBaO. C6 H5 O3 . 3C4 H3 O3 + 3BaO1 HO Saponification Making soaps from glycerides 104 All ordinary fats are glycerides the 3 atoms of HO in glycerine being replaced by 3 atoms of a fatty acid. C6 H5 O3, 3HO C6 H5 O3, 3 acetic acid C6 H5 O3, 3F F = fatty acid. Glycerides or common fats. Occur in the animal & vegetable kingdoms, embracing all the fats we know. Fats may be prepared artificially. Seal glycerin & stearic acid up in a tube & expose to high temp. These fatty glycerides are easily decomposed. They are generally mixed with other fats. To get stearine heat mutton fat with cold ether wh dissolves out palmitine & oleine 105 Stearine C114 H110 O12 = tristearate of glycerin C6 H5 O3 | C36 H35 O3 C36 H35 O3 C36 H35 O3 It is a colourless pearly fat, melts at 63° C. Insoluble in HO, slightly in cold alcohol & ether. Saponification is decomposing this fat, taking away the glycerin & putting in 3KO instead. Glycerine is triatomic so you put ?.=s of a monoatomic body instead KO| C36 H35 O3 KO| C36 H35 O3 KO| C36 H35 O3 Mix hot alcoholic solutions of KO & of stearine and on cooling you get a soap, the glycerine remaining dissolved in the alcohol. Glycerine | Acid A A 3KO In making soap. take a 106 glyceride & potash ley & pass steam thro' it [illustration] When the heat is great enough to melt the tallow a soap is formed. In ordinary soap making a soft soap is made when KO is employed, with NaO a hand soap is obtained. It is easier to make a KO than a NaO soap because it saponifies more easily. It is afterwards made into a NaO soap by salting. KOS + NaCl Yellow soap. Boil tallow or palm- oil with an alkali & add rosin & salt out. Mottled is got from tallow or palm oil, an Fe soap makes the mottling Castile or Marseilles soap is 107 got from olive oil & mottled with FeS. & alkaline sulphides. Chief fats. Palmitine Tripalmitate of glycerin ether. Exists in most fats, especially the softer kinds, in palm & cocoa nut oils May be got from olive oil by cooling Margarine. Supposed formerly to contain margaric acid wh is now known to be a mixture of palmitic & stearic acids. Oleine. Trioleate of glycerine ether Expose olive oil to cold to separate the palmitine & the oleine remains. Natural fats are of 3 kinds 1st solid like tallow 2nd,, semisolid like butter 3d,, liquid like oil They are all lighter than & insoluble in HO, all soluble 108 in ether many in alcohol They occur in the animal & vegetable kingdoms, in all animal fluids except urine Vegetable fats. Cocoa nut oil melts at 20ºC, contains various acids glyceride of coccinic Palm oil. Melts at 27ºC is a yellow butter like substance, 20000 tons of it as imported annually from Africa, it soon becomes rancid, contains palmitine & oleine Vegetable oils may be divided into drying & non drying. Non drying. Colza Drying Linseed croton & castor oils Animals fats. Suet. Fat of oxen & sheep, melted & freed from nitrogenous matter. consists of oleine, stearine & palmitine 109 palmitine Lard contains stearine & palmitine. Human fat is like lard melts at 25° C. Spermaceti. When pure contains cetine, not glycerine but a substance corresponding to it. Cetine C64 H64 O4 = ethal ether C32 H33 O, palmitic acid C32 H31 O3 Sperm & codliver oil are examples of liquid animal fats. Aromatic series. There are several of these radicals Phenyl C12 H5 Benzyl C14 H7 Xylyl C16 H9 Cumenyl C18 H11 Cymyl C20 H13 Phenyl. It is an important series. It contains benzole used in making coal tar colours Phenyl ether C12 H5 O It is got by distilling benzoate 110 of Cu. It is colourless, smells slightly like a geranium it soluble in alcohol. Chloride of Phenyl. C12 H4 Cl. Hydride of Phenyl or Benzol sometimes called Benzine C12 H5 H corresponds to C4 H5 H. Prep. Distil coal tar. [illustration] A vessel filled with HO surrounding the neck of the retort is kept at a temp. of 170° , the temp. at wh benzole distils other substances wh distil at a higher temp. are cooled & fall back into the retort while the benzole distils over. It is used for cleaning white kid gloves & for taking out grease spots. To use it rub the benzole all round the spot without touching it & bring it [illustration] 111 gradually over the spot. It is a colourless, thin oil, of an agreeable odour when pure, solid at 0ºC melts at 5ºC, burns with a smoky illuminating flame increases the illuminating power of gas. It is a good solvent for fats & camphors, it dissolves S.I. & Br readily possibly uniting to some extent with them. Benzyl C12 H5 H Benzyl ether - alcohol C12 H5 OHO When pure & free from HO it is a white crystalline solid substance. Kreosote consists of carbolic, cressylic & probably of some higher acid Phenyl alcohol or carbolic acid. C12 H6 O2. Boils at 185º 112 Found in cows urine, in coal tar. Solid when quite dry & crystallizes in needles, wh melt at 35ºC. It has a disagreeable smell, burning taste, is heavier than HO, in wh it is slightly soluble, it is soluble in alcohol & ether. It is an active poison to animals & plants. It is a strong antiseptic. A coffin filled with carbolate of lime preserved a body for 2 months. Carbolate of lime & sulphite of lime form Macdougal's disinfecting powder. Nitrophenyl ether C12 H5 NO4 Usually called nitrobenzol. It is C12 H5 H having the H replaced by NO4. Prep. Act on benzol by fuming HONO5. It is a yellow oily liquid, solid at 3ºC, smells like oil of bitter 113 almonds, for wh it is used in perfumery & confectionery with advantage since it is not poisonous while oil of bitter almonds often contains hydrocyanic acid. It has a sweet taste insoluble in HO, soluble in alcohol & ether. Used in making anilene. Anilene is NH3 in wh 1 equivalent of H is replaced by phenyl. N |H |H |H N |C12 H5 | H | H To obtain aniline act on nitrobenzol by some deoxidizing agent. That usually employed is acetate of KO. C12 H5 NO4 + 2HO + 47e = C12 H7 N + 27e2 O3 Or by acting with HS. C12 H5 NO4 + 6HS = C12 H7 N + 4HO + 6S Nitrophenyl alcohol C12 H2 (NO4)3 OHO. It is carbolic acid in wh part of the H is replaced by NO4 & has 114 the synonym of carbosotic acid Prepared by the prolonged action of HONO5 on kresote or carbolic acid. It is formed by oxidizing silk, salicin, indigo, alves, gum benzoate & resins. Prep. It crystallizes in brilliant yellow plates, maybe sublimed with care, soluble in alcohol & cold HO, more readily in hot HO soluble in hot HOSO3, is an active poison. May be used in small doses instead of quinine but makes the patients skin yellow. Used to dye silk & woolen. It has been proposed to mix it with As. before selling it in shops as it has an intensely bitter taste, & would be detected. In cases of slow poisoning it would make the skin yellow & thus draw 115 attention Carbosotates crystallize in well defined salts. The acid characted is due to the electronegative character of the radical. Benzyl C14 H7 - ether C14 H7 O. It is an oily liquid & is got by the action of BO2 on benzyl alcohol. Toluol. Hydride of Benzyl, C14 H7 H Obtained from liquid coal tar + tolubalsam. It is colourless & resembles benzol in it properties, is insoluble in HO soluble in alcohol & ether. HONO5 act on it in the same way as on benzol. Benzyl alcohol C14 H7 O, HO It is an oily colourless liquid insoluble in HO soluble in alcohol 116 alcohol & ether. By oxidation it becomes the oil of bitter almonds In the olifine view Benzyl alcohol C16 H6 " HO HO - ether C16 H6 " HO oil of bitter almonds = biatomic ether C14 H6 " OO benzoine is the aldehyd C14 H5 O " HO Benzoic acid C14 H5 O"OO. Oil of bitter almonds: general formula C14 H6 O2. liquid s.g l.043 boils at 180° C. Obtained when almonds are macerated & distilled with HO. It is fragrant oil, transparent very refractive, has a powerful smell is used in perfumery, is not poisonous in itself but often contains hydrocyanic acid When it contains this & is put in contact with lime it is 117 Changed into benzoin Benzoic acid. Occurs in putrid horses urine Obtained by sublimation from gum benzoate. It is volatile, slightly soluble in HO soluble in alcohol & ether. When taken as a medicine it is converted into hippuric & is found as such in the urine. Benzoates are crystalline, when heated they are decomposed into benzoin naphthaline Let us now go back to the phenyl series & consider the coal tar colours. The phenyl series differs from the benzyl by C2 H2 Phenyl C12 H5 or as olifine C12 H4 "H Benzyl C14 H7 Manufacture of benzol. Nitrobenzol 118 Nitrobenzol &c. When coal is distilled for gas it produces various substances, HO & tar distil over along with the gas. Ten to 12 gallons distil over of oil of from 1 ton of coal. It was formerly a waste product & even yet it is sold at a penny to three halfpence the gallon. [illustration] To get naphtha pass steam thro' the tar On a large scale 100 part tar yield Naphtha 9 parts Lead oil 60 - Pitch 31 - Naphtha is nearly the only thing wh comes over with the steam the pitch & dead oil 119 remain in the retort, & the is a afterwards distilled by a common fire. Naphtha is a rough commercial term & signifies a great variety of substances Roughly purified it is used for many purposes. Crude naphtha contains 3 substances. Basic oils Acid oils Neutral hydrocarbons. Basic oils may be got from the naphtha by agitating with HOSO3. They are all compound ammonias. Aniline exists in the basic oils but is not got from them. Acid oils. 120 Take naphtha & shake it with caustic NaO or KO the acid oils dissolve in the NaO or KO & are separated by adding HCl. When separated they form kreosote wh is carbolic acid C12 H6 O2 & cressilic acid C14 H8 O2 Carbolic acid is used in toothache & to preserve timber When acted on by NO5 it forms carbosotic acid. Carbolic acid C12 H6 O2 Carbosotic - C12 H3 (NO4)3 O2 Carbosotic acid is a strong dying agent. Dissolve a little in a little hot HO & then add some cold, you get a solution excellent for dying silk yellow. Wet the silk in HO & rinse in the carbosotic acid. This is the first use of coal tar in colouring substances. 121 Neutral hydrocarbons. Chiefly benzol & its homologues. The benzol is distilled by passing it thro a cistern of HO at 177°. Benzol is very volatile, & it is possible to burn air charged with it [illustration] Dried air is passed over heated asbestos B to heat the air, & thro' some benzol in A the air then may be burned as at C. It may be used for setting enemy's ships on fire by pouring it on the HO & throwing some K on it wh takes fire & inflames the benzol. Nitrobenzol. C12 H5 NO4 Benzal acted on by NO3. It is used in perfumery. To get colours from it, it is first 122 made into aniline C12 H5 NO4 + 2HO + 4Fe = aniline C12 H7 N + 2Fe2 O3 Aniline C12 H7 N It is a compound ammonia A short time ago 1/2 lb aniline would have been thought very valuable in a laboratory & probably none possessed so much as except perhaps who was making researches upon it It was a short time ago sold for a few shillings per gallon but has now risen in price in consequence of the demand for it & is now a few shillings per pound. From aniline are made Mauve or purple Violine Rosein Magenta or Rosaniline Azuline 123 These tar compounds are capable of producing colours [illustration] Put 2 drops of pyroline in a jar & shakes up- moistens a piece of pine wood in the shape of a dagger with HCl & put it into the jar, the moistened point becomes red. Mauve. [illustration] Put some aniline ( a very little will do ) into a bottle & add a little acetic acid to assist its solubility. you get a solution of acetate of aniline, pour into HO & add chloride of lime- [illustration] it becomes brown at first but afterwards becomes purple. On a large scale it is prepared by acting on sulpate of aniline by KO, 2CrO3 in equivalent quantities. You get a dark powder, wash 124 this with coal tar & dissolve it in alcohol The alcoholic solution is evaporated to dryness & you get a green powder wh is soluble in alcohol. It is from the alcoholic solution that we dye the colours. Pour a little tartaric acid into some hot HO & pour in a small quantity of alcoholic solution of mauve. Wet the silk to be dyed & put it in. The chemistry of the colour is not well understood. It is easily tested by HOSO3. Add a little strong HOSO3 to a little mauve & you get a dirty green solution. Add a little HO & you get a fine blue. Add a good deal of HO & it becomes mauve again 125 Magenta. The true red colouring matter is rosaniline. In making it take a weak deoxidizing agent instead of a strong as with mauve. [illustration] Take a small quantity of anhydrous bichloride of In as that in the sealed tube A, pour it into the flask B, add aniline cautiously, it forms a solid compound, gradually add more aniline till you have an excess Heat cautiously over a lamp The action is violent. Any weak anhydrous Acetic acid & As O5 are also used. It is necessary to boil off the excess of aniline. Blue de Paris a azuline Is got from carbolic acid 126 Put a very little mauve or magenta on a sheet of paper hanging up & spout alcohol from a washing bottle on it, the colour dissolves running over the paper. The chemistry of some of these colours is known Rosaniline is a triammonia 3 atoms of H coalescing into one. NH3 x 3 = N3 H9. The compounds radical substituting H is unknown. Let R signify rosaniline. R unites with 1 or 3 atoms of acid. R + 1A gives the strongest colour R + 3A - a less strong -. R is colourless by itself, but when dissolved in alcohol or acid it has a strong colour. Magenta is acetate of R. In the case of the purples we must use hot HO in dying but in the case of carbosotic 127 acid & magenta, cold will do. All animal fibres take up these colours readily. Cotton does not & you must treat it with tannic acid. Purple & violine are not true ammonias, they seem to be neutral In cotton printing, albumen is put on the place wh is desired to be coloured & exposed to steam & dried. It is then rinsed in a solution of the dye as silk is the vegetable fibres do not take it up but the albumen does. Malic acid 2HOC8 H4 O8 It is bibasic. It occurs frequently in unripe fruits, in the apple but is got most easily from the berries of the mountain ash. It has a strong acid, agreeable taste 128 When heated it is changed into fumaric acid fumaric acid. 2HOC8 H2 O6 . It is readily obtained from Iceland moss or malic acid. It forms micaceous scales wh require 200 parts of cold HO for solution. Tartaric acid. General formula C8 H6 O12 = 2HOC8 H4 O10. Occurs in the tamarinds & mountain ash berries, but is got chiefly from grapes. The substance called argol found in wine casks is bitartrate of KO. It is obtained in rather a curious way from this by converting it into neutral tartrate of lime. Argol Ko } Ho } T Add CaCl & lime if you added CaCl alone you would get CaO } HO } T but by adding lime too you get CaO} CaO} T 129 add HOSO3 to this CaO} CaO} T + 2HOSO3 = Ho} Ho } T + 2CaOSO3 . It crystallizes in oblique prisms is colourless transparent, of an acid agreeable taste, soluble in HO alcohol & wood spirit, its solution especially when hot exerts a right-handed rotation on polarized light There are two different crystalline forms. Sometimes, especially in the grapes of the Vosges, an acid of the same formula as tartaric acid called racemic. Racemic acid is rather difficult to get as it only appears sometimes. Racemates crystallize differently from tartrates & have a different number of atoms of 130 HO of crystallization. It was supposed to be an isomer of T & to have its atoms arranged differently. T produces a right-handed rotation of polarized light Racemic acid a left handed one. The crystals were unsymmetrical but in different directions. Pasteur showed that when put together they are symmetrical It is thus the same acid in different crystalline forms. Tartrates are used largely in medicine & the arts. Used in calico is printing. If in calico printing you wish a part to remain white you use tartaric acid as a resist to the mordant wh is always used. The mordant forms a very soluble 131 soluble tartrate & does not remain on that place, & so the dye does not adhere to that place. In all cases of bibasic acids as tartaric acid where you have 2 HO thus HO } HO } T you may replace 1 HO or both. HO } HO } T KO } HO } T KO } KO } T NaO } KO } T. Argol is cream of tartar or bitartrate of KO HO } KO } T. It is hard white & crystalline difficultly soluble in cold HO, more soluble in hot HO, has a sour taste & feels gritty to teeth. When heated it forms black flux. Bitartrate of KO is extensively used in medicine as a diuretic. Neutral tartrate. It is deliquescent. All acids even tartaric acid, convert it into cream of tartar. Rochelle salts KO,Na OT + 8HO. 132 KO } NaO } T crystallizes with 8Ho, in large clean, rhombic prisms, is used in medicine. forms the basis of seidlity powders. Tartar emetic. It is a double salt corresponding to cream of tartar. KO } SbO3 } T + aqua. Mix 3 parts SbO with 4 cream of tartar, make into a paste, digest It is soluble in 15 parts HO, is a violent emetic in larger doses acts as cathartic poison. Kinic Occurs in chinchona bark. Crystallizes in colourless prisms wh melt at 155°C. Solid on cooling at a higher temperature it is decomposed. Tribasic acids. Citric acid C12 H8 O14 . 133 Occurs in the lemon, gooseberry cherry & tamarind. As citrates in the tumours of the Jerusalem artichoke. Only the fruits wh contain acid united with alkali become sweet on ripening the acid being converted into sugar. Where acid is free as in the lemon, it does not become sugar. It is prepared like tartaric acid but is more easily made since it has no tendency to become uncrystalline as tartaric acid is apt to do. It crystallizes in large colourless prisms, very soluble in HO & alcohol, not in ether. It is used in calico printing both as a resist & to heighten the colours. Heated to 175° it is decomposed & becomes 134 C12 H8 O14 - 2HO = C12 H6 O12 Fused with lime it forms oxalate & acetate of lime. C12 H8 O14 + 2HO from the HOCaO = C4 H2 O8 + 2(C4 H4 O4). Citrates are necessarily a large class. Citric is tribasic acid. HO | HO | HO | C12 H5 O11 . Aquinitic acid. Found in aconitum Forms warty crystals easily soluble in HO. It is the acid in opium, it is a white silvery acid, loses its HO of crystallization at Gallic acid 2HOC14 H6 O10 It is bibasic, is contained in gull nuts in mango seeds in sumach. 135 It is got artificially by the splitting up of tannin when it is boiled. It is white silky crystalline. soluble in 3 parts of boiling HO & 100 cold HO, with a salt of Fe it forms ink. When heated to 210° it is decomposed, it loses C2 O6 & becomes pyrogallic acid. Pyrogallic acid C12 H6 O6 = Used for estimating O. With a little alkali it absorbs O completely. Tannic acid. Tannic acid is a general name for organic substances wh precipitate gelatine & form leather. It is contained in the leaves & bark of most forest trees, especially the oak, elm in the whortleberry, tea, coffee. Tannic acid except that from coffee. Precipitates protosalts 136 of Fe a blue black, or in acid solutions of a dark green. Some like tannic acid from catechu precipitate it a dark green. Gallotannic acid C54 H22 O34 Obtained from gall nuts. Take an ethereal solution of gall nuts, it divides into two parts the upper part is gallic & the lower tannic acid. Obtained thus it is a white, crystalline body soluble in HO, soluble in weak alcohol & ether. The aqueous solution absorbs O Gallotannic acid should be called tannin, it is a glucoside. Act on it by acid wt brings HO into play. 137 C54 H22 O34 + 8HO = 3(C14 H6 O10) + C12 H12 O12. Boil tannic acid with HCl, It is not certain whether it is a bi or tri [crossed out] basic acid. It is used in medicine as an astringent. Ink. Gallotannate of Fe. Take 3/4 lb of bruised gall nuts, dissolve them in 1 gallon of cold HO, add 6 oz of FeOSO3 . 6oz of gum arabic 5 drops of kreosote to prevent it moulding, digest at common temps. for 2 or 3 weeks, shaking frequently. Ink stain = Fe2 O3 To take it out heat with a little oxalic acid. it forms soluble oxalate of Fe. Gallotannate or tannate of gelatine. The object in tanning is to unite the skin with acid to prevent putrefaction, & yet leave the 138 skin supple. The time required varies, as, the hippopotamus skin is 2 inches thick & required nearly a year. While the kid's skin is only a fraction of an inch thick & requires only a few weeks. The processes are, 1st. Place the skin in lime, the root of the hair is attacked by it Remove the hair with a knife & open the pores by placing in a pit of HOSO3 & HO. Layers of skins & oak bark are laid in pits for 3 months, they are then taken out & fresh bark is added, the skins are then placed in again so that the one wh had been at the top is now at the bottom & allowed to remain there for some time. It is strange that no quicker 139 process can be employed The use of hydraulic presses to force the liquor into the pores, & of stronger solutions does not make such good leather If Simon the tanner of Joppa came back to this world he would find the trade precisely as he left it. In white kid gloves no tannic acid is used, it is protected by aluming Tawed leather The skins are cleaned & treated with Al2 Cl3 made by mixing alum & NaCl, & then rubbed with oily substances. In chamois leather as much oil is put in as possible. Compound haloid radicals. The chief representative is cyanogen C2 N. 140 It has perfectly parallel characters with any other haloid. Cl} 4 Cl} hyrdo Cl} chloride Cl} Cl} Cl} vols H} chloric acid K} of k I} O} C2N} 4 C2N} hydro C2N} cyanide C2N} C2N} cyanic C2N} vols H} cyanic K} of k I} O} acid acid Cl} Cl} 4 vols Cl} H} hydrochloric acid Cl} K} chloride of K Cl} I} Cl} O} C2 N} C2 N} 4 vols C2 N} H} hydrocyanic acid C2 N} K} Cyanide of K C2 N} I} C2 N} O} Cyanic acid Cyanogen was the 1st,, compound radical clearly established in organic chemistry. Cyanogen C2 N. = 26. if it has 2 vols 52 if 4 vols. S.G of gas 1.806. Symbol. Cy. It is monoatomic. The reason for this is that though N is pentatomic but is joined to 2 of C wh is biatomic & has thus 4 atoms filled up & only 1 left. N,,,,, - C2,,, = C2 N, Cy has the power of doubling itself & forming other radicals. Cy C2 N Bicy. C4 N2 Tricy C6 N3 Mellan C18 N13. 141 Cy is best got by heating cyanide of Hg in a tube. This corresponds to the method of getting O. [illustration] HgO2 heat = Hg + 2O HgCy2 - = H8 + 2Cy. A black substance is left in the tube wh has the same composition as Cy. Prop. It is colourless, has a peculiar prussic acid & odour at a pressure of 3 atmospheres it becomes liquid & the liquid solidifies at -35°C, it burns with a purple flame, producing CO2 & N, it is soluble in HO & alcohol the latter takes up 22 vols. of it The solutions decompose & urea is formed. Urea is an anomalous cyanate of NH4 . NH4 O C2 N K unites with Cy as it does with Cl. 142 Hydrocyanic or prussic acid. HCy= 27 s.g of the gas 0.9476. 4 vol vap. formula. Acc. Probably never found free but various seeds give it by distillation owing to the action of ferments on it. Almonds, peaches apricots, the leaves of peaches & the kernels of plums yield it. Mode of preparing it. Distil K Cy with HOSO3. pass over CaCl & condense by ice. s.g of liquid 0.967 boiled at 26ºC solid at -15ºC Has a smell like bitter almonds is an intense poison is soluble in all proportions in HO & alcohol. Does not keep well, after a while perhaps 2 or 3 years it becomes black & is apt to explode, you then break it under HO to prevent this, 143 Aqueous solution of HCy. Prep. Distil yellow prussiate of [illustration] KO & HOSO3. you get a solution of unknown strength. The medical strength is 2 percent of prussic acid. The London pharmacopia process for getting a solution of known strength, is. - Suspend 48 1/2 grams of cyanide of Ag in 1 oz HO & add 39 1/2 of HCl. An extemporaneous solution of HCy may be made by adding KCy to T & stirring, you get bitartrate of KO & a solution of HCy. The aqueous solution is more permanent if you add a little mineral acid. Solution of HCy under the action of strong acids or alkalis decomposes 144 decomposes into formiate of NH4 . C2 NH + 4HO = NHOC2 HO3 HCy is easily tested. Test. Take FeOSO3 wh has been a little rusted in air. If not rusted add a few drops of a persalt of Fe. Add HOKO to precipitate the oxide of Fe. Add HCl to neutralize the KO & take up the Fe. Add these to the suspected solution & if HCy be present prussian blue is produced. The rationale of this process is HCy, KO & a salt of Fe make yellow prussiate of KO, if you add HCl to make a solution of Fe prussian blue is produced. Another test. Put the suspected solution in a watch glass & add a drop or 2 of sulphide of NH4 to neutralize it, put over it another watch glass & [illustration] 145 evaporate it to dryness in a hot water bath. Add perchloride of Fe. You are producing sulphocyanide of K wh has the property of striking a blood red colour with perchloride of Fe. When used as a poison it quickly escapes from the system on account of its volatility so that 3 days after you cannot detect it in the body. Cyanides resemble the haloid salts of Cl & are got in the same way. To get KCl HCl + KO = KCl + HO - KCy HCy + KO = KCy + HO. On a large scale KCy is got by heating yellow prussiate of KO with KOCO2 . yellow prussiate of Ko. K4 Fe2 Cy6 K4 Fe2 Cy6 + 2KOCO2 = 5KCy + KoCyO + 2Fe + 2CO2 . You can prevent the 146 formation of KOCyO by adding a little C. K4 Fe2 Cy6 + 2KOCO2 + 2C = 6KCy + 2FeO + 2CO2 + 2CO. Dissolve it out & evaporate it down. It is use largely in electrotyping to dissolve Ag + Au, & as a reducing agent. Bicyanide of H8 - H8 Cy2 . Boil 4 parts prussian blue 3 of peroxide of H8 & 4O of HO. It crystallizes in prisms, soluble in HO more difficultly soluble in alcohol, very poisonous. Alkalis do not precipitate H8 O from it. Cyanide of Ag. AgCy. Prep. Add KCy to a salt of Ag. It unites with KCy & readily forms double salts. Haloid ethers of Cyanogen. Cy unites with ethyl as Cl does. 147 Prep of cyanide of ethyl. Add KCy to C4 H5 I. C4 H5 I + KCl = C4 H3 Cl + KI prep of chloride of ethyl C4 H5 I + KCy = KI + C4 H5 Cy cyanide of ethyl. We find the Cy has gone in more intimately to the ethyl than we would suppose On this account These compounds are called nitriles. Cyanide of ethyl. C4 H4 C2 N. It is a colourless liquid, mobile of an agreeable but garlicky odour Does not comport itself with alkalis like ordinary ether. It is soluble in alcohol & ether. C4 H5 Cl + KOHO = KCl + C4 H6 O2 propionate of KO C4 H5 C2 N + KOHO + 2HO = KOC6 H5 O3 + NH3 Propionic acid one above C4 H5 in the series. Act on a nitrile by an alkali & you get the acid one above it in the series. 148 Double electro negative cyanides. The cyanides form a remarkable series of salts when certain metals combine with them, especially Fe 4KCy + 2FeCy = yellow prussiate of KO. If you get an insoluble cyanide of Fe by adding FeOSO3 to KCy & add excess of KCy to the insoluble salt it gradually dissolves & you get a solution of yellow prussiate of KO. Suppose the Fe has a formed a compound radical with Cy. Fe2 Cy6 called Ferrocyanogen. Yellow prussiate of KO is this + 4K & crystallizes with 6HO. Add HCl to this Fe2 Cy6 + 4K + 4HCl = 4KCl + Fe2Cy6 4H. [illustration] Has a solution of yellow prussiate of KO in the tube add HCl & ether 149 Fe2 Cy6 4H = hydroferrocyanic acid is insoluble in ether. A bluish white compound is formed. Occurs in crystalline plates, soluble in HO, is readily precipitated by ether. The solution quickly becomes blue, when boiled HCy is evolved. When the 4H are substituted by 4K you get yellow prussiate of KO. Yellow prussiate of KO. It is used in the arts largely. Prep. Cast off woolen garments, horns & hoofs of cattle, flesh & blood any thing that contains N are mixed with scrap Fe & Montreal pearl ashes & heated. Fe2 Cy6 4H = Hydroferrocyanic acid 150 Fe2 Cy6 4K = yellow prussite of KO. It is formed when a substance containing N is fused with KOCO2 & Fe or allowed to digest on Fe. Occurs in lemonyellow tabular crystals soluble in HO not soluble in alcohol, of a bitter taste & purgative but not poisonous, If you take away 1 of K & make red prussiate it becomes intensely poisonous Yellow prussiate is tetrabasic. Fe2 Cy6 { 2Ba { 2K Fe2 Cy6 { 3Cu { K. We have doubled the formula on this account. [illustration] Add yellow prussiate to CuOSO3 & a mahogany red is produced. Ferrocyanide of NaO. Na4 Cy6 + 10HO. Ferrocyanide of Fe. Take a solution of Fe OSo3 & add yellow prussiate, you get a 151 a precipitate, while at first but wh absorbs o from the HO & becomes blue. It has this composition. Fe2 Cy6 {3Fe {K. Add yellow prussiate to a persalt of Fe & you get prussian blue at once Fe7 Cy9 . Prussian blue Prop. It is a beautiful blue of a coppery lustre when dry, after being washed in HO it may be dissolved in oxalic acid. This when thickened with gum forms steven's blue ink. It is readily decomposed by alkalis. Add caustic NaO or KO to prussian blue, it produces a reddish colour & forms oxide of Fe. Put a cloth dipped in a salt of Fe into prussiate of KO & it is dyed blue. 152 Ferridcyanogen. It has the same composition as ferrocyanogen but is tribasic instead of tetrabasic Fe2 Cy6,,,, radical of yellow prussiate Fe2 Cy6,,, - red - Pass Cl this is a solution of yellow prussiate. Fe2 Cy6 4K + Cl = KCl + Fe2 Cy6 3K. Hydroferridcyanic acid. Is got in the same way & has much the same properties as Hydroferrocyanic acid. Add HCl to red prussiate of KO & add ether. Or add HOSO3 to Ferricyanide of Pb. Crystallizes in brown needles, better easily decomposed. Ferridcyanides are generally red. They are distinguished from ferrocyanides by giving no precipitate with perchloride of Fe. 153 yellow prussiate with Protosalt of Fe gives a white precipitate Red prussiate - blue yellow- persalt - blue Red- dark brown. Ferridcyanide of K. Is generally called red prussiate of potash. Crystallizes in ruby red right rhombic prisms, soluble in HO insoluble in alcohol, gives a precipitate with metallic salts in wh all 3 of K are replaced by metal. K3 Fe2 Cy6 + 3AgONO5 = 3AgFe2 Cy6 + 3KONO5. Turnbulls prussian blue, is prussian blue got from red prussiate & FeOSO3. Nitroferrocyanides or nitroprussides Fe2 Cy6,,,, Fe2 Cy6,,, Fe2 Cy5 NO,, Nitroprusside of Na. 154 Made by the action of NO5 on Nitroprusside of K. When you add sulphide of NH4 to this a beautiful purple colour is produced wh is very transitory. It is the best test for S. Put a lock of hair into a test tube & dissolve it in caustic NaO or KO. heating it to aid the solution. You must always convert the S into an alkaline sulpide. Adds a good deal of HO so as not to act on the filter & filters it. Adds nitroprusside of Na & a deep purple is produced showing the presence of S in the hair. The nitroprussides give a salmon coloured precipitate with salts of Fe. Oxides chlorides & sulpides of Cy. It must be recollected that there are 3 sorts of Cy. Cy Cy2 & Cy3 . 155 Cyanic acid CyO. Cyanates are easily got by heating a cyanide with an oxide such as of Pb. CyO is not so easily got. Distil cyanuric acid & collect the product in a freezing mixture. It is colourless mobile A drop on the skin produces a sore. Above 0°C it changes into a procelain like mass. Cyanates. General formula MOCyO corresponding to MOClO. They bear heating to redness without decomposition. You do not obtain CyO by acting on them by acids Cyanate of KO. KOCyO. Prep. Heat prussiate of KO with 156 an oxidizing agent such as MNO2 . It is soluble in HO, the solution is decomposed when heated. KOC2 NO + 3HO = NH3 + HO} KO} C2 O4 Cyanite of NH4 . NH4 OCyO. Prep. Act on cyanate of KO by NH6 OSO3 It is white crystalline, soluble in HO & alcohol, it is not urea, wh is an anomalous cyanate of ammonia NH4 OC2 NO. Chloride of Cy. NCO2 Cl. vap. density 2.124 Act on cyanide of H8 by Cl. Colourless, very poisonous gas, of a disagreeable pungent small, at -53°C it becomes liquid. In closed tubes it becomes double CyCl = Cy2 Cl2 . Sulphocyanogen Sulphocyanates correspond to cyanates S playing the part of O. 157 CyO CyS . It has never been got in a separate state. A yellow compound got, has been called CyS but does not behave as such. It forms sulphocyanates wh are interesting because NaCyS at least exists in the saliva man & the sheep. Put some saliva in a watch glass & add perchloride of Fe. Sulphocyanide of K. KSCyS. Prep. Heat together yellow prussiate of KO1 KOCO2 & Bicyanogen Cy2 C4 N2 . Not known in its separate state Bicyanic acid Cy2 O2. It has the synonym fulminic acid . 158 2 HOCy2 O2 Fulminic acid Not known free. Fulminate of Hg. 2HgOCy2 O2 Prep. Heat HgONO5 & alcohol together It crystallizes in white needles very explosive not soluble in cold HO but soluble in hot. Add Zn to the solution & Hg is deposited & fulminate of Zn remains. Act on fulminate of Zn by Cl, & it becomes chloride of Cy & C2 (NO4 ) Cl3 chlor-carbasotic acid. It is possible that 1/2 the N in fulminic acid may not be present as Cy. It is closely allied to Cy. Persulphocyanic acid. Little soluble in alcohol & ether With alkalis it forms soluble 159 & with heavy metals insoluble salts. Bichloride of Cy It is formed when CyCl is left in a sealed tube. It is a colourless liquid boils at 15ºC. Tricyanogen. Cy3 . Forms cyanuric acid Cy3 O3 3HO. Got by the action of terchloride of Cy on HO. CyCl3 + 6HO = 3HOCy3 O3 + 3HCl Transparent crystals, no smell or taste, reacts acid. Cyanurates Cy3 Cl Expose anhydrous Crystallizes in brilliant needles wh melt at 140ºC boil at 190ºC Smells like the excrements 160 of mice, difficulty soluble in HO readily soluble in alcohol & ether. Characters of Cy. Cy has the character of a radical closely resembles Cl but has the power of duplicating & triplicating itself & forming other radicals Unites so intimately with metals as to appear to form radicals Polymerizes itself. Mellone C18 N13 Organic bases representative of alkalis & metallic oxides in organic chemistry. The bases resemble NH3 They act like NH3 on hydracids without expelling the H. They almost all unite with PtCl2 to form double salts. It is believed that they are all constituted on the NH3 type. 161 The general name is amines. NH3 N | | H | H | H Primary N | | A | H | H Secondary N | | A | B | H Tertiary N | | A | B | C Monamines Example N | | C4 H5 | H | H N | | C4 H5 | C2 H3 | H N | | C4 H5 | C2 H3 | C10 H11 All these are true ammonias, form salts with hydracids & take up HO when they unite with oxyacids. They are volatile alkalis & have a peculiar odour generally resembling NH3 . The replacing radicals are generally the common compound radicals. C12 H3 Cl2 | H | | N Chlorphenylamine C12 H3 ( NO4 )2 | H | | N dinitrophenylamine When you have such substitutions as these, electro negative 162 bodies replacing H, the basic power of the body is much impaired & in some cases destroyed. Glycocol C4 H3 O4 | H | H | | N neutral Benzamic acid C4 H5 O4 | H | H | | N Production of these compound ammonias. They are produced by the action of an iodide of an alcohol radical on NH3 . N | | H | H | H + C4 H5 I = N | | C4 H5 + I | H [cross out] | H Or by deoxidizing a nitro compound as in aniline* Ethylamine s.g 0.696 boils at 18.7°C It is a colourless liquid of an ammonaical odour, its causticity is nearly equal to that of KO. It blues red litmus, neutralizes powerful acids, raises a blister * C12 H5 ( NO4 ) + 6HS = N | | C12 H5 | H | H + 4HO + 6S. 163 on the tongue, drives NH3 from its salts Tri It is colourless liquid, inflammible slightly soluble in HO less so than ethylamine. Act on this with C4 H5 I, & you get iodide of ethylammonium a compound corresponding to NH4 I. N | | C4 H5 | C4 H5 | C4 H5 + C4 H5 I = N( C4 H5 )4 I. Act on the last body by AgO & you get AgI + N( C4 H5 )4 O corresponding to NH4 O. Oxide of tetrethylammonium You cannot distinguish it from KO in its chemical characters It acts as a caustic & forms a soap with fats. It precipitates metallic oxides like KO Add it to CuOSO3 & CuO is precipitated & sulpate of tetrethylammonium 164 tetrethylammonium formed In coal tar there is a remarkable set of organic bases You get them by treating with HOSO3, decomposing by KO & distilling Pyridine C10 H5,,, N Picoline C12 H7,,, N Lutidine C14 H9,,, N Lecoline C18 H7 N Lepidine C20 H9 N Put a mixture of Lutidine into a sealed tube into hot HO they being less soluble in hot than cold HO float on the top of the liquid on the tube Diamines. Where 2 atoms of NH3 have coalesced unto one. N2 | | H2 | H2 | H2 you may have primary, secondary & tertiary diamines N2 | | A2 | B2 | C2 165 Urea belongs to this class. Common urea. N2 | | C2 O2 | H2 | H2 Urea forms from 77 to percent of human urine Prep. Evaporate urine till it becomes syrupy & add an equal volume of colourless NO5 of s.g 1.35. It forms nitrate of urea, separate the acid by BaO & the urea by alcohol & crystallize. Artificial urea. KOC2 NO + NH4 OSO3 = KOSO3 + NH4 OC2 NO. Prop. It crystallizes in 4 sided prisms like KONO5 Soluble in HO & alcohol, when heated it is converted in great part into NH3 & Cyanuric acid. Unites with acids & forms salts. N2 | | C2 O2 | H2 | H2 N | | C2 O2 | C4 H5 | H2 Triamines. N3 | | H3 | H3 | H3 Organic alkaloids. It was long the opinion of chemists that vegetables only produce neutral & acid substances. In 1803 got an alkali from opium & in 1804 got another alkali. yet it was 12 years after, that the opinion became prevalent that alkalis were produced by vegetables. General properties. They behave like NH3 . They neutralize acids & form salts. They are all solid or liquid, generally fixed a few 167 are volatile. Some are soluble in HO some in alcohol. The sulphates, nitrates, chlorides & acetates are soluble. The tartrates They are generally violent poisons or active remedial agents. They may be divided into 3 classes A. Volatile alkalis free from O. B. Bases readily soluble in alcohol sparingly in HO. C. Bases soluble both in HO & alcohol. A. Example. Nicatine. Prep. Macerate tobacco in HO. The malate of nicotine dissolves Ni = nicotine. M = malic acid NiOM + KO = Ni + HO The Ni distils over. B. Prep. These bases are united 168 with acids such as Kinic acid or meconic acid. Add HCl the chlorides are dissolved out, add lime wh. forms CuCl & precipitates the alkali. Take it up by & crystallize from alcohol C. Dissolve in HCl & form chlorides. Neutralize the chlorides by NH3 & precipitate by oxalate of ammonium. Decompose by BaO & crystallize. Conia is a secondary monamine N | | C16 H14 | H. It is prepared from hemlock chiefly from the seed. It is a colourless oil of penetrating odour & burning taste it is strong poison, in presence of HO it acts strongly alkaline, difficultly soluble in HO. 169 especially when warm, readily soluble in alcohol & ether. Act on it by C4 H5 I & you get ethyl conia. Sparteia. A tertiary monamine N | C16 H13,,, Got from broom, heavier than HO, the liquid boils at 287°C. Alkaline & narcotic poison, has an odour like aniline nicotine, it is a diamine C20 H14 | N2 Occurs in tobacco chiefly in combination with malic It is a colourless liquid, absorbs O readily & becomes brown, has a burning taste, slight-odour of tobacco, is intensely poisonous There is from 2 to 7 Percent in tobacco. The mild kinds of tobacco as 170 Havannah used for smoking contain the least quantity, those sorts used for snuff contain most. The strength of snuff is due to nicotine, its pungency to ammonia salts. Snuff. The leaves of tobacco are allowed to ferment for 18 months. During this time there is a considerable absorption of O & the temp. often rises to 100°. They are then ground & sifted. In fermenting 2/3? of the nicotine is destroyed, NH4OCO2 is formed & a volatile oil to wh the aroma is due & 2 P.C. of nicotine remains. Alkaloids in opium. They are numerous. Morphia C34 H19 O6 N probably a monamine. 171 Codeia C36 H21 O6 N Thebeia C38 H21 O6 N Papaverin C40 H21 O6 N Narcotin C46 H25 O14 N. Narcein C46 H29 O18 N Opianine Pseudomorphine & phorphyroxine Morphine In crystallizing it takes 2HO. Occurs in opium in combination with mechonic & sometimes sulphuric acid. It is present in from 6 to 12 PC. Smyrna opium contains most, Crystallizes in brilliant prisms, taste slightly bitter, has a slight alkaline reaction when heated it parts with its HO of crystallization & at a higher heat is decomposed. HO dissolves 1/1000th part of its wt of it it is readily soluble in 172 alcohol slightly in ether It is a strong narcotic poison when heated with soda lime it becomes methylamine. Muriate of morphia. It crystallizes with 6HO in fine silky prisms, soluble in HO & alcohol. When impure it crystallizes in large crystals, the purer it is, it is more difficultly crystallizable. It forms double salts with PT Cl2 . Acetate of morphia It is a deliquescent salt, crystallizes in thin needles. Sulphate of morphia Salts of morphia are largely used in medicine. 173 5 grains to the ounce are administered like laudanum in small doses. Though less powerful than laudanum. Test. salts of Fe2 O3 3SO3 give a blue colour with it, concentrated NO5 a red colour at first fading to yellow. Conine Crystallizes with 2HO. Occurs in opium to the extent of 1 P.C.. Though homologous with morphia it is not analogous to it in its properties. Soluble in 8 parts cold HO & 17 hot. Melts at 150°C. Decomposes at higher temperatures is poisonous, produces tetanic convulsions like strychnine. 174 Papaverin Is not poisonous. Narcotin Is present from 6 to 8 PC in opium Crystallizes in small rhombic prisms, little soluble in alcohol or ether. Has very feeble alkaline properties many of its salts are decomposed by HO. Is poisonous. 2O grains will kill a dog. There are 3 homologues of narcotine in opium. Alkaloids in chinchona bark There are four. Quinine C40 H24 O4 | N2 Cinchonin C40 H24 O2 | N2 Chinidin C36 H22 O2 | N2 Arcin C46 H26 O8 | N2 They are all diamines. They are found united in cinchona bark with kinic & kinotannic acid. 175 Quinine Found chiefly in the yellow bark in about 3 1/2 P.C. Crystallizes in silky needles from ether, as a white curdy precipitate from its salts, soluble in ether, in 200 parts boiling HO, more soluble in lime water. Readily soluble in alcohol & ether. Intensely bitter, alkaline, melts at 120°C. Unites with acids so as to form 2 classes of salts. The pill used by Dr Livingston in cases of African fever & wh. never fails if the patient be removed to a higher district. 3 to 4 grains resin of julap 3 to 4 - calomel. 3 to 4 - quinine A drop or two of tincture of cardamums to dissolve the resin & 176 form the bolus. It ought not to purge but to occasion gentle movement Sulphate of quinine It unites with 1 atom of HOSO3 , crystallizes with 7 HO in long brilliant prisms, easily loses 5 HO, difficultly soluble in pure HO. Acid salt Q HO SO3 . Used in medicine, add a drop or 2 of HOSO3 to assist its solubility. It is often adulterated with CaOSO3 sugar, calomel, fats, starch, & salicin. To detect adulteration, burn a portion if CaOSO3 is in it, the CaOSO3 remains. If with calomel or sugar you can smell them. If not completely soluble in dilute HOSO3 it contains fats or starch. If salicin be mixed with it. 177 dissolve in 6 times its wt of HOSO3 add 12 parts HO, salicin will be precipitated. Cinchonine. Found chiefly in the grey bark Crystallizes in large anhydrous prisms, soluble in alcohol & ether The salts are intensely bitter, precipitated by gall nuts, heated with KO it becomes Chinodin or quinidine [crossed out] Brilliant prisms soluble in alcohol difficulty in ether Aracin. Found in China cusco. Alkaloids of strychnine family. found in seeds & bark of nux vomica in the 178 Ignata bean. Contains 2 alkaloids Strychnine C42 H22 O4 N2 Brucin C46 H26 O8 N2 Colourless 4 sided prisms, scarcely soluble in alcohol or HO, intensely bitter, soluble in aqueous alcohol when boiling, frightful poison Nitrate. have been used in medicine Tests. Add to the suspected solution Ko2CrO3 & HOSO3, it it produces a violet blue, passing to red. Brucin With 8HO. Crystallizes in colourless prisms 4 sided insoluble in HO & ether 179 readily in alkalis with strong oxidizing agents it forms methylic ether. Alkaloids of the solinacia family. There are 3. Nicotin Hyocyanin. - Atropin C34 H23 O6 N. Occurs in atropa. White, sharp bitter taste soluble in HO & alcohol. Fuses, & decomposes at higher temps. Salts decompose readily. Violent poison, dilates the pupil of the eye. Salts are soluble but difficulty crystallizable Hyocyanin. Has properties similar to atropin. Veratrin C64 H52 N2 O10 18 180 Found in veratrum, produces sneezing is a violent poison. Dervin. C60 H46 N2 O6 Delphinine C64 H32 N2 O4 Colchecine Aconitin Alkal Caffeine or theine. Found in tea & coffee & paraguay tea. In 3 quarters of the globe men have derived a beverage wh they take about the same time of the day. From plants not only of the same species but of a different order They all contain the same alkaloid theine or caffeine call it caffeine. Caffeine C16 H10 O4 N4 tetramine you may view diamines or tramines as monamines. N2 | | H2 | H2 | H2 maybe = N | | NH4 | H | H N | | NH3. | H | H | H In wh the radicals of compound 181 ammonias replace the H Theine or Caffeine. Occurs in tea & coffee. Prepared from tea by subliming it. Crystallizes in thin brilliant needles 177°C sublimes at a higher temp. Difficulty soluble in cold HO, is a weak base its salts are decomposed by HO. In large doses it produces increased action of the heart. irritability of temper If you take 3 grains of theine a day about 2 cups night & morning you [crossed out] may retain you usual temper & state of nerves. If you take 4 or 5 grains it produces irritability of temper & nervousness. If you feel in a nervous state 182 without being able to account for it, it us very probably from this cause. To cure it, take chocolate instead of tea or coffee for some days when it will most probably be cured. Theobromine Occurs in cocoa. It is methyl theine. Hydrates of Carbon Under this head are included all bodies wh have the genera formula CmHnOn Such bodies are starches, sugars gums, bodies wh have a neutral or indifferent character. Dilute acids convert most of them to grape sugar Acts on sawdust by HOSO3 & it is converted into grape sugar. Oxidizing agents convert them to oxalic acid. 183 The views of their chemical constitution are not certain They are at present supposed to be alcohols If the H & O be not present as HO it is in a form nearly approaching it. Take grape sugar for instance C12 H14 O14 It has the same volume as 14 atoms HO frozen to ice the C occupying no appreciable bulk When dissolved it occupies the same volume as 14 atoms of liquid HO. The H8-O comport themselves in solution as HO & when solid as ice. Cellulose C36 H30 O30. It is the basis of vegetable structures. You have it nearly pure in cotton wool. Occurs in the sap of growing vegetables. It is the same in composition from whatever source derived 184 Is nearly pure in the pith of elder rice paper, linen & cotton. Prop. It is a white, solid, sometimes parent Its s.g is a little higher than that of Ho. Its composition is the same but its physical characters differ according to the source whence it has been derived. It is compact in the branches of trees hard & dense in the shells of the filbert & cocoa nut. It is digested or not digested by animals according to its physical condition. It is easily transformed HOSO3 boiled with it converts it into dextrin & then to grape sugar. These all being the same in percentage composition. Digested with HONO3 it forms guncotton. 185 guncotton. [Illustration] Puts cotton in a mixture of HOSO3 & HONO5 washes & drys it. Part of the H has been substuted by NO4. There are several kinds according to the length of time it remains in the acid. Cellulose C36 H30 O30 Gun cotton A C36 H21 (NO4)9 O30 B C36 H22 (NO4)8 O30 C C36 H23 (NO6)7 O30 D C36 H24 (NO4)6 O30 Common paper is cellulose or lignin in another form . A curious transformation is effected by HOSO3 wh converts it into vegetable parchment. Take 2 volumes of the strongest oil of vitriol & one volume of HO carefully measured. 186 Dip ordinary unsized paper, which blotting paper into it & wash well the last HO should have a little NH3 in it to remove all traces of HOSO3. Wash again to remove the NH3 & dry it. The strength of the paper is much increased, a slip of paper that would have before broken by 5lbs will afterwards require 72lbs to break it. Starch. C12 H10 O10 Is very extensively distributed in nature. It varies in its forms according to the source from wh it is obtained Grains of starch in Tous les Moïs are 1/260th in. in diameter. Those in wheat are 1/1000th in. & in rice 1/3000th. in. Starch exist in various quantities in vegetables used for 187 food. There is in Wheat flour 57 to 67 P.C. of starch Rice 85-86 Barley 39 40 Oats 30 40 Rye 54 61 Lentiles 39 40 Maize 65 66 - flour 77 Buck Wheat 43 44 Beans 37 Peas 38 Potatoes 23. Prop. It is white tasteless, insoluble in cold HO & ether, when put in hot HO it swells up & forms a jelly. This is not a true solution for freezing separates it into grains of starch. The youngest grains separate first Test. Put a little Cl into a mixture 188 mixture of the starch solution & KI. The Cl is liberate I. Dilute acids convert starch into dextrin Heated with dilute HOSO3 it becomes grape sugar NO5 dissolves starch & HO precipitates it as an explosive compound as gun cotton in fact. By carefully heating it from 160° to 200°C it becomes dextrin. British gum is made in this way. Manufacture of starch. It exists with gluten in flour. To get rid of the gluten, subject starch to fermentation by wh. the gluten is destroyed, this causes a very bad smell. A new process has been proposed Dissolve the gluten by alkalis & then the starch remains. To get it from potatoes. 189 Grate the potatoes & put them on [illustration] a sieve, pour HO on them stirring them all the time The starch passes thro' the sieve & settles at the bottom of vessel placed below it. Wash the starch once or twice Special Starches. Several are sold for food. Sago is got from the pith of the sago palm. It is made into a paste & pressed thro' a perforated metallic plate & then exposed to the heat of steam to dry it. Tapioca. Is got from the root of the manioc. This root contains HCy wh is separated in the process of making. Arrowroot. Is got from the root stocks of various plants. Salep Is made from the root of the male orchis. 190 Starch in the animal kingdom Sometimes in healthy animals tissues, granules of starch have been found in the brain. The waxy appearance of the liver Inulin C26 H20 O20 + 3HO. Distinguished from starch by not giving a blue with I. Exists in chicory, dandelion Becomes yellow with I. Long boiling converts it into dextrin & then to grape sugar. Lichenin Found in Iceland moss, soluble in hot HO. Irish moss contains another kind C10 H10 O10 + 3HO. Peculiarly distinguished by forming a precipitate with gelatin. 191 Take a solution of Irish moss. & add it to a solution of gelatin no precipitate is formed Add a drop or two of alum & you get a stringy precipitate. Glycogen. Got from mans liver. I produces a dark red colour with it. It has no taste or smell forms a paste with HO Found in the saliva, pancreatic juice Diastase & dilute acids Its formula is given as C12 H10 O10 C12 H12 O12, & as C12 H16 O14. Dextrin C12 H10 O10. It is a product of the transformation of starch Got by roasting starch. 192 10 parts of starch are moistened with 3 of HO, the HO is to contain 1/150th of its weight of HONO5. The paste is allowed to dry spontaneously. It is a colourless transparent body like gum, deviates the plane of polarized light to the right hand, there seems to be an intermediate compound between starch & dextrin, soluble in HO wh starch is not & blued by I wh dextrin is not. Distinguished from gum by forming a beautiful blue solution with Cu OSO3 & KO. When this is heated suboxide of [illustration] Cu is deposited. Dextrin is used as a gum for 193 machinery as in calico printing To prepare glutinous bandages to reduce fractures. Gums. They have the same composition as starch, form a mucilaginous solution with HO. They all give mucic acid with HONO5 instead of oxalic acid as starch does. Quantities of cellulose & gum In one lb of the following substances there are. In Potatoes 327 grs cellulose 27 grs gum Rice 218 87 Wheat 109 109 Barley 2oz 146 Oats 2oz 218. Gums have the same percentage composition wherever 194 obtained but seem to have different combining proportions Gum arabin or arabic C12 H11 O11 Unites with bases as acetate of Pb. Is soluble in cold HO A solution of 18 P.C is so thick that it cannot be filtered, it is insoluble in alcohol. Cerasin The gum from cherry trees. Bassorin. Found in gum tragacanth seems to be a modification of pectin or vegetable jelly Pectin The gelatinous principle of fruits carrots, turnips &c. It is probably identical with Bassorine. It only swells in HO without dissolving. It seems to be a feeble acid. 195 It is rendered soluble by long boiling & passes into ordinary gum. Sugars Cane C12 H11 O11 Fruit C12 H12 O12 Grape C12 H12 O12 + 2HO Milk C24 H19 O19 + 5HO Mellitose C24 H24 O24 + 4HO Eucalyn C12 H12 O12 + 2HO Sorbin C12 H12 O12 Inosite C12 H12 O12 + 4HO Under the name of sugars are included all vegetable substances wh have a sweet taste They are formed during the life of the plant but are perfectly definite chemical compounds & crystallize They are so distinctive in their characters that they may be divided into 2 classes. 196 Sugars susceptible of vinous fermentation by yeast. Sugars not susceptible. Grape sugar or glucose C12 H12 O12 + 2HO is in crystallized state really C12 H14 O14. Occurs in the juice of grapes, in plums, cherries & dried fruits. Occurs in many of those as fructose. Fructose is uncrystallizable. Honey becomes crystalline after some time from the fructose in it becoming grape sugar. It occurs in the animal kingdom as a normal constituent of the liver. Occurs in diabetic urine. It is formed very quickly in the body under certain circumstances. If the fourth ventricle of 197 the brain is irritated by a needle diabetic sugar appears in the urine a few minutes after. Test. Heat a solution suspected of containing it with CuOSO3 & a few drops of KO. Cu2 O is formed. It first appears as a yellowish hydrate but afterwards reddish It is prepared on a large scale by allowing starch & HO at 130° F to flow into a vat containing HO & 1PC of HOSO3. It is boiled for 1/2 an hour when all the starch is converted into grape sugar. Neutralize by CaO & crystallize. Prop. It crystallizes with difficulty in warty concretions Tastes less sweet than cane 198 sugar, is soluble in HO & alcohol. Turns the plane of polarized light to the right. At 100°C it melts & loses 2HO at a higher heat it becomes brown does not taste sweet & is then called caramel, whose formula is C12 H9 O9 & is used for colouring Grape sugar unites with bases & forms saccharides 2(C12 H12 O12) 3 Pbo sesquisaccharate of Pb. Unites with NaCl & forms a crystalline compound It is also said to combine with organic acids. It is easily oxidized With HOSO3 it forms conjugate acids, act on that by strong bases & it forms glucic acid C8 H5 O5. 199 When a solution of grape sugar is acted on by yeast it is converted into alcohol & CO2. C12 H12 O12 acted on by yeast = 2eq. alc. 4 - CO2. When cheese, muscle or other nitrogenous ferment acts on sugar the change is quite different. Lactic acid C12 H12 O12 = (C6 H6 O6)2. If you carry this farther & the putrid cheese acts more on it. C12 H12 O12 = 1 Eq Butyric acid C8 H8 O4 4 - CO2 4 - H C4 O8 H4 C12 H12 O12. Ultimately sugar is converted into mucic acid or rather into a slimy acid whose composition is not well known. 200 Fruit sugar or fructose Has the same composition as grape sugar & only differs from it in not being crystallizable. Is found in honey & fruits. Cane sugar C12 H11 O11. Introduced into Europe some centuries before the Christian era but did not come into general use till the discovery of America. Occurs in sugar cane, beet root, sugar maple. Readily crystallizes in 3 forms. in the crystalline form as sugar candy, in the vitreous state as barley sugar. Barley sugar gives out much heat in passing into the crystalline form. The same thing takes place 201 with AsO3. Readily crystallizes in 4 sided rhomb The taste is sweeter & purer than that of grape sugar. Is soluble in 1/3 its wt of HO less soluble in alcohol than glucose. Heated to 160° it melts to a colourless liquid & cools in the vitreous state as barley sugar. Barley sugar after a time becomes crystalline. By a strong heat sugar becomes [crossed out] caramel. When a solution is boiled with dilute acid it becomes fructose & if for 2 hours longer grape sugar. With strong bases it forms saccharides. C12 H11 O11 BaO. Cane sugar cannot be fermented 202 fermented by yeast without becoming grape sugar. If you take equal wts of cane & grape sugar, the cane sugar will require more yeast than the glucose to ferment it, the extra yeast being employed in converting into glucose. Manufacture of sugar. It exists in various substances but that used in this country is chiefly obtained from cane. The sugar cane is cut before flowering & the juice expressed. The juice contains a good deal of albumen wh would act as a ferment & wh is separated by coagulating the albumen This is called defication. You put in a certain quantity of lime or as lately practised of CaOSO2. Boil & the 203 albumen is coagulated. The syrup is then evaporated. If you evaporate at too high a temp. it is converted into fructose, to prevent this it is boiled in vacuum pans in wh it boils at instead of 220°. It is then transferred to wooden cylinders & crystallized. It is drained from molasses by means of an extremely rapidly rotating perforated cylinder called the Jim Crow & sometimes the devil. The best canes contain about 18 PC of sugar but only 7 to 10 PC is got On the continent sugar is got from beet root. The roots are pulled in October They are rasped & the juice 204 expressed. The juice contains 10 PC of sugar but the manufacture is so much better conducted than that of cane sugar that 7 PC is obtained. In one manufactory in Belgium they got 8 1/2 P.C. There is the same defacation & evaporation as in cane sugar It is filtered thro animal charcoal. The crystals are longer & flatter than those of cane sugar, & its taste not so sweet maple sugar Holes from 1/4 to 1/2 an inch deep are made in the wood of the maple & the juice collected from them by reeds or spoub wh are stuck into them. The juice is collected in March April & May. 205 Each tree yields 3 lbs of sugar in a season & continues to do so for 30 years The juice is concentrated & crystallized every 24 hours. Refining of sugar. Raw sugar is dissolved in lime HO & mixed with bone charcoal & steam blown thro' it & if very impure bullock's blood is added. It is filtered thro bags of twilled cotton, & thro animal charcoal (burned bones). It is evaporated in vacuum pans. The syrup if evaporated in air may rise to 230° wh converts it into fructose, while if evaporated in vacuum pans 140° to 150° is sufficient. It is evaporated till the syrup is so strong that a thread 206 drawn from the finger will return to it without breaking. It is heated to 170° F run into conical moulds. Sweetness & uses of sugar. The sweetness of sugar is definite. 1 lb of cane sugar is equal to 2 1/2 lbs of grape on 3 lbs of milk sugar in sweetness. It is chiefly useful as a food in supporting active respiration, useful in keeping up the animal heat. It is good for infants for this purpose since being soluble it is more easily assimilated to the system. For this reason it exists in large quantity in milk. In the United States the consumption of sugar per 207 head of the population is [crossed out] 40 lbs. In France 4 lbs in Belgium 6 in Austria 2 1/2 in Russia 2 1/2 in the united kingdom 28 in Benzuela 110. Cane sugar is found in plants during the germination of seeds & previous to the unfolding of their buds. The bark of birch contains a good deal Grasses & palms contain most when about to blossom. Jaggery, cocoa nut & wine palms In America sugar is got from the stalks of maize. Relation of H & O in sugar. The H & O stand in the proportion necessary to form HO In such a state also as if it were present in the form of HO. 9 atoms of HO in the state of ice is equal in volume w 9.8 atoms of HO. 208 C12 H11 O11 = 171/3p.SM.1.6 = 106 atomic vol. 9.8 x 11 = 107.8- of 11 atoms of HO in the state of ice. The bulk of an atom of sugar is the same as that of the HO in it in the state of ice the C occupying no sensible space. Milk sugar = 180/1.543 = 116.6 at vol 9.8 x 12 = 117.6 at vol of HO in it. If you dissolve sugar in HO you only increase the HO by the bulk of the HO in the sugar the C occupying no sensible space. Sugar of milk. C12 H11 O11 + HO or more usually C24 H22 O22 + 2HO. milk sugar is only found in the animal kingdom Prep. Evaporate whey after the separation of the curd & crystallize 209 crystallize on twigs. Crystallizes in 4 sided prisms terminated by 4 sided pyramids. The crystals are hard & gritty, feebly sweet, soluble in HO, more difficulty than other sugars, in 6 parts of cold HO & 3 to 4 of hot. It does not become syrupy, on account of its small solubility & does not deliquesce in air. At 130°C it loses its HO of crystallization at higher temps. it becomes brown & is called Lacto caromel C12 H10 O12 It forms saccharides. Precipitates Cu2 O from solutions even in cold but less readily than glucose. Dilute acids convert it into lactose wh has the same formula as grape sugar but does not 210 form a compound with NaCl Although milk sugar does not ferment the Tartars ferment mares milk & make cumase Other fermentible sugars. Trehalose C12 H11 O11 Found in a substance called Trehala a substance used in the East for food a product of insects. Megatose. C12 H12 O12 + 2HO. Got from the twigs of the larch Mellitose C12 H12 O12 + 2HO. From the manna of Eucaliptas Non fermentable sugars. Inosite C12 H12 O12 + 4HO. This is muscle sugar Found in the muscle of the heart in the brain & nerves in unripe common beans & in the cells of the lung & the liver 211 Prep. Crystallizes in small crystals efflorescing in air. Soluble in HO & weak alcohol insoluble in alcohol & ether. At 210° it melts to a clear liquid. Dilute acids do not change it. It does not reduce Cu It does not suffer vinous fermentation, by cheese it suffers lactic or butyric fermentation. Scyllite Is found in the liver of shark If you evaporate Inosite nearly to dryness & add CaCl Sorbite is Is got from the berries of the mountain ash. Its taste is sweet It does not ferment & does not produce grape sugar when boiled with acids 212 Sugars unite with various organic substances. Salicin is one of these. They are called glucosides . Salicin C26 H18 O14. It is an antipyriodic like quinine When boiled with sugar it breaks up into sugar Occurs in willow, poplar Crystallizes in small brilliant colourless prisms, intensely bitter, melts at 120°c Soluble in hot HO, difficultly in cold, soluble in alcohol not in ether. Concentrated HOSO3 dissolves it with a purple red colour. By the action of amulcin, the ferment of almonds* it splits up into saligenin & grape sugar. C26 H18 O14 + 2HO taken up by the action of the amulcin = salignen C14 H8 O4 + glucose C12 H12 O12 x Or by the action of ptyalin the ferment in saliva. 213 Heated with acids it breaks up in a similar way but loses 2HO C26 H18 O14 = C14 H6 O2. salintene + C12 H12 O12 grape sugar.x Saligenin is the alcohol & salintene the ether of the alcohol. There is a large number of glucosides. Populene C40 H26 O20 Obtained from poplars. By the action of amulcin it is converted into glucose saligenin & benzoic acid. C40 H26 O20 = C12 H12 O12 + C14 H8 O4 + C14 H6 O4 Quercitrene Got from the quercus & the bark of the horse chestnut Convolvulene Obtained from jalap roots. Tannine. Is tannic acid & glucose. *Salicin distilled over CaO gives carbolate of lime. 214 Colouring matters These are associated together more by technical use than by chemical relations. They are unlike bodies. They are found in all parts of different plants. They are difficult of isolation Method of doing so. Boil with Ho, alcohol & ether according to their solubility; agitate with PbO wh takes up the colouring matter. Decompose the Pb compound by HS & evaporate in vacuo. Sometimes the colouring matter does not exist in the plant but is formed by oxidation or by the action of a ferment. Thus, madder root does not contain the colouring matter in it, till it has been acted on 215 by a ferment wh the root itself contains. It yields a whole series of colouring matters. Most of these colours attach themselves to an animal substance much more readily than to a vegetable one. Puts a little white of egg wh has been coagulated by heat in the bottom of a vessel into a colouring matter wh dyes it while a vegetable substance is not much affected unless a mordant is put on it. Silks & woolens are dyed directly by these colouring matters. To dye calico print a pattern on it by an acetate. To produce red with madder print with acetate of alumina 216 For purple with acetate of alumina & acetate of Fe. For black with acetate of Fe alone The cloth is hung up & the acetic acid flies off. Puts a cloth printed with alumina in logwood Mordants act more by their acid than basic characters they are sesquioxides. Protoxides are not good mordants. One method of dying is if you can put into the pores of the cloth a colour naturally insoluble & render it insoluble in the cloth itself. This is done in the case of indigo. Mix FeO & KO or CaO with indigo blue, this gives indigo white. Indigo blue differs from indigo 217 white by 1 H. Indigo blue C16 H5 NO2 white C16 H6 NO2 When indigo white is poured from one vessel to another the H is oxidized to HO & it becomes insoluble indigo blue. [illustration] It is large jar in wh is indigo while the sediment is at the bottom. It is called an indigo beck. Dips a cloth printed with an oxidizing substances (CuOSO3) into indigo white. The printed parts are left white, because the CuOSO3 oxidized the indigo white & rendered it insoluble on the surface of the cloth so that it could not penetrate. Adds some alum & a little NH3 to a solution of cochineal. The A2 O3 precipitates it as a 218 Lake. It is this property wh enables the mordant to take down the colour with it & fix it. Madder. Madder is got from the root of the Rubia tinctorum found in Turkey, Holland & the south of France. Fresh madder does not contain colouring matter but contains a resin called rubio erithric acid C32 H18 O18. By the action of a natural ferment within itself it becomes alizarin the colouring principle of madder & glucose. C32 H18 O18 = C20 H6 O6 + C12 H12 O12 The is a large number of colouring matters in madder Alizarin subliming is orange 219 it is red. Alizarin C20 H6 O6 Crystallizes in fine red prisms orange red after subliming. Sparingly soluble in cold HO readily soluble in alcohol, ether & hot HO. Alkalies dissolve it CaO & Bao give blue lakes. Al a deep red. Fe2 O3 a purple It has very much the composition of naphthalin. If you replace some of the H in naphthalin by Cl you get a chlor-alizarin. It is alleged that alizarin is obtained in France from naphthalin. Purpurin C18 H6 O6 Occurs in old madder not in 220 new. Prepared from alizarin acted on by yeast Crystallizes in yellow red prisms Fuses easily & sublimes. Alkalis dissolve it yellow. BaO + CaO give purple lakes. Rubiacine C32 H11 O10 A yellow colouring matter. Is a product of the natural fermentation of the original resin Crystallizes in yellow needles gives the yellow shades in madder dyeing When madder has been used in dyeing one half of the colouring matter is taken up the other half used to be thrown away. The spent madder is now digested with very dilute HOSO3 & steam blown 221 thro it. It is then produces dyes as good & perhaps even of more brilliant shades than the original did. Logwood It contains a honey yellow [crossed out] substance wh is called Hœmitoxalyn wh has no relation to the colouring matter of the blood. Its formula is C32 H14 O2 It forms a red with Al -black - Fe. Crystallizes in violet microscopic crystals wh dissolve red. By a nitrogenenous ferment especially by ammonia if produced it becomes much more powerfully tinctorial Brazil wood. None of the yellow dyes have been much examined Quercitron C. 222 Indigo. It is got from plants of the genus Indig ofera from is atus tinctoria or woad, found in the urine of cows & in that of men in some diseases. Sometimes occurs in milk to wh it gives the blue colour. Prep. The leaves of the indigo plant are macerated & CaO added & allowed to ferment; the indigo white is formed wh soon becomes insoluble indigo blue. Add a per salt of fe to indigo white & it becomes indigo blue. Indigo blue as it occurs in commerce has S.G 1.35. Crystallizes when quite pure in crystals wh have a coppery lustre. 223 HOSO3 dissolves it completely Pure indigo blue may be fused. You may suppose indigo blue to be the radical & indigo white the hydrate. Indigo blue C16 H5 NO2 - White C16 H5 NO2 H. There is one other method of dyeing. Topical dyeing. It is the means by wh you can get an insoluble powder on the surface of the cloth Albumen from blood & casein from cheese is sold for this. Casein is dissolved in NH3 mixed with the colouring matter & heated so as to allow the NH3 to evaporate. Very often these topical applications 224 applications are arsenic green. Or take albumen & colouring matter such as ultramarine expose to steam to coagulate the albumen. [Illustration] This method has enabled many styles of printing to be employed. Cu or As colours should not be employed as they occasion great injury to the health. Many colouring matters are glucosides. They seem to be weak bases. The best mordants are those oxides on the verge of being acids. Mordants are the metallic oxides Chemically they are called lakes. Colouring matter of lichens. They readily split themselves up into several acids, some of wh readily give colouring 225 matters with NH3. Erythric acid C46 H22 O20 Orsellenic C16 H8 O8 Orsellic C32 H14 O14 Evernic C34 H16 O14 Some when treated with stronger acids as HOSO3 or HONO5 break up into new compounds & produce colouring matters [Illustration.] adheres to albumen Albumen is printed on the cloth & coagulated by steam & dyed by the the archil colour. One or two animal colours are employed in the arts. Cochineal. It consists of the dried bodies of insects wh feed on a certain kind of fig. This dye contains carminic acid C28 H14 O14 226 This unites readily with bases. Another insect forms the lac dye used for dying cloth red. Volatile oils, resins & caoutchoue. Essential oils. They are occasionally found ready formed in plants as in the orange & lemon. In other cases it is made by the action of HO on seed as in bitter almond & mustard oil. In the animal kingdom These are rare, altho' they occur in ants. The general classification of essential oils is more pharmaceutical than chemical. They are either solid or liquid When solid they are easily fusible & are volatile Though the boiling points of some are high they generally 227 ally go over readily in steam. They produce a temporary stain on paper, fixed acids produce a permanent one. They have a peculiar penetrating odour generally agreeable. They are rarely pure in commerce They contain a solid substance wh is the oil oxidized or hydrated & wh are called stereoptenes. The oils are prepared in some cases as from the orange & lemon by pressure. More usually as from aromatic plants by hanging the plants in bags & passing steam thro' them & condensing it. They are prepared for perfumery by a peculiar process. A cake of tallow is taken & the flowering plants spread over it. It is then gently 228 heated not enough to melt the tallow. The tallow gradually extracts the oil. The tallow is then treated with alcohol wh dissolves out the oils. They may be divided into different classes. 1st Essential or volatile oils free from O. 2nd - containing O. 3d - S. 4th - wh suffer change by distillation. The central formula around wh they all turn is that of camphine C20 H16 for a 4 vol. formula. Some have only half that C10 H8. Some have these two formulas united C30 H24 229 Essences isomeric with camphine. Essence of bergamot - lemons - orange - birch - camomile - juniper - copaiba C30 H24 - carraway - cloves - ginger - cubebs - thyme - valerian Turpentine. By this is meant camphine C20 H16. Boils at 160°c S.G. 0.864. Got by wounding pines, when it flows out, this is distilled & gives essence of turpentine 230 In this state it is colourless transparent oil with a peculiar disagreeable odour & burning taste. Insoluble in HO, difficulty in common alcohol readily in absolute alcohol & ether concentrated acids dissolve it. It converts O into ozone. If you shake some up in a bottle with air you may detect the presence of the ozone formed applying the test. It contains so much H that if you moisten some cotton wool with it & having warmed it put it into some Cl, HCl fumes are formed & it takes fire. It combines with HO & forms solid stearoptines C20 H16 + 4 HO 231 C20 H16 + 3HO, C20 H16 + 2HO & C20 H16 + HO. These are called camphors of turpentine. Essences not isomeric with camphine. Oil of peppermint C20 H18 Contained as a solid hydrate in certain oils C20 H18 + 2HO. Essence of cedar wood C32 H26 C32 H20 + 2HO is a solid hydrate. Oxygenized essences. Camphors Common Camphor True laurel camphor C20 H16 O2 Obtained from camphor wood by chopping the wood in branches & distilling in HO. Fuses at 175°C boils at 205°C. Vap. density 5.32. Difficult to pound from its elasticity, but may be done 232 easily by putting a drop or two of alcohol on it & then pounding it. Borneo camphor C20 H18 O2. Got by puncturing the tree. Crystallizes in 6 sided prisms colourless & transparent Other camphors. Stearoptines of many plants are really camphors. In peppermint & cedar oil C20 H20 O2 C32 H26 O2 Resins These are exudations from They appear to be formed by the oxidation of the essential oils more oxidized than the camphors. Camphors C20 H16 O2 Resins C20 H16 O2 - n H + n O. 233 They are used for varnishes by mixing pounded glass with pounded resin & treating with alcohol or wood spirit Copal, Mastic, Sandarac Common varnish for maps 24 parts Mastic 3 - Venice turpentine 1 - Camphor 10 - pounded glass Mixed with 72 parts of oil of turpentine & filtered. Lac. Sold in 3 forms. Stick lac. An insect perforates certain trees & the lac It is sold in commerce on the twigs. This is pounded & heated with NaOCO2 wh dissolves out the colouring matter wh is used 234 for dye. The lac is melted in canvass bags & is squeezed on bamboos. & is then called shell lac. Got on ficus indigus or ficus religiosa. Used for sealing wax & for stiffening hats for wh purpose it is dissolved in wood spirit. Sealing wax 48 parts lac 12 venice turpentine 1 Balsam of Peru 36 Vermilion stirred up with it. For making lacquers of wh there are several kinds the usual one is, Lac is mixed with 1/2 its wt of sandarac & a little venice turpentine, dissolved in 10 to 12 parts alcohol. The brass is heated before it is applied. 235 Guayacum. Obtained from guayacum officinalis It is bluish green or brown The alcoholic solution is a good test for ozone wh makes it blue Jalaps. Contain glucosides Jalapin is a glucoside. Amber It is a fossil resin found in coal but chiefly thrown up on the shores of the Baltic between Memel Often contains insects of extinct species but related to present species. Seems to have been an exudation S.G 1.065. Insoluble in alcohol & ether, soluble in essential oils. After having been 236 once fused it is soluble in turpentine & then forms amber varnish By dry distillation it yields succinic acid & amber oil. With HONO5 it forms artificial camphor having a smell like musk. Caoutchouc. It is a resinous substance suspended in the milky juice of various plants. In its ordinary state in commerce it is impure. When separated from its impurities its formula shows it to be a hydrocarbon nC8 H7 Soluble in chloroform but is precipitated by alcohol, melts at 120°C & at 200°C it beings to decompose. Insoluble in HO & alcohol Soluble in turpentine, benzol 237 naphtha & chloroform. The solution in naphtha is used for water proofing cloths. Unites with S & forms vulcanized india rubber. Got by treating with sulphide of C or usually with chloride of S. S2 Cl . Gutta percha. Is like india rubber in its composition & many characters except its want of elasticity at common temps. Is the concrete juice of percha. Scarcely elastic at common temps. but becomes elastic at 212°f. Is worked at a high temp.; welds when soft is soluble in the same reagents as caoutchoue. Is not attacked by HFl. Vulcanized india rubber gradually 238 gradually loses its S & becomes brittle especially if kept in contact with metal wh takes the S. Asphalt & bitumen Occurs extensively in nature as springs some of wh contain the asphalt in solution The salt of the earth spoken of in the Bible probably means bitumen & when it is spoken of as having lost its savour it means that it had lost some of its volatile hydrocarbons. It was ordered to be used in burnt sacrifices & was probably smeared over the bodies & thus rendered them more combustible. Asphalt is the residue of mineral oils wh have lost their volatile hydrocarbons. 239 Occurs in Turkey Persia Egypt & even in our own country There was a spring near Edinburgh & there are in the Industrial Museum several black candles made from it. There is one near Alfreton in Derby from wh paraffine was first made. There are many mineral hydrocarbons like asphalt. Ozokerite C2 H2 n. Sheerit Found in brown coal in Germany Fichtilite C8 H7 Found in fossil pines. Hartit C6 H5. Idrialit C80 H28 O2 Found with cinnabar in Idria. 240 Animal Chemistry. We could make urea & grape sugar waste products of vital agency but chemistry has yet made but small progress in producing the The ruling agency in vegetable & animal life is vital agency. When we see plants growing on the same soil, nourished by the same substances, watered by the same rain & stimulated by the same manure & yet producing substances as different as starch & morphia we cannot tell what the hidden force wh produces these transformations is. Latterly we have got a more exact idea of force & know that, heat, electricity, chemical affinity &c 241 are all resolvable into motion. But although our ideas of force are extending & we can compare the animal body to a steam engine yet one force is left of wh we known nothing viz., vital force. We know the engine but not the engineer. Histogenetic substances. All those wh build up the frame- work of the animal body are termed histogenetic. They are the substances of wh the organs consist. Fat is not an organic, is not a histogenetic substance. Albumen Fibrin Casein Syntonin Fibrin in muscle Globulin found in the eye. 242 Hemato crystallin. Most of them, the first three at least are found indifferently in the animal & vegetable kingdoms. If you stir fresh blood with twigs fibrin coagulates on them. Whip fresh juice of cauliflower with twigs & you get fibrin Boil cabbage juice & you get albumen. You can get it from blood Add an acid such as HCl to casein & cheese is formed Add HCl to solution of peas & you get the same casein These substances exist both in plants & animals. General properties whence soever derived. Uncrystallizable translucent of a yellowish colour: tough 245 when dry, adhesive or jelly like when moist. Brittle gelatinous plates when dry. Exist in 2 forms In the soluble state as fibrin in the blood In the insoluble state as when the blood is out of the body. The exact cause of the transformation from the soluble to the insoluble state is not known They part with 2P.C of some proximate constituent* when they become insoluble. insoluble varieties They seem to dissolve unchanged in acetic & phosphoric acid. Mineral acids decompose them All are transformed by long boiling in HO When oxidized by HONO5 or *As soda or potash generally alkalies 244 other oxidizing acid they produce acids of the alcohol series beginning at formic & going up to caproic acid They also produce aldehydes. Some in oxidizing produce oil of bitter almonds & acids of benzyl series Digested with HOSO3 or strong HCl. they produce almost invariably Leucine & Tyrosine & commonly Glycine, besides NH3 salts under the influence of caustic alkalis When moistened they putrefy the elements dividing themselves according to their greatest affinities. Putrefaction thus differs from decay wh is a combustion. Among the products of their putrefaction are the carbonate butyrate & valerate of NH3 , NH4 S 245 Common test for these; for any of these nitrogenous bodies. Moisten with a salt of H8 having an excess of Hg & heat to [Illustration.] 212°. They become red on the surface. Do not heat too violently. This is a test for all histogenetic substances. Mulder argued that they all contained a substance called protein wh was the basis of them all. According to Mulder it has the formula C36 H25 N4 O10 + 2HO wh can be driven off by heat. Percentage composition of protein according to this formula. C = 54.7 N = 14.2 H = 6.8 O = 24.3 He supposed other bodies to be 246 protein combined with P & S. Though his views are no longer held by chemists the nomenclature is retained & they are called protein compounds. Probably they are all the same as regards organic composition & the ground work is the same in all & they differ merely in form. Albumen Is the chief type of the group. Exists in various states probably owing to the amount of alkali with wh it is united.* Occurs in vegetable juices in blood, chyle & lymph in all serous liquids, in the juice of flesh & cellular tissues, in white of egg. Prop. 1st. Soluble albumen As obtained from white of egg it is transparent, yellowish, *Thus its reactions are not always the same 247 soluble body of a glairy consistence. S.G 1.261. When put in HO it swells & dissolves, the solution reacts alkaline from the NaO it contains. Remove this by acetic acid & add HO & it becomes insoluble Metallic salts precipitate albumen Add HgCl to albumen & it forms an insoluble coagulum, on this account albumen is used in cases of poisoning by HgCl. When heated to 63°C it becomes opaline at 75°C it coagulates entirely. It is then insoluble in Tannic acid precipitates albumen. Albumen of blood. is not coagulated by dilute HOSO3 248 Insoluble albumen When albumen is acted on by heat it appears to be the first form from wh all the other nitrogenous substances are formed. It requires very little change to become muscle or the contents of nerve tubes Fibrin Occurs chiefly in blood, lymph & chyle in a state of solution Prop. Separates in an insoluble state in delicate filaments. We know nothing of pure soluble fibrin Coagulated fibrin is opaque yellowish fibrous mass hard & brittle when dry Swells in HO but is insoluble in it, dissolves in solution of KONO5 at 40°C but is coagulated by boiling & acetic acid 249 Digested at 150°C with HO under pressure, by sealing it up with HO in a tube. The fibrin is apparently converted into albumen. It becomes soluble & is coagulated by acids & behaves exactly like albumen. Vegetable fibrin is prepared by putting flour in a muslin bag & kneading it in a stream of HO. The starch is carried thro' the pores & the fibrin remains behind. Gluten of wheat is identical with fibrin Syntonine. Is fibrin of muscle Is the chief constituent of the striated muscles, is in smaller quantity in the smooth muscles & in the arterial coat & spleen When first taken from the body it is snow white. 250 Soluble in HO containing 1 PC of HCl, insoluble in KONO5. Is precipitated from its solutions in alkalis by KCl. or NaCl The solution in lime water is coagulated by heat. Casein. Occurs in the milk of mammals, in small quantity in blood under the name of serum casein. It exists in yolk of egg so intimately mixed with albumen that it used to be thought a separate substance & was called vitellin Exists in the juice of flesh in the juice of the thymous gland. In the vegetable kingdom in the seeds of leguminosæ Prop. Chiefly differs from the other allied substances in its mode of coagulating. Maybe got from milk by adding HCl or rennet 251 Acetic & Lactic acid precipitate it from solutions. Strong acetic acid however dissolves it. Rennet coagulates it. It is not precipitated by heat. The skin formed on the top of boiled milk is caused by the oxidation & not by the coagulation of casein. If boiled with CaCl or Mg OSO3 it is precipitated but the base goes down along with it. On account of this property it is used for cement for glass & earthenware. A poor cheese is made into a paste with lime. Vegetable casein of leguminosae or Legumin Occurs in leguminosae from 20 to 25 P.C. They are even too nutritive The casein is obtained by coagulating 252 coagulating their infusion by rennet or by adding acids. Casein of animals & vegetables is exactly the same Cheese is sold in China made from beans. Its solution when heated forms a skin on the top like milk heated. Globulin. Forms 36 P.C of the crystalline lens of the eye, & got its name from being supposed to be identical with the coagulable part of the corpuscles of the blood. Differs from albumen by coagulating at 93°C. The solution is not coagulable by acetic acid or NH3 . It becomes turbid when the acetic acid solution is heated. Is precipitated by CO2 253 Hemato crystalline It is albumen in a state in wh it can be crystallized Got from the blood of the guinea pig from wh it crystallizes in tetrahedra. Is in the blood of rats & mice. It is difficult to get from man's blood but from it & from the blood of carnivora it is in prisms From the hamster in rhombohedrous Differs from all other albuminous bodies by not being precipitated by metallic salts & Cl2 ONO5 It is obviously a glucoside* The characteristic of all histogenetic substances is that they all contain 15 P.C of N. B Derivatives from the albumenous group * the substance wh remains beside glucose has like same composition as albumen 254 They closely resemble albumenous bodies but contain rather less C. They differ in physical characters They do not form cells but form organic bases of certain tissues With strong HCl, HONO5, & prussiate of KO they are not precipitated Ossein. Prep. But a piece of bone in dilute HCl, & treat with alcohol & ether to take out the fat. Insoluble in HO, is converted into glutin by boiling *Glutin It is a transformed condition of ossein. Is called gelatin in commerce. It is colourless transparent & horny Brittle, heavier than HO, *Different form gluten wh is in wheat, Glutin is the general name for gelatine 255 tasteless insoluble in cold HO soluble in hot Water with 1 P.C of glutin is gelatinous. Long digestion in HO or destroys its gelatinous property Forms a precipitate with tannic acid. Dry distillation produces various bases from it as methytannin Glutin does not appear to be in the body except in the spleen. Chondrin Prep. Boil the permanent & articulate cartilages It much resembles glutin. It is precipitated by acetic acid, per salts of Fe, HCl alum Treated with Many albumenous bodies pass into glutin when boiled 256 Glutin & elasticin are known to us as common glue Glue is made from the parings of ox hides boiled in a coarse cloth cut into blocks & dried. Size is a less strong glue made from the parings of parchment & used in liquid state. Confectionery gelatine Made from the swimming bladders of fish & the parings of fine hides. Abroad it is made from the tendons of rats. In the abattoirs where horses are slaughtered, the carcases are put into rooms plastered so that the rats cannot make holes in them & two or three bricks are left wh can be removed & replaced at pleasure. The rats are allowed to enter at night to clean the bones of the 257 horses before the bones are sold to the P. makers. In the morning the bricks are replaced & a man having a mask & thick gloves & armed with a bludgeon enters & kills the rats, their skins are made into kid gloves & their thigh bones cleaned & made into toothpicks for the London clubs; the rest of the body is boiled down for gelatine. Leather is a tannate of gelatin There are various nitrogenous substances wh occur as derivatives in the animal body These substances are formed probably by the transformation of histogenetic substances arrested in their passage to complete oxidation. They are probably amides Amides contain their N as 258 amidogen NH2 . Kreatin C8 H9 N3 O4 + 2HO . Occurs in the striped & smooth muscles in urine in the brain in blood. It is best got from the flesh of fowls or skate fish in wh there are 3 parts of kreatin to 1000 parts of flesh. It is a clear, transparent colourless, brilliant body crystallizes in rhombic columns loses 2HO at 100°C. Insoluble in strong alcohol but soluble in dilute spirits of wine. Has a bitter taste, neutral in reactions. When heated with strong acids it becomes converted into kreatinin a substance wh also occurs in urine. C8 H9 N3 O4 = C8 H7 N3 O2 + 2HO. When heated with BaO it takes up 2HO, & becomes urea & sarkosine 259 C8 H9 N3 O4 + 2HO = Urea C2 H4 N4 O2 + sarkosine C6 H7 NO4 kreatinine Occurs in blood muscle & urine is is formed by the action of acids on kreatin Crystallizes in colourless rhombic prisms, soluble in HO + hot alcohol, the solution reacts alkaline & is a feeble base, when concentrated it tastes like dilute NH3 . By long keeping it becomes kreatin, especially in presence of lime water Kreatin & kreatinine are products of the oxidation of the tissues on their way to urea. Sarcosin. C6 H7 NO4 Although to be expected, yet it is not perfectly certain that it exists in the urine Prep. Act on kreatin by alkalis. BaOH5 It crystallizes in rhombic 260 prisms soluble in HO Seems to be ami When kreatin 2(C8 H9 N3 O4 ) + 10H8 O = 10Hg + 2HO + 4CO2 + (2C4 H7 N3, C4 H2 O8) Methyluramine C4 H7 N3. It is probably a triamine It is a strong base precipitates oxides, drives NH3 from salts, its constitution is unknown. Sarkin C10 H4 N4 O2 Occurs in the flesh of horses, oxen & men. Crystallizes in colourless transparent needles readily soluble in HO difficultly in alcohol Fuming NO5 converts it into Guanin Guanin C10 H5 N5 O2 . Occurs in guano & spider's 261 excrements in the liver & cavities of pancreas White or yellowish isomorphous mass without taste or smell Insoluble in HO alcohol & ether, soluble in alkalis. Unites with salts as ZnCl. By NO5 or HOSO3 & MnO2 it becomes xanthin. Guanin C10 H5 N5 O2 Xanthin C10 H4 N4 O4 Xanthin occurs in urine occasionally, forms calculi has been found in flesh & salivary ducts An amorphous white mass Soluble in acids & alkalis, little soluble in HO. Resembles sarkosin & in less decidedly basic then they. Cystin C6 H6 NS2 O4 Is a rare constituent of urinary 262 calculi. Has been lately found in nerves & liver Crystallizes in colourless transparent- 6 sided [crossed out] tables. Neutral, insoluble in HO & alcohol soluble in acids & alkalis. Allantoin C8 H6 N4 O6 Occurs in cows, [illegible] & in the urine of calves & dogs Is got by the oxidation of uric acid Is most easily got from calf's urine. Crystallizes in colourless brilliant prisms, tasteless having no smell neutral, soluble in hot HO & alcohol insoluble in ether soluble in alkalis but is decomposed when boiled with them taking up 10HO. C8 H6 N4 O6 + 10HO + 2(C4 H2 O8) + 4NH3 Tyrosin C18 H11 NO6 Occurs in the liver, pancreas in cochineal in root of 263 & is a general product of the decomposition of albuminous bodies by acids & alkalis. Prop. Occurs in white silky crystals. Soluble in hot HO insoluble in alcohol & ether Dissolves without change in alkalis & acids forms conjugate bodies with HOSO3. Aloxan C8 H2 N2 O8 + {2HO or 8HO} Made from guano. By the oxidation of uric acid by NO5. Occurs in octahedral crystals Soluble in HO, the solution colours the skin red. It reddens litmus paper. At 100°C it loses HO. Forms like alkalis HONO5 oxidizes it & forms parabanic acid. 264 Reducing agents as HS convert it into aloxantin. Aloxantin is readily changed Thyanuric acid is C8 H5 N3 O2 S2 Formed when aloxane is treated with SO2 & saturated with NH3. Aloxantin C8 H5 N2 O10 Got by acting on aloxan by reducing agents Crystallizes in colourless prisms dissolves in NH3 with a purple colour. The solution is acid. it gives a violet precipitate with BaO. Its products of oxidation are similar to those of alloxan. Cerebrin C34 H33 NO5 Occurs in the brain. It is a white porous powder, tasteless 265 tasteless, having no smell, insoluble in HO, soluble in alcohol & ether neutral. Decomposed by boiling acids at 80°C Amide acids. Taurin C4 H7 NO5 S2. Occurs in the muscles of all mollusca, in the lungs, sometimes in the kidneys & often in the liver of higher animals. Produced by the action of acids on Taurocholic acid a constituent of bile. Prep. Heat or bile with HCl. Evaporate & exhaust with alcohol. It has been got artificially by heating isotinate of ammonia C4 H9 O8 NS2 it loses 2HO H2 O2 C4 H7 O6 NS2 Taurin It is thus the amide of isatinic 266 acid. It forms colourless transparent 6 sided prisms dissolves easily in HO, insoluble in alcohol & ether. dissolves in acids, is neutral. Leucin C12 H13 NO4 Exists in blood vascular glands spleen, in thymous gland In liver & bile, the pancreas & salivary glands & thin secretions. In the contents of small intestines in the lungs & kidneys* It is always produced by the action of strong acids & alkalis on albumenous bodies Prepared synthetically by heating valeric anhydride with HCy. Valeric anhydride C10 H10 O2 + HC2 N + 2HO = C12 H13 NO4 Leucin is the amide of caproic acid. Caproic acid C12 H11 O3, HO Leucin C12 H10 (NH2 )O3 , HO * has been found in diseased brain 267 Prop. When quite pure it crystallizes in colourless brilliant plates, Freely soluble in HO less so in alcohol & insoluble in ether. The solutions are neutral. With HONO5 it gives various products among others Leucic & Lactic acid. Uric acid. C10 H4 N4 O6 It is biatomic = 2HO C10 H2 N4 O4 . Occurs in small quantity in the urine of man & carnivora, scarcely at all in that of herbivora. The urine of birds & serpents chiefly consists of this & also that of tortoises. Largely in the excrements of butterflies & beetles Traces of it in healthy blood Increases in gout & Brights disease Is in excess in cholera, bronchitis & pneumonia Is a frequent substance in calculi. 268 Prep. Urates in serpents excrements are urate of amonia principally. Treat with alkalis (KO) & add HCl & the sparinly soluble uric acid is precipitated. It is a white crystalline powder difficultly soluble in HO insoluble in alcohol & ether. When heated it is converted into urea, cyamuric acid, NH4 oeo2 HCy. Peroxide of Pb makes it into alantoin, urea, oxalic acid & CO2. This is important. It is only a feeble acid but is bibasic & forms acid & neutral salts. Urates. General formula MO} HO} = Uric Urate of NaO. NaO HO /U 1 eq of HO in uric acid is replaced by 1 of NaO. 269 Difficulty soluble in cold HO, more so in hot. This is the reason that urine sometimes though clear when ejected becomes turbid on cooling. Acid urate of ammonia NHO HO /U Crystallizes in fine needles or an amorphour precipitate scarcely soluble in cold HO Urate of lime CaO HO /U Occurs in calculi & sometimes as a urinary sediment Forms chalk stones in the joints of gouty persons. White amorphous & difficultly soluble in cold HO. Derivatives of Uric acid. When HONO5 acts on uric acid, it is dissolved with a yellow colour & various products are formed. By careful evaporation to dryness & treating with NH3, it becomes purple. 270 Bestway. Take 4 grs. aloxantin & 7 of hydrated alloxan, dissolves in 1/2 an oz. of HO by boiling. Add to 1/6 oz. by measure of saturated solution of NH4 OCO2, & murexide is formed. It must be boiling before adding to NH4 OCO2 . Murexide C16 H8 N6 O12 Has the synonym of precipitate of ammonia. Is used in dyeing. Its owing to the formation of murexide that the guano colours are formed. Guano consists of the excrements of sea fowl It is treated with KO to dissolve the uric acid. The uric acid when treated with NH3 forms murexide. It is then treated with salts of PbO & Hg. Properties of murexide 271 Crystallizes in 4 sided prisms, of a golden green beautiful metallic lustre. Difficultly soluble in HO readily in KO with a purple colour. Test for uric acid. Dissolve uric acid in HONO5 & alloxan is formed It is supposed that murexide contains a compound called purpuric acid & that it is a NH3 compound of this. NH4O} HO} purpuric acid C16 H3 N5 O10 No substance has yielded so many compounds to organic chemistry as uric acid. Some of the chief are, Uric acid & nitric acid form alloxan C10 H4 N4 O6 + 2HO +20 = alloxan C8 H2 N2 O8 + Urea C2 H4 N2 O2 Act on alloxan by a feebly oxidizing agent as KO. 272 C8 H2 N2 O8 + 4HO = mesoxalic acid C6 H2 O10 + Urea C2 H4 N2 O2 Cynuric acid Seems to take the place of uric acid in the urine of the dog. Crystallizes in 4 sided prisms Melts when heated & exhales the odour of hemp nitrile Dissolves in acids & alkalis & has all the charactes of a feeble acid. Inosic acid. HO, C10 H6 N2 O10 . Found in the juice of flesh in small quantity. Forms a solid white uncrystalline mass, soluble in HO, insoluble in alcohol & ether. Reddens litmus, tastes like flesh forms salts. Acids of bile. Bile besides less essential constituents contains NaO salts of 2 nitrogenous acids. 273 These acids are like glucosides They do not contain grape sugar but bodies corresponding to it. The one contains glycin the other taurin instead of glucose. Both contain the same acid. viz, cholic acid. Cholic acid with taurin & glycin forms conjugate acids. Glycocholic acid HOC52 H42 NO11 Occurs as glycocholate of NaO in bile. Is the main constituent of ox gall & is in small quantity in that of other animals except the pig. Glycocholic acid crystallizes in very delicate needles, soluble in hot HO & alcohol, difficulty in ether. The solution tastes sweet & then intensely bitter, reddens litmus With HOSO3 & sugar it gives 274 an intense purple red. Soluble in concentrated acids, without colour at first but absorbs O & becomes coloured. When long boiled with BaO it is decomposed C52 H43 NO12 + 2HO = cholic acid C48 H40 O10 + glycin C4 H5 NO4 glycin is the amide of acetic acid & is a product of the action of acids on gelatin Hence glycocholic acid is a conjugate acid. Taurocholic acid C52 H45 NO14 S2 So called because it contains taurin instead of glycin. It is the second chief acid in bile Occurs as the NaO salt in the bile of man, ox, dog, goat frog boar, anaconda &c. In certain fresh water fishes. Has been detected in the blood in transudations *In the boar is is apparently alone not accompanied by other acid 275 & in urine in cases of suppressed excretion of bile. White amorphous bitter powder soluble in HO Easily decomposed by heating Is decomposed by boiling with BaO taking 2HO. cholic acid taurin C52 H45 NO14 S2 + 2HO = C48 H40 O10 + C4 H7 NO6 S2 Taurin is the amide of isithionic acid. With HOSO3 & sugar it gives the same reaction as glycocholic acid. With ferments the taurs & glycocholic acids are broken up as with [ferment] alkalis. Cholic acid C48 H40 O10 . Crystallizes in transparent colourless tetrahedral crystals Has a bitter but sweet taste, readily soluble in alcohol & ether, difficulty in HO. Its alcoholic solution reddens litmus & dries CO2 from its salts. 276 With alkalis it forms crystalline salts. With HOSO3 & sugar it gives the purple reaction of bile. Hyoglycholic acid C54 H43 NO10 . Substitutes these other acids in the bile of the pig. Not found in that of any other animal. A white resinous substance melts in boiling HO. Insoluble in HO & ether It is a conjugate acid & contains glycin & Hyocholic acid Hyocholic acid C50 H40 O8 . There is another corresponding to it in the bile of the pig. Hyotaurocholic acid C54 H45 NO12 S2 . Lithofellinic acid C40 H36 O8. Exists in oriental. in the biliary concretions of antelopes & goats, of wh it forms the chief part. 277 It belongs to the same class as these others When cholic acid is acted on by acids it forms several substances one of wh is called choloidic acid. Cholic C48 H40 O10 - 2HO = choloidic C48 H33 O8 Amorphous mass melts on boiling readily soluble in alcohol. Cholosterin C52 H44 O2. It is a crystalline fatty substance found in bile but generally in biliary concretions. It is like a monoatomic alcohol Found in the brain blood, lungs It is neutral melts at 145°C sublimes at 360° Gives an aromatic oil by distilling having a smell like the geranium Insoluble in cold alcohol, soluble in boiling alcohol & ether. * Found abundantly in biliary concretions 278 Solutions of bile dissolve it readily It unites with one equivalent of acetic acid with displacement of one eq. of HO. Compound ethers may begot from it as from cedernal C52 H44 O2 C4 H3 O3. All bile of animals is coloured by a substance wh forms a bile pigment. Originally brown in man but, becomes green by oxidation Solid constituents of animals Bones. Those of vertebrate animals are tolerably constant in composition When dried at 212° they have 1/3d. of their weight of organic matter & 2/3ds of mineral matter. Large bones & those wh have much work have more mineral matter General average of the composition of bones taken from various analyses. 279 3CaO, PO5 57 parts. CaO CO2 8 Ca Fl 1 3MgO, PO5 1- mineral matter 67 Cartilage 33 The mineral matter in bones increases with age. The teeth resemble the bones in composition. Dentin is like dense bone. Organic matter in it 28 P.C. The enamel contains no cartilage. Mineral matter in teeth 3CaO PO5 81-88 P.C CaO CO2 7-8 Ca Fl 3-4 3MgO, PO5 1-1 1/2 Muscular tissues. They are extremely complicated & contain many substances but may be on an average. HO 74-80 P.C Solid ingredients 26-20 PC. Among the solid ingredients 280 There are in the 26 parts. Syntonin 15.4-17.7 Gelatinous substances 0.6-1.9 Albumen 2.2 -3.0 Kreatin } Kreatinine } Inosite } Inosic acid } Hypoxanthin } Traces Fat 1.50-2.30 Lactic acid 0.60-0.68 PO5 0.66-.70 NaO 0.07-0.09 KO 0.50-0.54 Mgo } ZnO 0.02-0.03 } Traces. NaO is chiefly confined to the blood & KO is in the flesh. Many of these are dissolved in the fluid surrounding the fibres of the muscles. Healthy muscles have an alkaline reaction but after the rigour of death an acid reaction. Contraction of muscle is always accompanied by oxidation CO2 being evolved 281 In this the sapid constituents of the meat reside & the bodies wh. are so important for nutrition as the phosphates. If you take the flesh of the fox & venison & express the juice & dip the flesh of the fox in the juice of the venison & cook it, you cannot distinguish it from venison. If you take away these juices Supposing you wish to make soup you wish to get out the sapid constituents, in boiling meat you want to keep in these. To make the strongest soup. Mince the meat, put it in cold HO & gradually raise the temperature. You must go beyond 150°F before you coagulate the blood & till this is done the soup 282 has a red colour. To boil meat plunge it at once into boiling HO on about 1/4 hour & then reduce the temp. to 160° by adding cold HO. x The boiling HO at once coagulates the albumen on the surface & the sort of crust thus formed keeps in the sapid & nourishing constituents. To make the strongest possible soup for invalids Take one lb of lean beef mince it & mix with 1lb of HO, heat it very slowly till it boils & all the soluble & gelatinous matters are extracted. You then strain it thro' a cloth The effect on the patient is very different if you leave it with its straw colour or colour it with burnt sugar or burnt onion. If you colour it they think it is much stronger. * Keep simmering & about the end of the operation you may raise to [illegible] again 283 Evaporate this to dryness & you get the true extract of flesh. That sold in shops is only glue. In boiling beef the albumen coagulates at 140°F but the blood globules do not coagulate before 158°F. On this account in roast meat although it is perfectly cooked, the inside sometimes appears raw, the heat there having never been up to 158°. Relative values of meat In 1 lb of each. Veal Beef Mutton Pork HO 10oz-0grs. 8oz-0grs 7oz 16.6.69 3 grs Gelatine 1-2 1-62 1-52 0.385 Fibrin & albumen 1-199 1-122 0-385 0-315 Fat 2-281 4-340 6.176 8-0 Mineral matter 0-312 0-350 0-245 0-105. Salting of meat. When meat is placed in salt a curious action goes on. 284 From its affinity for HO the salt takes the HO from the outside of the meat & dries it. The juice from the inside of the meat is then diffused into this & thence into the brine. But the brine does not easily penetrate into the meat. The sapid constituents & the mineral salts come out. A great part of its nutriment is thus removed from salted meat. When it is long used scurvy & other diseases arising from defective nourishment make their appearance. Components of the brain. They are not satisfactorily made out. Among them are oleine, oleic acid, leucin, margaric acid Cholesterine, stearic & palmitic acid 285 The two characteristic ingredients are cerebric acid & oleophosphoric acid. Cerebric acid. It is a phosphorized fatty acid. & is found partly free & partly in combination with NaO. Insoluble in HO but swells like starch when the HO is heated. Oleophosphoric acid. It is a greasy oily liquid partly found free & partly in combination. Found also in the yolk of egg. When long boiled it is decomposed into oleine & phosphoric acid. Mineral ingredients are of very small amount. They amount in the human brain to 0.027 PC of these 3KO, PO5 55 P.C 286 3NaOPO5 23 PC 3MgOPO5 3FeOPO5 3CaOPO5 There is also PO5 either as stronly acid phosphates of free also SiO2 Glands & their juices Leucin is in the pancreas & spleen, in thymous gland in thyroid body & in living ox. Lyrosin Hypoxanthin in the spleen thymous gland Uric acid in spleen. Formic, acetic, succinic & lactic acid are found in these glands. Inosite in the spleen, liver, kidney Thymous gland pancreas & lungs. Cystin. Taurin Guanin in the pancreas of ox. The mineral ingredients in glands vary much In the liver the KO salts predominate 287 predominate over those of NaO. The reverse is the case in the spleen. Cl forms 2 1/2 P.C. of the ash of the spleen & 3/10 PC of the spleen PO5 forms 33.5 PC of ash of liver & 18.5 P.C of ash of spleen. CaOMgO in small quantity In spleen Fe is abundant, forming 7 to 16 PC of the ash. Mn, Cu & Pb are commonly but not always found both in the liver & spleen. In occasionally Digestive fluids Saliva S.g 1.004 to 1.006 It is always alkaline but more so during meals than when fasting. The saliva of the pyrotid gland contains ptyalin as a marked ingredient It has the same power as diastase of converting starch first into [illegible] & then into sugar It is an albuminous matter in a state of change 288 Ptyalin It is an albumenate of NaO. Forms 1/3 of the whole sold residue of saliva. It is very prone to decomposition or putrefaction. It is a strong ferment. The conversion is almost instantaneous. Composition of saliva of pyrotid gland. In 1000 parts from the dog. HO 995.3 Solid residue 4.7 Of the residue Organic matter 1.7 Alkaline chlorides & sulphocyanides 2.1 CaOCo2 1.2 In certain animals the sulphocyanides exist more than in others. Add a per salt of Fe to saliva & a red color is produced showing the presence of sulphocyanogen. The composition of human saliva is like that of the dog's. 289 HO 994.10 solid residue 5.90 The presence of sulphocyanide of NaO is characteristic. The daily secretion of saliva by an adult man is about 48oz. but differs according to his food. Mineral matter in it consists of KO, NaO & CaO salts. The last when acted on by the air & converted into CaOCo2 forms the solid encrustration froth on horses mouths. CaOCo2, 3CaOPO5 & mucus form tartar. The sulphocyanide of K on the teeth is a medicine The function of saliva is partly chemical & partly mechanical. Healthy saliva is frothy & carries down 0 into the stomach * The KSCy exists chiefly in saliva of man & sheep 290 stomach wh aids the digestion Its chief function is to convert the starch of food into sugar. The [crossed out] saliva from the pyrotid gland alone has not this power. Various nations have found out this power of saliva. The formation of diastase is the use of malting. In South America there is a fermented drink made from maize. Old women chew it & spit it into jars, it is then fermented. The pancreatic fluid is like saliva. It is alkaline like it & converts starch into sugar It is a colourless clear, frothy, tenacious substance S.G 1.008. Coagulates only slightly when gives 1.36 P.C of solid matter Contains a solid substance, like albumenate of NaO but not identical 291 identical with it is prone to decomposition Ptyalin An adult man secrets 10lbs of pancreatic juice daily. Pancreatic juice of dogs. HO 980.45 solid residue 19.55 pancreatic ferment 12.71 Mineral bodies 6.84 Its chief juice is to convert into sugar the starchy matters wh have escaped the action of the saliva. Bernard of Paris asserts that it acts as amulcin & breaks up fats* Pancreatic juice does this out of the body It is possible that the pancreatic juice may reform the NaCl broken up in the process of digestion. Gastric juice It is the fluid poured out from Into glycerin & fatty acids 292 the lining membrane of the stomach. It is neutral in the empty stomach. acid when food has been recently taken in. S.G 1.0023. The acid is generally lactic acid. Shmidt's analysis HO 994.4 solid ingredients 5.596 peculiar ferment pepsin 3.195 free HCl 0.2 CCl 0.06 NaCl 1.46 Lactic acid is with it in varying quantity. The saliva is mixed with it in analysis. Marked ingredients. Pepsin & free acid. Pepsin. It is an albumenous body soluble in HO insoluble in alcohol. The HO solution is precipitated by [illegible] H8, Pb. 293 Converts coagulated albumen into the soluble form only does so in presence of free acid, The fresh gastric juice of the dog dissolve 1/20th of its wt of coagulated albumen. Its function is to render the nitrogenous parts of the food soluble but to accomplish this it must have free acid. Bile immediately suspends the action of pepsin. * The quantity of gastric juice secreted by animals is almost incredible about 1/4 of their wt daily. In the case of Katharine Cutt a person who had a fistula thro' wh the stomach could be observed it was about 30 lbs daily. Yet it is not sufficient to dissolve all the albumenous bodies introduced as food. *Thus the gastric juices has no effect on food after it has passed into the intestine 294 The stomach is protected from the action of the gastric juice by the epithelium & not by its vitality for the hand legs of a frog introduced into the stomach thro' a fistula were digested, the vitality of the frog not preventing it. The intestinal juice seems to combine the effects of the pancreatic & gastric juice. About 10oz one secreted daily Bile is the liquid produced from venous blood by the liver. It is a viscid tenacious fluid of a brown or green colour & musty odour & bitter taste S.G 1.02. It putrefies readily but if freed from mucus it does not change. Sometimes alkaline often neutral. Composition. HO [crossed out] 90.44 Biliary bodies 8. 295 Aqueous extract, alkaline salts. phosphates chlorides & lactates 0.85 Mucus 0.30 NaO & KO 0.41 Characteristic bodies Resinous matter. Cholic acid. Tauro & Glyco-cholic. It unites with alkalis like resins Cholosterine is always in healthy bile in small quantity 1 part in 10000 parts of bile. Retention of bile concentrates it. A man of 10 stone secrets 5 lbs daily. Its main use is to promote the digestion of fatty matters. Lehman considers the bile as the waste matter of formation of blood corpuscles If you moisten one capillary tube with HO & the other with bile & put them in a fatty substance the fat rises higher in the tube wetted with bile than in that wetted with HO. 296 It probably neutralizes the acid chyme from the stomach. Excrement It consists of undigested particles of food of epithelium & mucus decomposed biliary constituents. Its smell is due to decomposed biliary constituents or the imperfect combustion of albumen. If you distil albumen with KOHO you get essence of excrements. When the diet is mixed the colour is yellow brown on a flesh diet it is darker & on a milk diet it is yellow. Its action is generally alkaline In an adult man there are about 5oz daily. It contains 73 PC HO 27 PC solid constituents. The N in the fœces & in the urine 297 correspond closely to the N introduced in the food. There are few soluble salts in the foeces these having passed out in the urine. There is more MgO than CaO in proportion to the food, showing that some CaO has been taken into the system. The foecal ash gives 31 P.C. of tribasic PO5 . Taurin is always found & a peculiar crystalline body very unpleasant to prepare called excretin C78 H78 O2 S. Intestinal gases They owe their origin partly to air conveyed to the stomach & partly to the decomposition of the intestinal contents The O has disappeared in the large & middle of the small intestine The chief gases are CO2 & N. 298 H sometimes appears & when it does so in large quantity to extent of 25 PC Carbonetted H sometimes appears. HS rarely exceeds 1-2 P.C. Blood. General properties. It is a thick viscid fluid S.G 1.055 in human blood, usually of a bright cherry red, arterial blood is lighter coloured than venous when removed from the body it changes & separates into the clot or cross amentum & serum. When warm it has a peculiar odour stronger in the blood of man than women. If you add HOSO3 to blood it gives a stronger smell If you add HOSO3 to the blood of the horse & heat the smell of the stable becomes perceptible, or if to cows blood, the smell of the cow 299 house. The S.G of women's blood especially during pregnancy is less than that of men's. Blood is not only a solution but an emulsion holding solid particles suspended in it. It contains blood corpuscles, lymph corpuscles fat globules Blood corpuscles. They are thick circular slightly biconcave discs. In human blood they about 1/3200 th of an inch in diameter. In most mammals except the elephant they are smaller than in man. In amphibia they are very large. Lymph corpuscles. They are lighter than blood. The fluid in wh they float is called the liquor sanguinis 300 & contains fibrin in addition to the solid constituents of the serum The clot is coagulated fibrin & contains the blood corpuscles & some serum. The composition of living & dead blood is different Living blood Blood corpuscles Liquor sanguinis Dead blood 2 minutes after being taken from body. clot = fibrin & corpuscles Serum. Average of 22 analysis of healthy human blood. HO 781.60 } solid constituents 218.40 } in 1000 parts. Of the solid constituents Blood corpuscles 135.0 Albumen in serum 70.0 Fibrin 2.50 Fats 1.55 Soluble salts 6.0 Earthy phosphates 0.35 301 Fe 0.55 Extracted matter 2.45 Various analyses have been given of blood corpuscles & liquor sanguinis. The blood corpuscles contain 16.75 hæmatin } 241.07 hematocrystalline } in 1000 parts Liquor sanguinis contains neither of these but contains 4.05 fibrin 78.84 Albumen. The two characteristic constituents are hematin & hematocrystalline. Hematocrystallin is a glucoside Prep. of Hemat Mix defibrinated blood with a saturated solution of NaOSO3 & wash with alcohol & ether. C44 H22 N3 O6 Fe. Hæmatin Occurs in blood in the soluble form. 302 It is got also as a brownish black substance without smell or taste On ignition it leaves a considerable quantity of Fe2 O3 Dissolves in alkalis but is precipitated by acids. If you add KONO5 to blood the fibrin does not coagulate. HCl, NaCl, KOSO3, acid phosphate of KO & of NaO, bibasic phosphate of CaO & MgO are the mineral constituents of blood. In the liquor sanguinis NaCl, phosphate of NaO & HCl in small quantity are found. Gases in blood. CO2, N & O. They are found almost entirely in the blood corpuscles & hardly in the serum. If you shake up serum with gases it does not absorb them, but the blood corpuscles 303 corpuscles do to a considerable extent. In arterial blood there is relatively but not positively more O than in venous blood. Ratio of O to CO2 in arterial blood is as 6 to 16 & as 4 to 16 in venous blood. Coagulum. The clot is produced by the coagulation of fibrin. The cause of this is due to a considerable extent to the escape of NH3. 1 part NH3 keeps 3000 parts of blood fluid in a close vessel at 98°F. Agitation hastens coagulation & free access of air also Dilute solution of salts retard coagulation. In inflammatory diseases there is a constant increase of fibrin in the blood. In inflammatory blood it is covered with free corpuscles. In dysentery the fibrin also increases & albumen diminishes 304 Serum After the separation of the blood corpuscles & fibrin the serum is sometimes turbid owing to fat globules in drunkards & pregnant women's blood It is usually a straw coloured liquid The serum of womens blood contains 1 P.C. more of HO than men's. In mans blood 90.71 PC -women's- 91.71 The serum of arterial contains more HO than that of venous blood. Albumen in serum 7.9-9.8 - in collective blood 6.3-7.1 Albumen decreases in most diseases especially scurvy Bright's disease In intermittent fever & cholera it increases & after drastic purgatives Dropsy begins when the albumen in the serum is below 6 PC. 305 Various salts in small quantity are found in the serum. Analysis of ash serum. KCl 4.054 P.C NaCl 61.087 NaOCO2 28.78 acid phosp. NaO. 3.195 KOSO3 2.784 NaOCO2 & KOSO3 probably exist in the blood as lactates of NaO & KO. Chyle It is the liquid into wh the nutritious portion of the blood is converted. Its composition varies according to the food. It is an opalescent fluid, has a feebly alkaline reaction. & maukish taste When boiled it deposits a small quantity of floculent albumen. That from the lacteals does not coagulate. The fibrin in chyle seems to be less elaborated than in blood 306 Casein, fat, lactic acid & sugar are said to occur in chyle. There have been few opportunities of examining healthy human chyle. That of animals seems to be a dilute kind of blood. When exposed to air it becomes red. There is 12 P.C. of mineral residue in the solid residue. NaCl is abundant & alkalis combined with albumen. Lymph. It is a colourless or yellowish fluid got from the lymphatic. The ingredients seem to be the same as those of blood It coagulates in from 5 to 20 minutes after being taken out. Analysis of lymph. HO 957.6} Solid ingredients 42.4} in 1000 parts. Fibrin & lymph corpuscles 0.37 307 Albumen & extractive matter 34.72 Mineral matter 7.31 It is supposed that 22 lbs of lymph are formed in the body of an adult man in 24 hours. Fluids of generation & development The seminal fluid has been mixed with secretions of prostate & other glands before analyzed. It is commonly heavier than HO slightly alkaline, is coagulated by alcohol but not by heating. Characteristic ingredient Seminal filaments The motions of these are arrested by various solutions, as of kreosote.* Fluids of the egg. Generally consist of 2 parts the yolk & the white. The yolk contains fat globules & corpucles surrounded by fluid The corpuscles are phosphorized *And neutral salts &c. 308 fat probably glycerophosphoric acid The molecular granules are casein They form 14 P.C. of yolk. Albumen 3 . Collective fats 30. Glucose is always in the yolk. There are two pigments yellow & red. Mineral of constituents 15 P.C. White of egg contains 12 1/2 PC of albumenous ingredients, & ale Margarine oleine & glucose. The mineral ingredients are soluble & consist in a great measure of NaCl. The shell contains 97 PC. of CaOCO2 . & a little phosphate of CaO, MgO & organic matter Milk. It is an opaque fluid, of a white, bluish white or yellow colour. It is generally alkaline, sometimes acid.* s.g of women's milk 1.032. *as in carnivores 309 Under the microscope it is a clear liquid with fat globules wh have a fibrous covering. When this cover is broken in churning it allows the butter to gather These globules floating to the top produce cream. It does not coagulate but on heating it forms a scum from oxidation. Average of 89 analyses of human milk. HO 889.08} solid ingredients 110.92} in 1000 Milk sugar 43.64 P.C. Casein 39.24 P.C. Butter 26.66 Salts. 1.38 The quantity of casein increases with animal food During suckling the milk becomes changed. The butter remains tolerably constant 310 The casein increases as the child becomes developed Milk of dark haired women is better than of blondes & is richer in fats. The composition of asses milk is nearer that of women than any other animal. Composition of Cows Milk. HO 86.2 P.C Casein 4.2 Butter 5. Milk sugar 4.1 Mineral matter Urine. The urine is a liquid secreted by the kidneys from the blood. It removes the nitrogenous parts of decomposed tissues. Human urine is a clear fluid of a bitter saltish taste & bright amber colour 311 S.G 1.015 to 1.025. In a state of health it never exceeds 1.03. It has an acid reaction. In clean vessels it has no great tendency to putrefy but if there is any decaying organic matter present it does so readily. As it cools it often deposits a cloudy sediment, especially morning urine. On standing crystals of uric acid appear The composition of urine varies according to the food & exercise. In an experiment a man of 11 stone passed 52 oz of urine in the 24 hours. In this Urea 520 grs Uric acid 8 Hippuric acid 15 Kreatin 7 Kreatinine 4.5 Xanthin & Hypoxanthin Traces *Found after eating green [illegible] & fruits containing benzoic acid 21 312 Mineral matter 376 grs. Of wh NaCl forms 266 grs. The chief characteristic ingredient is urea. It is a product of the oxidation of the tissues. It is said that when albumen is oxidized by MnO2 urea is produced but this is doubtful. It is however certainly produced in the system from the oxidation of the tissues It is also got by the oxidation of uric acid & by the action of alkalis on kreatin & [crossed out] alloxan. NH4 O CyO when heated becomes urea Urea has the same empirical formula as NH4 OCyO though it is arranged in a different way N2} } H2 } H2 } H2 Na} } C2 O2 } H2 } H2 313 Crystallizes in 4 sided prisms like KONO5 soluble in alcohol & HO forms salts. It forms 77 to 82 P.C of urine evaporated There are about 25 parts of urea in 1000 parts of common urine. A man of 10 stones wt excretes daily 442 grs urea. - " - 520 grs. From 58 observations on young men the average is 549 grs per day. The average of 58 observations on young women is 425 grs. If the same weight of children from 6 to 3 years old & of old men. The children secrete 3 times as much as the old men. The average of urea is 244 Adult man on mixed diet 518 grs - vegetable - 389 - 314 Adult woman on mixed diet 412 grs - vegetable - 309 Professor Fry of Trinity College Dublin made various experiments on the students. Well fed flesh eating wine drinking students yeilded 576 grs daily Well fed water drinking vegetarians 394 grs Certain diseases influence the quantity of urea. it is increased in typhoid fever, in pneumonia pleurisy & rheumatic fever. Uric acid in urine. In urine it is generally combined with NaO. It is rarely more than 1/10 P.C in urine. From 7-8 grs in an adult man. In perfect health there ought to be no uric acid. In Professor experiments on students he found 315. Beef eating wine drinking students 4 1/2 grs daily HO drinking vegetarians 1 1/2 grs - Hippuric acid. Occurs chiefly in the urine of herbivora. If you become a vegetarian, hippuric acid takes the place of uric acid in the urine. A large amount of HO taken into the system lessens the uric acid as also sulphate of quinine taken as a medicine. Xanthin & Hypoxanthin Kreatin 5-7 grs in 24 hours Kreatinine is a product of the metamorphosis of kreatine. Extractive matters are less abundant in the urine of the child than of adults. Extractive matters are uncrystallizable bodies wh we do not 316 know. In starvation the exceed the ureaic in quantity. Among them are damaluric, carbolic & other acids & some volatile acids. Urine pigments. Indican the glucoside of indigo blue. Mineral ingredients. Of these NaCl is far the largest in amount Daily average in 8 students. .269 grams in 24 hours The average is generally taken as 200 grs for an adult male & less for women & children In acute diseases of the febrile sort the chlorides rapidly diminish, but when convalescence begins the chlorides increase rapidly. 317 The chlorides are carried off in the watery stools & in perspiration Sulphates. They occur in varying quantity The HOSO3 excreted daily as sulphates is 32 grs. The proportion rises in the afternoon & during digestion Animal food & active exercise increases the amount of the sulphates Phosphates PO5 is found in the urine partly as NaO PO5 & partly as phosphates of MgO & CaO In an adult man 50 to 60 grs of PO5 are excreted daily as phosphates. The maximum & minimum is the same as with the sulphates. Animals food increases the phosphates. Earthy phosphates excreted daily 318 are 15 grs. Fe in minute quantity is in urine. SiO2 & Fl in very minute traces. Secreted daily by an adult man. NaCl 266 grs HOSO3 (as sulphates) 32 PO5 (as phosphates) 55 Alkalis, CaO MgO & other salts. Undetermined. Abnormal ingredients. The presence of albumen in the urine often indicates Bright's disease, but it may be due to accidental causes. The urine may sometimes coagulate in health. Taking cantharides or a stimulant diuretic & pressure of blood in the kidney as in heart disease produces albumen in the urine. In boiling urine always add a 319 drop of NO5 after the operation When albumen remains persistently in the urine it is dangerous symptom. Fibrin sometimes occurs in urine Sugar does not exist in healthy urine but in diabetes & gout When the flow of 4th ventricle of the brain is punctured sugar appears in the urine & remains for some hours Sugar appears to be in the foetal urine. Fat does not occur in healthy urine but does in Bright's disease & chronic insanity. fatty degeneration of kidneys in in rapid emaciation but generally from Biliary compounds are found in jaundice. NH3 never occurs in healthy urine unless it has been accidentally 320 changed in the kidneys as by too long retention. In scarlatina it appears even though the urine be acid. When urine is alkaline NH3 generally is present, urea being very readily decomposed. Urine of animals The composition of that of the carnivora most nearly approaches to the human. It is light yellow & nasty odour bitter taste Has an acid reaction It contains much urea, little or no uric acid & much pigment. Dogs urine contains cyanuric acid That of the herbivora is yellow turbid. Contains hippuric but no uric acid. oxalate of lime & only a small amount 321 amount of phosphates relatively to man When they are fed on animals diet as the calf while suckling they give urine like that of the carnivora. The urine of birds forms a white coating to the solid excrement consists chiefly of urates of NH3 & CaO The urine of frogs is liquid & contains urea NaCl & phosphates. That of serpents is at first pulpy but soon dries & consists mainly of urates of alkalis, with a little urea Urinary sediments The occurrence of sediment in fresh urine as soon as cooled may sometimes show disease. It consists either of organized or unorganized substances. Inorganic sediment Uric acid Urates Organized Mucus & epithelial scales. 322 Inorg. Hippuric acid Oxalate of lime Earthy phosphates Cystin Org. Blood corpuscles Pus corpuscles Cancerous & tubercular matter Fibunous coats of the tubes of the kidneys Spermatozoa fungous bodies and infusoria Uric acid. Only occurs in strongly acid urine in any quantity; may be deposited after fermentation from decomposition of urates When free lactic acid is voided it decomposes urates & deposits uric acid. Uric acid sediment is always coloured, generally yellow or brown. Test. With HONO5 & NH3 it forms murexide. The urates are the most common of the sediments all occur in acid urine except that of NH3 Their colour varies from greyish white 323 to brownish red or purple. Urate of NaO. The cause of the sediments is partly their greater solubility in hot than cold HO. Sometimes from the HO in the bladder having exuded & left too little to dissolve them. Hippuric acid rarely occurs as a sediment. If a fruit like greengages containing benzoic acid be taken freely or if benzoic acid be taken as medicine or otherwise, hippuric acid appears in the urine Oxalate of lime It is sometimes produced by changes in old urine so it is not to be confounded with that deposited from fresh urine Earthy phosphates always appear when the urine is alkaline. 324 Urinary Calculi. They are formed in the kidneys or bladder by deposition or retention of urinary sediment. Around a nucleus more matter gradually accumulates. Sometimes the matter is not all of one kind The composition of the calculi is generally the same as that of the sediment. Uric acid or urates Kanthin Cystin Oxalate of lime CaOCO2 . Phosphate of lime Phosphates of MgO & NH3 . Fibrin & mucous compound Phosphate of MgO may be formed by throwing MgOSO3 into urine & allowing it to stand. The substances valuable as manure 325 manure may thus be removed, Fibrin & mucous compounds Respiration. The act of respiration consists essentially in the interchange of gases existing in the blood with those in the air. In animals low in the scale it takes place on the surface of the body but most animals have definite respiratory organs. The gases given out from the body are in the venous blood, but this does not come in the direct contact with the air. The lung tubes branch out into small ramifications & thus present an immense surface in small space. The air & blood are separated by a thin moist membrane thro wh the gases interchange by exismosis. The O is changed for CO2. 326 The change of colour in the venous blood from dark to light red is due not so much to the absorption of O as to the expulsion of CO2. If the CO2 be expelled & H substituted the same change takes place. The O taken in is in greater volume than the CO2 given out. The reason of this is that the O has to oxidize the tissues & convert them into urea & to make H into HO. When O is converted into CO2 it occupies the same volume so the interchange would be volume for volume if the O had not more work to perform in the body. For each volume of O absorbed in the lungs, there is only 0.8516 vol. of CO2 evolved. Hence there is 1/7th more O taken into the body than what is required for conversion into CO2 327 When we examine the volume of air expired after it has cooled & dried it is less than that inspired. The aqueous vapour expired in 24 hours is from 11 to 14 oz. Some of this is due to the HO taken as drink as well as to that formed in the system. The N in the air is little affected by respiration. A very slight increase of N in the air expired may be due to that dissolved in the HO we drink. The air expired is 0.402 ricer in O than that inspired. There is a very small quantity of NH3 to be detected in the air expired. The most important gas is CO2. The expired air of a healthy man contains 4.334 P.C of CO2. 328 Only a small part of the O of the air is taken up. Weight of gases expired by an adult man taking a general average during 24 hours. CO2 27.8 oz N in excess that inhaled .5 Aqueous vapour 14. Inhaled. O. 23.3 So that about 3 oz of O are retained in the system or go out in other excretions. The amount of CO2 in expired air depends on the frequency of respiration In Gerhardts' experiments Acts of respiration per minute 6 12 24 CO2 in 100 vols of air expired 5.528 4.262 3.355 329 48 2.984 96 2.662 When the breathing is undisturbed 30.5 cub. in. are expired in one respiration. But the rhythm of the respiration is Not all the CO2 in the pulmonary vessels is removed as it passes thro' the lungs. The respiration of air richer in O than common air produces no marked difference in the CO2. An animal breathes undisturbed though the O be increased to 3 times its normal amount. When decreased by one third they show no change but when decreased by two thirds they show great distress & if reduced to 3 P.C they rapidly 330 die. CO2 if added gradually to air does not impede respiration up to 12 P.C. When the animal has absorbed about 1/3 of their bodily volume of CO2 they show symptoms of poisoning tho' the O supplied along with the CO2 [illegible] The CO2 cannot escape by diffusion The largest portion of inhaled air goes back unchanged, only 1/5 th of the air in the lungs is changed in one respiration. Gases have no tendency to diffuse into themselves & when the air is charged with CO2 that in the system does not diffuse out. It is this wh renders CO2 a poison. A rabbit may breathe in an atmosphere of 20 P.C. CO2 for 20 hours if there be a constant supply. 331 CO in minute quantity will produce death if there be no ready method of diffusion. An atmosphere of 1 P.C. CO2 has been known to produce death especially if mixed with CO. According to Dr. Edward Smith's experiments the expiration of CO2 is less in hot parts of the season than in the cold. In the middle of August the CO2 is 30 P.C less than in the cold season. The maximum is in April & May & begins to fall at the end of May or in the beginning of June. It ascends in October & is high in December. Moisture in the air increases When there is change of barometric pressure in either direction there is an increased amount of CO2. 332 The effect of fasting is to diminish the amount of CO2. Some cats experimented on at first converted 80 P.C.O into CO2. 77 P.C the 2nd day & when they died of starvation 73 P.C. Dr E. Smith fasted for 27 hours & expired 0.25 P.C less CO2. There was a remarkable uniformity in the composition of the expired air but the number of respirations was less. Influence of sex & age. The male expires more CO2 than the female. Boys of like age expire more than girls. Charling's experiments age weight in kilograms CO2 per hour in grams CO2 per hour for every 1000 grams of wh Man 35 65.5 33.53 0.5119 youth 16 57.75 34.28 0.5887 soldier 28 82. 36.62 0.446 girl 17 55.75 25.34 0.454 333 Boy 10 22. 20.338 0.924 Girl 10 23. 19.162 0.883 Effect of exercise Exercise increases the CO2. Influence of food. The food influences the CO2 evolved. More O is absorbed to form CO2 when starch is used than when animal food is used. Less N is evolved on a vegetable than on an animal diet. In dogs fed on suet 6g P.C of the absorbed O was evolved as CO2. Fats contain a good deal of H as well as as C & O is required to oxidize this. In starch the H is combined with O.* Respiratory equivalents or amounts of food required to produce the animal heat in the body itself. 100 parts fat require 292.14 Oxygen *Animal food requires much O to oxidize albuminates & form urea 334 100 Starch 118.52 100 Sugar 106.67 Malic acid 82.78 Albumenous bodies 153.31 Dr E. Smith has drawn some conclusions wh however require farther confirmation. He says that food may be divided into 2 classes, those wh excite respiration & those wh do not. Exciters. Nitrogenous foods, milk sugar rum, beer, stout, the cereals Nonexciters. Starch, fat, certain alcoholic compounds, volatile elements of urine & spirits & coffee leaves. Pure alcohol, rum, ale & porter generally increased the respiration. Sherry lessened the air inspired but increased the CO2. Tea, coffee, chicory, & cocoa are respiratory exciters. Tea is the most *Brandy lessened it 335 powerful*, next coffee, next cocoa & lastly chicory. The addition of sugar & milk increases the respiratory effect. Its influence is immediate, its maximum is in about 20 minutes its duration is from 1 to 2 hours. Cause of sleep When trying to sleep the first thing we do is to take away the pressure, of the column of blood on the heart, wh we do by getting into a horizontal position. We lessen the respiration by lying in a fixed posture. The amount of O dissolved in the blood in the system is lessened. At every vital act there is change of matter. They are only destroyed in the act of oxygenation. *Therefore recommends tea to be given in suspended animation as a respiratory waiter 336 In every thought a portion of the brain is destroyed & as we get the O diminished in the blood the brain finds more difficulty in manifesting itself to the external world. In the case of the drunkard the O unites with the alcohol & the brain refuses to manifest itself & he becomes dead drunk. Sleep of hybernating animals During summer they accumulate fat round the heart & gradually push up the diaphragm against the lungs, this prevents the O being inspired readily & it falls asleep. Some wh do not accumulate so much fat as the tortoise take a roll of grass to push up the diaphragm. They are like a lamp slowly 337 burning the fat being the fuel. When this is consumed the diaphragm falls down the lungs begin to play the brain becomes active & the animal awakes. The conditions in wh we are most prone to sleep are when we have taken a large dinner wh pushes up the diaphragm. As there will be less combustion during sleep & so less animal heat we draw near the fire to compensate for this. Respiration of the lower animals. Carnivora living on ordinary food exhale more N & CO2 in proportion to their wt than herbivora Active birds consume 10 times more O than sluggish birds. Frogs & lizards convert 75 P.C & the salamander 82 P.C of O into 338 CO2. The wakeful ones consume 9 times & the half torpid ones 3 times as much as those wh are entirely rigid in winter. Origin of the CO2 It was once supposed that the CO2 was produced in the lungs. There seems to be no combustion at all in the lungs, for if there were the blood should be warmer there. This is not the case, as the blood is cooled in the lungs the blood of the left side of the heart is 2° colder than that on the right side: It seems to be produced in the tissues Every vital tissue of animals yields CO2 to the air pump. Gustave Liebig says that the muscles of the frog possess irritability * so long as the exhale *So long as they absorb O. If placed in H their irritability stops. 339 CO2. The changes are produced in the muscles . General conclusions That 8 1/2 oz of C are converted into CO2. in 24 hours, for wh. 22.66 of O would be necessary, but as only 85 P.C of O is used for CO2, 26.7 oz of O or 1 1/2 lb are daily consumed by an adult man. He destroys daily 117 oz of air wh. is equal to 164900 cub. in. In the course of the year he destroys 7 hundred weight of O. 1/5 is made into the body. It is an old tradition that the body of an animal changes once in 7 years, but this is not true as all the C would be burned in 3 days*. A man of 11 stones has 4 lbs albumenous bodies in blood. 27.5 in tissues *If there were no supply of Co you may calculate the rate of concrete from the N in the urine & excrement. 340 5lbs in bones The whole body would be changed in 18 weeks supposing that they were all changed at the same rate. Animal Nutrition Plants live on mineral food, wh they find in the atmosphere, CO2 HO & NH3. They assimilate the C from the CO2 into their system & give out the O. They get their N from NH3 & sometimes though rarely from NO5 but not from the N of the air. They get their H from HO. They have nothing to do with volition & on this account they have the property of moulding inorganic substances into organic forms. Animals have the function of volition to preform & so have not this property. 341 All animals are essentially herbivorous, even carnivora being so although indirectly. All food may be divided into 2 classes characterized by one essential difference. Those wh contain N. Those wh are destitute of it. Nothing destitute of N can build up the muscle of an animal. Those wh contain N are the histogenetic substances, casein, albumen &c, whether got from plants or animals We may call the one sort wh contain N flesh formers & the other heat givers. There is necessity for a mixture of food of both classes* It was long supposed that gelatine was an extremely nourshing substance but a commision both *If only one kind be given the animal dies just as if it received no food as only one part of its nut is supplied 342 of France & Holland appointed to examine into this found that when animals were fed entirely on it they died. In milk there is an admirable admixture of both kinds of food. Casein flesh formers Butter, sugar heat givers There is also mineral matter in it In all cookery we try to obtain this mixture. We eat beef with potatoes mutton with rice & pork with peas or beans Nitrogenous food or flesh formers. All the tissues wh form any part of an organ of an animal contain 15 P.C of N. Animals are certainly unable to take N from the atmosphere. There is one apparent exception: when an animal takes benzoic acid containing, no N it voids hippuric acid wh does. This is however in question of excretion; not of nutrition. There is no ground to suppose *and also the blood 343 that flesh can be formed from nonnitrogenous substances by assimilating N from any other source. The nutrition of a carnivorous animal is very simple. It takes the flesh & blood wh it finds ready formed & appropriates them to its own system. That of a sucking animal is equally simple. It is like a carnivorous animal eating its mother. It finds casein in the milk & appropriates it. The nutrition of every animal is equally simple. We find the histogenetic substances in plants. Thus the juice of the cauliflower contains fibrin assitedd of blood. Animals do not form the components of their flesh & blood out of unlike matters but they find 344 them ready formed in vegetables The process of nutrition consist in extracting them & giving them a place & form in the organism. This is the great law of animal nutrition Plastic elements { {Flesh animal Fibrin {Blood Albumen {Casein This excludes gelatine Gelatine may indirectly act as food by supplying food for the cellular tissue & thus saving the other food. Gelatine may thus in the case of a very weak person be of use when administered along with some other food, not alone, by supplying material for the cellular tissue wh has been much wasted by illness. & thus allowing the other food to be applied to the purpose of building up the organs. 348 Non nitrogenous substances. Fat, starch, gum, cane sugar, grape sugar, milk sugar, pectin bassarin, wine beer & spirits Since they are wholly free from N they cannot build up the frame work of the body yet they fulfil a very important function viz. supporting the animal heat. The temp. of fishes and amphibia is only a few degrees above the medium in wh they live. That of quadrupeds is 99-100° F birds 105 man 98-99 child 102 In lower animals even in health the temp. is to a certain degree regulated by the medium in 103 they been In the higher animals there is always a fixed temp. in health. Depression of this temp is attended 346 attended with a depression of the functions of an animal. There must be some means of regulating this temp. since the temp. of a man at sunny Palermo or of a traveller in the polar regions is the same. The appetite of the man is the regulator. Non-nitrogenous substances are usually the fuel. though the tissues of the body are sometimes as in the carnivora. The hyena moves about in order to burn his tissues to keep up the animal heat. From the known composition of food it is easy to calculate how much food is required to keep up the same temp. on different kinds of food. The heat giving equivalents 347 or the quantity of food required to keep the animal heat the same. Weights of different bodies requires to produce the same amount of heat. Fat 40.2 Cane sugar 100 Alcohol 53.8 Grape - 106 Starch 97.2 Flesh 309.7 Flesh has 8 times less respiratory value than fat. After deducting the heat necessary to evaporate HO as vapour in the breath we find that the rest taken in diet is sufficient to raise 143 lbs of HO from 32° to 99° & the specific heat of the substances wh compose the body is less than that of HO. Varying quantity of respiratory food. The body of a man may be represented as a chamber to be kept at the same temp in 348 summer & winter & in different climates. If you transport a man from India to the poles the temp. of his body remains the same but you must put in more food to sustain it. In extreme cold man takes enormous quantities of food. Sir John Franklin says that during the whole of the march they found that no clothing could keep them warm as long as they were fasting but when they could go to bed with full stomachs they could sleep comfortably. Parry took an Esquimaux lad not full grown & set him down to a weighed repast. the quantities he devoured are the following., 349 lbs oz Sea horse flesh hard frozen 4 - 4 -boiled 4 - 4 Bread & bread dust 1 - 12 Rich gravy soup 1 1/4 pints Spirit 3 glasses Strong grog 1 tumbler Water 1 gallon 1 pint Ross says that an Esquimaux eats daily on an average 20 lbs of flesh & oil Admiral Sarcheff says that a yacot took in 24 hours the hindquarter of an ox & 20 lbs of fats. [illegible] proportionate quantity of melted butter for drink. These accounts are not more astonishing than the difference between the coal we burn in summer & winter. The character of the food is made to suit the climate. Fruits & rice contain 20-30 PC of C. Blubber 80-90 In India beer & butter are freely 350 taken but apparently less as food than to unctuate the body & prevent excessive perspiration. Ordinary food contains fat In Cocoa 50 PC In coffee 12 PC A man inhales daily to consume these about 3000 gallons of air, much of the O of wh is burned by the food. The starchy matters & fat in the food produce fat in the body. In a grate where there is a free access of air the fuel is converted into CO2 , but in a gas retort where there is only a very limited supply of air various tarry matters distil over. Thus in the muscular arm of an Arab who is almost constantly in the open air & taking exercise 351 exercise there is no fat, but in a man leading a sedentary life & taking little exercise the fat accumulates. If there is a free introduction of air the starch is converted into CO2. In hybernating animals the fat is formed by imperfect combustion of the food in summer & in winter they live on it. There was a very fat pig weighed to be sent to an agricultural show, but just before being sent a slip of land from a neighbouring hill overwhelmed it. It was thought to be dead & no farther trouble was taken about it. About 120 days after the slip was removed for the purpose of building & the pig was found alive but it had decreased 352 140 lbs in weight. Proportion between flesh formers & heat givers. Plastic Cow's milk 10 30 Woman's - 10 40 Lentiles 10 21 Beans 10 22 Peas 10 23 Fat mutton 10 27 - pork 10 30 Beef 10 17 Hare 10 2 Veal 10 1 Wheat flour 10 46 Oatmeal 10 50 Rye - 10 57 Barley 10 57 White potatoes 10 86 Blue - 10 115 Rice 10 123 353 Buck wheat meal 10 130 Mineral matter in food The body of a man weighing 150 lbs contains Phosphate of lime 5lbs 13oz 0 grs Carbonate - 1 - 0 - 0 CaFe 0 - 3 - 0 NaCl 0 - 3 - 376 NaOCO2 acid phosphate of soda 0 - 0 - 400 KoSO3 0-0-400 Feo 0-0-150 KCl 0-0-12 Phosphate of potash 0-0-100 3MgOPO5 0-0-75 SiO2 0 - 0 - 3 The different organs exercise a selection, thus, P is taken to the brain,* Ca Fl to the teeth, SiO2 to the hair & nails, S is generally distributed but is taken especially *3CaOPO5 354 especially to the hair, phosphates of MgO & KO to the flesh, phosphate of NaO to the blood & cartilages. NaCl may act by facilitating absorption of HO by diffusion or by aiding the solubility of albumen or by affording HCl to the gastric juice & NaO to bile & pancreatic fluid. Fe is an essential ingredient of blood, gastric juice, hair & the black colouring matter of the eyes. To find the proportion of flesh formers in the food estimate the N in it & multiply by 6 3/10ths. Amount of the several kinds of food required The circumstances of age variation of climate &.c. influence this. There are two ways of finding how much food is required. We might find how much C was expired as CO2 & how much C & N 355 are in the foeces & urine, An adult man Expires as CO2 8.8oz C daily in urine & foeces 2.2oz C N in urine foeces & mucus 334 grams The C excreted daily is thus about 11 oz & the N is equal to 4 8/10 oz of flesh formers. Average diet 4 oz flesh formers 3 oz fat. 10 1/2 oz amylceous food 1 oz injested salts. 84 oz HO. 33 oz O. Another mode is take the experience of public dietaries We find by these on an average that for an adult man, daily 5 oz flesh formers 10 oz C *The amount of N in excrements in health indicates the amount of urine wasted in the day, By multiplying it by 6.25 you get the amount of tissues 356 are required When we contrast the diet of the aged with this we find that with them the flesh formers have sunk to 40oz but that the C is the same The proportion of C in the heat givers to that in the flesh formers is now as one to five. In children form 10 to 12 years of age flesh formers 2 1/2 oz C 8 oz In the young the process of supply is greater than that of waste. In the adult it is equal & in the aged less. It is during sleep that the body is built up. An adult spends 17 waking hours & in mechanical labour & 7 in sleep. An infant spends 4 waking 357 hours & 20 in sleep during wh its growth takes place. An old man spends 20 waking hours & 4 in sleep. In an adult the waste is to the supply as 100 to 100 In an infant as 25 to 250 In the aged as 125 to 50 In an infant there would not be ptyalin enough to convert its [illegible] food into sugar & so it finds the sugar ready formed in the milk. The casein is also in a soluble state. in the milk so the gastric juice has not to convert it into a soluble state. In cooking we try to get the same proportion of the different kinds of food as in milk. Pauper & prison diets. Prison diets were & still are by no means well regulated. 358 It was thought that a man on long confinement required much more food than one on short confinement. The question however is what is the waste if the tissues. Work-house diet is about 3 1/2 oz of flesh formers daily. The hard labour diet is no more than this & is quite insufficient for hard labour. Besides they are on the system of alteration according to the time of excrement. 1st Cerials yield nutritious meals of varying composition. The finest flour is not the most nutritious on an average they contain 14.6 PC flesh formers 69. heat givers Mineal matter 1.6 P.C 359 Oats contain 5 PC. of fat 17 flesh formers 66.4 heat givers 3.0 mineral matters Probably half the human race partake of tea Tea leaves contain 5 P.C. HO 3 Theine 15 Casein 6.7 aromatic oil The casein does not come out unless you put in soda. 360 The peculiar aroma of coffee is due to an essential oil wh it contains Action of alcoholic beverages. Their action is to reduce the waste of the tissues When the amount of food is sufficient this is injurious acting like too much food The cheapest way of taking alcohol is in beer The cost of one oz of alcohol taken in different beverages is as follows in beer 2D. spirits 4D wines 18 6 D. 361 For the support of strength you can get an equal amount of nourishment from vegetables or animals. The character of men depends much on the food they take. It required 5oz. of flesh formers daily to do good day's work. To get this from potatoes, it is necessary to take 25 lbs, but even an Irishman's stomach can only take in half that quantity, so that an Irishman living on potatoes alone could only do half a day's work. The Irish famine caused new material for food to be introduced* wh being more nourishing than potatoes *And spread his work over the whole year instead of only 2ce a year 362 enough for a good days work could be taken without inconvenience. Who gave us trouble in the Indian mutiny? Not the rice eaters of Bengal but the pulse eaters We may sum up the general conclusions in the words of Prior. Was ever Tartar fierce or cruel Upon the strength of water gruel. Balance between animal & vegetable life The functions of animals & vegetables are precisely opposite in a chemical sense. A vegetable is a reducing apparatus, reducing CO2 An animal is an apparatus for oxidation. 363 Vegetables are fixed Animals have the power of locomotion A vegetable evolves O absorbs heat & electricity Decomposes CO2 - HO - NH3 Produces organic substances Transforms inorganic matter into organic Derives its elements from earth & air An animal absorbs o evolves heat & electricity Produces CO2 - HO - NH3 Consumes organic substances. Transforms organic matter into inorganic Restores its elements to earth & air Functions of vegetables. Animals find their substance in vegetables. The vegetable kingdom is 364 the great laboratory of organic life. They are powerful reducing agents. For every cubic foot of CO2 they reduce 1 cubic foot of O is restored to the atmosphere. The vital force of a plant growing in the dark is unable to reduce CO2, light is required for this. Nitrate of ammonia is formed by lightning flashes. 365 Functions of animals. In animals we certainly find organic matter in its highest forms but for a limited time only Then function is not to create organic matter but to transform it into inorganic matter. They use the organic matter of vegetables & make it into organs wh have high functions to perform. Broken down from the complex molecule, into wh it was formed by vegetables it becomes less & less complex at every change. Every change of them is a degradation. they being finally converted into CO2 & NH3 The process of decay produces CO2 & NH3. 366 [illustration] The substances of dead animals passes thro' the same change as the non-nitrogenous substances in their bodies The animal stands midway between the vegetable & mineral kingdoms. It has nothing to do with forming organic bodies 367 Mutual relation of plants & animals. Animals derive nutrition from plants. Plants truly feed animals but animals as truly feed plants. It is certain that the atoms of wh. we are composed have passed thro' a succession of animals & men. Perhaps the brain with wh. I (Professor Playfair) am now thinking once formed part of the liver of the Emperor of China. There is the mineral kingdom as represented by air & soil. The vegetable elaborating organic matter from the mineral. The animal living on plants but breaking them 368 down to mineral matter. Index Absorption in animals Acetates 76 Acetic acid artificial production of 73 Acetification process of 74 Acetone 68 & 75 Acetyl 67 Aconitin 100 Acrolene 100 Acid acetic 72 - anhydrous 70 - glacial 75 aconitic 134 acrylic 100 amido - acetic (glycocoll) angelic 101 benzoic 117 butyric 79 capric caproic Caprylic Carbazolic 113 Carbolic 111 Carminic Cerebric 285 Choleic [tairiochalic] 274 cholic 275 citraconic citric 132 cyanuric 159 dextroracemic 129 erythric 218 excretolic formic fulminic 158 fumaric 128 gallic 134 gallobaunic 136 glucic 198 glycocholic 273 glycolic 92 hippuric 315 humic hydrocyanic 142 hydroferrocyanic 149 hyocholic 276 hyoglycholic 276 hyofaurocholic 276 indigotic kinic (quinic) lactic 92 lauric licanoric leucic lithofellic malic 127 margaric meconic melanuric mesoxalic Mucic 199 Nitrobenzoic Nitrocinnanic Nitrococcussic Nitrophenic Oenanthic Oenanthylic Oleic oleophosphoric orsellesic oxaluric oxamic palmitic 82 parabanic 263 parellagic pectic pelargonic phenic picric 113 pinic propionic pyrogallic 135 pyroligneous quinic 132 quercitannic racemic 129 ruberythric 218 rutic 82 saccharic salicylic sebacic sorbic stearic 83 suberic succinic sulphobenzoic tannic 135 tartaric 128 taurocholic thionuric toluic ulmic uric 267 usnic vaccinic valeric xanthic Acids acetic group of - series of amidated 265 fatty oleic oxalic stearic dyective colours Albumen Albumenoid group pro- perties of. Albuminous urine Alcoates Alcohol, absolute - action of acids on allylic amylic - bases, mode of preparing butylic benzoin caproic cerotic caprylic cuminic ethylic hexylic (camoic) caurylic melissylic methylic oetylic price of propylic radicles synthesis of alkoliolic fermentation T.L. Brunton Edin. University Session 1861-2 Lecture notes Of lectures on Organic Chemistry by Professor Lyon Playfair [illegible] Contents [Inorganic] Table of Contents Table of organic substances wh may be formed from their elements without vital agency 1 Difference between organic & inorganic substances 4 Definitions of organic chemistry 6 Preparation of a higher from a lower alcohol 7 Empirical & rational formulas 8 Homologous series 10 Heterologous class 11 Qualitative examination of organic bodies 12 Quantitative analysis 15 Example of organic analysis 31 Olifines Ethylene series, Olefiant gas, Propylene, Butylene, Amylene, Hesylene &c 19 Marsh gas series, Hydricles of ethylene series 26 Alcohol radicals. Preparation 29 Table. Transformation of organic compounds by different ferments 32 Reduction of other series to olifines 33 Definition of radical 35 Ethers. 36 Substitution products of methylic ether 37 Haloid compounds of ether 41 Ethers as a class 42 Alcohols 44 Wines & spirits 48 Fermentation 51 Theory of the action of ferments 53 Brewing 55 Composition of malt liquors. Table 56 Homologues of the alcohols 57 General properties of alcohols 58 Compound ethers 59 Biatomic ethers & alcohols 62 Aldehyds 65 Ketones 68&74 Anhydrides or acids 69 Hydrated acids. Relation of these to alcohol & ether 71 Relation between the alcohols, aldehyds, & ketones 74 Acetates 76 Acids homologous to acetic acid 79 Fatty acids 82 Candles 84 Saponification 86 Candles from coal 88 Acids produced from bratomic alcohols 91 Oxalates 96 Negative radicals. Acetoyl. Allyl. Angelyl 98 Oxidized radicals of allyl 100 Table. Homologues of acrlylic acid 101 Glycerine 102 Glycerides on common fats 104 Soap 105 Chief fats 107 Aromatic series 109 Phenyl 109 & 117 Benzyl 115 Distillation of coal. Naphtha 118 Coal tar colours 122 Malic Tumaric, Tartaric, Racemic & Kainic Acids 127-132 Trebasic acids Citric, gallic, tanine &c 132 Tanning 137 Compound haloid radicals 139 Cyanogen 140 Hydrocyanic acid 142 Cyanides 145 Haloid ethers of cyanogen 146 Nitriles 147 Preparation of higher acids from nitriles 147 Double electronegative cyanides 148 Ferrocyanogen 148 Ferridcyanogen 152 Nitroferrocyanides or nitroprussides 153 Cyanates 155 Sulphocyanogen 156 Sulphocyanates & sulphocyanides 157 Bicyanogen 157 Fulminates 158 Tricyanogen 159 Characters of cyanogen 160 Organic bases representative of alkalis & metallic oxides in organic chemistry 160 Amines 161 Monameries 161 Production of these compound ammonias 162 Organic bases coal tar 164 Diamines. Urea. 164 Triamines 166 Organic alkaloids 166 alkaloids from hemlock, broom, tobacco, opium, chinchona bark, strychnine family, solinacia family. tea &c. 168-182 Hydrates of Carbon Action of dilute acids & oxidizing agents on them 182 Views of their chemical constitution 183 Cellulose-gum cotton-vegetable parchment 183 Starch. Starch in vegetables 186 British gum. Manufacture of starch 188 Special starches 189 Starch in the animal kingdom 190 Inulin Lichenin 190 Glycogen. Dextrin 191 Gums 193 Quantities of cellulose & gum in different vegetable substances 193 Arabin. Cerasine. Bassorin. Pectin 194 Sugars 195 Grape sugar or glucose 196 Test for diabetic sugar 197 Caramel. Saccharides. Glucic acid 198 Action of yeast & of nitrogenous ferments on grape sugar. mucic acid 199 Fruit sugar on fructose 200 Cane sugar or sucrose 200 Barley sugar. Caramel. Conversion of sucrose into glucose. Saccharides 201 Fermentation of sucrose 202 Manufacture of sugar 202 Refining of sugar 205 Sweetness & uses of sugar 206 Relation of H+O in sugar 207 Milk sugar 208 Lacto-carmel. Lactose 209 Trehulose. Megatose. Mellitose 210 Non fermentible sugars. Inosite 210 Seyllite. Sorbite 211 Glucosides. Salicin 212 Action of amulcin & acids on salicin 212 Saligenin. Populin. Quercitrin Convolvulin 213 Colouring matters 214 Isolation of colouring matters 214 Dyeing. Mordants. Printing 215 Madder. Ruberithric acid 218 Aliyacin. Lakes. Resemblance to 219 naphthalin. Production of Chloralizarin from naphthalin Purpurine. Rubiacine 219 Logwood Hematoxylin. Brazilwood 221 yellow dyes 221 Indigo 222 Topical dyeing 223 Colouring matters of lichens 224 Cochineal. Carminic acid 225 Volatile oils, resins & caoutchouc Essential oils 226 Stereoptines 227 Preparation of essential oils 227 Classification of these oils. Central formula 228 Essences isomeric with camphine 229 Turpentine 229 Essences not isomeric with camphine 231 Oxygenized essences Camphors 231 Resins, Copal. Mastic. Sandarac. Lac. 232 Sealing wan Lacquers 234 Guayacum. Jalaps. Amber 235 Caoutchouc. Gutta-percha 236 Asphalt & bitumen 238 Ozokerite. Sheerite. Fichtilite. Hartite Idualite 239 Animal chemistry Vital agency 240 Histogenetic substances 241 Existence of some both in animals & vegetables 242 Soluble & insoluble states Action of acids & alkalis on them 243 Putrefaction 244 Test for any of these nitrogenous bodies 245 Protein 245 Albumen albumen of blood 246 Insoluble albumen 248 Fibrin 248 Syntonine 249 Casein Vitellin 250 Globulin 252 Hemato crystalline 253 Derivatives from the albumenous group 253 Ossein Glutin 254 Glue confectionary gelatine 256 Theory of the formation of nitrogenous substances occuring as derivatives in the animal body 257 Kreatin. Kreatinine Sarkosine 258 Methyluramine. Sarkin. Guanine 260 Kanthin Cystin 261 Allantoin Tyrosine 262 Alloxan Parabanic acid 263 Thyanicric acid Alloxantin. Cerebrin. 264 Amide acids. Taurin. Leucin 265 Uric acid. Action of peroxide of Plouit. 267 Urates 268 Derivatives of uric acid 269 Murexide. Guanocolours. Purpuric acid. 270 Compounds from uric acid 271 Cyanuric acid. Inosic acid 272 Acids of bile 272 Glycocholic acid 273 Taurocholic acid 274 Cholic acid 275 Hyoglycholic acid 276 Hyocholic acid. Hyotaurcholic acid 276 Lithofellinic acid 276 Action of acids on cholic acid. Cholordic acid 277 Cholosterin 277 Solid constituents of animals. Bones 278 Teeth. Dentin. 279 Muscular Tissues Composition 280 Sapid constituents of flesh 281 To make strong soup. To boil meat 281 & 2 Extract of flesh 283 Relative values of meat 283 Salting of meat 283 Components of the brain 284 Cerebric acid, Oleophosphoric acid 285 Glands & their juices 286 Digestive fluids Saliva, Ptyalin, Froth, Tartar 287 Functions of saliva 289 Pancreatic fluid 290 Gastric juice, Pepsin. 291 Intestinal juice. Bile. 294 Excrement 296 Intestinal gases 297 Blood 298 Blood corpuscles. Lymph corpuscles 299 Composition of blood 300 Composition of blood corpuscles & liquor sanguinis 301 Hematin, Hematocrystallin 301 Gases in blood 302 Coagulum. Serum 303 Relation of dropsy to the quantity of albumen in serum 304 Chyle 305 Lymph 306 Fluids of generation & developement. 307 Milk 308 Urine 310 Urea 312 Uric acid 314 Hippuric acid 315 Extractive matter, what it is. 315 Mineral ingredients 316 Abnormal ingredients 318 Urine of animals 320 Urinary sediments 321 Urinary calculi 324 Respiration 325 Difference in volume between air inspired & expired 326 Cause of difference in colour between venous & arterial blood 326 N1 NH3 & CO2 in air expired 327 Effects of air richer or poorer in O than usual on respiration 329 Effect of air containing CO2 on respiration. Cause of CO2 acting as a poison 330 Differences in the expiration of CO2 331 Effect of fasting on the quantity of CO2 332 Influence of sex & age 332 Effect of exercise. Influence of food 333 Respiratory equivalents 333 Exciters & nonexciters of respiration 334 Cause of sleep 335 Sleep of hybernating animals 336 Conditions in wh we are most prone to sleep 337 Respiration of the lower animals 337 Origin of the co2 338 General conclusions 339 Animal nutrition 340 Classes of food. Flesh formers & heat givers 341 Flesh formers 342 Use of gelatine 344 Non-nitrogenous substances or heat givers 345 Varying quantity of respiratory food. 347 Formation of fat. 350 Use of fat to hybernating animals 351 Proportion between flesh formers & heat givers in various foods 352 Mineral matter in food 353 Amount of several kinds of food required. Manner of finding uses 354 Pauper & prison diets 357 Action of alcoholic beverages 360 Cost of 1 oz of alcohol in different beverages 360 Relation between character of men & their food 361 Balance between animal & vegetable life 362 Functions of animals 365 Mutual relation of plants & animals 367 [illegible] 13 1 Organic Chemistry Table of the most of important bodies capable of being formed from their elements without vital agency. Cyanogen (C2 N)=Cy Hydrocyanic acid CyH. Ferrocyanide of Fe2 Cy6 Potassium 4k+6HO. Ferricyanide of K. Fe2 Cy6 3K. Urea NH3 CyO } Ho } Marsh gas C2 H4 Oxalic acid C2 O3 HO } C2 O3 HO } Formic acid C2 HO3 } HO } Chloroform C2 H Cl3 Acetic acid C4 H3 O3 } HO } Alcohol C4 H5 O } HO } 2 Ether C4 H5 O } C4 H5 O } Olefiant gas C4 H4 Acetic Ether C4 H5 O } C4 H3 O3 } Oil of garlic C6 H5 S } C6 H5 S } Oil of mustard C6 H5 S } Cy S } Glycerine C6 H8 O6 Butyric acid C8 H7 O3 } HO } Oil of pine apples C4 H5 O } C8 H7 O3 } Oil of pears C10 H11 O } C4 H3 O } Oil of apples C10 H11 O } C10 H9 O3 } Valerianic acid C10 H9 O3 } HO } Grape sugar C12 H12 O12 Lactic acid C12 H12 O12 3 Caproic acid C12 H11 O3 } HO } Benzole C12 H6 Nitrobenzol C12 H5 NO4 C12 H5 O } HO } Picric acid C12 H2 (NO4)3 O } HO } Salicylate of methyl C14 H5 O5 } Oil of Wintergreen C2 H3 O } Naphth C20 H8 4 Organic chemistry is that part of the science wh relates to living bodies. Organic substances are either those with build up living bodies or are produced by living bodies or by submitting these products to different processes in the laboratory. If you compare alcohol an organic base with KO an inorganic base you perceive a great difference between them. Place alcohol in contact with an acid & it does not combine with it while KO does forming a salt. If you add chloroform an organic substance rich in Cl to acetate of Pb you get no precipitate of Pb.Cl. while if you add NaCl an inorganic substance containing Cl. you get a precipitate 5 precipitate If you take a solution of a salt & try reactions with it to-day & then try the same reactions with it to-morrow you will get the same result. If you can do this with an organic compound you may very probably get a different result. If you break up an organic compound you get C, O, H, & N but if you put these together in a flask you cannot make them combine. If you place Na, O & P together you will get NaOPO5 Place C, H & O together & you will not get an organic body. It was supposed at the beginning of the century that there were two different sciences. 6 It was sought to give a definition & in order to do this it was sought whether there was not some element common to organic chemistry & peculiar to it. It was proposed to call it the chemistry of carbon. But CO2, cyanogen & cyanide of K can be made without vital agency. There are bodies not organic wh contain carbon. Liebig defined it as the chemistry of compound radicals you deal in it, not with elements but with little systems. We have however as much right to consider SO2 as a compound 7 compound radical as many of the organic. The last definition was, In organic chemistry combination is ternary or quaternary in inorganic chemistry it is binary. A chemical definition could not be got. It was shown that many products of vital action could be obtained in the laboratory Wöhler made urea & acetic acid artificially. Any alcohol, can be made from a lower one by making a cyanide of an alcohol radical & from this a compound ammonium by acting on it by nascent H The alcohol can be made from this. 8 We see then that the laws of transformation are the same & why then is it necessary to break up the science? The division is empirical. The compounds of C have been farther investigated than the compounds of any other element. These compounds of C occur in living beings & for this reason we call it organic chemistry. The compounds of C are particularly complex. It is important to distinguish between empirical or rational formulæ. The empirical formula is merely the translation of the analysis. Some chemists believe that the rational formula expresses the mode in wh the atoms 9 are arranged. The chemists who hold this doctrine seldom come to an agreement regarding the rational formula of a body. The empirical formula is a fact, the rational is a conjecture. When two chemists were arguing about the formula, it resolved itself into an enumeration of what could be got from the body ; & when one chemist was hard pressed he said "although you show that a certain body" can be taken from this body you cannot show that it exists in the body. Gerhardt proposed that you should make the formula indicate the transformations wh a body could undergo. 10 Thus alcohol C4 H5 } O2 H } Meaning that H & O could be replaced by other substances & that ethers could be got from it in wh C4 H5 exists. The importance of rational formulae is apparent when we consider isomeric bodies Acetate of methyl C4 H3 O2 } O2 = C6 H6 O4 C2 H3 } Formiate of ethyl C2 HO2 } O2 = C6 H6 O4 C4 H5 } These bodies have the same empirical formula but different properties. In organic chemistry the notion of homologous series is important. A homologous series is a series of bodies differing from one 11 another by n times C2 H2. The members represent one another in function, if you apply the same reagents you get the same result. C4 H6 O2 act on it by C4 H5 I C6 H8 O2 C6 H7 I C10 H12 O2 C10 H11 I Heterologous Class. If you compare the bodies you derive from common alcohol you get bodies said to be heterologous. Alcohol C4 H6 O2 C6 H8 O2 Ether C4 H5 O C6 H7 O Aldehyd C4 H4 O2 C6 H6 O2 In the horizontal line the bodies are heterologous & in the vertical lines homologous The boiling pt of alcohol uses 19 degrees Centigrade for every addition of C2 H2. 12 The qualitative examination of organic bodies is peculiar. Examination of bodies for C. When you heat a body rich in C decomposition takes place CO2 being given off & some residual C deposited Organic bodies when heated, as a rule deposit C. Heat sugar in a tube Organic matter when heated either deposits carbonaceous matter or gives off a peculiar smell due to empyreumatic oils. This is the test for C. We seldom test for it. Organic bodies frequently contain N. the testing for which is very important. When a body containing N is burned a peculiar smell is given off. Burns a feather. 13 When a body containing N is heated to redness with a mixture of soda & lime called soda-lime NH3 on a compound NH4 is given off. Another method. When you heat an organic body to redness with Na. you can get the N transformed into Cy or NaCy. Dissolve the residue in HO & add a mixture of per & proto salts of Fe & HCl, if N be present you get prussian blue. The detection of Br. S. & c in organic bodies is attended with difficulty. When organic bodies contain Cl & the like the properties of the Cl are masked & you must heat to redness or with some strongly oxidizing body. Cause the organic body to come 14 into contact with red hot NaOCO2 the Cl combines with the Na & you get Na Cl from which you may calculate the Cl. In place of heating to redness you may heat it to 150°C with strong No5. If you seal up an organic body containing Cl with NO5 & Ag O No5. you get the Cl as AgCl. Detection of S. Not to miss the S you must effect complete destruction of the body. 15 Quantitative Analysis. When organic bodies are heated to redness with great excess of O all the C becomes CO2 & all the H becomes HO. This is universally true. Organic analysis is founded on this fact As certain how much CO2 & HO a given weight of the substance will yield. Several methods may be employed. Bring the body into contact with red hot Cu O. The apparatus consists of 2 parts the combustion & absorption parts. Previously to using the Cu O must be heated red hot since anything exposed to the air takes up dust wh is often organic. You may conveniently heat the Cuo in a Cu crucible. [illustration] The absorption part consists of a 16 Ca Cl Tube + KO bulls. The solution of the KO is made by dissolving 1 part of stick caustic KO in 2 1/2 parts HO. The connections must be light. To test this warm the bulbs so as to expel some air & if the liquid keeps its level afterward for 2 or 3 minutes the joints are tight. In place of CuO, PbO CrO3 is often used. It fuses at a red heat & buries the substance to be burned. Oils are burned by PbO CrO3 O must be passed thro' the tube at the end of the operation, either from a gas holder or from some KO Cl O5 in the tube. When a substance contains N a little alteration is necessary in this arrangement. When a body containing N is heated to redness with CuO, the 17 C Becomes CO2 & the Hi HO, the N appears partly as N & partly as NO2. The NO2 would interfere with the CO2. To remedy this you introduce clean Cu turnings NO2 when slowly passed over Cu turnings is decomposed. Cu turnings prevent NO2 from becoming NO. When a substance contains Cl it is essential to make the combustion with PbOCrO3. If it contains I you must place a long layer of Cu turnings in the front of the tube, these at a red heat absorb the I. To make combustion of liquids make a small glass bulb & seal one end [illustration], weigh it, fill it with liquid by warming it, seal it & weigh again. 18 The difference of the wts is the wt of the liquid taken up. You allow the liquid to distil very slowly over the CuO. When gas ceases to escape the operation is finished. Then pass o over it. Determination of N. Most organic bodies when heated to redness with a caustic alkali yield NH3, the HO of the caustic alkali being decomposed, the C taking the O & forming CO2 & the N taking H & forming NH3 thus– { CN } = NH3 { C1/2 } { O H } { O H } CO2 = { O H } Will & Varrenhapp's method. [illustration] In this case you use a mixture of NaO + CaO for combustion The N is converted into NH3 & absorbed 19 by the HCl with wh the bulbs are filled If you were to operate on KoNo5 you would get no NH3 You would only get traces if you were working with indigo. Where the N is present in the oxidized or nitrous state you get no NH3. Mix a body with CuO, heat to redness, cause the products to pass over Cu turnings & collect the gas in a mercurial trough All the C is got as CO2 the H as HO & you measure the N. General formula of Olefines C2n H2n. Olefiant gas was described in the inorganic part of the course Olefiant gas or Ethylene C4 H4 atomic wt 28 S.G. 9784 20 When HOSO3 is heated with alcohol C4 H6 is produced. [illustration] Alcohol C4 H6 O2 C4 H6 O2 = C4 H6 & H2 O2 taken by HOSO3 . C6 H4 is a colourless gas, has a faint smell, is poisonous, produces headache if much gets into the atmosphere, burns with a very luminous flame. It is contained in a small quantity in common illuminating gas. The name of the gas is got from the fact that when it brought into contact with Cl an oily liquid is formed. [illustration] B is a gas holder containing C4 H4 & C a bottle containing Cl. Pass the C46H4 into C & an oily liquid is seen on the sides C4 H4 readily unites with Br [illustration] 21 C is a glass stopcock fitting tightly into the mouth of the vessel B, into wh some Br is put, C4 H4 is then passed thru it & B is gently heated, & afterwards the liquid formed is poured out of B The Brome liquid is not miscible with HO. C6 H4 takes up 2 equivalents of Cl, Br or I forming Dutch liquid C4 H4 Cl2 C6 H4 Br2 C6 H6 I2 C6 H4 unites with hydracids C4 H4 + HCl = C4 H4 Chloride of ethyl C4 H4 + HBr = Bromide C4 H4 + HI = Iodide C4 H4 unites with HOSO3 C4 H4 HOSO3 sulphurinic acid. HOSO3 These reactions require time To get the reaction with HOSO3 22 Seal up C4 H4 with HOSO3 & Hg & shake up. Berthelot the discoverer of the process shook it 5000 times. If Cl be made to act on C4 H4 Cl2 substitution products are obtained. Act in the sunshine on C4 H4 Cl2. by Cl & you may get C4 Cl4 Cl2. Dutch liquid is not attacked by aqueous caustic KO but when digested for some time with an alcoholic solution of KO it yields C4 H3 Cl + HCl wh the alcohol takes away. Monochloride of ethylene is acted on by Cl yielding C4 H3 Cl, Cl2 . If you act on this by a solution of caustic KO in alcohol you get C4 H3 Cl2 + H CL. 23 Ethylene C4 H6 C4 H3 Cl2 C4 H2 Cl2 C4 H Cl3 C4 Cl4 C4 H4 Cl2 C4 H3 Cl Cl2 C4 H2 Cl2 Cl2 C4 H Cl3 Cl2 C4 Cl4 Cl2 A similar set of reactions can be got with every [oliferic] Propylene. C6 H6 A gas having a very disagreeable smell, very noxious C6 H5 I + 2Hg + HCl = C6 H6 + HgI + HgCl C6 H6 exists in many mixtures it represents C4 H4 exactly. It combines with Br I & hydracids With HCl it forms chloride of propyl. HI - iodide HoSo3 Butylene C8 H8. 24 C8 H8 occurs in small quantity in coral gas, it is colourless. slightly soluble in HO, soluble in alcohol, combines with Br & I. Amylene C10 H10. A A colourless liquid, boils at a temp. very little above the ordinary one of the atmosphere has a disagreeable smell, very volatile. Distil potato spirit with Zn Cl Potato spirit = C10 H12 O2 C10 H12 O2 + Zn Cl = C10 H10 It is a liquid heavier than HO. Readily combines with Cl & Br producing much heat. [illustration] Pours some Br from a pipette into some C10 H10 in a flask. Violent action takes place. Combines with hydracids. With H CL it forms chloride of amyl. 25 Unites with NO4 forming a beautiful crystalline compound. C10 H10 (NO4)2 The higher olifines are very little known Hexylene C12 H12 Distil oleic acid. May be got pure from mannite It is a colourless liquid boils at 60°C . resembles amylene. Unites with Cl violently with Br. C14 H14 Caprylene C16 H16 Elaene C18 H18 Paramylene C20 H20 Cetylene C32 H32 got from spermaceti The composition of olifines above C12 H12 is little known 26 Marsh gas C2 H4 = 16.S.G.5596 Marsh gas is derived from C2 H2 by adding 2 equivalents. Add H2 to any olifine & you get corresponding member of the marsh gas family C2 H4 occurs native, bubbles up in marshy places, exists in considerable quantity in coal mines, & in common gas Prep. Heat acetate of KO with HO KO Acetate of KO = C2 O2 C2 H3 K/O2 HOKO=H/K/O2 C2 O2 C2 H3 K/O2 + H K / O2 = C2 O2 K K/O4 + H C2 H3 Marsh gas = hydride of ethyl Zinc ethyl is a colourless liquid of enimense energy, as great as that of K. It unites with great energy with Ho. ZN C2 H3 + Ho = ZnO + C2 H3 H. 27 [illustration] Break the end off a small bulb of Zn methyl under HO. You may collect & measure the gas produced. Break the end of a glass bulb & the liquid will take fire depositing ZnO & metallic Zn C2 H4 burns without much smoke, it is inert, Br does not act on it Expose C2 H4 + CL to sunlight & you get action Members of the olifine family may be absorbed by fuming HOSO3. You may make this by adding anhydrous SO3 to HOSO3 There are not many members of the marsh gas family well known. C2 H4 Marsh gas C4 H6 hydride of Ethyl. C6 H8 } exist but not C8 H10 } well examined 28 C10 H12 hydride of amyl C12 H16 - hexyl. Hydride of Ethyl atomic wt 30 S.G. Place Zn Ethyl in HO. Take propionate of KO + HOKO heat together & you get hydride of ethyl. It is a colourless gas. It closely resembles hydride of methyl in its properties Hydride of Amyl. Boils at about 30°c, has a smell like chloroform [illustration] Iodide of amyl Zn + HO are sealed up in a table & heated in the water bath for some time Zn amyl forms first & then acts on the HO. It is very light, the lightest liquid known, has a pleasant smell. 29 Hydride of Hexyl C6 H14 May be got from mannite Colourless, very light boils at 60°C. It is very probable that it is the H representative of the sugar family. Very little certain is known of the higher families Family of alcohol radicals. Methyl C2 H3 C2 H3 Ethyl C4 H5 Propyl Butyl Amyl C10 H11 C10 H11 Amyl boils at a very high temp. is a colourless mobile liquid with a peculiar smell 30 When an iodide of an alcohol radical is heated strongly with Zn you get Zn I & the radical. C4 H5 } I } C4 H5 } I } + Zn2 = Zn } I } Zn } I } + C4 H5 C4 H5 Alcohol radicals may be got from fatty acids If you electrolyse acetic acid you get CO2 & methyl. Acetic acid = C2 O2 C2 H3 } H } O2 C2 O2 C2 H3 } H } O2 + O = C2 O2 O2 + HO + C2 H3 Take any other fatty acid of the series & you get an alcohol radical having C2 less than the acid is an extremely indifferent body The alcohols have not yet been 31 got from alcohol radicals Example of organic analysis Analysis of mannite. .3532 grams mannite gave .5069 - CO2 diff. of wt of KO bulb .2505 - HO - of CaCl tube Since 22 grams of CO2 contain 6C you multiply the co2 by 3 & divide by 11. .5069 x 3 = 1.5207 ÷ 11 = .1382 C To find the H divide the HO by 9 .2505 ÷ 9 = .0277 .3512 : .1382 :: 100 : 39.13 Percentage of C .3512 : .0277 :: 100 : 7.8 - H The diff between the wts of C + H & of the mannite is 0. 39.1C ÷ 6 = 6.5C = 65 7.8H ÷ 1 = 7.8H = 78 53.1O ÷ 8 = 6.60 = 66 100. To find the formula divide the percentage by the equivalents 32 of the bodies. The percentage of C should not be 2/10 ° below the theoretical quantity of the percentage of H 1/10 above it. Transformation of organic compounds by different ferments. Diatase Starch { C12 H10 O10 + 4HO = Grape sugar { C12 H14 O14 2 yeast Grape sugar { C12 H14 O14 = alcohol { 2C4 H6 O2 + 4CO2 + 2HO 3 Casein Milk sugar { C24 H24 O24 = Lactic acid { 2(C12 H10 O10, 2HO) Lactic acid { C12 H12 O12 = Butyric acid { C8 H8 O4 + 4CO2 + 4H 33 4 Synaptase Amygdalin { C40 H27 NO22 = Hydrocyanic acid { HC2 N + Oil of bitter almonds { 2C14 H6 O2 + Formic acid 2C2 H4 O6+3HO + Grape sugar { C12 H14 O14 /2 Salicin C26 H18 O14 + 4HO = Salicenin { C14 HO + Grape sugar We have considered the olifines the homologues of marsh gas & the alcohol radicals. We can reduce nearly all the others to the olifines Methyline C2 H2 supposed to exist in wood spirit, not known in a separate state. Ethylene C4 H4 Propylene C6 H6 Butylene C8 H8 Amylene C10 H10 These are distinctly radicals in themselves they unite 34 with Cl. They are biatomic. This is expressed by two dots thus C6 H6,, They unite with 2 atoms Cl, Br &c. Homologous of marsh gas These are olifines having their biatomicity gratified by 2 atoms, H. C2 H4 C4 H6 &c There are some instances where the biatomicity is not fully gratified having only 1 atom of H & 1 atom to be filled up by something else. These are the alcohol radicals. C2 H2 , H = C2 H3 methyl C4 H4 , H = C4 H5 ethyl C6 H6 , H = C6 H7 propyl C8 H8 , H = C8 H9 butyl C10 H10 , H = C10 H11 amyl. These are olifines stepping towards 35 the gratification of their biatomicity Suppose you add 1 atom Cl to C2 H3 you get chloride of methyl C2 H3 Cl or to C4 H5 you get chloride of ethyl C4 H4 HCl = C4 H5 Cl Suppose instead of Cl you substitute O, thus, C4 H6 HO You get ethers, of wh common ether is the type General formula of ethers Cn Hn HO corresponding to marsh gas Cn Hn HH. A radical is merely a body wh moves about Act on PbO by HCl. PbO + HCl = PbCl + H O. What is the radical ? The body you can move about viz., Pb. In the same way C4 H4 H O + H Cl = C4 H5 CL + HO. Instead of C4 H4 H you write 36 C4 H5. the radical because you move it about. What are the ethers wood spirit n methylic common propylic butylic amylic Methylic ether C2 H3 O = 23. Or when free it is doubled, as instead of C4 H5 to get a four volume formula you have C8 H10 (C4 H4 ) H this is lob sided having H on one pole & not on the other H (C4 H4) (C4 H4) H When doubled it is symmetrical. Why does ether double itself. O(C4 H4) H. The symmetry is not quite complete, tho' it is thus when in combination H O H (C4 H4) (C4 H4) H H O When free it doubles its combining vol. 37 wh is 2 Methylic ether vap. density Prep. Heat wood spirit with 4 parts HOSO3 & pass thro HOKO. It is a colourless etherial gas not condensible at 60°C, burn, with a pale blue flame, very soluble in HO to the extent of soluble in alcohol. Combines readily with HOSO3 & HCl. Act on KO by HCl. KO + HCl = KCl + HO. - C2 H3 O - C2 H3 O + HCl = C2 H3 Cl + HO. You may get chloride, iodide & bromide of methyl. Substitution products of Chloride of methyl, C2 H3 Cl. Chloroform. Two equivalents of H are substituted by Cl. (C2 H Cl2) Cl. The arbitrary formula is C2 H Cl3. 38 s.g of liquid chloroform 1.48 boils at 60.8°C Put 20 lbs Ca Cl in 120 lbs HO place in a Cu retort 1/3 full add 4 lbs alcohol. Heat quickly to 80°c & then withdraw the fire. You get 2 fluids the heavier is chloroform, wash with It is a colourless liquid, of an etherial sweet odour, sharp & sweetish taste. It is inflamed with difficulty. Place some on cotton wool it burns & gives off HCl. It falls thro' HO without dissolving. It is a good solvent of india rubber, P. Vinic ether, C4 H5 0 combining formula. & C8 H10 O2 its free formula. 39 formula. s.g of liquid .03736 at 0°C & .0724 at 16°C or 257. Boils at 35.5°C or 957. Vap. den. 2.586 Prep. Act on common alcohol with HOSO3 [illustration] C4 H6 O2 common alcohol HO - C4 H5 O = ether. you may suppose alcohol to be the hydrate of ether. There have been many treatises on this reaction. The HOSO3 has an affinity for HO & takes it away. Seal up anhydrous MgOSO3 & alcohol in a tube, the MgOSO3 takes away the HO & you get ether. There is no difficulty 40 in this case. But in distilling alcohol & HOSO3 , the HOSO3 does not combine with the HO. In the receiver you get HO & ether equal in bulk to the alcohol. There are many like instances in catalyses. The HOSO3 takes the HO but the heat drives it off. There are other theories. One is that a body called sulphorinic acid is formed. first. There is reason to suppose that HOSO3 is S2 O6 = HO/ HO/ S2 O6 Ho | C4 H5 O | S2 O6 sulphorinic acid KO | C4 H5 O | S2 O6 sulphorinate of Ko. They say that the sulphorinic 41 sulphorinic acid is decomposed, Haloid compounds of ether. Hydrochloric ether, C4 H5 Cl Pass HCl thro' ether or better thro' alcohol, you get C4 H5 Cl, chloride of ethyl. S.g of liquid 0.874 boils at 11°C A colourless, very volatile liquid & has a penetrating etherial odour. Slightly soluble in HO, soluble in alcohol. Analogous to an oxide KO + HCl = KCl + HO C4 H5 O + HCl = C4 H5 Cl+ HO. Iodide of ethyl. C4 H5 I. s.g boils at 72°C Colourless of an etherial smell. Much used to get radicals Act on hydrochloric ether by Cl & you get chlorinated ether. Act on it with Cl in sunlight 42 sunlight & you get Dichlorinated ether. Act with Cl by sunlight & heat & you get Trichlorinated ether. Ethers as a class. They represent the protoxides of metals Ko when free is probably not KO but KKO2 or K2 02. Ether when separate is not C4 H4 O but C8 H10 O2. Two atoms of radical united with 2 of O. What happens to KO when it is hydrated? KH/O2 = KO1 HO. one atom k going out & one of H going in. Take 1 atom of radical from ether & add 1 of H. (C4 H5) O2 alcohol is one of the H radicals of the double 43 ether taken out & 1 atom H put in its place. That the ethers are really duplicated in their separate state follows from the fact that you are able to substi- tute one radical by another C4 H5 } C4 H5 } O2 C4 H5 } C2 H3 } O2 C2 H3 } C2 H3 } O2 C2 H3 } C4 H5 } O2 When not in a free state they halve themselves & unite with a base. KO + NO5 = KONO5 C4 H5 O + NO5 = C4 H5 O NO5 you can form a whole set of ethers. The ethers are to be considered as the protoxides of the metals & the alcohols as the 44 hydrates of the protoxides KO (C4 H5 O) HO KO. (C4 H5 O) HO. Alcohols = 4 vols. S.G liquid vap. Boiling point Wood spirit C2 H4 O2 0.798 1.12 150° Spirit of wine C4 H6 O2 0.796 1.61 173 Propylic alcohol C6 H8 O2 - 2.02 206 Butylic C8 H10 O2 0.803 2.59 233 Amylic C10 H12 02 0.818 3.14 270 Caproic C12 H16 O2 0.830 3.53 304 Caprylic C16 H18 02 0.820 4.5 356 Lauric C24 H26 O2 Cetylic C32 H34 O2 Cerylic C54 H56 O2 Melissic C60 H62 O2 Aldehydes. Formic aldehyd Acetic Propionic Butyric 45 Valerianic aldehyd Caproic Oenauthylic Capric Euodic Ethers form a homologous series corresponding to the alcohols. The general formula of an alcohol is that of an ether + 1HO Ether = Cn Hn,, Ho1 + HO = Cn Hn an alcohol. The alcohols belong to a different class from the ethers, as a hydrate does not represent a protoxide but a peroxide. O | O | K2 O | O | (CnHn)2 | O | | O | K O | HO | K O | HO | C4 H5 O | NO5 | K O | NO5 | C4 H5 Alcohol is a hydrate of ether & is a salt. 46 Wood spirit on methylic alcohol C2 H6 O2 = O| HO | C2 H3. equals 32. s.g of liquid 0.818 at 32°, at 65° 0.798 vap. density 1.12 boils at 150° F Prep Distil wood, acetic acid & wood spirit are given off it is purified by lime & distilled from Ca Cl. When pure, it is colourless has the odour of acetic ether is a good solvent for resins when oxidized it forms formic acid. Vinic alcohol or spirit of wine. C4 H6 O2. O| HO| C4 H5 = 46. s.g when free at 60° is 0.794 vap. den. 1.613 boils at 173°F or 78°C. Alcohol has been made synthetically. We believe it contains C4 H4 47 add 2 atoms HO & you alcohol. C4 H4 " H2 O2 - C4 H6 O2 Pass C4 H4 into HOSO3 add HO & distil, alcohol comes over. [illustration] Prep. Distil from fermented add KOCO2 wh has been heated & the KOCO2 takes the HO & falls to the bottom. you distil again from Ca Cl or dried CuO. It is a colourless, volatile mobile liquid of an aromatic smell & burning taste It has a strong affinity for HO, & the mixture contracts. burns without smoke. It has never been solidified by cold, at -166° F it becomes viscid, is a good solvent for Br, I, S, Na & bodies containing H. In using it as a fuel it is 48 completely burnt. C4 H6 O2 + 120 = 4CO2 + 6HO. It unites with salts as HO does & forms alcoates instead of hydrates. Wines & spirits. Proof spirit 50.76 P.C. alcohol & 49.74 HO [illustration] Proof used to be -set some gunpowder on a tile pour spirit over it. & set the spirit on fire. If the spirit be above proof the gunpowder should go off when the spirit is burned. if under proof the HO it contains wets the powder so that it does not go off. Distilled spirits. Brandy contains 55 P.C. alcohol in its ordinary state it is coloured with burnt sugar 49 & peach kernels are added during distillation to flavour it. gin is got from fermented grain & flavoured by juniper berries. Whisky is distilled from grain & has a slightly smoky taste. Rum is got from sugar Arrack from fermented rice betel nuts or palm juice Potato brandy is get by converting potato starch into glucose & distilling it. Wines are the fermented fluid without distilling. When all the sugar is converted into alcohol they are called dry. when much sugar remains they are called fruity. The bouquet is due 1st,, to the completion or 50 non completion of these actions 2nd to the deposition of cream of tartar 3d to the formation of fragrant ethers by the action of vegetable acids on the strength of wines Port or Madeira 15-20 P.C alcohol Sherry 15-17 Lisbon 16 Malmsey 13 Champagne 12 French clarets 9-10 Rhenish wines 10-12 Cider 4-8 Perry 6-8 Ale 6-8 Porter 5 Small beer 1 1/2 The market value of wines depends on their flavour 51 One imperial pint of the following wines contains HO oz alcohol oz sugar grs Tartaric acid grs. Port 16 4 1-2 80 Brown sherry 4 1/2 360 90 Claret 2 none 161 Burgundy 12 1/2 2 1/2 160 Fermentation It is the process by wh sugar is converted into alcohol. Grape sugar in honey C12 H12 O12 Act by yeast = 4Co2 + 2(C4 H6 O2) Yeast does not appear in the final product Conditions for fermentation The temperature must be 50°-60° F HO must be present to keep the sugar in solution Air must be present to make the yeast live & effect the transformation Nitrogenized substances 52 must be present & a body capable of fermenting. There is spontaneous fermentation as in crushed grapes the air acts on the nitrogenous matter in the cells. When we add a ferment to sugar, & the ferment disappears or forms a heavy substance wh falls to bottom. The yeast is a vegetable growing body, & consists of cells wh when placed in a warm saccharine fluid increase, one cell giving off many others, about 1/250th of an inch in diameter. They finally cease to produce gas. 53 Composition Before fermentation after C 47.71 p.c 48.31 H 6.7 7.33 N 10.15 5.07 O 35.44 39.29 SoP Traces Traces. The N is only one half of what it was when the operation commenced. When yeast is active it is acid if you add an alkali to it, it stops its action & the fermentation. Weak acids favour fermentation, strong acids destroy it. Some poisons destroy it others do not. Theory of action of ferments Liebig's view is that the ferment is in a state of internal change & that it communicates this change to the other body 54 wh is in a state of statical equilibrium. Pasteur considers that it is an action not correlative with the death of the plant but with its life. He burnt yeast & added the ashes & an ammonia salt to sugar. The NH3 disappeared from the solution. The result of fermentation is complex. Glycerin & butylic acid are produced as well as alcohol & CO2. Suppose you put a piece of putrid cheese or casein into sugar, you get a different action & lactic acid is produced If the cheese is very putrid the lactic acid becomes butyric 55 acid. C12 H12 O12 The brewing of beer is a reproductive fermentation A certain quantity of yeast is added to the fermenting liquid & grows so much that much more yeast is obtained. Malting is the germination of barley. When the young sprout is about 1/2 inch in length & begins to bifurcate, its life is destroyed by roasting. The barley in malting contains diastase. Diastase can convert starch into dextrin, it then changes the dextrin into grape sugar. One part diastase can convert 4000 parts of starch into sugar malt contains 1/500th of its weight of diastase, so there is enough 56 diastase left to An infusion of the malt is made & 4 or 5 parts of fresh barley added It converts the barley into sugar you then add say 1 part yeast wh produces 2 parts of alcohol 4CO2 + 2HO In the barley there is gluten a body of the same composition as the muscle of our bodies. The yeast acts on the gluten & it receives so much food from the gluten that it grows with great rapidity & produces much new yeast. Composition of 1 imperial pint HO oz ale oz sugar grs acetic acid grs London stout 18 1/2 1 1/2 281 54 - porter 19 1/4 3/4 267 45 pale ale 17 1/2 2 1/2 240 40 mild - 18 3/4 1 1/4 280 38 strong - 18 2 2.136 54 57 Homologues of the alcohols. Propylic alcohol. C6 H8 O2. Found in the product of the fermentation of grape skins. It is a colourless liquid with an agreeable fruity smell, lighter than HO. Prepared by synthesis from propylene. Propylene is passed into HOSO3 HO is added & it is distilled. Butylic alcohol C8 H10 O2 Found in small quantity in fusel oil. It is a colourless liquid, smelling like fusel oil & wine, soluble in HO but separates on the addition of salt. Amylic alcohol. C10 H12 O2 S.G of the liquid 0.818 vap. density 3.147 boils at 58 Has a higher boiling pt than the previous ones. Brandy contains a little fusel oil & whiskey a good deal. Test pour some of the spirit thought to contain it on your hand & allow it to evaporate you can then smell the fusel oil. It is though a colourless, mobile liquid, of a disagreeable odour burning taste, slightly soluble in HO, soluble in alcohol & ether when strong it is poisonous & produces a cough & spasm of the glottis Caproic alcohol. Formed in the fermentation of grape skins, Refracts light strongly: insoluble in HO General properties of alcohols. The chemical reactions of alcohols 59 alcohols are nearly all the same. If we act on them by acids you get ethers. C4 H5 O HO + NO5 = C4 H5 O NO5 + HO KO HO + NO5 = KONO5 + HO. The compound ethers are on the same type as alcohols, but acids replacing the HO. Boiling pts Vinic alcohol 78°C } difference Propylic 96C } 18°C Butylic 112° } 16°C Amylic 132 } 20°C Caproic 150°} 18°C Compound ethers are derived from the alcohols, & are salts of the ethers, the HO of the alcohol being replaced by acid. Sulphuric ether, not that of shops wh is common ether but that of chemists C4 H5 OSO3 Prep. Act on ether by anhydrous 60 anhydrous SO3 in the cold, Colourless, aromatic liquid not miscible with HO. Nitric ether. C6 H5 ONO5. Used in pharmacy. S.G of liquid 1.11 boils at 85°C. Distil HONO5 with alcohol & a little urea. When pure it is a colourless aromatic liquid, with a faint smell of apples, explodes when quickly heated. Nitrous ether C4 H5 ONO3 s.g of liq boils at 16.4°C Distil spirit of wine with HONO5 It is yellow, inflammible insoluble in HO soluble in alcohol. Decomposed in heating with the evolution of N. Even the feeble acids have 61 been made to unite with ether. C4 H5 O CO2 C4 H5 O Sc O2 a proposition was made for covering the houses of Parliament with a coating of silica by means of C4 H5 OSiO2. Sulphovenates, are salts of ether in wh one of the equivalents of HO in HOSO3 viewed as a bibasic acid is replaced by ether. HO | HO | S2 O6 HO | C4 H5 O | S2 O6 add KO KO | C4 H5 O | S2 O6 Sulphovenate of Ko It is not HOSO3 alone wh acts in this way, PO5 does it also HO | HO | HO | PO5 HO | HO | C4 H5 O | PO5 Phosphovenic acid As every ether has its alcohol & every alcohol can form a compound ether you might 62 go on in the series but when you know the properties of one in a series the others much resemble it. Nitrite of amyl. It is amylic alcohol with HO displaced & NO3 added C10 H11 O HO C10 H11 O NO3 It has properties the very reverse of chloroform. It increases the action of the heart, & produces acute headache. In cases of long suspended syncope it might be useful. Biatomic ethers & alcohols. An ether is monoatomic when it unites with 1 atom acid or with of HO to form alcohol. C4 H4 " HH. marsh gas. C4 H4 ClCl C4 H4 HO ether. 63 C4 H4 O O Cn Hn" O O biatomic ether Cn Hn OO + 2HO - alcohol Why should those be biatomic? KOHO it has one of O in the base KONO5 Sn O2, 2HO it has 2 of O in the base Sn O2, 2NO5 The same with biatomic alcohol. Ethylene ether C4 H4 O2 corresponding to dutch liquid Has been imperfectly studied. 2b hydrate or ethylene alcohol C4 H4 O2 + 2HO generally called glycol is better known. Empirical formula C4 H6 O4 Obtained by the action of HOKO on acetate of ethylene. C4 H4 O2, 2C4 H3 O3 + 2KO HO = 2(KOC4 H3 O3) + C4 H4 O2 + 2HO. A clear thick sweet liquid 15 64 Soluble in HO & alcohol, the vapour burn & is converted into acid by oxidation. Acetate of ethylene. Act on Bromide of ethylene a dutch liquid by acetate of KO. C4 H4 I2 + 2KOC4 H3 O3 = 2 KI + C4 H4 O2, 2C4 H3 O3 Acetic ether is a colourless liquid, at a high temp. it smells feebly of acetic acid. We can produce the homologues of glycol thro the whole series. C4 H4 HO common ether C6 H6 OO biatomic - . C4 H4 HO + HO common alcohol. C4 H4 OO + 2HO biatomic - Cn Hn HO + HO common Cn Hn OO + 2HO biatomic Cn Hn OO, 2HO Cn Hn OO, 2A C6 H6 OO 2(C4 H3 O3) binacetate of ether of olifine 65 Every homologous olifine has an ether & alcohol belonging to it. We now consider a stepping stone between the alcohols & acids, the aldehydes. Alcohol Aldehyde Acids of alcohols. Cn Hn + 1. +1 means that there is 1 atom of H more than the number of C. alcohol Cn Hn +1 O, HO = HO + ether General way of forming aldehydes from alcohols. Cn Hn +1 HO - 2H = aldehyde. It is simply by oxidation that you do this. [illustration] Put a heated Pt wire into a glass in wh is a little ether. Aldehyde vapours form round the Pt. You are forcing the H to combine with the O by the action 66 of the Pt. [illustration] Distil alcohol, HOSO3 & Mn O2 in a capacious retort & aldehyde is produced. Add 2 atoms of H to an aldehyde & you get an alcohol. Vinic or acetic aldehyde C4 H6 O2. s.g of liq 0.79. vapour density 1.53 4 volume formula boils at 21°C. Distil in a capacious retort 6 parts HOSO3, 4 alcohol of 85 P.C.. 4HOO 6 MnO2. The loss is considerable. you get a colourless liquid of an irritating pungent odour, burns with a white flame, with alkaline bisulphides it forms a white solid compounds. It is singularly unstable, if you seal it up in a tube it changes after a time to porcelain 67 like substance, it is then probably C12 H12 O6 There are several of these varieties. General process to get aldehydes. Suppose you wish acetic aldehyde. Distil acetate of lime with one equivalent of formiate of lime acetic aldehyde. Ca O C4 H3 O3 + Ca O C2 HO3 = 2Ca O CO2 + C6 H4 O2 General view of the constitution of aldehydes There are several views. Gerhardt thinks they are constituted on the type of H. H = H } H } C4 H3 O2 } H } = acetic aldehyde. That one H is replaced by C4 H3 O2 a radical he calls acetyle. Liebig thinks that they are alcohols of unknown radicals 68 & that the radicals are negative or are Cn Hn -1 having 1 atom less H than C. C4 H3 O HO = aldehyde = hydrate of oxide of acetyle. He calls C4 H3 O acetyle. In our view we view aldehyde as the alcohols of oxidized olifines C4 H4 " HO common ether C4 H3 O, " HO aldehyde 1 H being replaced by O. Every alcohol has its ether - aldehyde - ketone. If you take the acid salt of any as Acetate of Pt + distil you get a tarry liquid wh when purified is a acetone the ketone of the ketone the aldehyde in wh 1 H is substituted by the alcohol radical below it in the series 69 C2 H3 methyl is the radical below C4 H5 ethyl in the series. C4 H5 O, HO substitute the H by methyl C4 H5 O (C2 H3) O. Ketone of the series. Acetone C6 H8 O2 = C4 H5 O2 C2 H3/ C6 H8 O2 Heat chloride of acetyle with Zn methyl. It is a clear colourless liquid of an etherial smell, soluble in HO but separates readily on the addition of salt, readily soluble in alcohol & ether. Absorbs H Cl readily & polymerizes Anhydrides or acids. When monoatomic alcohols homologous with methylic are fully oxidized they are changed into aldehydes & then into 70 acids. All the acids are derived from corresponding alcohols by oxidation It was long supposed that there was no anhydrous acid in the organic series. KOSO3 = KSO4 There is a great disposition among chemists to reduce to the binary type. They have got anhydrous acids mode. General reaction. By acting on a salt such as an acetate with a body wh is oxichloride of P, P Cl3 O2. Example. To get anhydrous acetic acid. Take acetate of KO. C4 H3 O3, HO, From chloride of P. you can get chloride of acetyle C4 H3 O2 Cl, = anhydrous acetic 71 acid in wh 1 of O is replaced by Cl. C4 H3 O3 KO + C4 H3 O2 Cl = 2(C4 H3 O3)+ KCl. Anhydrous acetic acid. Its formula is doubled C8 H6 O6 liquid s.g 1.073 vapour density 3.47 boils at 140°C. It is a colourless mobile, highly refracting liquid. It sinks thro HO like oil but gradually unites with it & forms vinegar All other anhydrous acids could be prepared. Hydrated acids Relation of these acids to alcohol & ether. Ether C4 H6 " HO Ethylene ether C4 H6 " OO - Alcohol or glyeds C4H4 OO HO HO Oxydized series Aldehyde C4 H3 O " HO Anhydride C4 H3 O " OO Acetic acid C4 H3 O OO/HO 72 Formic Acid. empirical formula C2 H2 O4 s.g of liquid 1.235 vapour density 1.554. Occurrence. Called formic acid because it occurs in the red ant Formica rufa: occurs in the stinging nettle urtica urens & in various animal secretions. Obtained by synthesis. By passing CO over HO KO KO HO + 2CO = KOC2 H3 O3. Distil starch with HOSO3 + MnO2 This is not the best way. Mix syrupy glycerine with oxalic acid & heat. It was formerly got by crushing & distilling ants. It forms many salts wh crystallize readily & form definite & permanent compounds. Acetic acid. HO C4 H3 O3 or C4 H4 O4 s.g of liquid 1.063 vapour density 73 2.08 boils at 119°C. Occurs as acetates in various vegetable juices in the perspiration of animals, in the juice of flesh Prepared by synthesis. By the action of CO2 on Zn methyl. C2 H3 Na + C2 O4 = Na C6 H3 O3. you get acetate of Na Commercially. Distil wood & you get pyroligneous acid & pyroxylic spirit. The ash, oak & beech are preferred. Add lime & you get acetate of lime, distil over & you get glacial acetic acid, it is so called because it becomes solid when exposed to cold. If you pass alcohol over spongy Pt in presence of air you get acetic acid Oxidize alcohol. A large cask is 74 taken, wh allows air to pass thro it, & filled with beech wood shavings & alcohol [illustration] poured over it, it is done two or three times & in its passage is oxidized to acetic acid. 1 part alcohol + 6 HO + 1/1000 th part of honey are taken. Relation between the alcohols aldehydes & ketones. alcohol C4 H4 H1 O1 HO double ether C4 H4 " H1 O1 (C2 H3)O Aldehyd C4 H3 O " H1 O. Acetone C4 H3 O " (C2 H3)O. is not a common alcohol in wh the H is replaced by the radical neat lower in the series it is the aldehyd in wh the H is replaced by the radical 1 below it in the series. Thus, Butyrone, C8 H7 O " (C6 H7)O. 75 16 [illustration] Prep of acetone C is a Cu retort in wh Acetic acid. C4 H4 O2 At 55° it is solid & crystalline melts at 62°, has a pungent peculiar smell, burning taste, acid taste, miscible with HO, ether & alcohol, it dissolves camphor & essential oils, the strongest acetic acid forms aromatic vinegar & is generally flavoured with essence of camphor or bergamot. It is used in medicine as a rubefacient, when too strong it blisters the skin. Most acetates are soluble. Vinegar is dilute acetic acid is is made from bad wine The temp necessary to produce oxidation is 70-80°F. Malt vinegar is now largely 76 used, it contains about 5 P.C of acetic acid. Acetic acid may be acted on by Cl & forms a very complete substitution acid. KO C4 H3 O3 acetate of KO. KO C4 Cl3 O3 chloracetate of KO. Acetates. Acetate of KO. KO C4 H3 O3 Prep. Dissolve KO CO2 in acetic acid Prep. Anhydrous. foliated, deliquescent. Acetate of NaO. NaOC6 H3 O3 + 6HO. Colourless transparent effloresent cooling taste. Acetate of ammonia. NH4 OC6 H3 O3. White crystalline easily solube decomposes when heated. distilled. Nh4 OC6 H3 O3 = 4HO + C4 H3 N = C2 H3 C2 N or cyanide of methyl. The cyanide of the radical below that from wh acid is derived. 77 another example propionate of ammonia. NH4 OC6 H5 O3 = 4HOC6 H5 N = C6 H5 C2 N NH4 OC2 H3 O3 is used in medicine as a refrigerent & to act on the kidneys Acetate of PG. PGOC4 H3 O3 + 3HO this is neutral acetate. Prep. Dissolve PGO in acetic acid & crystallize. It is often called sugar of PG. It crystallizes in transparent rhombic prisms, has a sweet taste, soluble in twice its wt of HO & alcohol, it is used as a lotion is poisonous. There are some subacetates. 3PbO, 1C4 H3 O3 6PbO 1 C4 H3 O3. Acetates of Cu. There are several. Neutral acetate 1 CuO 5 acetic acid 78 & 5HO. There are various insoluble subacetates. Verdigris. Expose sheets of Cu in alternate layers with fermented grape skins. The crust is scraped off & made into a paste with vinegar & made into moulds. Glycocol is connected with acetic acid. Occurs in the transformation of many animal substances in the decomposition of hippuric acid &c. It is crystalline sweet, fusible at 78°C soluble in HO & hydrated alcohol, insoluble in ether & absolute alcohol. It is a very weak acid acting partly as an acid & partly as a base. 79 It is acetic acid in wh 1 atom H ionical is substituted by amidoger NH2 . Acetic acid (C4 H2 HO)"OO Glycolic -- (C4 H2 OO)"OO Glycocol C4 H2 (NH2)O) OO NH3 thought to be (NH2) H hydride of amidogen Acids homologous to acetic acid Propionic acid. HOC6 H5 O3 liquid s.g 0.991 boils at 140°C Its synthesis has been effected by Na ethyl . C4 H5 Na + C2 O4 = NaOC6 H5 O3 proprionate of NaO. Butyric acid C8 H8 O4 = HOC8 H7 O3 liquid s.g 0.978 Occurs ready formed in certain fruits, in sourkrout. In the animal organism it is found sometimes in sweat, in gastric juice, in 80 certain diseases in wh the expectorations have a bad smell. In the bad smelling juices of certain animals. In the oxidation of casein & fibrin By fermenting sugar by poor cheese or curd in presence of chalk. you get butyrate of lime, lactate of lime is first formed. Add HCl & distil & you get butyric acid. It is a colourless liquid, with a very disgusting odour. Crystallized by intense cold. Slightly soluble in HO. Butyrates crystallize & have no disagreeable smell when dry, tho when wet the CO2 of the air liberates some 81 butyric acid & causes a smell. They have more the character of soaps than any salts we have yet dealt with. Butyrate of lime. It is much more soluble in than Butyric ether C4 H5 OC8 H7 O3. liquid s.g .901 boils at 119°C, a clear, mobile, liquid, & fragrant ether It occurs in the pineapple, melon strawberry & other fruits Some fragrant ethers are got from acids having an abominable smell A strong alcoholic solution of butyric ether is sold under the name of essence of pineapples, & more diluted as essence of strawberries. Amylic or valeric acid C10 H10 O6 = HO1 C10 H9 O3 82 liquid s.g 0.937 vapour density 3.66 boiling point 347° Occurs in valerian & angelica root, in putrid cheese in train & sperm oil Prep. Distil valerian root with HO. Or Distil fusel oil with HOSO3 + KO2CrO3 It is limpid, has an odour like cheese floats on HO. Forms valeriates wh are soapy substances. Fatty acids Rutic is the first true fatty acid or oil when melted. It occurs in the fat of goats. Palmitic acid C32 H32 O4 or Ho C32 H31 O3 Melts at 62°C. All the fats vegetable & animal are compound ethers, the ether they contain is that of Glycerin united with a fatty acid Palmitic acid in combination 83 with glycerin is in almost all fats especially human & pigs It is obtained by saponification Fat = Glycerin } Fatty acid } + KO = KO } fatty acid } = soap. Act on soap by alcohol & you get the acid in a free state. Prep. Tasteless white fat crystallizes in tufts insoluble in HO soluble in alcohol & ether. Palmitates are soaps insoluble when the bases are earths, soluble when they are fats. Stearic acid C36 H36 O4 melts at 69.2°C occurs in combination with glycerine in most fats, in all animal fats the richer the fat in stearic acid the harder it is. It is got from stearate of KO by HCl insoluble in HO. 84 When distilled it is converted into palmitic acid. Stearates of alkalis are soluble Neutral stearates are decomposed by HO into alkalis & Lamps were used before candles were introduced. Torches were the first candles & were probably used with lanterns. Pling alludes to candles wh were probably of wax. The only cheap candles in this country were the fats themselves. They had a low fusing point & ran & the wick did not burn away and required snuffing. [illustration] Palmers candlestick was meant to remedy this. The candle was kept at the level of the candlestick by a spiral spring & the 85 wick wh was double turned outwards so that the end was always exposed to the air & thus burned away. Improvements in candles. It was discovered that tallow consisted of stearine & oleine & that by heating tallow to the fusing pt of oleine but not to that of stearine the oleine might be pressed out & stearine left. Tallow melts at 102° Stearine 144 Stearic acid 15° Candles of stearic acid would thus be better than those of stearine The stearine was saponified & the soap acted on by HCl. There were many objections to the use of stearic acid candles The wick got clogged up. This was found to be owing to the wick 86 leaving alkaline ashes & forming a soap with the stearic acid This was remedied by dipping the wick in HOSO3. C6 H5 O3"' Glycerine ether (C6 H5 O3"') 3HO Glycerine (C6 H5 O3"') 3A A fat. Tallow is a mixture of fats, as, oleine. palmitine & stearine glycerine itself is not combustible. In the stearic acid candles, the oleine & glycerine are both removed. Stearic acid candles so called, are generally palmitic acid & are got from palm oil. The improvements in candle making depend chiefly on Chevreuls researches on fats. Saponification. The fat is boiled with lime, & HOSO3 added. 87 to the lime salt of the fatty acid thus obtained. the acid is then got in free state (C6 H5 O3"') 3a + CaO = lime salt 3HO = glycerine 3SO3 Another difficulty in the use of stearic acid candles is that it has a tendency to crystallize. The crystalline flakes often broke off the candles. By putting a little arsenic into the acid the crystallization was stopped, but fumes of as were given off while the candle was burning & hurt the health of those who used it. This nearly put a stop to the manufacture but after some time it was found that a small percentage of wax served the same purpose as the As. The saponification was next 58 effected by HOSO3 instead of lime. Mix the fat with HOSO3 & heat by blowing steam thro' them C6 H5 O3"' 3A + 6HOSO3 = C6 H5 O3"', 3SO3 + 3A,3S03. Pass superheated steam at about 600° thro' the fat. it splits it up into the acid & the ether. C6 H5 O3"' | 3A. The glycerin & acid both distil, separately. Candles from Coal. Coal when distilled produces various gases. among others olefiant gas C4 H4 & other higher homologues. C8 H8 C10 H10 Cn Hn 89 If you distil at a low temperature Cn Hn comes over chiefly in a solid state. if at a higer temp. you get liquid products; & higer still gaseous products Boghead coal is distilled at as low a temp. as possible & an oil comes over. wh. is called paraffin because it possesses almost no affinities This when cooled from 40° to 32° deposits solid paraffine. In 1852 L. Playfair thought that paraffine could be got from the oil, but the maker of the oil would not try it, so Playfair obtained a quantity from him & by experimenting succeeded in getting it. Paraffine contains the conditions of illumination in the highest degree. The illuminant in coal gas is C4 H4 & its homologues 90 Paraffine is C4 H4 in a condensed state. All the paraffine is burned. It is not fat wh burns in a candle it is gas. The pores of the carbonized part of the wick act as so many retorts. Acids heterologous Melissic HOC62 H59 O3 Cerotic HOC34 H53 O3 Arachidic Stearic Palmitic Myristic Lauric Rutic Pelargonic Caprylic Ænanpylic Caproic Valeric 91 Butyric Propionic Acetic Formic Acids produced from biatomic alcohols. C4 H4 " HOHO monoatomic alcohol. C4 H4 "OO2HO bi -. In examining the oxidation of monoatomic alcohols we found that aldehydes were first produced & then acids.. C4 H4 "HO C4 H4 O"HO C4 H3 O"OO. Products of the oxidation of Glycol. We find two acids result. In the first 2 atoms of H in C4 H4 are replaced by O. In the second all the H is replaced by O. 92 Glycol ether C4 H4 "OO glycolic acid C4 H2 O2"OO Oxalic - C4 O4 "OO. What would be the acid for methylene C2 H2 if it were fully oxidized? C2 O2 OO = C2 O4 = 2CO2 . Formic acid C2 HO"OO Carbonic C2 O2 "OO Acetic C4 H3 O"OO Glycolic C4 H2 O3 "OO Glycolic acid. Got by the slow oxidation of glycol. It is a syrupy acid liquid The anhydride is got by distilling tartaric acid Lactic acid C6 H6 O6 = 2HOC6 H4 O4 Occurrence. It is extensively distributed in the animal kingdom it is found free in the gastric juice, found in muscle, in 93 the pancreas, in milk, in the brain & lungs & abnormally in urine blood & saliva. It is supposed to be the acid wh dissolves out the mineral matter in bones & produces rickets. It stands in the same relation to propylic wh the latter bears the glycol. Glycol or ethylene alcohol C4 H6 O41 - 2H + 2O = C4 H4 O6 Glycolic acid. Propylene alcohol C6 H8 O4 - 2H + 2O = C6 H6 O6 Lactic acid. Prep. 8 parts of sugar are dissolved in 50 parts HO, 1 part of poor cheese & 8 of chalk are added, & fermented at 80°. Lactate of lime is thus got & by adding HOSO3 you get the acid. It is a transparent, uncrystalline liquid, of a sharp taste It is not volatile & can displace volatile acids, when heated it 94 loses HO & becomes lactic anhydride. Lactates of alkalies do not crystallize - earths & metallic oxides do. Lactate of Zn unites with 3HO. Flesh juice lactates all contain 1 equivalent less of HO than those of that got by fermenting sugar. Fully oxidized olifine acids in wh the H is substituted by O. Formic acid C2 HO"OO Carbonic C2 OO"OO Carbonic oxide C2 O2 is a radical. Sulphocarbonic C2 O2 S2 acid Chloro - C2 O2 Cl2 Oxalic C4 H2 O8 C6 H4 O8 Succinic C8 H6 O8 Lupinic C10 H8 O8 Sebacic C20 H18 O8 Oxalic acid 2HOC4 O6 Occurs in vegetable juices, as acid 95 oxalates, in common sorrel, in lichens in rhubarb, sometimes free. Rarely in the animal kingdom as oxalates of lime in calculi & in urine in an abnormal state. Prep. Heat starch gently with HONO5. It has been obtained by another method. Heat sawdust with caustic Ko & NaO. The H is removed & the O goes You get a mixture of oxalates of NaO & KO. Add CaO & you get insoluble oxalate of lime. Add HOSO3 & you get oxalic acid free. 2Nao, C4 O6 + 2CaO = 2CaOC4 O6 2CaO, C4 O6 + 2SO3 = 2CaOSO3 + C4 O6. It is a crystalline acid crystallizes in colourless transparent like Epsom salts, for wh 96 it is sometimes mistaken. The remedy is chalk, CaOCO2 or magnesia It forms a numerous class of salts, the oxalates, the principal are those of KO & NH3 . Oxalate of KO. 2KO1 C4 O6 + 2HO. Soluble in HO. crystallizes in There is a bin- & quadroxalate wh is is found in sorrel & cress. Neutral Ko| Ko| C4O6 Binoxalate Ho| Ko| C4O6 Quadroxalate Ho| Ko| C4O6 + Ho| Ho| C4O6 + 4HO. Oxalate of ammonia . Prep. Saturate oxalic acid with NH3 & crystallize. It is largely used for testing, as for salts of lime, with wh it gives a white precipitate of 97 neutral oxalate of lime. Oxalate of lime Occurs native in the animal & vegetable kingdoms. Succinic acid 2HOC8 H4 O6 It is homologous with acetic acid It occurs in amber in various fossil resins. in turpentine in the animal kingdom, in the spleen of oxen. It is formed by the oxidation of some organic substances, by the putrefaction of plants of the asparagus kind & by the fermentation of malate of lime. Prop. It is a white brilliant, crystalline acid, crystallizes in rhombic prisms, not easily soluble in cold alcohol, soluble in hot alcohol soluble in HO. From 175 to 180° C it sublimes 98 It is a fixed acid not easily acted on by reagents. Like most bilasic acids it forms neutral & acid succinates. Negative radicals. We have been considering positive radicals. the radicals of the alcohols, the general formula for wh is Cn Hn +1 as for example ethyl C4 H5 = C4 H4 + H The general formula of negative radicals is Cn Hn -1 as for example Acetoyl C4 H3 Allyl C6 H5 Angelyl C10 H9 How can we consider these as olifines? C has a great tendency to unite with itself. Allyl C6 H5 ={(C4 {(C2 H4)"H. C2 having united with the C in the olifine. & the biatonicty of the radical thus formed not being fully 99 gratified by uniting with 1 of H as ethyl C4 H5 = C4 H4 H. It is not mere speculation that C unites with itself. It may be so in the case of allyl but it is known in the case of naphthalene C20 H8 a body wh chokes up gas pipes & wh has all the characters of an olifine. Allyl C6 H5 or in the separate state C12 H10. liquid s.g 0.58 boils at 59ºC. It has the synonym acryl. It has been got in a separate state. Got by the action of Na on iodide of allyl. It is a volatile ethereal liquid burns with an illuminating flame unites with Br & I & forms compounds. Sulphide of allyl or oil of garlic C6 H5 S. boils at 140ºC. 100 occurs in garlic & may be distilled from it & then forms sulpo of allyl. Oil of mustard is the sulphocyanide of allyl. Oil of garlic C6 H5 S. - mustard C6 H5 CyS. It may be got artificially. Act on iodide of allyl by KS. C6 H5 I + KS Allyl ether C6 H5. - alcohol C6 H5 OHO. When oxidized it forms an acid corresponding to acetic, acrylic acid, Oxidized radicals of allyl. Alcohol C4 H6 O2 - 2H = C4 H4 O2 aldehyde. - C4 H6 O2 - 2H + 2O = C4 H4 O4 acetic acid Allyl alcohol C6 H6 O2 - 2H = C6 H4 O4 acryl aldehyd - C6 H6 O2 - 2H + 2O = C6 H4 O4 acrylic acid. Allyl or acryl aldehyde synonym acrolene. It is the nasty smell you perceive when you blow out a candle 101 candle In this case it is got from glycerin wh is distilled in the red hot part of the wick. It has a frightful smell, extremely pungent. attacks the eyes, & if concentrated burns the skin. Oxidized allyl alcohol. Homologues of acrylic acid (with 2C added Acrylic acid C6 H4 O4 same as acetic acid series Angelic C10 H8 O4 from angelica root Damaluric C14 H12 O4 in urine of cows Hypogaic C32 H30 O4 in earth nuts Oleic C36 H34 O6 in most fats C38 H36 O4 C in mustard seed Oleic acid C36 H34 O4 = HOC36 H33 O3 Occurs in most oils & fats as a glyceride. May be got from almond oil by saponifying & converting it 102 into a lead soap & acting on this by HCl. It is tasteless has no smell, does not act on vegetable colours It is solid below 14° C, is insoluble in HO. soluble in alcohol & ether. With NO4 it forms a solid substance. Pass NO4 thro castor oil wh contains much oleic acid Glycerine. The basis of fats. It appears to contain the same radical as allyl. C6 H5 OHO allyl alcohol C6 H5 O3 3HO Glycerin The atoms cannot be arranged in the same way (C4 H4") (C2 ) HO (C4 H4) (C2 O2) HO in Glycerine ether. Glycerin C6 H8 O6 liquid s.g 1.97. 103 Prep. Distil fats with super- heated steam. It is a colourless, syrupy, liquid does not crystallize, has no smell, sugary sweet taste, not volatile except in the vapour of steam. When distilled by itself it is decomposed. When acted on by yeast it yields propionic, acetic & formic acid When heated with KO C6 H8 O6 + 2KO = Acetate of KO KOC4 H3 O3 + Formeate of KO KOC2 HO3 + 4H Made by synthesis. Make iodide of allyl C6 H5 I. Act on it by 3Br. C6 H5 I + 3Br = C6 H5 Br3 + I. C6 H5 "'Br3 + 3KOC4 H3 O3 = 3KBr + C6 H5 O3 , 3C4 H3 O3 Decompose with HOKO or HOBaO. C6 H5 O3 . 3C4 H3 O3 + 3BaO1 HO Saponification Making soaps from glycerides 104 All ordinary fats are glycerides the 3 atoms of HO in glycerine being replaced by 3 atoms of a fatty acid. C6 H5 O3, 3HO C6 H5 O3, 3 acetic acid C6 H5 O3, 3F F = fatty acid. Glycerides or common fats. Occur in the animal & vegetable kingdoms, embracing all the fats we know. Fats may be prepared artificially. Seal glycerin & stearic acid up in a tube & expose to high temp. These fatty glycerides are easily decomposed. They are generally mixed with other fats. To get stearine heat mutton fat with cold ether wh dissolves out palmitine & oleine 105 Stearine C114 H110 O12 = tristearate of glycerin C6 H5 O3 | C36 H35 O3 C36 H35 O3 C36 H35 O3 It is a colourless pearly fat, melts at 63° C. Insoluble in HO, slightly in cold alcohol & ether. Saponification is decomposing this fat, taking away the glycerin & putting in 3KO instead. Glycerine is triatomic so you put ?.=s of a monoatomic body instead KO| C36 H35 O3 KO| C36 H35 O3 KO| C36 H35 O3 Mix hot alcoholic solutions of KO & of stearine and on cooling you get a soap, the glycerine remaining dissolved in the alcohol. Glycerine | Acid A A 3KO In making soap. take a 106 glyceride & potash ley & pass steam thro' it [illustration] When the heat is great enough to melt the tallow a soap is formed. In ordinary soap making a soft soap is made when KO is employed, with NaO a hand soap is obtained. It is easier to make a KO than a NaO soap because it saponifies more easily. It is afterwards made into a NaO soap by salting. KOS + NaCl Yellow soap. Boil tallow or palm- oil with an alkali & add rosin & salt out. Mottled is got from tallow or palm oil, an Fe soap makes the mottling Castile or Marseilles soap is 107 got from olive oil & mottled with FeS. & alkaline sulphides. Chief fats. Palmitine Tripalmitate of glycerin ether. Exists in most fats, especially the softer kinds, in palm & cocoa nut oils May be got from olive oil by cooling Margarine. Supposed formerly to contain margaric acid wh is now known to be a mixture of palmitic & stearic acids. Oleine. Trioleate of glycerine ether Expose olive oil to cold to separate the palmitine & the oleine remains. Natural fats are of 3 kinds 1st solid like tallow 2nd,, semisolid like butter 3d,, liquid like oil They are all lighter than & insoluble in HO, all soluble 108 in ether many in alcohol They occur in the animal & vegetable kingdoms, in all animal fluids except urine Vegetable fats. Cocoa nut oil melts at 20ºC, contains various acids glyceride of coccinic Palm oil. Melts at 27ºC is a yellow butter like substance, 20000 tons of it as imported annually from Africa, it soon becomes rancid, contains palmitine & oleine Vegetable oils may be divided into drying & non drying. Non drying. Colza Drying Linseed croton & castor oils Animals fats. Suet. Fat of oxen & sheep, melted & freed from nitrogenous matter. consists of oleine, stearine & palmitine 109 palmitine Lard contains stearine & palmitine. Human fat is like lard melts at 25° C. Spermaceti. When pure contains cetine, not glycerine but a substance corresponding to it. Cetine C64 H64 O4 = ethal ether C32 H33 O, palmitic acid C32 H31 O3 Sperm & codliver oil are examples of liquid animal fats. Aromatic series. There are several of these radicals Phenyl C12 H5 Benzyl C14 H7 Xylyl C16 H9 Cumenyl C18 H11 Cymyl C20 H13 Phenyl. It is an important series. It contains benzole used in making coal tar colours Phenyl ether C12 H5 O It is got by distilling benzoate 110 of Cu. It is colourless, smells slightly like a geranium it soluble in alcohol. Chloride of Phenyl. C12 H4 Cl. Hydride of Phenyl or Benzol sometimes called Benzine C12 H5 H corresponds to C4 H5 H. Prep. Distil coal tar. [illustration] A vessel filled with HO surrounding the neck of the retort is kept at a temp. of 170° , the temp. at wh benzole distils other substances wh distil at a higher temp. are cooled & fall back into the retort while the benzole distils over. It is used for cleaning white kid gloves & for taking out grease spots. To use it rub the benzole all round the spot without touching it & bring it [illustration] 111 gradually over the spot. It is a colourless, thin oil, of an agreeable odour when pure, solid at 0ºC melts at 5ºC, burns with a smoky illuminating flame increases the illuminating power of gas. It is a good solvent for fats & camphors, it dissolves S.I. & Br readily possibly uniting to some extent with them. Benzyl C12 H5 H Benzyl ether - alcohol C12 H5 OHO When pure & free from HO it is a white crystalline solid substance. Kreosote consists of carbolic, cressylic & probably of some higher acid Phenyl alcohol or carbolic acid. C12 H6 O2. Boils at 185º 112 Found in cows urine, in coal tar. Solid when quite dry & crystallizes in needles, wh melt at 35ºC. It has a disagreeable smell, burning taste, is heavier than HO, in wh it is slightly soluble, it is soluble in alcohol & ether. It is an active poison to animals & plants. It is a strong antiseptic. A coffin filled with carbolate of lime preserved a body for 2 months. Carbolate of lime & sulphite of lime form Macdougal's disinfecting powder. Nitrophenyl ether C12 H5 NO4 Usually called nitrobenzol. It is C12 H5 H having the H replaced by NO4. Prep. Act on benzol by fuming HONO5. It is a yellow oily liquid, solid at 3ºC, smells like oil of bitter 113 almonds, for wh it is used in perfumery & confectionery with advantage since it is not poisonous while oil of bitter almonds often contains hydrocyanic acid. It has a sweet taste insoluble in HO, soluble in alcohol & ether. Used in making anilene. Anilene is NH3 in wh 1 equivalent of H is replaced by phenyl. N |H |H |H N |C12 H5 | H | H To obtain aniline act on nitrobenzol by some deoxidizing agent. That usually employed is acetate of KO. C12 H5 NO4 + 2HO + 47e = C12 H7 N + 27e2 O3 Or by acting with HS. C12 H5 NO4 + 6HS = C12 H7 N + 4HO + 6S Nitrophenyl alcohol C12 H2 (NO4)3 OHO. It is carbolic acid in wh part of the H is replaced by NO4 & has 114 the synonym of carbosotic acid Prepared by the prolonged action of HONO5 on kresote or carbolic acid. It is formed by oxidizing silk, salicin, indigo, alves, gum benzoate & resins. Prep. It crystallizes in brilliant yellow plates, maybe sublimed with care, soluble in alcohol & cold HO, more readily in hot HO soluble in hot HOSO3, is an active poison. May be used in small doses instead of quinine but makes the patients skin yellow. Used to dye silk & woolen. It has been proposed to mix it with As. before selling it in shops as it has an intensely bitter taste, & would be detected. In cases of slow poisoning it would make the skin yellow & thus draw 115 attention Carbosotates crystallize in well defined salts. The acid characted is due to the electronegative character of the radical. Benzyl C14 H7 - ether C14 H7 O. It is an oily liquid & is got by the action of BO2 on benzyl alcohol. Toluol. Hydride of Benzyl, C14 H7 H Obtained from liquid coal tar + tolubalsam. It is colourless & resembles benzol in it properties, is insoluble in HO soluble in alcohol & ether. HONO5 act on it in the same way as on benzol. Benzyl alcohol C14 H7 O, HO It is an oily colourless liquid insoluble in HO soluble in alcohol 116 alcohol & ether. By oxidation it becomes the oil of bitter almonds In the olifine view Benzyl alcohol C16 H6 " HO HO - ether C16 H6 " HO oil of bitter almonds = biatomic ether C14 H6 " OO benzoine is the aldehyd C14 H5 O " HO Benzoic acid C14 H5 O"OO. Oil of bitter almonds: general formula C14 H6 O2. liquid s.g l.043 boils at 180° C. Obtained when almonds are macerated & distilled with HO. It is fragrant oil, transparent very refractive, has a powerful smell is used in perfumery, is not poisonous in itself but often contains hydrocyanic acid When it contains this & is put in contact with lime it is 117 Changed into benzoin Benzoic acid. Occurs in putrid horses urine Obtained by sublimation from gum benzoate. It is volatile, slightly soluble in HO soluble in alcohol & ether. When taken as a medicine it is converted into hippuric & is found as such in the urine. Benzoates are crystalline, when heated they are decomposed into benzoin naphthaline Let us now go back to the phenyl series & consider the coal tar colours. The phenyl series differs from the benzyl by C2 H2 Phenyl C12 H5 or as olifine C12 H4 "H Benzyl C14 H7 Manufacture of benzol. Nitrobenzol 118 Nitrobenzol &c. When coal is distilled for gas it produces various substances, HO & tar distil over along with the gas. Ten to 12 gallons distil over of oil of from 1 ton of coal. It was formerly a waste product & even yet it is sold at a penny to three halfpence the gallon. [illustration] To get naphtha pass steam thro' the tar On a large scale 100 part tar yield Naphtha 9 parts Lead oil 60 - Pitch 31 - Naphtha is nearly the only thing wh comes over with the steam the pitch & dead oil 119 remain in the retort, & the is a afterwards distilled by a common fire. Naphtha is a rough commercial term & signifies a great variety of substances Roughly purified it is used for many purposes. Crude naphtha contains 3 substances. Basic oils Acid oils Neutral hydrocarbons. Basic oils may be got from the naphtha by agitating with HOSO3. They are all compound ammonias. Aniline exists in the basic oils but is not got from them. Acid oils. 120 Take naphtha & shake it with caustic NaO or KO the acid oils dissolve in the NaO or KO & are separated by adding HCl. When separated they form kreosote wh is carbolic acid C12 H6 O2 & cressilic acid C14 H8 O2 Carbolic acid is used in toothache & to preserve timber When acted on by NO5 it forms carbosotic acid. Carbolic acid C12 H6 O2 Carbosotic - C12 H3 (NO4)3 O2 Carbosotic acid is a strong dying agent. Dissolve a little in a little hot HO & then add some cold, you get a solution excellent for dying silk yellow. Wet the silk in HO & rinse in the carbosotic acid. This is the first use of coal tar in colouring substances. 121 Neutral hydrocarbons. Chiefly benzol & its homologues. The benzol is distilled by passing it thro a cistern of HO at 177°. Benzol is very volatile, & it is possible to burn air charged with it [illustration] Dried air is passed over heated asbestos B to heat the air, & thro' some benzol in A the air then may be burned as at C. It may be used for setting enemy's ships on fire by pouring it on the HO & throwing some K on it wh takes fire & inflames the benzol. Nitrobenzol. C12 H5 NO4 Benzal acted on by NO3. It is used in perfumery. To get colours from it, it is first 122 made into aniline C12 H5 NO4 + 2HO + 4Fe = aniline C12 H7 N + 2Fe2 O3 Aniline C12 H7 N It is a compound ammonia A short time ago 1/2 lb aniline would have been thought very valuable in a laboratory & probably none possessed so much as except perhaps who was making researches upon it It was a short time ago sold for a few shillings per gallon but has now risen in price in consequence of the demand for it & is now a few shillings per pound. From aniline are made Mauve or purple Violine Rosein Magenta or Rosaniline Azuline 123 These tar compounds are capable of producing colours [illustration] Put 2 drops of pyroline in a jar & shakes up- moistens a piece of pine wood in the shape of a dagger with HCl & put it into the jar, the moistened point becomes red. Mauve. [illustration] Put some aniline ( a very little will do ) into a bottle & add a little acetic acid to assist its solubility. you get a solution of acetate of aniline, pour into HO & add chloride of lime- [illustration] it becomes brown at first but afterwards becomes purple. On a large scale it is prepared by acting on sulpate of aniline by KO, 2CrO3 in equivalent quantities. You get a dark powder, wash 124 this with coal tar & dissolve it in alcohol The alcoholic solution is evaporated to dryness & you get a green powder wh is soluble in alcohol. It is from the alcoholic solution that we dye the colours. Pour a little tartaric acid into some hot HO & pour in a small quantity of alcoholic solution of mauve. Wet the silk to be dyed & put it in. The chemistry of the colour is not well understood. It is easily tested by HOSO3. Add a little strong HOSO3 to a little mauve & you get a dirty green solution. Add a little HO & you get a fine blue. Add a good deal of HO & it becomes mauve again 125 Magenta. The true red colouring matter is rosaniline. In making it take a weak deoxidizing agent instead of a strong as with mauve. [illustration] Take a small quantity of anhydrous bichloride of In as that in the sealed tube A, pour it into the flask B, add aniline cautiously, it forms a solid compound, gradually add more aniline till you have an excess Heat cautiously over a lamp The action is violent. Any weak anhydrous Acetic acid & As O5 are also used. It is necessary to boil off the excess of aniline. Blue de Paris a azuline Is got from carbolic acid 126 Put a very little mauve or magenta on a sheet of paper hanging up & spout alcohol from a washing bottle on it, the colour dissolves running over the paper. The chemistry of some of these colours is known Rosaniline is a triammonia 3 atoms of H coalescing into one. NH3 x 3 = N3 H9. The compounds radical substituting H is unknown. Let R signify rosaniline. R unites with 1 or 3 atoms of acid. R + 1A gives the strongest colour R + 3A - a less strong -. R is colourless by itself, but when dissolved in alcohol or acid it has a strong colour. Magenta is acetate of R. In the case of the purples we must use hot HO in dying but in the case of carbosotic 127 acid & magenta, cold will do. All animal fibres take up these colours readily. Cotton does not & you must treat it with tannic acid. Purple & violine are not true ammonias, they seem to be neutral In cotton printing, albumen is put on the place wh is desired to be coloured & exposed to steam & dried. It is then rinsed in a solution of the dye as silk is the vegetable fibres do not take it up but the albumen does. Malic acid 2HOC8 H4 O8 It is bibasic. It occurs frequently in unripe fruits, in the apple but is got most easily from the berries of the mountain ash. It has a strong acid, agreeable taste 128 When heated it is changed into fumaric acid fumaric acid. 2HOC8 H2 O6 . It is readily obtained from Iceland moss or malic acid. It forms micaceous scales wh require 200 parts of cold HO for solution. Tartaric acid. General formula C8 H6 O12 = 2HOC8 H4 O10. Occurs in the tamarinds & mountain ash berries, but is got chiefly from grapes. The substance called argol found in wine casks is bitartrate of KO. It is obtained in rather a curious way from this by converting it into neutral tartrate of lime. Argol Ko } Ho } T Add CaCl & lime if you added CaCl alone you would get CaO } HO } T but by adding lime too you get CaO} CaO} T 129 add HOSO3 to this CaO} CaO} T + 2HOSO3 = Ho} Ho } T + 2CaOSO3 . It crystallizes in oblique prisms is colourless transparent, of an acid agreeable taste, soluble in HO alcohol & wood spirit, its solution especially when hot exerts a right-handed rotation on polarized light There are two different crystalline forms. Sometimes, especially in the grapes of the Vosges, an acid of the same formula as tartaric acid called racemic. Racemic acid is rather difficult to get as it only appears sometimes. Racemates crystallize differently from tartrates & have a different number of atoms of 130 HO of crystallization. It was supposed to be an isomer of T & to have its atoms arranged differently. T produces a right-handed rotation of polarized light Racemic acid a left handed one. The crystals were unsymmetrical but in different directions. Pasteur showed that when put together they are symmetrical It is thus the same acid in different crystalline forms. Tartrates are used largely in medicine & the arts. Used in calico is printing. If in calico printing you wish a part to remain white you use tartaric acid as a resist to the mordant wh is always used. The mordant forms a very soluble 131 soluble tartrate & does not remain on that place, & so the dye does not adhere to that place. In all cases of bibasic acids as tartaric acid where you have 2 HO thus HO } HO } T you may replace 1 HO or both. HO } HO } T KO } HO } T KO } KO } T NaO } KO } T. Argol is cream of tartar or bitartrate of KO HO } KO } T. It is hard white & crystalline difficultly soluble in cold HO, more soluble in hot HO, has a sour taste & feels gritty to teeth. When heated it forms black flux. Bitartrate of KO is extensively used in medicine as a diuretic. Neutral tartrate. It is deliquescent. All acids even tartaric acid, convert it into cream of tartar. Rochelle salts KO,Na OT + 8HO. 132 KO } NaO } T crystallizes with 8Ho, in large clean, rhombic prisms, is used in medicine. forms the basis of seidlity powders. Tartar emetic. It is a double salt corresponding to cream of tartar. KO } SbO3 } T + aqua. Mix 3 parts SbO with 4 cream of tartar, make into a paste, digest It is soluble in 15 parts HO, is a violent emetic in larger doses acts as cathartic poison. Kinic Occurs in chinchona bark. Crystallizes in colourless prisms wh melt at 155°C. Solid on cooling at a higher temperature it is decomposed. Tribasic acids. Citric acid C12 H8 O14 . 133 Occurs in the lemon, gooseberry cherry & tamarind. As citrates in the tumours of the Jerusalem artichoke. Only the fruits wh contain acid united with alkali become sweet on ripening the acid being converted into sugar. Where acid is free as in the lemon, it does not become sugar. It is prepared like tartaric acid but is more easily made since it has no tendency to become uncrystalline as tartaric acid is apt to do. It crystallizes in large colourless prisms, very soluble in HO & alcohol, not in ether. It is used in calico printing both as a resist & to heighten the colours. Heated to 175° it is decomposed & becomes 134 C12 H8 O14 - 2HO = C12 H6 O12 Fused with lime it forms oxalate & acetate of lime. C12 H8 O14 + 2HO from the HOCaO = C4 H2 O8 + 2(C4 H4 O4). Citrates are necessarily a large class. Citric is tribasic acid. HO | HO | HO | C12 H5 O11 . Aquinitic acid. Found in aconitum Forms warty crystals easily soluble in HO. It is the acid in opium, it is a white silvery acid, loses its HO of crystallization at Gallic acid 2HOC14 H6 O10 It is bibasic, is contained in gull nuts in mango seeds in sumach. 135 It is got artificially by the splitting up of tannin when it is boiled. It is white silky crystalline. soluble in 3 parts of boiling HO & 100 cold HO, with a salt of Fe it forms ink. When heated to 210° it is decomposed, it loses C2 O6 & becomes pyrogallic acid. Pyrogallic acid C12 H6 O6 = Used for estimating O. With a little alkali it absorbs O completely. Tannic acid. Tannic acid is a general name for organic substances wh precipitate gelatine & form leather. It is contained in the leaves & bark of most forest trees, especially the oak, elm in the whortleberry, tea, coffee. Tannic acid except that from coffee. Precipitates protosalts 136 of Fe a blue black, or in acid solutions of a dark green. Some like tannic acid from catechu precipitate it a dark green. Gallotannic acid C54 H22 O34 Obtained from gall nuts. Take an ethereal solution of gall nuts, it divides into two parts the upper part is gallic & the lower tannic acid. Obtained thus it is a white, crystalline body soluble in HO, soluble in weak alcohol & ether. The aqueous solution absorbs O Gallotannic acid should be called tannin, it is a glucoside. Act on it by acid wt brings HO into play. 137 C54 H22 O34 + 8HO = 3(C14 H6 O10) + C12 H12 O12. Boil tannic acid with HCl, It is not certain whether it is a bi or tri [crossed out] basic acid. It is used in medicine as an astringent. Ink. Gallotannate of Fe. Take 3/4 lb of bruised gall nuts, dissolve them in 1 gallon of cold HO, add 6 oz of FeOSO3 . 6oz of gum arabic 5 drops of kreosote to prevent it moulding, digest at common temps. for 2 or 3 weeks, shaking frequently. Ink stain = Fe2 O3 To take it out heat with a little oxalic acid. it forms soluble oxalate of Fe. Gallotannate or tannate of gelatine. The object in tanning is to unite the skin with acid to prevent putrefaction, & yet leave the 138 skin supple. The time required varies, as, the hippopotamus skin is 2 inches thick & required nearly a year. While the kid's skin is only a fraction of an inch thick & requires only a few weeks. The processes are, 1st. Place the skin in lime, the root of the hair is attacked by it Remove the hair with a knife & open the pores by placing in a pit of HOSO3 & HO. Layers of skins & oak bark are laid in pits for 3 months, they are then taken out & fresh bark is added, the skins are then placed in again so that the one wh had been at the top is now at the bottom & allowed to remain there for some time. It is strange that no quicker 139 process can be employed The use of hydraulic presses to force the liquor into the pores, & of stronger solutions does not make such good leather If Simon the tanner of Joppa came back to this world he would find the trade precisely as he left it. In white kid gloves no tannic acid is used, it is protected by aluming Tawed leather The skins are cleaned & treated with Al2 Cl3 made by mixing alum & NaCl, & then rubbed with oily substances. In chamois leather as much oil is put in as possible. Compound haloid radicals. The chief representative is cyanogen C2 N. 140 It has perfectly parallel characters with any other haloid. Cl} 4 Cl} hyrdo Cl} chloride Cl} Cl} Cl} vols H} chloric acid K} of k I} O} C2N} 4 C2N} hydro C2N} cyanide C2N} C2N} cyanic C2N} vols H} cyanic K} of k I} O} acid acid Cl} Cl} 4 vols Cl} H} hydrochloric acid Cl} K} chloride of K Cl} I} Cl} O} C2 N} C2 N} 4 vols C2 N} H} hydrocyanic acid C2 N} K} Cyanide of K C2 N} I} C2 N} O} Cyanic acid Cyanogen was the 1st,, compound radical clearly established in organic chemistry. Cyanogen C2 N. = 26. if it has 2 vols 52 if 4 vols. S.G of gas 1.806. Symbol. Cy. It is monoatomic. The reason for this is that though N is pentatomic but is joined to 2 of C wh is biatomic & has thus 4 atoms filled up & only 1 left. N,,,,, - C2,,, = C2 N, Cy has the power of doubling itself & forming other radicals. Cy C2 N Bicy. C4 N2 Tricy C6 N3 Mellan C18 N13. 141 Cy is best got by heating cyanide of Hg in a tube. This corresponds to the method of getting O. [illustration] HgO2 heat = Hg + 2O HgCy2 - = H8 + 2Cy. A black substance is left in the tube wh has the same composition as Cy. Prop. It is colourless, has a peculiar prussic acid & odour at a pressure of 3 atmospheres it becomes liquid & the liquid solidifies at -35°C, it burns with a purple flame, producing CO2 & N, it is soluble in HO & alcohol the latter takes up 22 vols. of it The solutions decompose & urea is formed. Urea is an anomalous cyanate of NH4 . NH4 O C2 N K unites with Cy as it does with Cl. 142 Hydrocyanic or prussic acid. HCy= 27 s.g of the gas 0.9476. 4 vol vap. formula. Acc. Probably never found free but various seeds give it by distillation owing to the action of ferments on it. Almonds, peaches apricots, the leaves of peaches & the kernels of plums yield it. Mode of preparing it. Distil K Cy with HOSO3. pass over CaCl & condense by ice. s.g of liquid 0.967 boiled at 26ºC solid at -15ºC Has a smell like bitter almonds is an intense poison is soluble in all proportions in HO & alcohol. Does not keep well, after a while perhaps 2 or 3 years it becomes black & is apt to explode, you then break it under HO to prevent this, 143 Aqueous solution of HCy. Prep. Distil yellow prussiate of [illustration] KO & HOSO3. you get a solution of unknown strength. The medical strength is 2 percent of prussic acid. The London pharmacopia process for getting a solution of known strength, is. - Suspend 48 1/2 grams of cyanide of Ag in 1 oz HO & add 39 1/2 of HCl. An extemporaneous solution of HCy may be made by adding KCy to T & stirring, you get bitartrate of KO & a solution of HCy. The aqueous solution is more permanent if you add a little mineral acid. Solution of HCy under the action of strong acids or alkalis decomposes 144 decomposes into formiate of NH4 . C2 NH + 4HO = NHOC2 HO3 HCy is easily tested. Test. Take FeOSO3 wh has been a little rusted in air. If not rusted add a few drops of a persalt of Fe. Add HOKO to precipitate the oxide of Fe. Add HCl to neutralize the KO & take up the Fe. Add these to the suspected solution & if HCy be present prussian blue is produced. The rationale of this process is HCy, KO & a salt of Fe make yellow prussiate of KO, if you add HCl to make a solution of Fe prussian blue is produced. Another test. Put the suspected solution in a watch glass & add a drop or 2 of sulphide of NH4 to neutralize it, put over it another watch glass & [illustration] 145 evaporate it to dryness in a hot water bath. Add perchloride of Fe. You are producing sulphocyanide of K wh has the property of striking a blood red colour with perchloride of Fe. When used as a poison it quickly escapes from the system on account of its volatility so that 3 days after you cannot detect it in the body. Cyanides resemble the haloid salts of Cl & are got in the same way. To get KCl HCl + KO = KCl + HO - KCy HCy + KO = KCy + HO. On a large scale KCy is got by heating yellow prussiate of KO with KOCO2 . yellow prussiate of Ko. K4 Fe2 Cy6 K4 Fe2 Cy6 + 2KOCO2 = 5KCy + KoCyO + 2Fe + 2CO2 . You can prevent the 146 formation of KOCyO by adding a little C. K4 Fe2 Cy6 + 2KOCO2 + 2C = 6KCy + 2FeO + 2CO2 + 2CO. Dissolve it out & evaporate it down. It is use largely in electrotyping to dissolve Ag + Au, & as a reducing agent. Bicyanide of H8 - H8 Cy2 . Boil 4 parts prussian blue 3 of peroxide of H8 & 4O of HO. It crystallizes in prisms, soluble in HO more difficultly soluble in alcohol, very poisonous. Alkalis do not precipitate H8 O from it. Cyanide of Ag. AgCy. Prep. Add KCy to a salt of Ag. It unites with KCy & readily forms double salts. Haloid ethers of Cyanogen. Cy unites with ethyl as Cl does. 147 Prep of cyanide of ethyl. Add KCy to C4 H5 I. C4 H5 I + KCl = C4 H3 Cl + KI prep of chloride of ethyl C4 H5 I + KCy = KI + C4 H5 Cy cyanide of ethyl. We find the Cy has gone in more intimately to the ethyl than we would suppose On this account These compounds are called nitriles. Cyanide of ethyl. C4 H4 C2 N. It is a colourless liquid, mobile of an agreeable but garlicky odour Does not comport itself with alkalis like ordinary ether. It is soluble in alcohol & ether. C4 H5 Cl + KOHO = KCl + C4 H6 O2 propionate of KO C4 H5 C2 N + KOHO + 2HO = KOC6 H5 O3 + NH3 Propionic acid one above C4 H5 in the series. Act on a nitrile by an alkali & you get the acid one above it in the series. 148 Double electro negative cyanides. The cyanides form a remarkable series of salts when certain metals combine with them, especially Fe 4KCy + 2FeCy = yellow prussiate of KO. If you get an insoluble cyanide of Fe by adding FeOSO3 to KCy & add excess of KCy to the insoluble salt it gradually dissolves & you get a solution of yellow prussiate of KO. Suppose the Fe has a formed a compound radical with Cy. Fe2 Cy6 called Ferrocyanogen. Yellow prussiate of KO is this + 4K & crystallizes with 6HO. Add HCl to this Fe2 Cy6 + 4K + 4HCl = 4KCl + Fe2Cy6 4H. [illustration] Has a solution of yellow prussiate of KO in the tube add HCl & ether 149 Fe2 Cy6 4H = hydroferrocyanic acid is insoluble in ether. A bluish white compound is formed. Occurs in crystalline plates, soluble in HO, is readily precipitated by ether. The solution quickly becomes blue, when boiled HCy is evolved. When the 4H are substituted by 4K you get yellow prussiate of KO. Yellow prussiate of KO. It is used in the arts largely. Prep. Cast off woolen garments, horns & hoofs of cattle, flesh & blood any thing that contains N are mixed with scrap Fe & Montreal pearl ashes & heated. Fe2 Cy6 4H = Hydroferrocyanic acid 150 Fe2 Cy6 4K = yellow prussite of KO. It is formed when a substance containing N is fused with KOCO2 & Fe or allowed to digest on Fe. Occurs in lemonyellow tabular crystals soluble in HO not soluble in alcohol, of a bitter taste & purgative but not poisonous, If you take away 1 of K & make red prussiate it becomes intensely poisonous Yellow prussiate is tetrabasic. Fe2 Cy6 { 2Ba { 2K Fe2 Cy6 { 3Cu { K. We have doubled the formula on this account. [illustration] Add yellow prussiate to CuOSO3 & a mahogany red is produced. Ferrocyanide of NaO. Na4 Cy6 + 10HO. Ferrocyanide of Fe. Take a solution of Fe OSo3 & add yellow prussiate, you get a 151 a precipitate, while at first but wh absorbs o from the HO & becomes blue. It has this composition. Fe2 Cy6 {3Fe {K. Add yellow prussiate to a persalt of Fe & you get prussian blue at once Fe7 Cy9 . Prussian blue Prop. It is a beautiful blue of a coppery lustre when dry, after being washed in HO it may be dissolved in oxalic acid. This when thickened with gum forms steven's blue ink. It is readily decomposed by alkalis. Add caustic NaO or KO to prussian blue, it produces a reddish colour & forms oxide of Fe. Put a cloth dipped in a salt of Fe into prussiate of KO & it is dyed blue. 152 Ferridcyanogen. It has the same composition as ferrocyanogen but is tribasic instead of tetrabasic Fe2 Cy6,,,, radical of yellow prussiate Fe2 Cy6,,, - red - Pass Cl this is a solution of yellow prussiate. Fe2 Cy6 4K + Cl = KCl + Fe2 Cy6 3K. Hydroferridcyanic acid. Is got in the same way & has much the same properties as Hydroferrocyanic acid. Add HCl to red prussiate of KO & add ether. Or add HOSO3 to Ferricyanide of Pb. Crystallizes in brown needles, better easily decomposed. Ferridcyanides are generally red. They are distinguished from ferrocyanides by giving no precipitate with perchloride of Fe. 153 yellow prussiate with Protosalt of Fe gives a white precipitate Red prussiate - blue yellow- persalt - blue Red- dark brown. Ferridcyanide of K. Is generally called red prussiate of potash. Crystallizes in ruby red right rhombic prisms, soluble in HO insoluble in alcohol, gives a precipitate with metallic salts in wh all 3 of K are replaced by metal. K3 Fe2 Cy6 + 3AgONO5 = 3AgFe2 Cy6 + 3KONO5. Turnbulls prussian blue, is prussian blue got from red prussiate & FeOSO3. Nitroferrocyanides or nitroprussides Fe2 Cy6,,,, Fe2 Cy6,,, Fe2 Cy5 NO,, Nitroprusside of Na. 154 Made by the action of NO5 on Nitroprusside of K. When you add sulphide of NH4 to this a beautiful purple colour is produced wh is very transitory. It is the best test for S. Put a lock of hair into a test tube & dissolve it in caustic NaO or KO. heating it to aid the solution. You must always convert the S into an alkaline sulpide. Adds a good deal of HO so as not to act on the filter & filters it. Adds nitroprusside of Na & a deep purple is produced showing the presence of S in the hair. The nitroprussides give a salmon coloured precipitate with salts of Fe. Oxides chlorides & sulpides of Cy. It must be recollected that there are 3 sorts of Cy. Cy Cy2 & Cy3 . 155 Cyanic acid CyO. Cyanates are easily got by heating a cyanide with an oxide such as of Pb. CyO is not so easily got. Distil cyanuric acid & collect the product in a freezing mixture. It is colourless mobile A drop on the skin produces a sore. Above 0°C it changes into a procelain like mass. Cyanates. General formula MOCyO corresponding to MOClO. They bear heating to redness without decomposition. You do not obtain CyO by acting on them by acids Cyanate of KO. KOCyO. Prep. Heat prussiate of KO with 156 an oxidizing agent such as MNO2 . It is soluble in HO, the solution is decomposed when heated. KOC2 NO + 3HO = NH3 + HO} KO} C2 O4 Cyanite of NH4 . NH4 OCyO. Prep. Act on cyanate of KO by NH6 OSO3 It is white crystalline, soluble in HO & alcohol, it is not urea, wh is an anomalous cyanate of ammonia NH4 OC2 NO. Chloride of Cy. NCO2 Cl. vap. density 2.124 Act on cyanide of H8 by Cl. Colourless, very poisonous gas, of a disagreeable pungent small, at -53°C it becomes liquid. In closed tubes it becomes double CyCl = Cy2 Cl2 . Sulphocyanogen Sulphocyanates correspond to cyanates S playing the part of O. 157 CyO CyS . It has never been got in a separate state. A yellow compound got, has been called CyS but does not behave as such. It forms sulphocyanates wh are interesting because NaCyS at least exists in the saliva man & the sheep. Put some saliva in a watch glass & add perchloride of Fe. Sulphocyanide of K. KSCyS. Prep. Heat together yellow prussiate of KO1 KOCO2 & Bicyanogen Cy2 C4 N2 . Not known in its separate state Bicyanic acid Cy2 O2. It has the synonym fulminic acid . 158 2 HOCy2 O2 Fulminic acid Not known free. Fulminate of Hg. 2HgOCy2 O2 Prep. Heat HgONO5 & alcohol together It crystallizes in white needles very explosive not soluble in cold HO but soluble in hot. Add Zn to the solution & Hg is deposited & fulminate of Zn remains. Act on fulminate of Zn by Cl, & it becomes chloride of Cy & C2 (NO4 ) Cl3 chlor-carbasotic acid. It is possible that 1/2 the N in fulminic acid may not be present as Cy. It is closely allied to Cy. Persulphocyanic acid. Little soluble in alcohol & ether With alkalis it forms soluble 159 & with heavy metals insoluble salts. Bichloride of Cy It is formed when CyCl is left in a sealed tube. It is a colourless liquid boils at 15ºC. Tricyanogen. Cy3 . Forms cyanuric acid Cy3 O3 3HO. Got by the action of terchloride of Cy on HO. CyCl3 + 6HO = 3HOCy3 O3 + 3HCl Transparent crystals, no smell or taste, reacts acid. Cyanurates Cy3 Cl Expose anhydrous Crystallizes in brilliant needles wh melt at 140ºC boil at 190ºC Smells like the excrements 160 of mice, difficulty soluble in HO readily soluble in alcohol & ether. Characters of Cy. Cy has the character of a radical closely resembles Cl but has the power of duplicating & triplicating itself & forming other radicals Unites so intimately with metals as to appear to form radicals Polymerizes itself. Mellone C18 N13 Organic bases representative of alkalis & metallic oxides in organic chemistry. The bases resemble NH3 They act like NH3 on hydracids without expelling the H. They almost all unite with PtCl2 to form double salts. It is believed that they are all constituted on the NH3 type. 161 The general name is amines. NH3 N | | H | H | H Primary N | | A | H | H Secondary N | | A | B | H Tertiary N | | A | B | C Monamines Example N | | C4 H5 | H | H N | | C4 H5 | C2 H3 | H N | | C4 H5 | C2 H3 | C10 H11 All these are true ammonias, form salts with hydracids & take up HO when they unite with oxyacids. They are volatile alkalis & have a peculiar odour generally resembling NH3 . The replacing radicals are generally the common compound radicals. C12 H3 Cl2 | H | | N Chlorphenylamine C12 H3 ( NO4 )2 | H | | N dinitrophenylamine When you have such substitutions as these, electro negative 162 bodies replacing H, the basic power of the body is much impaired & in some cases destroyed. Glycocol C4 H3 O4 | H | H | | N neutral Benzamic acid C4 H5 O4 | H | H | | N Production of these compound ammonias. They are produced by the action of an iodide of an alcohol radical on NH3 . N | | H | H | H + C4 H5 I = N | | C4 H5 + I | H [cross out] | H Or by deoxidizing a nitro compound as in aniline* Ethylamine s.g 0.696 boils at 18.7°C It is a colourless liquid of an ammonaical odour, its causticity is nearly equal to that of KO. It blues red litmus, neutralizes powerful acids, raises a blister * C12 H5 ( NO4 ) + 6HS = N | | C12 H5 | H | H + 4HO + 6S. 163 on the tongue, drives NH3 from its salts Tri It is colourless liquid, inflammible slightly soluble in HO less so than ethylamine. Act on this with C4 H5 I, & you get iodide of ethylammonium a compound corresponding to NH4 I. N | | C4 H5 | C4 H5 | C4 H5 + C4 H5 I = N( C4 H5 )4 I. Act on the last body by AgO & you get AgI + N( C4 H5 )4 O corresponding to NH4 O. Oxide of tetrethylammonium You cannot distinguish it from KO in its chemical characters It acts as a caustic & forms a soap with fats. It precipitates metallic oxides like KO Add it to CuOSO3 & CuO is precipitated & sulpate of tetrethylammonium 164 tetrethylammonium formed In coal tar there is a remarkable set of organic bases You get them by treating with HOSO3, decomposing by KO & distilling Pyridine C10 H5,,, N Picoline C12 H7,,, N Lutidine C14 H9,,, N Lecoline C18 H7 N Lepidine C20 H9 N Put a mixture of Lutidine into a sealed tube into hot HO they being less soluble in hot than cold HO float on the top of the liquid on the tube Diamines. Where 2 atoms of NH3 have coalesced unto one. N2 | | H2 | H2 | H2 you may have primary, secondary & tertiary diamines N2 | | A2 | B2 | C2 165 Urea belongs to this class. Common urea. N2 | | C2 O2 | H2 | H2 Urea forms from 77 to percent of human urine Prep. Evaporate urine till it becomes syrupy & add an equal volume of colourless NO5 of s.g 1.35. It forms nitrate of urea, separate the acid by BaO & the urea by alcohol & crystallize. Artificial urea. KOC2 NO + NH4 OSO3 = KOSO3 + NH4 OC2 NO. Prop. It crystallizes in 4 sided prisms like KONO5 Soluble in HO & alcohol, when heated it is converted in great part into NH3 & Cyanuric acid. Unites with acids & forms salts. N2 | | C2 O2 | H2 | H2 N | | C2 O2 | C4 H5 | H2 Triamines. N3 | | H3 | H3 | H3 Organic alkaloids. It was long the opinion of chemists that vegetables only produce neutral & acid substances. In 1803 got an alkali from opium & in 1804 got another alkali. yet it was 12 years after, that the opinion became prevalent that alkalis were produced by vegetables. General properties. They behave like NH3 . They neutralize acids & form salts. They are all solid or liquid, generally fixed a few 167 are volatile. Some are soluble in HO some in alcohol. The sulphates, nitrates, chlorides & acetates are soluble. The tartrates They are generally violent poisons or active remedial agents. They may be divided into 3 classes A. Volatile alkalis free from O. B. Bases readily soluble in alcohol sparingly in HO. C. Bases soluble both in HO & alcohol. A. Example. Nicatine. Prep. Macerate tobacco in HO. The malate of nicotine dissolves Ni = nicotine. M = malic acid NiOM + KO = Ni + HO The Ni distils over. B. Prep. These bases are united 168 with acids such as Kinic acid or meconic acid. Add HCl the chlorides are dissolved out, add lime wh. forms CuCl & precipitates the alkali. Take it up by & crystallize from alcohol C. Dissolve in HCl & form chlorides. Neutralize the chlorides by NH3 & precipitate by oxalate of ammonium. Decompose by BaO & crystallize. Conia is a secondary monamine N | | C16 H14 | H. It is prepared from hemlock chiefly from the seed. It is a colourless oil of penetrating odour & burning taste it is strong poison, in presence of HO it acts strongly alkaline, difficultly soluble in HO. 169 especially when warm, readily soluble in alcohol & ether. Act on it by C4 H5 I & you get ethyl conia. Sparteia. A tertiary monamine N | C16 H13,,, Got from broom, heavier than HO, the liquid boils at 287°C. Alkaline & narcotic poison, has an odour like aniline nicotine, it is a diamine C20 H14 | N2 Occurs in tobacco chiefly in combination with malic It is a colourless liquid, absorbs O readily & becomes brown, has a burning taste, slight-odour of tobacco, is intensely poisonous There is from 2 to 7 Percent in tobacco. The mild kinds of tobacco as 170 Havannah used for smoking contain the least quantity, those sorts used for snuff contain most. The strength of snuff is due to nicotine, its pungency to ammonia salts. Snuff. The leaves of tobacco are allowed to ferment for 18 months. During this time there is a considerable absorption of O & the temp. often rises to 100°. They are then ground & sifted. In fermenting 2/3? of the nicotine is destroyed, NH4OCO2 is formed & a volatile oil to wh the aroma is due & 2 P.C. of nicotine remains. Alkaloids in opium. They are numerous. Morphia C34 H19 O6 N probably a monamine. 171 Codeia C36 H21 O6 N Thebeia C38 H21 O6 N Papaverin C40 H21 O6 N Narcotin C46 H25 O14 N. Narcein C46 H29 O18 N Opianine Pseudomorphine & phorphyroxine Morphine In crystallizing it takes 2HO. Occurs in opium in combination with mechonic & sometimes sulphuric acid. It is present in from 6 to 12 PC. Smyrna opium contains most, Crystallizes in brilliant prisms, taste slightly bitter, has a slight alkaline reaction when heated it parts with its HO of crystallization & at a higher heat is decomposed. HO dissolves 1/1000th part of its wt of it it is readily soluble in 172 alcohol slightly in ether It is a strong narcotic poison when heated with soda lime it becomes methylamine. Muriate of morphia. It crystallizes with 6HO in fine silky prisms, soluble in HO & alcohol. When impure it crystallizes in large crystals, the purer it is, it is more difficultly crystallizable. It forms double salts with PT Cl2 . Acetate of morphia It is a deliquescent salt, crystallizes in thin needles. Sulphate of morphia Salts of morphia are largely used in medicine. 173 5 grains to the ounce are administered like laudanum in small doses. Though less powerful than laudanum. Test. salts of Fe2 O3 3SO3 give a blue colour with it, concentrated NO5 a red colour at first fading to yellow. Conine Crystallizes with 2HO. Occurs in opium to the extent of 1 P.C.. Though homologous with morphia it is not analogous to it in its properties. Soluble in 8 parts cold HO & 17 hot. Melts at 150°C. Decomposes at higher temperatures is poisonous, produces tetanic convulsions like strychnine. 174 Papaverin Is not poisonous. Narcotin Is present from 6 to 8 PC in opium Crystallizes in small rhombic prisms, little soluble in alcohol or ether. Has very feeble alkaline properties many of its salts are decomposed by HO. Is poisonous. 2O grains will kill a dog. There are 3 homologues of narcotine in opium. Alkaloids in chinchona bark There are four. Quinine C40 H24 O4 | N2 Cinchonin C40 H24 O2 | N2 Chinidin C36 H22 O2 | N2 Arcin C46 H26 O8 | N2 They are all diamines. They are found united in cinchona bark with kinic & kinotannic acid. 175 Quinine Found chiefly in the yellow bark in about 3 1/2 P.C. Crystallizes in silky needles from ether, as a white curdy precipitate from its salts, soluble in ether, in 200 parts boiling HO, more soluble in lime water. Readily soluble in alcohol & ether. Intensely bitter, alkaline, melts at 120°C. Unites with acids so as to form 2 classes of salts. The pill used by Dr Livingston in cases of African fever & wh. never fails if the patient be removed to a higher district. 3 to 4 grains resin of julap 3 to 4 - calomel. 3 to 4 - quinine A drop or two of tincture of cardamums to dissolve the resin & 176 form the bolus. It ought not to purge but to occasion gentle movement Sulphate of quinine It unites with 1 atom of HOSO3 , crystallizes with 7 HO in long brilliant prisms, easily loses 5 HO, difficultly soluble in pure HO. Acid salt Q HO SO3 . Used in medicine, add a drop or 2 of HOSO3 to assist its solubility. It is often adulterated with CaOSO3 sugar, calomel, fats, starch, & salicin. To detect adulteration, burn a portion if CaOSO3 is in it, the CaOSO3 remains. If with calomel or sugar you can smell them. If not completely soluble in dilute HOSO3 it contains fats or starch. If salicin be mixed with it. 177 dissolve in 6 times its wt of HOSO3 add 12 parts HO, salicin will be precipitated. Cinchonine. Found chiefly in the grey bark Crystallizes in large anhydrous prisms, soluble in alcohol & ether The salts are intensely bitter, precipitated by gall nuts, heated with KO it becomes Chinodin or quinidine [crossed out] Brilliant prisms soluble in alcohol difficulty in ether Aracin. Found in China cusco. Alkaloids of strychnine family. found in seeds & bark of nux vomica in the 178 Ignata bean. Contains 2 alkaloids Strychnine C42 H22 O4 N2 Brucin C46 H26 O8 N2 Colourless 4 sided prisms, scarcely soluble in alcohol or HO, intensely bitter, soluble in aqueous alcohol when boiling, frightful poison Nitrate. have been used in medicine Tests. Add to the suspected solution Ko2CrO3 & HOSO3, it it produces a violet blue, passing to red. Brucin With 8HO. Crystallizes in colourless prisms 4 sided insoluble in HO & ether 179 readily in alkalis with strong oxidizing agents it forms methylic ether. Alkaloids of the solinacia family. There are 3. Nicotin Hyocyanin. - Atropin C34 H23 O6 N. Occurs in atropa. White, sharp bitter taste soluble in HO & alcohol. Fuses, & decomposes at higher temps. Salts decompose readily. Violent poison, dilates the pupil of the eye. Salts are soluble but difficulty crystallizable Hyocyanin. Has properties similar to atropin. Veratrin C64 H52 N2 O10 18 180 Found in veratrum, produces sneezing is a violent poison. Dervin. C60 H46 N2 O6 Delphinine C64 H32 N2 O4 Colchecine Aconitin Alkal Caffeine or theine. Found in tea & coffee & paraguay tea. In 3 quarters of the globe men have derived a beverage wh they take about the same time of the day. From plants not only of the same species but of a different order They all contain the same alkaloid theine or caffeine call it caffeine. Caffeine C16 H10 O4 N4 tetramine you may view diamines or tramines as monamines. N2 | | H2 | H2 | H2 maybe = N | | NH4 | H | H N | | NH3. | H | H | H In wh the radicals of compound 181 ammonias replace the H Theine or Caffeine. Occurs in tea & coffee. Prepared from tea by subliming it. Crystallizes in thin brilliant needles 177°C sublimes at a higher temp. Difficulty soluble in cold HO, is a weak base its salts are decomposed by HO. In large doses it produces increased action of the heart. irritability of temper If you take 3 grains of theine a day about 2 cups night & morning you [crossed out] may retain you usual temper & state of nerves. If you take 4 or 5 grains it produces irritability of temper & nervousness. If you feel in a nervous state 182 without being able to account for it, it us very probably from this cause. To cure it, take chocolate instead of tea or coffee for some days when it will most probably be cured. Theobromine Occurs in cocoa. It is methyl theine. Hydrates of Carbon Under this head are included all bodies wh have the genera formula CmHnOn Such bodies are starches, sugars gums, bodies wh have a neutral or indifferent character. Dilute acids convert most of them to grape sugar Acts on sawdust by HOSO3 & it is converted into grape sugar. Oxidizing agents convert them to oxalic acid. 183 The views of their chemical constitution are not certain They are at present supposed to be alcohols If the H & O be not present as HO it is in a form nearly approaching it. Take grape sugar for instance C12 H14 O14 It has the same volume as 14 atoms HO frozen to ice the C occupying no appreciable bulk When dissolved it occupies the same volume as 14 atoms of liquid HO. The H8-O comport themselves in solution as HO & when solid as ice. Cellulose C36 H30 O30. It is the basis of vegetable structures. You have it nearly pure in cotton wool. Occurs in the sap of growing vegetables. It is the same in composition from whatever source derived 184 Is nearly pure in the pith of elder rice paper, linen & cotton. Prop. It is a white, solid, sometimes parent Its s.g is a little higher than that of Ho. Its composition is the same but its physical characters differ according to the source whence it has been derived. It is compact in the branches of trees hard & dense in the shells of the filbert & cocoa nut. It is digested or not digested by animals according to its physical condition. It is easily transformed HOSO3 boiled with it converts it into dextrin & then to grape sugar. These all being the same in percentage composition. Digested with HONO3 it forms guncotton. 185 guncotton. [Illustration] Puts cotton in a mixture of HOSO3 & HONO5 washes & drys it. Part of the H has been substuted by NO4. There are several kinds according to the length of time it remains in the acid. Cellulose C36 H30 O30 Gun cotton A C36 H21 (NO4)9 O30 B C36 H22 (NO4)8 O30 C C36 H23 (NO6)7 O30 D C36 H24 (NO4)6 O30 Common paper is cellulose or lignin in another form . A curious transformation is effected by HOSO3 wh converts it into vegetable parchment. Take 2 volumes of the strongest oil of vitriol & one volume of HO carefully measured. 186 Dip ordinary unsized paper, which blotting paper into it & wash well the last HO should have a little NH3 in it to remove all traces of HOSO3. Wash again to remove the NH3 & dry it. The strength of the paper is much increased, a slip of paper that would have before broken by 5lbs will afterwards require 72lbs to break it. Starch. C12 H10 O10 Is very extensively distributed in nature. It varies in its forms according to the source from wh it is obtained Grains of starch in Tous les Moïs are 1/260th in. in diameter. Those in wheat are 1/1000th in. & in rice 1/3000th. in. Starch exist in various quantities in vegetables used for 187 food. There is in Wheat flour 57 to 67 P.C. of starch Rice 85-86 Barley 39 40 Oats 30 40 Rye 54 61 Lentiles 39 40 Maize 65 66 - flour 77 Buck Wheat 43 44 Beans 37 Peas 38 Potatoes 23. Prop. It is white tasteless, insoluble in cold HO & ether, when put in hot HO it swells up & forms a jelly. This is not a true solution for freezing separates it into grains of starch. The youngest grains separate first Test. Put a little Cl into a mixture 188 mixture of the starch solution & KI. The Cl is liberate I. Dilute acids convert starch into dextrin Heated with dilute HOSO3 it becomes grape sugar NO5 dissolves starch & HO precipitates it as an explosive compound as gun cotton in fact. By carefully heating it from 160° to 200°C it becomes dextrin. British gum is made in this way. Manufacture of starch. It exists with gluten in flour. To get rid of the gluten, subject starch to fermentation by wh. the gluten is destroyed, this causes a very bad smell. A new process has been proposed Dissolve the gluten by alkalis & then the starch remains. To get it from potatoes. 189 Grate the potatoes & put them on [illustration] a sieve, pour HO on them stirring them all the time The starch passes thro' the sieve & settles at the bottom of vessel placed below it. Wash the starch once or twice Special Starches. Several are sold for food. Sago is got from the pith of the sago palm. It is made into a paste & pressed thro' a perforated metallic plate & then exposed to the heat of steam to dry it. Tapioca. Is got from the root of the manioc. This root contains HCy wh is separated in the process of making. Arrowroot. Is got from the root stocks of various plants. Salep Is made from the root of the male orchis. 190 Starch in the animal kingdom Sometimes in healthy animals tissues, granules of starch have been found in the brain. The waxy appearance of the liver Inulin C26 H20 O20 + 3HO. Distinguished from starch by not giving a blue with I. Exists in chicory, dandelion Becomes yellow with I. Long boiling converts it into dextrin & then to grape sugar. Lichenin Found in Iceland moss, soluble in hot HO. Irish moss contains another kind C10 H10 O10 + 3HO. Peculiarly distinguished by forming a precipitate with gelatin. 191 Take a solution of Irish moss. & add it to a solution of gelatin no precipitate is formed Add a drop or two of alum & you get a stringy precipitate. Glycogen. Got from mans liver. I produces a dark red colour with it. It has no taste or smell forms a paste with HO Found in the saliva, pancreatic juice Diastase & dilute acids Its formula is given as C12 H10 O10 C12 H12 O12, & as C12 H16 O14. Dextrin C12 H10 O10. It is a product of the transformation of starch Got by roasting starch. 192 10 parts of starch are moistened with 3 of HO, the HO is to contain 1/150th of its weight of HONO5. The paste is allowed to dry spontaneously. It is a colourless transparent body like gum, deviates the plane of polarized light to the right hand, there seems to be an intermediate compound between starch & dextrin, soluble in HO wh starch is not & blued by I wh dextrin is not. Distinguished from gum by forming a beautiful blue solution with Cu OSO3 & KO. When this is heated suboxide of [illustration] Cu is deposited. Dextrin is used as a gum for 193 machinery as in calico printing To prepare glutinous bandages to reduce fractures. Gums. They have the same composition as starch, form a mucilaginous solution with HO. They all give mucic acid with HONO5 instead of oxalic acid as starch does. Quantities of cellulose & gum In one lb of the following substances there are. In Potatoes 327 grs cellulose 27 grs gum Rice 218 87 Wheat 109 109 Barley 2oz 146 Oats 2oz 218. Gums have the same percentage composition wherever 194 obtained but seem to have different combining proportions Gum arabin or arabic C12 H11 O11 Unites with bases as acetate of Pb. Is soluble in cold HO A solution of 18 P.C is so thick that it cannot be filtered, it is insoluble in alcohol. Cerasin The gum from cherry trees. Bassorin. Found in gum tragacanth seems to be a modification of pectin or vegetable jelly Pectin The gelatinous principle of fruits carrots, turnips &c. It is probably identical with Bassorine. It only swells in HO without dissolving. It seems to be a feeble acid. 195 It is rendered soluble by long boiling & passes into ordinary gum. Sugars Cane C12 H11 O11 Fruit C12 H12 O12 Grape C12 H12 O12 + 2HO Milk C24 H19 O19 + 5HO Mellitose C24 H24 O24 + 4HO Eucalyn C12 H12 O12 + 2HO Sorbin C12 H12 O12 Inosite C12 H12 O12 + 4HO Under the name of sugars are included all vegetable substances wh have a sweet taste They are formed during the life of the plant but are perfectly definite chemical compounds & crystallize They are so distinctive in their characters that they may be divided into 2 classes. 196 Sugars susceptible of vinous fermentation by yeast. Sugars not susceptible. Grape sugar or glucose C12 H12 O12 + 2HO is in crystallized state really C12 H14 O14. Occurs in the juice of grapes, in plums, cherries & dried fruits. Occurs in many of those as fructose. Fructose is uncrystallizable. Honey becomes crystalline after some time from the fructose in it becoming grape sugar. It occurs in the animal kingdom as a normal constituent of the liver. Occurs in diabetic urine. It is formed very quickly in the body under certain circumstances. If the fourth ventricle of 197 the brain is irritated by a needle diabetic sugar appears in the urine a few minutes after. Test. Heat a solution suspected of containing it with CuOSO3 & a few drops of KO. Cu2 O is formed. It first appears as a yellowish hydrate but afterwards reddish It is prepared on a large scale by allowing starch & HO at 130° F to flow into a vat containing HO & 1PC of HOSO3. It is boiled for 1/2 an hour when all the starch is converted into grape sugar. Neutralize by CaO & crystallize. Prop. It crystallizes with difficulty in warty concretions Tastes less sweet than cane 198 sugar, is soluble in HO & alcohol. Turns the plane of polarized light to the right. At 100°C it melts & loses 2HO at a higher heat it becomes brown does not taste sweet & is then called caramel, whose formula is C12 H9 O9 & is used for colouring Grape sugar unites with bases & forms saccharides 2(C12 H12 O12) 3 Pbo sesquisaccharate of Pb. Unites with NaCl & forms a crystalline compound It is also said to combine with organic acids. It is easily oxidized With HOSO3 it forms conjugate acids, act on that by strong bases & it forms glucic acid C8 H5 O5. 199 When a solution of grape sugar is acted on by yeast it is converted into alcohol & CO2. C12 H12 O12 acted on by yeast = 2eq. alc. 4 - CO2. When cheese, muscle or other nitrogenous ferment acts on sugar the change is quite different. Lactic acid C12 H12 O12 = (C6 H6 O6)2. If you carry this farther & the putrid cheese acts more on it. C12 H12 O12 = 1 Eq Butyric acid C8 H8 O4 4 - CO2 4 - H C4 O8 H4 C12 H12 O12. Ultimately sugar is converted into mucic acid or rather into a slimy acid whose composition is not well known. 200 Fruit sugar or fructose Has the same composition as grape sugar & only differs from it in not being crystallizable. Is found in honey & fruits. Cane sugar C12 H11 O11. Introduced into Europe some centuries before the Christian era but did not come into general use till the discovery of America. Occurs in sugar cane, beet root, sugar maple. Readily crystallizes in 3 forms. in the crystalline form as sugar candy, in the vitreous state as barley sugar. Barley sugar gives out much heat in passing into the crystalline form. The same thing takes place 201 with AsO3. Readily crystallizes in 4 sided rhomb The taste is sweeter & purer than that of grape sugar. Is soluble in 1/3 its wt of HO less soluble in alcohol than glucose. Heated to 160° it melts to a colourless liquid & cools in the vitreous state as barley sugar. Barley sugar after a time becomes crystalline. By a strong heat sugar becomes [crossed out] caramel. When a solution is boiled with dilute acid it becomes fructose & if for 2 hours longer grape sugar. With strong bases it forms saccharides. C12 H11 O11 BaO. Cane sugar cannot be fermented 202 fermented by yeast without becoming grape sugar. If you take equal wts of cane & grape sugar, the cane sugar will require more yeast than the glucose to ferment it, the extra yeast being employed in converting into glucose. Manufacture of sugar. It exists in various substances but that used in this country is chiefly obtained from cane. The sugar cane is cut before flowering & the juice expressed. The juice contains a good deal of albumen wh would act as a ferment & wh is separated by coagulating the albumen This is called defication. You put in a certain quantity of lime or as lately practised of CaOSO2. Boil & the 203 albumen is coagulated. The syrup is then evaporated. If you evaporate at too high a temp. it is converted into fructose, to prevent this it is boiled in vacuum pans in wh it boils at instead of 220°. It is then transferred to wooden cylinders & crystallized. It is drained from molasses by means of an extremely rapidly rotating perforated cylinder called the Jim Crow & sometimes the devil. The best canes contain about 18 PC of sugar but only 7 to 10 PC is got On the continent sugar is got from beet root. The roots are pulled in October They are rasped & the juice 204 expressed. The juice contains 10 PC of sugar but the manufacture is so much better conducted than that of cane sugar that 7 PC is obtained. In one manufactory in Belgium they got 8 1/2 P.C. There is the same defacation & evaporation as in cane sugar It is filtered thro animal charcoal. The crystals are longer & flatter than those of cane sugar, & its taste not so sweet maple sugar Holes from 1/4 to 1/2 an inch deep are made in the wood of the maple & the juice collected from them by reeds or spoub wh are stuck into them. The juice is collected in March April & May. 205 Each tree yields 3 lbs of sugar in a season & continues to do so for 30 years The juice is concentrated & crystallized every 24 hours. Refining of sugar. Raw sugar is dissolved in lime HO & mixed with bone charcoal & steam blown thro' it & if very impure bullock's blood is added. It is filtered thro bags of twilled cotton, & thro animal charcoal (burned bones). It is evaporated in vacuum pans. The syrup if evaporated in air may rise to 230° wh converts it into fructose, while if evaporated in vacuum pans 140° to 150° is sufficient. It is evaporated till the syrup is so strong that a thread 206 drawn from the finger will return to it without breaking. It is heated to 170° F run into conical moulds. Sweetness & uses of sugar. The sweetness of sugar is definite. 1 lb of cane sugar is equal to 2 1/2 lbs of grape on 3 lbs of milk sugar in sweetness. It is chiefly useful as a food in supporting active respiration, useful in keeping up the animal heat. It is good for infants for this purpose since being soluble it is more easily assimilated to the system. For this reason it exists in large quantity in milk. In the United States the consumption of sugar per 207 head of the population is [crossed out] 40 lbs. In France 4 lbs in Belgium 6 in Austria 2 1/2 in Russia 2 1/2 in the united kingdom 28 in Benzuela 110. Cane sugar is found in plants during the germination of seeds & previous to the unfolding of their buds. The bark of birch contains a good deal Grasses & palms contain most when about to blossom. Jaggery, cocoa nut & wine palms In America sugar is got from the stalks of maize. Relation of H & O in sugar. The H & O stand in the proportion necessary to form HO In such a state also as if it were present in the form of HO. 9 atoms of HO in the state of ice is equal in volume w 9.8 atoms of HO. 208 C12 H11 O11 = 171/3p.SM.1.6 = 106 atomic vol. 9.8 x 11 = 107.8- of 11 atoms of HO in the state of ice. The bulk of an atom of sugar is the same as that of the HO in it in the state of ice the C occupying no sensible space. Milk sugar = 180/1.543 = 116.6 at vol 9.8 x 12 = 117.6 at vol of HO in it. If you dissolve sugar in HO you only increase the HO by the bulk of the HO in the sugar the C occupying no sensible space. Sugar of milk. C12 H11 O11 + HO or more usually C24 H22 O22 + 2HO. milk sugar is only found in the animal kingdom Prep. Evaporate whey after the separation of the curd & crystallize 209 crystallize on twigs. Crystallizes in 4 sided prisms terminated by 4 sided pyramids. The crystals are hard & gritty, feebly sweet, soluble in HO, more difficulty than other sugars, in 6 parts of cold HO & 3 to 4 of hot. It does not become syrupy, on account of its small solubility & does not deliquesce in air. At 130°C it loses its HO of crystallization at higher temps. it becomes brown & is called Lacto caromel C12 H10 O12 It forms saccharides. Precipitates Cu2 O from solutions even in cold but less readily than glucose. Dilute acids convert it into lactose wh has the same formula as grape sugar but does not 210 form a compound with NaCl Although milk sugar does not ferment the Tartars ferment mares milk & make cumase Other fermentible sugars. Trehalose C12 H11 O11 Found in a substance called Trehala a substance used in the East for food a product of insects. Megatose. C12 H12 O12 + 2HO. Got from the twigs of the larch Mellitose C12 H12 O12 + 2HO. From the manna of Eucaliptas Non fermentable sugars. Inosite C12 H12 O12 + 4HO. This is muscle sugar Found in the muscle of the heart in the brain & nerves in unripe common beans & in the cells of the lung & the liver 211 Prep. Crystallizes in small crystals efflorescing in air. Soluble in HO & weak alcohol insoluble in alcohol & ether. At 210° it melts to a clear liquid. Dilute acids do not change it. It does not reduce Cu It does not suffer vinous fermentation, by cheese it suffers lactic or butyric fermentation. Scyllite Is found in the liver of shark If you evaporate Inosite nearly to dryness & add CaCl Sorbite is Is got from the berries of the mountain ash. Its taste is sweet It does not ferment & does not produce grape sugar when boiled with acids 212 Sugars unite with various organic substances. Salicin is one of these. They are called glucosides . Salicin C26 H18 O14. It is an antipyriodic like quinine When boiled with sugar it breaks up into sugar Occurs in willow, poplar Crystallizes in small brilliant colourless prisms, intensely bitter, melts at 120°c Soluble in hot HO, difficultly in cold, soluble in alcohol not in ether. Concentrated HOSO3 dissolves it with a purple red colour. By the action of amulcin, the ferment of almonds* it splits up into saligenin & grape sugar. C26 H18 O14 + 2HO taken up by the action of the amulcin = salignen C14 H8 O4 + glucose C12 H12 O12 x Or by the action of ptyalin the ferment in saliva. 213 Heated with acids it breaks up in a similar way but loses 2HO C26 H18 O14 = C14 H6 O2. salintene + C12 H12 O12 grape sugar.x Saligenin is the alcohol & salintene the ether of the alcohol. There is a large number of glucosides. Populene C40 H26 O20 Obtained from poplars. By the action of amulcin it is converted into glucose saligenin & benzoic acid. C40 H26 O20 = C12 H12 O12 + C14 H8 O4 + C14 H6 O4 Quercitrene Got from the quercus & the bark of the horse chestnut Convolvulene Obtained from jalap roots. Tannine. Is tannic acid & glucose. *Salicin distilled over CaO gives carbolate of lime. 214 Colouring matters These are associated together more by technical use than by chemical relations. They are unlike bodies. They are found in all parts of different plants. They are difficult of isolation Method of doing so. Boil with Ho, alcohol & ether according to their solubility; agitate with PbO wh takes up the colouring matter. Decompose the Pb compound by HS & evaporate in vacuo. Sometimes the colouring matter does not exist in the plant but is formed by oxidation or by the action of a ferment. Thus, madder root does not contain the colouring matter in it, till it has been acted on 215 by a ferment wh the root itself contains. It yields a whole series of colouring matters. Most of these colours attach themselves to an animal substance much more readily than to a vegetable one. Puts a little white of egg wh has been coagulated by heat in the bottom of a vessel into a colouring matter wh dyes it while a vegetable substance is not much affected unless a mordant is put on it. Silks & woolens are dyed directly by these colouring matters. To dye calico print a pattern on it by an acetate. To produce red with madder print with acetate of alumina 216 For purple with acetate of alumina & acetate of Fe. For black with acetate of Fe alone The cloth is hung up & the acetic acid flies off. Puts a cloth printed with alumina in logwood Mordants act more by their acid than basic characters they are sesquioxides. Protoxides are not good mordants. One method of dying is if you can put into the pores of the cloth a colour naturally insoluble & render it insoluble in the cloth itself. This is done in the case of indigo. Mix FeO & KO or CaO with indigo blue, this gives indigo white. Indigo blue differs from indigo 217 white by 1 H. Indigo blue C16 H5 NO2 white C16 H6 NO2 When indigo white is poured from one vessel to another the H is oxidized to HO & it becomes insoluble indigo blue. [illustration] It is large jar in wh is indigo while the sediment is at the bottom. It is called an indigo beck. Dips a cloth printed with an oxidizing substances (CuOSO3) into indigo white. The printed parts are left white, because the CuOSO3 oxidized the indigo white & rendered it insoluble on the surface of the cloth so that it could not penetrate. Adds some alum & a little NH3 to a solution of cochineal. The A2 O3 precipitates it as a 218 Lake. It is this property wh enables the mordant to take down the colour with it & fix it. Madder. Madder is got from the root of the Rubia tinctorum found in Turkey, Holland & the south of France. Fresh madder does not contain colouring matter but contains a resin called rubio erithric acid C32 H18 O18. By the action of a natural ferment within itself it becomes alizarin the colouring principle of madder & glucose. C32 H18 O18 = C20 H6 O6 + C12 H12 O12 The is a large number of colouring matters in madder Alizarin subliming is orange 219 it is red. Alizarin C20 H6 O6 Crystallizes in fine red prisms orange red after subliming. Sparingly soluble in cold HO readily soluble in alcohol, ether & hot HO. Alkalies dissolve it CaO & Bao give blue lakes. Al a deep red. Fe2 O3 a purple It has very much the composition of naphthalin. If you replace some of the H in naphthalin by Cl you get a chlor-alizarin. It is alleged that alizarin is obtained in France from naphthalin. Purpurin C18 H6 O6 Occurs in old madder not in 220 new. Prepared from alizarin acted on by yeast Crystallizes in yellow red prisms Fuses easily & sublimes. Alkalis dissolve it yellow. BaO + CaO give purple lakes. Rubiacine C32 H11 O10 A yellow colouring matter. Is a product of the natural fermentation of the original resin Crystallizes in yellow needles gives the yellow shades in madder dyeing When madder has been used in dyeing one half of the colouring matter is taken up the other half used to be thrown away. The spent madder is now digested with very dilute HOSO3 & steam blown 221 thro it. It is then produces dyes as good & perhaps even of more brilliant shades than the original did. Logwood It contains a honey yellow [crossed out] substance wh is called Hœmitoxalyn wh has no relation to the colouring matter of the blood. Its formula is C32 H14 O2 It forms a red with Al -black - Fe. Crystallizes in violet microscopic crystals wh dissolve red. By a nitrogenenous ferment especially by ammonia if produced it becomes much more powerfully tinctorial Brazil wood. None of the yellow dyes have been much examined Quercitron C. 222 Indigo. It is got from plants of the genus Indig ofera from is atus tinctoria or woad, found in the urine of cows & in that of men in some diseases. Sometimes occurs in milk to wh it gives the blue colour. Prep. The leaves of the indigo plant are macerated & CaO added & allowed to ferment; the indigo white is formed wh soon becomes insoluble indigo blue. Add a per salt of fe to indigo white & it becomes indigo blue. Indigo blue as it occurs in commerce has S.G 1.35. Crystallizes when quite pure in crystals wh have a coppery lustre. 223 HOSO3 dissolves it completely Pure indigo blue may be fused. You may suppose indigo blue to be the radical & indigo white the hydrate. Indigo blue C16 H5 NO2 - White C16 H5 NO2 H. There is one other method of dyeing. Topical dyeing. It is the means by wh you can get an insoluble powder on the surface of the cloth Albumen from blood & casein from cheese is sold for this. Casein is dissolved in NH3 mixed with the colouring matter & heated so as to allow the NH3 to evaporate. Very often these topical applications 224 applications are arsenic green. Or take albumen & colouring matter such as ultramarine expose to steam to coagulate the albumen. [Illustration] This method has enabled many styles of printing to be employed. Cu or As colours should not be employed as they occasion great injury to the health. Many colouring matters are glucosides. They seem to be weak bases. The best mordants are those oxides on the verge of being acids. Mordants are the metallic oxides Chemically they are called lakes. Colouring matter of lichens. They readily split themselves up into several acids, some of wh readily give colouring 225 matters with NH3. Erythric acid C46 H22 O20 Orsellenic C16 H8 O8 Orsellic C32 H14 O14 Evernic C34 H16 O14 Some when treated with stronger acids as HOSO3 or HONO5 break up into new compounds & produce colouring matters [Illustration.] adheres to albumen Albumen is printed on the cloth & coagulated by steam & dyed by the the archil colour. One or two animal colours are employed in the arts. Cochineal. It consists of the dried bodies of insects wh feed on a certain kind of fig. This dye contains carminic acid C28 H14 O14 226 This unites readily with bases. Another insect forms the lac dye used for dying cloth red. Volatile oils, resins & caoutchoue. Essential oils. They are occasionally found ready formed in plants as in the orange & lemon. In other cases it is made by the action of HO on seed as in bitter almond & mustard oil. In the animal kingdom These are rare, altho' they occur in ants. The general classification of essential oils is more pharmaceutical than chemical. They are either solid or liquid When solid they are easily fusible & are volatile Though the boiling points of some are high they generally 227 ally go over readily in steam. They produce a temporary stain on paper, fixed acids produce a permanent one. They have a peculiar penetrating odour generally agreeable. They are rarely pure in commerce They contain a solid substance wh is the oil oxidized or hydrated & wh are called stereoptenes. The oils are prepared in some cases as from the orange & lemon by pressure. More usually as from aromatic plants by hanging the plants in bags & passing steam thro' them & condensing it. They are prepared for perfumery by a peculiar process. A cake of tallow is taken & the flowering plants spread over it. It is then gently 228 heated not enough to melt the tallow. The tallow gradually extracts the oil. The tallow is then treated with alcohol wh dissolves out the oils. They may be divided into different classes. 1st Essential or volatile oils free from O. 2nd - containing O. 3d - S. 4th - wh suffer change by distillation. The central formula around wh they all turn is that of camphine C20 H16 for a 4 vol. formula. Some have only half that C10 H8. Some have these two formulas united C30 H24 229 Essences isomeric with camphine. Essence of bergamot - lemons - orange - birch - camomile - juniper - copaiba C30 H24 - carraway - cloves - ginger - cubebs - thyme - valerian Turpentine. By this is meant camphine C20 H16. Boils at 160°c S.G. 0.864. Got by wounding pines, when it flows out, this is distilled & gives essence of turpentine 230 In this state it is colourless transparent oil with a peculiar disagreeable odour & burning taste. Insoluble in HO, difficulty in common alcohol readily in absolute alcohol & ether concentrated acids dissolve it. It converts O into ozone. If you shake some up in a bottle with air you may detect the presence of the ozone formed applying the test. It contains so much H that if you moisten some cotton wool with it & having warmed it put it into some Cl, HCl fumes are formed & it takes fire. It combines with HO & forms solid stearoptines C20 H16 + 4 HO 231 C20 H16 + 3HO, C20 H16 + 2HO & C20 H16 + HO. These are called camphors of turpentine. Essences not isomeric with camphine. Oil of peppermint C20 H18 Contained as a solid hydrate in certain oils C20 H18 + 2HO. Essence of cedar wood C32 H26 C32 H20 + 2HO is a solid hydrate. Oxygenized essences. Camphors Common Camphor True laurel camphor C20 H16 O2 Obtained from camphor wood by chopping the wood in branches & distilling in HO. Fuses at 175°C boils at 205°C. Vap. density 5.32. Difficult to pound from its elasticity, but may be done 232 easily by putting a drop or two of alcohol on it & then pounding it. Borneo camphor C20 H18 O2. Got by puncturing the tree. Crystallizes in 6 sided prisms colourless & transparent Other camphors. Stearoptines of many plants are really camphors. In peppermint & cedar oil C20 H20 O2 C32 H26 O2 Resins These are exudations from They appear to be formed by the oxidation of the essential oils more oxidized than the camphors. Camphors C20 H16 O2 Resins C20 H16 O2 - n H + n O. 233 They are used for varnishes by mixing pounded glass with pounded resin & treating with alcohol or wood spirit Copal, Mastic, Sandarac Common varnish for maps 24 parts Mastic 3 - Venice turpentine 1 - Camphor 10 - pounded glass Mixed with 72 parts of oil of turpentine & filtered. Lac. Sold in 3 forms. Stick lac. An insect perforates certain trees & the lac It is sold in commerce on the twigs. This is pounded & heated with NaOCO2 wh dissolves out the colouring matter wh is used 234 for dye. The lac is melted in canvass bags & is squeezed on bamboos. & is then called shell lac. Got on ficus indigus or ficus religiosa. Used for sealing wax & for stiffening hats for wh purpose it is dissolved in wood spirit. Sealing wax 48 parts lac 12 venice turpentine 1 Balsam of Peru 36 Vermilion stirred up with it. For making lacquers of wh there are several kinds the usual one is, Lac is mixed with 1/2 its wt of sandarac & a little venice turpentine, dissolved in 10 to 12 parts alcohol. The brass is heated before it is applied. 235 Guayacum. Obtained from guayacum officinalis It is bluish green or brown The alcoholic solution is a good test for ozone wh makes it blue Jalaps. Contain glucosides Jalapin is a glucoside. Amber It is a fossil resin found in coal but chiefly thrown up on the shores of the Baltic between Memel Often contains insects of extinct species but related to present species. Seems to have been an exudation S.G 1.065. Insoluble in alcohol & ether, soluble in essential oils. After having been 236 once fused it is soluble in turpentine & then forms amber varnish By dry distillation it yields succinic acid & amber oil. With HONO5 it forms artificial camphor having a smell like musk. Caoutchouc. It is a resinous substance suspended in the milky juice of various plants. In its ordinary state in commerce it is impure. When separated from its impurities its formula shows it to be a hydrocarbon nC8 H7 Soluble in chloroform but is precipitated by alcohol, melts at 120°C & at 200°C it beings to decompose. Insoluble in HO & alcohol Soluble in turpentine, benzol 237 naphtha & chloroform. The solution in naphtha is used for water proofing cloths. Unites with S & forms vulcanized india rubber. Got by treating with sulphide of C or usually with chloride of S. S2 Cl . Gutta percha. Is like india rubber in its composition & many characters except its want of elasticity at common temps. Is the concrete juice of percha. Scarcely elastic at common temps. but becomes elastic at 212°f. Is worked at a high temp.; welds when soft is soluble in the same reagents as caoutchoue. Is not attacked by HFl. Vulcanized india rubber gradually 238 gradually loses its S & becomes brittle especially if kept in contact with metal wh takes the S. Asphalt & bitumen Occurs extensively in nature as springs some of wh contain the asphalt in solution The salt of the earth spoken of in the Bible probably means bitumen & when it is spoken of as having lost its savour it means that it had lost some of its volatile hydrocarbons. It was ordered to be used in burnt sacrifices & was probably smeared over the bodies & thus rendered them more combustible. Asphalt is the residue of mineral oils wh have lost their volatile hydrocarbons. 239 Occurs in Turkey Persia Egypt & even in our own country There was a spring near Edinburgh & there are in the Industrial Museum several black candles made from it. There is one near Alfreton in Derby from wh paraffine was first made. There are many mineral hydrocarbons like asphalt. Ozokerite C2 H2 n. Sheerit Found in brown coal in Germany Fichtilite C8 H7 Found in fossil pines. Hartit C6 H5. Idrialit C80 H28 O2 Found with cinnabar in Idria. 240 Animal Chemistry. We could make urea & grape sugar waste products of vital agency but chemistry has yet made but small progress in producing the The ruling agency in vegetable & animal life is vital agency. When we see plants growing on the same soil, nourished by the same substances, watered by the same rain & stimulated by the same manure & yet producing substances as different as starch & morphia we cannot tell what the hidden force wh produces these transformations is. Latterly we have got a more exact idea of force & know that, heat, electricity, chemical affinity &c 241 are all resolvable into motion. But although our ideas of force are extending & we can compare the animal body to a steam engine yet one force is left of wh we known nothing viz., vital force. We know the engine but not the engineer. Histogenetic substances. All those wh build up the frame- work of the animal body are termed histogenetic. They are the substances of wh the organs consist. Fat is not an organic, is not a histogenetic substance. Albumen Fibrin Casein Syntonin Fibrin in muscle Globulin found in the eye. 242 Hemato crystallin. Most of them, the first three at least are found indifferently in the animal & vegetable kingdoms. If you stir fresh blood with twigs fibrin coagulates on them. Whip fresh juice of cauliflower with twigs & you get fibrin Boil cabbage juice & you get albumen. You can get it from blood Add an acid such as HCl to casein & cheese is formed Add HCl to solution of peas & you get the same casein These substances exist both in plants & animals. General properties whence soever derived. Uncrystallizable translucent of a yellowish colour: tough 245 when dry, adhesive or jelly like when moist. Brittle gelatinous plates when dry. Exist in 2 forms In the soluble state as fibrin in the blood In the insoluble state as when the blood is out of the body. The exact cause of the transformation from the soluble to the insoluble state is not known They part with 2P.C of some proximate constituent* when they become insoluble. insoluble varieties They seem to dissolve unchanged in acetic & phosphoric acid. Mineral acids decompose them All are transformed by long boiling in HO When oxidized by HONO5 or *As soda or potash generally alkalies 244 other oxidizing acid they produce acids of the alcohol series beginning at formic & going up to caproic acid They also produce aldehydes. Some in oxidizing produce oil of bitter almonds & acids of benzyl series Digested with HOSO3 or strong HCl. they produce almost invariably Leucine & Tyrosine & commonly Glycine, besides NH3 salts under the influence of caustic alkalis When moistened they putrefy the elements dividing themselves according to their greatest affinities. Putrefaction thus differs from decay wh is a combustion. Among the products of their putrefaction are the carbonate butyrate & valerate of NH3 , NH4 S 245 Common test for these; for any of these nitrogenous bodies. Moisten with a salt of H8 having an excess of Hg & heat to [Illustration.] 212°. They become red on the surface. Do not heat too violently. This is a test for all histogenetic substances. Mulder argued that they all contained a substance called protein wh was the basis of them all. According to Mulder it has the formula C36 H25 N4 O10 + 2HO wh can be driven off by heat. Percentage composition of protein according to this formula. C = 54.7 N = 14.2 H = 6.8 O = 24.3 He supposed other bodies to be 246 protein combined with P & S. Though his views are no longer held by chemists the nomenclature is retained & they are called protein compounds. Probably they are all the same as regards organic composition & the ground work is the same in all & they differ merely in form. Albumen Is the chief type of the group. Exists in various states probably owing to the amount of alkali with wh it is united.* Occurs in vegetable juices in blood, chyle & lymph in all serous liquids, in the juice of flesh & cellular tissues, in white of egg. Prop. 1st. Soluble albumen As obtained from white of egg it is transparent, yellowish, *Thus its reactions are not always the same 247 soluble body of a glairy consistence. S.G 1.261. When put in HO it swells & dissolves, the solution reacts alkaline from the NaO it contains. Remove this by acetic acid & add HO & it becomes insoluble Metallic salts precipitate albumen Add HgCl to albumen & it forms an insoluble coagulum, on this account albumen is used in cases of poisoning by HgCl. When heated to 63°C it becomes opaline at 75°C it coagulates entirely. It is then insoluble in Tannic acid precipitates albumen. Albumen of blood. is not coagulated by dilute HOSO3 248 Insoluble albumen When albumen is acted on by heat it appears to be the first form from wh all the other nitrogenous substances are formed. It requires very little change to become muscle or the contents of nerve tubes Fibrin Occurs chiefly in blood, lymph & chyle in a state of solution Prop. Separates in an insoluble state in delicate filaments. We know nothing of pure soluble fibrin Coagulated fibrin is opaque yellowish fibrous mass hard & brittle when dry Swells in HO but is insoluble in it, dissolves in solution of KONO5 at 40°C but is coagulated by boiling & acetic acid 249 Digested at 150°C with HO under pressure, by sealing it up with HO in a tube. The fibrin is apparently converted into albumen. It becomes soluble & is coagulated by acids & behaves exactly like albumen. Vegetable fibrin is prepared by putting flour in a muslin bag & kneading it in a stream of HO. The starch is carried thro' the pores & the fibrin remains behind. Gluten of wheat is identical with fibrin Syntonine. Is fibrin of muscle Is the chief constituent of the striated muscles, is in smaller quantity in the smooth muscles & in the arterial coat & spleen When first taken from the body it is snow white. 250 Soluble in HO containing 1 PC of HCl, insoluble in KONO5. Is precipitated from its solutions in alkalis by KCl. or NaCl The solution in lime water is coagulated by heat. Casein. Occurs in the milk of mammals, in small quantity in blood under the name of serum casein. It exists in yolk of egg so intimately mixed with albumen that it used to be thought a separate substance & was called vitellin Exists in the juice of flesh in the juice of the thymous gland. In the vegetable kingdom in the seeds of leguminosæ Prop. Chiefly differs from the other allied substances in its mode of coagulating. Maybe got from milk by adding HCl or rennet 251 Acetic & Lactic acid precipitate it from solutions. Strong acetic acid however dissolves it. Rennet coagulates it. It is not precipitated by heat. The skin formed on the top of boiled milk is caused by the oxidation & not by the coagulation of casein. If boiled with CaCl or Mg OSO3 it is precipitated but the base goes down along with it. On account of this property it is used for cement for glass & earthenware. A poor cheese is made into a paste with lime. Vegetable casein of leguminosae or Legumin Occurs in leguminosae from 20 to 25 P.C. They are even too nutritive The casein is obtained by coagulating 252 coagulating their infusion by rennet or by adding acids. Casein of animals & vegetables is exactly the same Cheese is sold in China made from beans. Its solution when heated forms a skin on the top like milk heated. Globulin. Forms 36 P.C of the crystalline lens of the eye, & got its name from being supposed to be identical with the coagulable part of the corpuscles of the blood. Differs from albumen by coagulating at 93°C. The solution is not coagulable by acetic acid or NH3 . It becomes turbid when the acetic acid solution is heated. Is precipitated by CO2 253 Hemato crystalline It is albumen in a state in wh it can be crystallized Got from the blood of the guinea pig from wh it crystallizes in tetrahedra. Is in the blood of rats & mice. It is difficult to get from man's blood but from it & from the blood of carnivora it is in prisms From the hamster in rhombohedrous Differs from all other albuminous bodies by not being precipitated by metallic salts & Cl2 ONO5 It is obviously a glucoside* The characteristic of all histogenetic substances is that they all contain 15 P.C of N. B Derivatives from the albumenous group * the substance wh remains beside glucose has like same composition as albumen 254 They closely resemble albumenous bodies but contain rather less C. They differ in physical characters They do not form cells but form organic bases of certain tissues With strong HCl, HONO5, & prussiate of KO they are not precipitated Ossein. Prep. But a piece of bone in dilute HCl, & treat with alcohol & ether to take out the fat. Insoluble in HO, is converted into glutin by boiling *Glutin It is a transformed condition of ossein. Is called gelatin in commerce. It is colourless transparent & horny Brittle, heavier than HO, *Different form gluten wh is in wheat, Glutin is the general name for gelatine 255 tasteless insoluble in cold HO soluble in hot Water with 1 P.C of glutin is gelatinous. Long digestion in HO or destroys its gelatinous property Forms a precipitate with tannic acid. Dry distillation produces various bases from it as methytannin Glutin does not appear to be in the body except in the spleen. Chondrin Prep. Boil the permanent & articulate cartilages It much resembles glutin. It is precipitated by acetic acid, per salts of Fe, HCl alum Treated with Many albumenous bodies pass into glutin when boiled 256 Glutin & elasticin are known to us as common glue Glue is made from the parings of ox hides boiled in a coarse cloth cut into blocks & dried. Size is a less strong glue made from the parings of parchment & used in liquid state. Confectionery gelatine Made from the swimming bladders of fish & the parings of fine hides. Abroad it is made from the tendons of rats. In the abattoirs where horses are slaughtered, the carcases are put into rooms plastered so that the rats cannot make holes in them & two or three bricks are left wh can be removed & replaced at pleasure. The rats are allowed to enter at night to clean the bones of the 257 horses before the bones are sold to the P. makers. In the morning the bricks are replaced & a man having a mask & thick gloves & armed with a bludgeon enters & kills the rats, their skins are made into kid gloves & their thigh bones cleaned & made into toothpicks for the London clubs; the rest of the body is boiled down for gelatine. Leather is a tannate of gelatin There are various nitrogenous substances wh occur as derivatives in the animal body These substances are formed probably by the transformation of histogenetic substances arrested in their passage to complete oxidation. They are probably amides Amides contain their N as 258 amidogen NH2 . Kreatin C8 H9 N3 O4 + 2HO . Occurs in the striped & smooth muscles in urine in the brain in blood. It is best got from the flesh of fowls or skate fish in wh there are 3 parts of kreatin to 1000 parts of flesh. It is a clear, transparent colourless, brilliant body crystallizes in rhombic columns loses 2HO at 100°C. Insoluble in strong alcohol but soluble in dilute spirits of wine. Has a bitter taste, neutral in reactions. When heated with strong acids it becomes converted into kreatinin a substance wh also occurs in urine. C8 H9 N3 O4 = C8 H7 N3 O2 + 2HO. When heated with BaO it takes up 2HO, & becomes urea & sarkosine 259 C8 H9 N3 O4 + 2HO = Urea C2 H4 N4 O2 + sarkosine C6 H7 NO4 kreatinine Occurs in blood muscle & urine is is formed by the action of acids on kreatin Crystallizes in colourless rhombic prisms, soluble in HO + hot alcohol, the solution reacts alkaline & is a feeble base, when concentrated it tastes like dilute NH3 . By long keeping it becomes kreatin, especially in presence of lime water Kreatin & kreatinine are products of the oxidation of the tissues on their way to urea. Sarcosin. C6 H7 NO4 Although to be expected, yet it is not perfectly certain that it exists in the urine Prep. Act on kreatin by alkalis. BaOH5 It crystallizes in rhombic 260 prisms soluble in HO Seems to be ami When kreatin 2(C8 H9 N3 O4 ) + 10H8 O = 10Hg + 2HO + 4CO2 + (2C4 H7 N3, C4 H2 O8) Methyluramine C4 H7 N3. It is probably a triamine It is a strong base precipitates oxides, drives NH3 from salts, its constitution is unknown. Sarkin C10 H4 N4 O2 Occurs in the flesh of horses, oxen & men. Crystallizes in colourless transparent needles readily soluble in HO difficultly in alcohol Fuming NO5 converts it into Guanin Guanin C10 H5 N5 O2 . Occurs in guano & spider's 261 excrements in the liver & cavities of pancreas White or yellowish isomorphous mass without taste or smell Insoluble in HO alcohol & ether, soluble in alkalis. Unites with salts as ZnCl. By NO5 or HOSO3 & MnO2 it becomes xanthin. Guanin C10 H5 N5 O2 Xanthin C10 H4 N4 O4 Xanthin occurs in urine occasionally, forms calculi has been found in flesh & salivary ducts An amorphous white mass Soluble in acids & alkalis, little soluble in HO. Resembles sarkosin & in less decidedly basic then they. Cystin C6 H6 NS2 O4 Is a rare constituent of urinary 262 calculi. Has been lately found in nerves & liver Crystallizes in colourless transparent- 6 sided [crossed out] tables. Neutral, insoluble in HO & alcohol soluble in acids & alkalis. Allantoin C8 H6 N4 O6 Occurs in cows, [illegible] & in the urine of calves & dogs Is got by the oxidation of uric acid Is most easily got from calf's urine. Crystallizes in colourless brilliant prisms, tasteless having no smell neutral, soluble in hot HO & alcohol insoluble in ether soluble in alkalis but is decomposed when boiled with them taking up 10HO. C8 H6 N4 O6 + 10HO + 2(C4 H2 O8) + 4NH3 Tyrosin C18 H11 NO6 Occurs in the liver, pancreas in cochineal in root of 263 & is a general product of the decomposition of albuminous bodies by acids & alkalis. Prop. Occurs in white silky crystals. Soluble in hot HO insoluble in alcohol & ether Dissolves without change in alkalis & acids forms conjugate bodies with HOSO3. Aloxan C8 H2 N2 O8 + {2HO or 8HO} Made from guano. By the oxidation of uric acid by NO5. Occurs in octahedral crystals Soluble in HO, the solution colours the skin red. It reddens litmus paper. At 100°C it loses HO. Forms like alkalis HONO5 oxidizes it & forms parabanic acid. 264 Reducing agents as HS convert it into aloxantin. Aloxantin is readily changed Thyanuric acid is C8 H5 N3 O2 S2 Formed when aloxane is treated with SO2 & saturated with NH3. Aloxantin C8 H5 N2 O10 Got by acting on aloxan by reducing agents Crystallizes in colourless prisms dissolves in NH3 with a purple colour. The solution is acid. it gives a violet precipitate with BaO. Its products of oxidation are similar to those of alloxan. Cerebrin C34 H33 NO5 Occurs in the brain. It is a white porous powder, tasteless 265 tasteless, having no smell, insoluble in HO, soluble in alcohol & ether neutral. Decomposed by boiling acids at 80°C Amide acids. Taurin C4 H7 NO5 S2. Occurs in the muscles of all mollusca, in the lungs, sometimes in the kidneys & often in the liver of higher animals. Produced by the action of acids on Taurocholic acid a constituent of bile. Prep. Heat or bile with HCl. Evaporate & exhaust with alcohol. It has been got artificially by heating isotinate of ammonia C4 H9 O8 NS2 it loses 2HO H2 O2 C4 H7 O6 NS2 Taurin It is thus the amide of isatinic 266 acid. It forms colourless transparent 6 sided prisms dissolves easily in HO, insoluble in alcohol & ether. dissolves in acids, is neutral. Leucin C12 H13 NO4 Exists in blood vascular glands spleen, in thymous gland In liver & bile, the pancreas & salivary glands & thin secretions. In the contents of small intestines in the lungs & kidneys* It is always produced by the action of strong acids & alkalis on albumenous bodies Prepared synthetically by heating valeric anhydride with HCy. Valeric anhydride C10 H10 O2 + HC2 N + 2HO = C12 H13 NO4 Leucin is the amide of caproic acid. Caproic acid C12 H11 O3, HO Leucin C12 H10 (NH2 )O3 , HO * has been found in diseased brain 267 Prop. When quite pure it crystallizes in colourless brilliant plates, Freely soluble in HO less so in alcohol & insoluble in ether. The solutions are neutral. With HONO5 it gives various products among others Leucic & Lactic acid. Uric acid. C10 H4 N4 O6 It is biatomic = 2HO C10 H2 N4 O4 . Occurs in small quantity in the urine of man & carnivora, scarcely at all in that of herbivora. The urine of birds & serpents chiefly consists of this & also that of tortoises. Largely in the excrements of butterflies & beetles Traces of it in healthy blood Increases in gout & Brights disease Is in excess in cholera, bronchitis & pneumonia Is a frequent substance in calculi. 268 Prep. Urates in serpents excrements are urate of amonia principally. Treat with alkalis (KO) & add HCl & the sparinly soluble uric acid is precipitated. It is a white crystalline powder difficultly soluble in HO insoluble in alcohol & ether. When heated it is converted into urea, cyamuric acid, NH4 oeo2 HCy. Peroxide of Pb makes it into alantoin, urea, oxalic acid & CO2. This is important. It is only a feeble acid but is bibasic & forms acid & neutral salts. Urates. General formula MO} HO} = Uric Urate of NaO. NaO HO /U 1 eq of HO in uric acid is replaced by 1 of NaO. 269 Difficulty soluble in cold HO, more so in hot. This is the reason that urine sometimes though clear when ejected becomes turbid on cooling. Acid urate of ammonia NHO HO /U Crystallizes in fine needles or an amorphour precipitate scarcely soluble in cold HO Urate of lime CaO HO /U Occurs in calculi & sometimes as a urinary sediment Forms chalk stones in the joints of gouty persons. White amorphous & difficultly soluble in cold HO. Derivatives of Uric acid. When HONO5 acts on uric acid, it is dissolved with a yellow colour & various products are formed. By careful evaporation to dryness & treating with NH3, it becomes purple. 270 Bestway. Take 4 grs. aloxantin & 7 of hydrated alloxan, dissolves in 1/2 an oz. of HO by boiling. Add to 1/6 oz. by measure of saturated solution of NH4 OCO2, & murexide is formed. It must be boiling before adding to NH4 OCO2 . Murexide C16 H8 N6 O12 Has the synonym of precipitate of ammonia. Is used in dyeing. Its owing to the formation of murexide that the guano colours are formed. Guano consists of the excrements of sea fowl It is treated with KO to dissolve the uric acid. The uric acid when treated with NH3 forms murexide. It is then treated with salts of PbO & Hg. Properties of murexide 271 Crystallizes in 4 sided prisms, of a golden green beautiful metallic lustre. Difficultly soluble in HO readily in KO with a purple colour. Test for uric acid. Dissolve uric acid in HONO5 & alloxan is formed It is supposed that murexide contains a compound called purpuric acid & that it is a NH3 compound of this. NH4O} HO} purpuric acid C16 H3 N5 O10 No substance has yielded so many compounds to organic chemistry as uric acid. Some of the chief are, Uric acid & nitric acid form alloxan C10 H4 N4 O6 + 2HO +20 = alloxan C8 H2 N2 O8 + Urea C2 H4 N2 O2 Act on alloxan by a feebly oxidizing agent as KO. 272 C8 H2 N2 O8 + 4HO = mesoxalic acid C6 H2 O10 + Urea C2 H4 N2 O2 Cynuric acid Seems to take the place of uric acid in the urine of the dog. Crystallizes in 4 sided prisms Melts when heated & exhales the odour of hemp nitrile Dissolves in acids & alkalis & has all the charactes of a feeble acid. Inosic acid. HO, C10 H6 N2 O10 . Found in the juice of flesh in small quantity. Forms a solid white uncrystalline mass, soluble in HO, insoluble in alcohol & ether. Reddens litmus, tastes like flesh forms salts. Acids of bile. Bile besides less essential constituents contains NaO salts of 2 nitrogenous acids. 273 These acids are like glucosides They do not contain grape sugar but bodies corresponding to it. The one contains glycin the other taurin instead of glucose. Both contain the same acid. viz, cholic acid. Cholic acid with taurin & glycin forms conjugate acids. Glycocholic acid HOC52 H42 NO11 Occurs as glycocholate of NaO in bile. Is the main constituent of ox gall & is in small quantity in that of other animals except the pig. Glycocholic acid crystallizes in very delicate needles, soluble in hot HO & alcohol, difficulty in ether. The solution tastes sweet & then intensely bitter, reddens litmus With HOSO3 & sugar it gives 274 an intense purple red. Soluble in concentrated acids, without colour at first but absorbs O & becomes coloured. When long boiled with BaO it is decomposed C52 H43 NO12 + 2HO = cholic acid C48 H40 O10 + glycin C4 H5 NO4 glycin is the amide of acetic acid & is a product of the action of acids on gelatin Hence glycocholic acid is a conjugate acid. Taurocholic acid C52 H45 NO14 S2 So called because it contains taurin instead of glycin. It is the second chief acid in bile Occurs as the NaO salt in the bile of man, ox, dog, goat frog boar, anaconda &c. In certain fresh water fishes. Has been detected in the blood in transudations *In the boar is is apparently alone not accompanied by other acid 275 & in urine in cases of suppressed excretion of bile. White amorphous bitter powder soluble in HO Easily decomposed by heating Is decomposed by boiling with BaO taking 2HO. cholic acid taurin C52 H45 NO14 S2 + 2HO = C48 H40 O10 + C4 H7 NO6 S2 Taurin is the amide of isithionic acid. With HOSO3 & sugar it gives the same reaction as glycocholic acid. With ferments the taurs & glycocholic acids are broken up as with [ferment] alkalis. Cholic acid C48 H40 O10 . Crystallizes in transparent colourless tetrahedral crystals Has a bitter but sweet taste, readily soluble in alcohol & ether, difficulty in HO. Its alcoholic solution reddens litmus & dries CO2 from its salts. 276 With alkalis it forms crystalline salts. With HOSO3 & sugar it gives the purple reaction of bile. Hyoglycholic acid C54 H43 NO10 . Substitutes these other acids in the bile of the pig. Not found in that of any other animal. A white resinous substance melts in boiling HO. Insoluble in HO & ether It is a conjugate acid & contains glycin & Hyocholic acid Hyocholic acid C50 H40 O8 . There is another corresponding to it in the bile of the pig. Hyotaurocholic acid C54 H45 NO12 S2 . Lithofellinic acid C40 H36 O8. Exists in oriental. in the biliary concretions of antelopes & goats, of wh it forms the chief part. 277 It belongs to the same class as these others When cholic acid is acted on by acids it forms several substances one of wh is called choloidic acid. Cholic C48 H40 O10 - 2HO = choloidic C48 H33 O8 Amorphous mass melts on boiling readily soluble in alcohol. Cholosterin C52 H44 O2. It is a crystalline fatty substance found in bile but generally in biliary concretions. It is like a monoatomic alcohol Found in the brain blood, lungs It is neutral melts at 145°C sublimes at 360° Gives an aromatic oil by distilling having a smell like the geranium Insoluble in cold alcohol, soluble in boiling alcohol & ether. * Found abundantly in biliary concretions 278 Solutions of bile dissolve it readily It unites with one equivalent of acetic acid with displacement of one eq. of HO. Compound ethers may begot from it as from cedernal C52 H44 O2 C4 H3 O3. All bile of animals is coloured by a substance wh forms a bile pigment. Originally brown in man but, becomes green by oxidation Solid constituents of animals Bones. Those of vertebrate animals are tolerably constant in composition When dried at 212° they have 1/3d. of their weight of organic matter & 2/3ds of mineral matter. Large bones & those wh have much work have more mineral matter General average of the composition of bones taken from various analyses. 279 3CaO, PO5 57 parts. CaO CO2 8 Ca Fl 1 3MgO, PO5 1- mineral matter 67 Cartilage 33 The mineral matter in bones increases with age. The teeth resemble the bones in composition. Dentin is like dense bone. Organic matter in it 28 P.C. The enamel contains no cartilage. Mineral matter in teeth 3CaO PO5 81-88 P.C CaO CO2 7-8 Ca Fl 3-4 3MgO, PO5 1-1 1/2 Muscular tissues. They are extremely complicated & contain many substances but may be on an average. HO 74-80 P.C Solid ingredients 26-20 PC. Among the solid ingredients 280 There are in the 26 parts. Syntonin 15.4-17.7 Gelatinous substances 0.6-1.9 Albumen 2.2 -3.0 Kreatin } Kreatinine } Inosite } Inosic acid } Hypoxanthin } Traces Fat 1.50-2.30 Lactic acid 0.60-0.68 PO5 0.66-.70 NaO 0.07-0.09 KO 0.50-0.54 Mgo } ZnO 0.02-0.03 } Traces. NaO is chiefly confined to the blood & KO is in the flesh. Many of these are dissolved in the fluid surrounding the fibres of the muscles. Healthy muscles have an alkaline reaction but after the rigour of death an acid reaction. Contraction of muscle is always accompanied by oxidation CO2 being evolved 281 In this the sapid constituents of the meat reside & the bodies wh. are so important for nutrition as the phosphates. If you take the flesh of the fox & venison & express the juice & dip the flesh of the fox in the juice of the venison & cook it, you cannot distinguish it from venison. If you take away these juices Supposing you wish to make soup you wish to get out the sapid constituents, in boiling meat you want to keep in these. To make the strongest soup. Mince the meat, put it in cold HO & gradually raise the temperature. You must go beyond 150°F before you coagulate the blood & till this is done the soup 282 has a red colour. To boil meat plunge it at once into boiling HO on about 1/4 hour & then reduce the temp. to 160° by adding cold HO. x The boiling HO at once coagulates the albumen on the surface & the sort of crust thus formed keeps in the sapid & nourishing constituents. To make the strongest possible soup for invalids Take one lb of lean beef mince it & mix with 1lb of HO, heat it very slowly till it boils & all the soluble & gelatinous matters are extracted. You then strain it thro' a cloth The effect on the patient is very different if you leave it with its straw colour or colour it with burnt sugar or burnt onion. If you colour it they think it is much stronger. * Keep simmering & about the end of the operation you may raise to [illegible] again 283 Evaporate this to dryness & you get the true extract of flesh. That sold in shops is only glue. In boiling beef the albumen coagulates at 140°F but the blood globules do not coagulate before 158°F. On this account in roast meat although it is perfectly cooked, the inside sometimes appears raw, the heat there having never been up to 158°. Relative values of meat In 1 lb of each. Veal Beef Mutton Pork HO 10oz-0grs. 8oz-0grs 7oz 16.6.69 3 grs Gelatine 1-2 1-62 1-52 0.385 Fibrin & albumen 1-199 1-122 0-385 0-315 Fat 2-281 4-340 6.176 8-0 Mineral matter 0-312 0-350 0-245 0-105. Salting of meat. When meat is placed in salt a curious action goes on. 284 From its affinity for HO the salt takes the HO from the outside of the meat & dries it. The juice from the inside of the meat is then diffused into this & thence into the brine. But the brine does not easily penetrate into the meat. The sapid constituents & the mineral salts come out. A great part of its nutriment is thus removed from salted meat. When it is long used scurvy & other diseases arising from defective nourishment make their appearance. Components of the brain. They are not satisfactorily made out. Among them are oleine, oleic acid, leucin, margaric acid Cholesterine, stearic & palmitic acid 285 The two characteristic ingredients are cerebric acid & oleophosphoric acid. Cerebric acid. It is a phosphorized fatty acid. & is found partly free & partly in combination with NaO. Insoluble in HO but swells like starch when the HO is heated. Oleophosphoric acid. It is a greasy oily liquid partly found free & partly in combination. Found also in the yolk of egg. When long boiled it is decomposed into oleine & phosphoric acid. Mineral ingredients are of very small amount. They amount in the human brain to 0.027 PC of these 3KO, PO5 55 P.C 286 3NaOPO5 23 PC 3MgOPO5 3FeOPO5 3CaOPO5 There is also PO5 either as stronly acid phosphates of free also SiO2 Glands & their juices Leucin is in the pancreas & spleen, in thymous gland in thyroid body & in living ox. Lyrosin Hypoxanthin in the spleen thymous gland Uric acid in spleen. Formic, acetic, succinic & lactic acid are found in these glands. Inosite in the spleen, liver, kidney Thymous gland pancreas & lungs. Cystin. Taurin Guanin in the pancreas of ox. The mineral ingredients in glands vary much In the liver the KO salts predominate 287 predominate over those of NaO. The reverse is the case in the spleen. Cl forms 2 1/2 P.C. of the ash of the spleen & 3/10 PC of the spleen PO5 forms 33.5 PC of ash of liver & 18.5 P.C of ash of spleen. CaOMgO in small quantity In spleen Fe is abundant, forming 7 to 16 PC of the ash. Mn, Cu & Pb are commonly but not always found both in the liver & spleen. In occasionally Digestive fluids Saliva S.g 1.004 to 1.006 It is always alkaline but more so during meals than when fasting. The saliva of the pyrotid gland contains ptyalin as a marked ingredient It has the same power as diastase of converting starch first into [illegible] & then into sugar It is an albuminous matter in a state of change 288 Ptyalin It is an albumenate of NaO. Forms 1/3 of the whole sold residue of saliva. It is very prone to decomposition or putrefaction. It is a strong ferment. The conversion is almost instantaneous. Composition of saliva of pyrotid gland. In 1000 parts from the dog. HO 995.3 Solid residue 4.7 Of the residue Organic matter 1.7 Alkaline chlorides & sulphocyanides 2.1 CaOCo2 1.2 In certain animals the sulphocyanides exist more than in others. Add a per salt of Fe to saliva & a red color is produced showing the presence of sulphocyanogen. The composition of human saliva is like that of the dog's. 289 HO 994.10 solid residue 5.90 The presence of sulphocyanide of NaO is characteristic. The daily secretion of saliva by an adult man is about 48oz. but differs according to his food. Mineral matter in it consists of KO, NaO & CaO salts. The last when acted on by the air & converted into CaOCo2 forms the solid encrustration froth on horses mouths. CaOCo2, 3CaOPO5 & mucus form tartar. The sulphocyanide of K on the teeth is a medicine The function of saliva is partly chemical & partly mechanical. Healthy saliva is frothy & carries down 0 into the stomach * The KSCy exists chiefly in saliva of man & sheep 290 stomach wh aids the digestion Its chief function is to convert the starch of food into sugar. The [crossed out] saliva from the pyrotid gland alone has not this power. Various nations have found out this power of saliva. The formation of diastase is the use of malting. In South America there is a fermented drink made from maize. Old women chew it & spit it into jars, it is then fermented. The pancreatic fluid is like saliva. It is alkaline like it & converts starch into sugar It is a colourless clear, frothy, tenacious substance S.G 1.008. Coagulates only slightly when gives 1.36 P.C of solid matter Contains a solid substance, like albumenate of NaO but not identical 291 identical with it is prone to decomposition Ptyalin An adult man secrets 10lbs of pancreatic juice daily. Pancreatic juice of dogs. HO 980.45 solid residue 19.55 pancreatic ferment 12.71 Mineral bodies 6.84 Its chief juice is to convert into sugar the starchy matters wh have escaped the action of the saliva. Bernard of Paris asserts that it acts as amulcin & breaks up fats* Pancreatic juice does this out of the body It is possible that the pancreatic juice may reform the NaCl broken up in the process of digestion. Gastric juice It is the fluid poured out from Into glycerin & fatty acids 292 the lining membrane of the stomach. It is neutral in the empty stomach. acid when food has been recently taken in. S.G 1.0023. The acid is generally lactic acid. Shmidt's analysis HO 994.4 solid ingredients 5.596 peculiar ferment pepsin 3.195 free HCl 0.2 CCl 0.06 NaCl 1.46 Lactic acid is with it in varying quantity. The saliva is mixed with it in analysis. Marked ingredients. Pepsin & free acid. Pepsin. It is an albumenous body soluble in HO insoluble in alcohol. The HO solution is precipitated by [illegible] H8, Pb. 293 Converts coagulated albumen into the soluble form only does so in presence of free acid, The fresh gastric juice of the dog dissolve 1/20th of its wt of coagulated albumen. Its function is to render the nitrogenous parts of the food soluble but to accomplish this it must have free acid. Bile immediately suspends the action of pepsin. * The quantity of gastric juice secreted by animals is almost incredible about 1/4 of their wt daily. In the case of Katharine Cutt a person who had a fistula thro' wh the stomach could be observed it was about 30 lbs daily. Yet it is not sufficient to dissolve all the albumenous bodies introduced as food. *Thus the gastric juices has no effect on food after it has passed into the intestine 294 The stomach is protected from the action of the gastric juice by the epithelium & not by its vitality for the hand legs of a frog introduced into the stomach thro' a fistula were digested, the vitality of the frog not preventing it. The intestinal juice seems to combine the effects of the pancreatic & gastric juice. About 10oz one secreted daily Bile is the liquid produced from venous blood by the liver. It is a viscid tenacious fluid of a brown or green colour & musty odour & bitter taste S.G 1.02. It putrefies readily but if freed from mucus it does not change. Sometimes alkaline often neutral. Composition. HO [crossed out] 90.44 Biliary bodies 8. 295 Aqueous extract, alkaline salts. phosphates chlorides & lactates 0.85 Mucus 0.30 NaO & KO 0.41 Characteristic bodies Resinous matter. Cholic acid. Tauro & Glyco-cholic. It unites with alkalis like resins Cholosterine is always in healthy bile in small quantity 1 part in 10000 parts of bile. Retention of bile concentrates it. A man of 10 stone secrets 5 lbs daily. Its main use is to promote the digestion of fatty matters. Lehman considers the bile as the waste matter of formation of blood corpuscles If you moisten one capillary tube with HO & the other with bile & put them in a fatty substance the fat rises higher in the tube wetted with bile than in that wetted with HO. 296 It probably neutralizes the acid chyme from the stomach. Excrement It consists of undigested particles of food of epithelium & mucus decomposed biliary constituents. Its smell is due to decomposed biliary constituents or the imperfect combustion of albumen. If you distil albumen with KOHO you get essence of excrements. When the diet is mixed the colour is yellow brown on a flesh diet it is darker & on a milk diet it is yellow. Its action is generally alkaline In an adult man there are about 5oz daily. It contains 73 PC HO 27 PC solid constituents. The N in the fœces & in the urine 297 correspond closely to the N introduced in the food. There are few soluble salts in the foeces these having passed out in the urine. There is more MgO than CaO in proportion to the food, showing that some CaO has been taken into the system. The foecal ash gives 31 P.C. of tribasic PO5 . Taurin is always found & a peculiar crystalline body very unpleasant to prepare called excretin C78 H78 O2 S. Intestinal gases They owe their origin partly to air conveyed to the stomach & partly to the decomposition of the intestinal contents The O has disappeared in the large & middle of the small intestine The chief gases are CO2 & N. 298 H sometimes appears & when it does so in large quantity to extent of 25 PC Carbonetted H sometimes appears. HS rarely exceeds 1-2 P.C. Blood. General properties. It is a thick viscid fluid S.G 1.055 in human blood, usually of a bright cherry red, arterial blood is lighter coloured than venous when removed from the body it changes & separates into the clot or cross amentum & serum. When warm it has a peculiar odour stronger in the blood of man than women. If you add HOSO3 to blood it gives a stronger smell If you add HOSO3 to the blood of the horse & heat the smell of the stable becomes perceptible, or if to cows blood, the smell of the cow 299 house. The S.G of women's blood especially during pregnancy is less than that of men's. Blood is not only a solution but an emulsion holding solid particles suspended in it. It contains blood corpuscles, lymph corpuscles fat globules Blood corpuscles. They are thick circular slightly biconcave discs. In human blood they about 1/3200 th of an inch in diameter. In most mammals except the elephant they are smaller than in man. In amphibia they are very large. Lymph corpuscles. They are lighter than blood. The fluid in wh they float is called the liquor sanguinis 300 & contains fibrin in addition to the solid constituents of the serum The clot is coagulated fibrin & contains the blood corpuscles & some serum. The composition of living & dead blood is different Living blood Blood corpuscles Liquor sanguinis Dead blood 2 minutes after being taken from body. clot = fibrin & corpuscles Serum. Average of 22 analysis of healthy human blood. HO 781.60 } solid constituents 218.40 } in 1000 parts. Of the solid constituents Blood corpuscles 135.0 Albumen in serum 70.0 Fibrin 2.50 Fats 1.55 Soluble salts 6.0 Earthy phosphates 0.35 301 Fe 0.55 Extracted matter 2.45 Various analyses have been given of blood corpuscles & liquor sanguinis. The blood corpuscles contain 16.75 hæmatin } 241.07 hematocrystalline } in 1000 parts Liquor sanguinis contains neither of these but contains 4.05 fibrin 78.84 Albumen. The two characteristic constituents are hematin & hematocrystalline. Hematocrystallin is a glucoside Prep. of Hemat Mix defibrinated blood with a saturated solution of NaOSO3 & wash with alcohol & ether. C44 H22 N3 O6 Fe. Hæmatin Occurs in blood in the soluble form. 302 It is got also as a brownish black substance without smell or taste On ignition it leaves a considerable quantity of Fe2 O3 Dissolves in alkalis but is precipitated by acids. If you add KONO5 to blood the fibrin does not coagulate. HCl, NaCl, KOSO3, acid phosphate of KO & of NaO, bibasic phosphate of CaO & MgO are the mineral constituents of blood. In the liquor sanguinis NaCl, phosphate of NaO & HCl in small quantity are found. Gases in blood. CO2, N & O. They are found almost entirely in the blood corpuscles & hardly in the serum. If you shake up serum with gases it does not absorb them, but the blood corpuscles 303 corpuscles do to a considerable extent. In arterial blood there is relatively but not positively more O than in venous blood. Ratio of O to CO2 in arterial blood is as 6 to 16 & as 4 to 16 in venous blood. Coagulum. The clot is produced by the coagulation of fibrin. The cause of this is due to a considerable extent to the escape of NH3. 1 part NH3 keeps 3000 parts of blood fluid in a close vessel at 98°F. Agitation hastens coagulation & free access of air also Dilute solution of salts retard coagulation. In inflammatory diseases there is a constant increase of fibrin in the blood. In inflammatory blood it is covered with free corpuscles. In dysentery the fibrin also increases & albumen diminishes 304 Serum After the separation of the blood corpuscles & fibrin the serum is sometimes turbid owing to fat globules in drunkards & pregnant women's blood It is usually a straw coloured liquid The serum of womens blood contains 1 P.C. more of HO than men's. In mans blood 90.71 PC -women's- 91.71 The serum of arterial contains more HO than that of venous blood. Albumen in serum 7.9-9.8 - in collective blood 6.3-7.1 Albumen decreases in most diseases especially scurvy Bright's disease In intermittent fever & cholera it increases & after drastic purgatives Dropsy begins when the albumen in the serum is below 6 PC. 305 Various salts in small quantity are found in the serum. Analysis of ash serum. KCl 4.054 P.C NaCl 61.087 NaOCO2 28.78 acid phosp. NaO. 3.195 KOSO3 2.784 NaOCO2 & KOSO3 probably exist in the blood as lactates of NaO & KO. Chyle It is the liquid into wh the nutritious portion of the blood is converted. Its composition varies according to the food. It is an opalescent fluid, has a feebly alkaline reaction. & maukish taste When boiled it deposits a small quantity of floculent albumen. That from the lacteals does not coagulate. The fibrin in chyle seems to be less elaborated than in blood 306 Casein, fat, lactic acid & sugar are said to occur in chyle. There have been few opportunities of examining healthy human chyle. That of animals seems to be a dilute kind of blood. When exposed to air it becomes red. There is 12 P.C. of mineral residue in the solid residue. NaCl is abundant & alkalis combined with albumen. Lymph. It is a colourless or yellowish fluid got from the lymphatic. The ingredients seem to be the same as those of blood It coagulates in from 5 to 20 minutes after being taken out. Analysis of lymph. HO 957.6} Solid ingredients 42.4} in 1000 parts. Fibrin & lymph corpuscles 0.37 307 Albumen & extractive matter 34.72 Mineral matter 7.31 It is supposed that 22 lbs of lymph are formed in the body of an adult man in 24 hours. Fluids of generation & development The seminal fluid has been mixed with secretions of prostate & other glands before analyzed. It is commonly heavier than HO slightly alkaline, is coagulated by alcohol but not by heating. Characteristic ingredient Seminal filaments The motions of these are arrested by various solutions, as of kreosote.* Fluids of the egg. Generally consist of 2 parts the yolk & the white. The yolk contains fat globules & corpucles surrounded by fluid The corpuscles are phosphorized *And neutral salts &c. 308 fat probably glycerophosphoric acid The molecular granules are casein They form 14 P.C. of yolk. Albumen 3 . Collective fats 30. Glucose is always in the yolk. There are two pigments yellow & red. Mineral of constituents 15 P.C. White of egg contains 12 1/2 PC of albumenous ingredients, & ale Margarine oleine & glucose. The mineral ingredients are soluble & consist in a great measure of NaCl. The shell contains 97 PC. of CaOCO2 . & a little phosphate of CaO, MgO & organic matter Milk. It is an opaque fluid, of a white, bluish white or yellow colour. It is generally alkaline, sometimes acid.* s.g of women's milk 1.032. *as in carnivores 309 Under the microscope it is a clear liquid with fat globules wh have a fibrous covering. When this cover is broken in churning it allows the butter to gather These globules floating to the top produce cream. It does not coagulate but on heating it forms a scum from oxidation. Average of 89 analyses of human milk. HO 889.08} solid ingredients 110.92} in 1000 Milk sugar 43.64 P.C. Casein 39.24 P.C. Butter 26.66 Salts. 1.38 The quantity of casein increases with animal food During suckling the milk becomes changed. The butter remains tolerably constant 310 The casein increases as the child becomes developed Milk of dark haired women is better than of blondes & is richer in fats. The composition of asses milk is nearer that of women than any other animal. Composition of Cows Milk. HO 86.2 P.C Casein 4.2 Butter 5. Milk sugar 4.1 Mineral matter Urine. The urine is a liquid secreted by the kidneys from the blood. It removes the nitrogenous parts of decomposed tissues. Human urine is a clear fluid of a bitter saltish taste & bright amber colour 311 S.G 1.015 to 1.025. In a state of health it never exceeds 1.03. It has an acid reaction. In clean vessels it has no great tendency to putrefy but if there is any decaying organic matter present it does so readily. As it cools it often deposits a cloudy sediment, especially morning urine. On standing crystals of uric acid appear The composition of urine varies according to the food & exercise. In an experiment a man of 11 stone passed 52 oz of urine in the 24 hours. In this Urea 520 grs Uric acid 8 Hippuric acid 15 Kreatin 7 Kreatinine 4.5 Xanthin & Hypoxanthin Traces *Found after eating green [illegible] & fruits containing benzoic acid 21 312 Mineral matter 376 grs. Of wh NaCl forms 266 grs. The chief characteristic ingredient is urea. It is a product of the oxidation of the tissues. It is said that when albumen is oxidized by MnO2 urea is produced but this is doubtful. It is however certainly produced in the system from the oxidation of the tissues It is also got by the oxidation of uric acid & by the action of alkalis on kreatin & [crossed out] alloxan. NH4 O CyO when heated becomes urea Urea has the same empirical formula as NH4 OCyO though it is arranged in a different way N2} } H2 } H2 } H2 Na} } C2 O2 } H2 } H2 313 Crystallizes in 4 sided prisms like KONO5 soluble in alcohol & HO forms salts. It forms 77 to 82 P.C of urine evaporated There are about 25 parts of urea in 1000 parts of common urine. A man of 10 stones wt excretes daily 442 grs urea. - " - 520 grs. From 58 observations on young men the average is 549 grs per day. The average of 58 observations on young women is 425 grs. If the same weight of children from 6 to 3 years old & of old men. The children secrete 3 times as much as the old men. The average of urea is 244 Adult man on mixed diet 518 grs - vegetable - 389 - 314 Adult woman on mixed diet 412 grs - vegetable - 309 Professor Fry of Trinity College Dublin made various experiments on the students. Well fed flesh eating wine drinking students yeilded 576 grs daily Well fed water drinking vegetarians 394 grs Certain diseases influence the quantity of urea. it is increased in typhoid fever, in pneumonia pleurisy & rheumatic fever. Uric acid in urine. In urine it is generally combined with NaO. It is rarely more than 1/10 P.C in urine. From 7-8 grs in an adult man. In perfect health there ought to be no uric acid. In Professor experiments on students he found 315. Beef eating wine drinking students 4 1/2 grs daily HO drinking vegetarians 1 1/2 grs - Hippuric acid. Occurs chiefly in the urine of herbivora. If you become a vegetarian, hippuric acid takes the place of uric acid in the urine. A large amount of HO taken into the system lessens the uric acid as also sulphate of quinine taken as a medicine. Xanthin & Hypoxanthin Kreatin 5-7 grs in 24 hours Kreatinine is a product of the metamorphosis of kreatine. Extractive matters are less abundant in the urine of the child than of adults. Extractive matters are uncrystallizable bodies wh we do not 316 know. In starvation the exceed the ureaic in quantity. Among them are damaluric, carbolic & other acids & some volatile acids. Urine pigments. Indican the glucoside of indigo blue. Mineral ingredients. Of these NaCl is far the largest in amount Daily average in 8 students. .269 grams in 24 hours The average is generally taken as 200 grs for an adult male & less for women & children In acute diseases of the febrile sort the chlorides rapidly diminish, but when convalescence begins the chlorides increase rapidly. 317 The chlorides are carried off in the watery stools & in perspiration Sulphates. They occur in varying quantity The HOSO3 excreted daily as sulphates is 32 grs. The proportion rises in the afternoon & during digestion Animal food & active exercise increases the amount of the sulphates Phosphates PO5 is found in the urine partly as NaO PO5 & partly as phosphates of MgO & CaO In an adult man 50 to 60 grs of PO5 are excreted daily as phosphates. The maximum & minimum is the same as with the sulphates. Animals food increases the phosphates. Earthy phosphates excreted daily 318 are 15 grs. Fe in minute quantity is in urine. SiO2 & Fl in very minute traces. Secreted daily by an adult man. NaCl 266 grs HOSO3 (as sulphates) 32 PO5 (as phosphates) 55 Alkalis, CaO MgO & other salts. Undetermined. Abnormal ingredients. The presence of albumen in the urine often indicates Bright's disease, but it may be due to accidental causes. The urine may sometimes coagulate in health. Taking cantharides or a stimulant diuretic & pressure of blood in the kidney as in heart disease produces albumen in the urine. In boiling urine always add a 319 drop of NO5 after the operation When albumen remains persistently in the urine it is dangerous symptom. Fibrin sometimes occurs in urine Sugar does not exist in healthy urine but in diabetes & gout When the flow of 4th ventricle of the brain is punctured sugar appears in the urine & remains for some hours Sugar appears to be in the foetal urine. Fat does not occur in healthy urine but does in Bright's disease & chronic insanity. fatty degeneration of kidneys in in rapid emaciation but generally from Biliary compounds are found in jaundice. NH3 never occurs in healthy urine unless it has been accidentally 320 changed in the kidneys as by too long retention. In scarlatina it appears even though the urine be acid. When urine is alkaline NH3 generally is present, urea being very readily decomposed. Urine of animals The composition of that of the carnivora most nearly approaches to the human. It is light yellow & nasty odour bitter taste Has an acid reaction It contains much urea, little or no uric acid & much pigment. Dogs urine contains cyanuric acid That of the herbivora is yellow turbid. Contains hippuric but no uric acid. oxalate of lime & only a small amount 321 amount of phosphates relatively to man When they are fed on animals diet as the calf while suckling they give urine like that of the carnivora. The urine of birds forms a white coating to the solid excrement consists chiefly of urates of NH3 & CaO The urine of frogs is liquid & contains urea NaCl & phosphates. That of serpents is at first pulpy but soon dries & consists mainly of urates of alkalis, with a little urea Urinary sediments The occurrence of sediment in fresh urine as soon as cooled may sometimes show disease. It consists either of organized or unorganized substances. Inorganic sediment Uric acid Urates Organized Mucus & epithelial scales. 322 Inorg. Hippuric acid Oxalate of lime Earthy phosphates Cystin Org. Blood corpuscles Pus corpuscles Cancerous & tubercular matter Fibunous coats of the tubes of the kidneys Spermatozoa fungous bodies and infusoria Uric acid. Only occurs in strongly acid urine in any quantity; may be deposited after fermentation from decomposition of urates When free lactic acid is voided it decomposes urates & deposits uric acid. Uric acid sediment is always coloured, generally yellow or brown. Test. With HONO5 & NH3 it forms murexide. The urates are the most common of the sediments all occur in acid urine except that of NH3 Their colour varies from greyish white 323 to brownish red or purple. Urate of NaO. The cause of the sediments is partly their greater solubility in hot than cold HO. Sometimes from the HO in the bladder having exuded & left too little to dissolve them. Hippuric acid rarely occurs as a sediment. If a fruit like greengages containing benzoic acid be taken freely or if benzoic acid be taken as medicine or otherwise, hippuric acid appears in the urine Oxalate of lime It is sometimes produced by changes in old urine so it is not to be confounded with that deposited from fresh urine Earthy phosphates always appear when the urine is alkaline. 324 Urinary Calculi. They are formed in the kidneys or bladder by deposition or retention of urinary sediment. Around a nucleus more matter gradually accumulates. Sometimes the matter is not all of one kind The composition of the calculi is generally the same as that of the sediment. Uric acid or urates Kanthin Cystin Oxalate of lime CaOCO2 . Phosphate of lime Phosphates of MgO & NH3 . Fibrin & mucous compound Phosphate of MgO may be formed by throwing MgOSO3 into urine & allowing it to stand. The substances valuable as manure 325 manure may thus be removed, Fibrin & mucous compounds Respiration. The act of respiration consists essentially in the interchange of gases existing in the blood with those in the air. In animals low in the scale it takes place on the surface of the body but most animals have definite respiratory organs. The gases given out from the body are in the venous blood, but this does not come in the direct contact with the air. The lung tubes branch out into small ramifications & thus present an immense surface in small space. The air & blood are separated by a thin moist membrane thro wh the gases interchange by exismosis. The O is changed for CO2. 326 The change of colour in the venous blood from dark to light red is due not so much to the absorption of O as to the expulsion of CO2. If the CO2 be expelled & H substituted the same change takes place. The O taken in is in greater volume than the CO2 given out. The reason of this is that the O has to oxidize the tissues & convert them into urea & to make H into HO. When O is converted into CO2 it occupies the same volume so the interchange would be volume for volume if the O had not more work to perform in the body. For each volume of O absorbed in the lungs, there is only 0.8516 vol. of CO2 evolved. Hence there is 1/7th more O taken into the body than what is required for conversion into CO2 327 When we examine the volume of air expired after it has cooled & dried it is less than that inspired. The aqueous vapour expired in 24 hours is from 11 to 14 oz. Some of this is due to the HO taken as drink as well as to that formed in the system. The N in the air is little affected by respiration. A very slight increase of N in the air expired may be due to that dissolved in the HO we drink. The air expired is 0.402 ricer in O than that inspired. There is a very small quantity of NH3 to be detected in the air expired. The most important gas is CO2. The expired air of a healthy man contains 4.334 P.C of CO2. 328 Only a small part of the O of the air is taken up. Weight of gases expired by an adult man taking a general average during 24 hours. CO2 27.8 oz N in excess that inhaled .5 Aqueous vapour 14. Inhaled. O. 23.3 So that about 3 oz of O are retained in the system or go out in other excretions. The amount of CO2 in expired air depends on the frequency of respiration In Gerhardts' experiments Acts of respiration per minute 6 12 24 CO2 in 100 vols of air expired 5.528 4.262 3.355 329 48 2.984 96 2.662 When the breathing is undisturbed 30.5 cub. in. are expired in one respiration. But the rhythm of the respiration is Not all the CO2 in the pulmonary vessels is removed as it passes thro' the lungs. The respiration of air richer in O than common air produces no marked difference in the CO2. An animal breathes undisturbed though the O be increased to 3 times its normal amount. When decreased by one third they show no change but when decreased by two thirds they show great distress & if reduced to 3 P.C they rapidly 330 die. CO2 if added gradually to air does not impede respiration up to 12 P.C. When the animal has absorbed about 1/3 of their bodily volume of CO2 they show symptoms of poisoning tho' the O supplied along with the CO2 [illegible] The CO2 cannot escape by diffusion The largest portion of inhaled air goes back unchanged, only 1/5 th of the air in the lungs is changed in one respiration. Gases have no tendency to diffuse into themselves & when the air is charged with CO2 that in the system does not diffuse out. It is this wh renders CO2 a poison. A rabbit may breathe in an atmosphere of 20 P.C. CO2 for 20 hours if there be a constant supply. 331 CO in minute quantity will produce death if there be no ready method of diffusion. An atmosphere of 1 P.C. CO2 has been known to produce death especially if mixed with CO. According to Dr. Edward Smith's experiments the expiration of CO2 is less in hot parts of the season than in the cold. In the middle of August the CO2 is 30 P.C less than in the cold season. The maximum is in April & May & begins to fall at the end of May or in the beginning of June. It ascends in October & is high in December. Moisture in the air increases When there is change of barometric pressure in either direction there is an increased amount of CO2. 332 The effect of fasting is to diminish the amount of CO2. Some cats experimented on at first converted 80 P.C.O into CO2. 77 P.C the 2nd day & when they died of starvation 73 P.C. Dr E. Smith fasted for 27 hours & expired 0.25 P.C less CO2. There was a remarkable uniformity in the composition of the expired air but the number of respirations was less. Influence of sex & age. The male expires more CO2 than the female. Boys of like age expire more than girls. Charling's experiments age weight in kilograms CO2 per hour in grams CO2 per hour for every 1000 grams of wh Man 35 65.5 33.53 0.5119 youth 16 57.75 34.28 0.5887 soldier 28 82. 36.62 0.446 girl 17 55.75 25.34 0.454 333 Boy 10 22. 20.338 0.924 Girl 10 23. 19.162 0.883 Effect of exercise Exercise increases the CO2. Influence of food. The food influences the CO2 evolved. More O is absorbed to form CO2 when starch is used than when animal food is used. Less N is evolved on a vegetable than on an animal diet. In dogs fed on suet 6g P.C of the absorbed O was evolved as CO2. Fats contain a good deal of H as well as as C & O is required to oxidize this. In starch the H is combined with O.* Respiratory equivalents or amounts of food required to produce the animal heat in the body itself. 100 parts fat require 292.14 Oxygen *Animal food requires much O to oxidize albuminates & form urea 334 100 Starch 118.52 100 Sugar 106.67 Malic acid 82.78 Albumenous bodies 153.31 Dr E. Smith has drawn some conclusions wh however require farther confirmation. He says that food may be divided into 2 classes, those wh excite respiration & those wh do not. Exciters. Nitrogenous foods, milk sugar rum, beer, stout, the cereals Nonexciters. Starch, fat, certain alcoholic compounds, volatile elements of urine & spirits & coffee leaves. Pure alcohol, rum, ale & porter generally increased the respiration. Sherry lessened the air inspired but increased the CO2. Tea, coffee, chicory, & cocoa are respiratory exciters. Tea is the most *Brandy lessened it 335 powerful*, next coffee, next cocoa & lastly chicory. The addition of sugar & milk increases the respiratory effect. Its influence is immediate, its maximum is in about 20 minutes its duration is from 1 to 2 hours. Cause of sleep When trying to sleep the first thing we do is to take away the pressure, of the column of blood on the heart, wh we do by getting into a horizontal position. We lessen the respiration by lying in a fixed posture. The amount of O dissolved in the blood in the system is lessened. At every vital act there is change of matter. They are only destroyed in the act of oxygenation. *Therefore recommends tea to be given in suspended animation as a respiratory waiter 336 In every thought a portion of the brain is destroyed & as we get the O diminished in the blood the brain finds more difficulty in manifesting itself to the external world. In the case of the drunkard the O unites with the alcohol & the brain refuses to manifest itself & he becomes dead drunk. Sleep of hybernating animals During summer they accumulate fat round the heart & gradually push up the diaphragm against the lungs, this prevents the O being inspired readily & it falls asleep. Some wh do not accumulate so much fat as the tortoise take a roll of grass to push up the diaphragm. They are like a lamp slowly 337 burning the fat being the fuel. When this is consumed the diaphragm falls down the lungs begin to play the brain becomes active & the animal awakes. The conditions in wh we are most prone to sleep are when we have taken a large dinner wh pushes up the diaphragm. As there will be less combustion during sleep & so less animal heat we draw near the fire to compensate for this. Respiration of the lower animals. Carnivora living on ordinary food exhale more N & CO2 in proportion to their wt than herbivora Active birds consume 10 times more O than sluggish birds. Frogs & lizards convert 75 P.C & the salamander 82 P.C of O into 338 CO2. The wakeful ones consume 9 times & the half torpid ones 3 times as much as those wh are entirely rigid in winter. Origin of the CO2 It was once supposed that the CO2 was produced in the lungs. There seems to be no combustion at all in the lungs, for if there were the blood should be warmer there. This is not the case, as the blood is cooled in the lungs the blood of the left side of the heart is 2° colder than that on the right side: It seems to be produced in the tissues Every vital tissue of animals yields CO2 to the air pump. Gustave Liebig says that the muscles of the frog possess irritability * so long as the exhale *So long as they absorb O. If placed in H their irritability stops. 339 CO2. The changes are produced in the muscles . General conclusions That 8 1/2 oz of C are converted into CO2. in 24 hours, for wh. 22.66 of O would be necessary, but as only 85 P.C of O is used for CO2, 26.7 oz of O or 1 1/2 lb are daily consumed by an adult man. He destroys daily 117 oz of air wh. is equal to 164900 cub. in. In the course of the year he destroys 7 hundred weight of O. 1/5 is made into the body. It is an old tradition that the body of an animal changes once in 7 years, but this is not true as all the C would be burned in 3 days*. A man of 11 stones has 4 lbs albumenous bodies in blood. 27.5 in tissues *If there were no supply of Co you may calculate the rate of concrete from the N in the urine & excrement. 340 5lbs in bones The whole body would be changed in 18 weeks supposing that they were all changed at the same rate. Animal Nutrition Plants live on mineral food, wh they find in the atmosphere, CO2 HO & NH3. They assimilate the C from the CO2 into their system & give out the O. They get their N from NH3 & sometimes though rarely from NO5 but not from the N of the air. They get their H from HO. They have nothing to do with volition & on this account they have the property of moulding inorganic substances into organic forms. Animals have the function of volition to preform & so have not this property. 341 All animals are essentially herbivorous, even carnivora being so although indirectly. All food may be divided into 2 classes characterized by one essential difference. Those wh contain N. Those wh are destitute of it. Nothing destitute of N can build up the muscle of an animal. Those wh contain N are the histogenetic substances, casein, albumen &c, whether got from plants or animals We may call the one sort wh contain N flesh formers & the other heat givers. There is necessity for a mixture of food of both classes* It was long supposed that gelatine was an extremely nourshing substance but a commision both *If only one kind be given the animal dies just as if it received no food as only one part of its nut is supplied 342 of France & Holland appointed to examine into this found that when animals were fed entirely on it they died. In milk there is an admirable admixture of both kinds of food. Casein flesh formers Butter, sugar heat givers There is also mineral matter in it In all cookery we try to obtain this mixture. We eat beef with potatoes mutton with rice & pork with peas or beans Nitrogenous food or flesh formers. All the tissues wh form any part of an organ of an animal contain 15 P.C of N. Animals are certainly unable to take N from the atmosphere. There is one apparent exception: when an animal takes benzoic acid containing, no N it voids hippuric acid wh does. This is however in question of excretion; not of nutrition. There is no ground to suppose *and also the blood 343 that flesh can be formed from nonnitrogenous substances by assimilating N from any other source. The nutrition of a carnivorous animal is very simple. It takes the flesh & blood wh it finds ready formed & appropriates them to its own system. That of a sucking animal is equally simple. It is like a carnivorous animal eating its mother. It finds casein in the milk & appropriates it. The nutrition of every animal is equally simple. We find the histogenetic substances in plants. Thus the juice of the cauliflower contains fibrin assitedd of blood. Animals do not form the components of their flesh & blood out of unlike matters but they find 344 them ready formed in vegetables The process of nutrition consist in extracting them & giving them a place & form in the organism. This is the great law of animal nutrition Plastic elements { {Flesh animal Fibrin {Blood Albumen {Casein This excludes gelatine Gelatine may indirectly act as food by supplying food for the cellular tissue & thus saving the other food. Gelatine may thus in the case of a very weak person be of use when administered along with some other food, not alone, by supplying material for the cellular tissue wh has been much wasted by illness. & thus allowing the other food to be applied to the purpose of building up the organs. 348 Non nitrogenous substances. Fat, starch, gum, cane sugar, grape sugar, milk sugar, pectin bassarin, wine beer & spirits Since they are wholly free from N they cannot build up the frame work of the body yet they fulfil a very important function viz. supporting the animal heat. The temp. of fishes and amphibia is only a few degrees above the medium in wh they live. That of quadrupeds is 99-100° F birds 105 man 98-99 child 102 In lower animals even in health the temp. is to a certain degree regulated by the medium in 103 they been In the higher animals there is always a fixed temp. in health. Depression of this temp is attended 346 attended with a depression of the functions of an animal. There must be some means of regulating this temp. since the temp. of a man at sunny Palermo or of a traveller in the polar regions is the same. The appetite of the man is the regulator. Non-nitrogenous substances are usually the fuel. though the tissues of the body are sometimes as in the carnivora. The hyena moves about in order to burn his tissues to keep up the animal heat. From the known composition of food it is easy to calculate how much food is required to keep up the same temp. on different kinds of food. The heat giving equivalents 347 or the quantity of food required to keep the animal heat the same. Weights of different bodies requires to produce the same amount of heat. Fat 40.2 Cane sugar 100 Alcohol 53.8 Grape - 106 Starch 97.2 Flesh 309.7 Flesh has 8 times less respiratory value than fat. After deducting the heat necessary to evaporate HO as vapour in the breath we find that the rest taken in diet is sufficient to raise 143 lbs of HO from 32° to 99° & the specific heat of the substances wh compose the body is less than that of HO. Varying quantity of respiratory food. The body of a man may be represented as a chamber to be kept at the same temp in 348 summer & winter & in different climates. If you transport a man from India to the poles the temp. of his body remains the same but you must put in more food to sustain it. In extreme cold man takes enormous quantities of food. Sir John Franklin says that during the whole of the march they found that no clothing could keep them warm as long as they were fasting but when they could go to bed with full stomachs they could sleep comfortably. Parry took an Esquimaux lad not full grown & set him down to a weighed repast. the quantities he devoured are the following., 349 lbs oz Sea horse flesh hard frozen 4 - 4 -boiled 4 - 4 Bread & bread dust 1 - 12 Rich gravy soup 1 1/4 pints Spirit 3 glasses Strong grog 1 tumbler Water 1 gallon 1 pint Ross says that an Esquimaux eats daily on an average 20 lbs of flesh & oil Admiral Sarcheff says that a yacot took in 24 hours the hindquarter of an ox & 20 lbs of fats. [illegible] proportionate quantity of melted butter for drink. These accounts are not more astonishing than the difference between the coal we burn in summer & winter. The character of the food is made to suit the climate. Fruits & rice contain 20-30 PC of C. Blubber 80-90 In India beer & butter are freely 350 taken but apparently less as food than to unctuate the body & prevent excessive perspiration. Ordinary food contains fat In Cocoa 50 PC In coffee 12 PC A man inhales daily to consume these about 3000 gallons of air, much of the O of wh is burned by the food. The starchy matters & fat in the food produce fat in the body. In a grate where there is a free access of air the fuel is converted into CO2 , but in a gas retort where there is only a very limited supply of air various tarry matters distil over. Thus in the muscular arm of an Arab who is almost constantly in the open air & taking exercise 351 exercise there is no fat, but in a man leading a sedentary life & taking little exercise the fat accumulates. If there is a free introduction of air the starch is converted into CO2. In hybernating animals the fat is formed by imperfect combustion of the food in summer & in winter they live on it. There was a very fat pig weighed to be sent to an agricultural show, but just before being sent a slip of land from a neighbouring hill overwhelmed it. It was thought to be dead & no farther trouble was taken about it. About 120 days after the slip was removed for the purpose of building & the pig was found alive but it had decreased 352 140 lbs in weight. Proportion between flesh formers & heat givers. Plastic Cow's milk 10 30 Woman's - 10 40 Lentiles 10 21 Beans 10 22 Peas 10 23 Fat mutton 10 27 - pork 10 30 Beef 10 17 Hare 10 2 Veal 10 1 Wheat flour 10 46 Oatmeal 10 50 Rye - 10 57 Barley 10 57 White potatoes 10 86 Blue - 10 115 Rice 10 123 353 Buck wheat meal 10 130 Mineral matter in food The body of a man weighing 150 lbs contains Phosphate of lime 5lbs 13oz 0 grs Carbonate - 1 - 0 - 0 CaFe 0 - 3 - 0 NaCl 0 - 3 - 376 NaOCO2 acid phosphate of soda 0 - 0 - 400 KoSO3 0-0-400 Feo 0-0-150 KCl 0-0-12 Phosphate of potash 0-0-100 3MgOPO5 0-0-75 SiO2 0 - 0 - 3 The different organs exercise a selection, thus, P is taken to the brain,* Ca Fl to the teeth, SiO2 to the hair & nails, S is generally distributed but is taken especially *3CaOPO5 354 especially to the hair, phosphates of MgO & KO to the flesh, phosphate of NaO to the blood & cartilages. NaCl may act by facilitating absorption of HO by diffusion or by aiding the solubility of albumen or by affording HCl to the gastric juice & NaO to bile & pancreatic fluid. Fe is an essential ingredient of blood, gastric juice, hair & the black colouring matter of the eyes. To find the proportion of flesh formers in the food estimate the N in it & multiply by 6 3/10ths. Amount of the several kinds of food required The circumstances of age variation of climate &.c. influence this. There are two ways of finding how much food is required. We might find how much C was expired as CO2 & how much C & N 355 are in the foeces & urine, An adult man Expires as CO2 8.8oz C daily in urine & foeces 2.2oz C N in urine foeces & mucus 334 grams The C excreted daily is thus about 11 oz & the N is equal to 4 8/10 oz of flesh formers. Average diet 4 oz flesh formers 3 oz fat. 10 1/2 oz amylceous food 1 oz injested salts. 84 oz HO. 33 oz O. Another mode is take the experience of public dietaries We find by these on an average that for an adult man, daily 5 oz flesh formers 10 oz C *The amount of N in excrements in health indicates the amount of urine wasted in the day, By multiplying it by 6.25 you get the amount of tissues 356 are required When we contrast the diet of the aged with this we find that with them the flesh formers have sunk to 40oz but that the C is the same The proportion of C in the heat givers to that in the flesh formers is now as one to five. In children form 10 to 12 years of age flesh formers 2 1/2 oz C 8 oz In the young the process of supply is greater than that of waste. In the adult it is equal & in the aged less. It is during sleep that the body is built up. An adult spends 17 waking hours & in mechanical labour & 7 in sleep. An infant spends 4 waking 357 hours & 20 in sleep during wh its growth takes place. An old man spends 20 waking hours & 4 in sleep. In an adult the waste is to the supply as 100 to 100 In an infant as 25 to 250 In the aged as 125 to 50 In an infant there would not be ptyalin enough to convert its [illegible] food into sugar & so it finds the sugar ready formed in the milk. The casein is also in a soluble state. in the milk so the gastric juice has not to convert it into a soluble state. In cooking we try to get the same proportion of the different kinds of food as in milk. Pauper & prison diets. Prison diets were & still are by no means well regulated. 358 It was thought that a man on long confinement required much more food than one on short confinement. The question however is what is the waste if the tissues. Work-house diet is about 3 1/2 oz of flesh formers daily. The hard labour diet is no more than this & is quite insufficient for hard labour. Besides they are on the system of alteration according to the time of excrement. 1st Cerials yield nutritious meals of varying composition. The finest flour is not the most nutritious on an average they contain 14.6 PC flesh formers 69. heat givers Mineal matter 1.6 P.C 359 Oats contain 5 PC. of fat 17 flesh formers 66.4 heat givers 3.0 mineral matters Probably half the human race partake of tea Tea leaves contain 5 P.C. HO 3 Theine 15 Casein 6.7 aromatic oil The casein does not come out unless you put in soda. 360 The peculiar aroma of coffee is due to an essential oil wh it contains Action of alcoholic beverages. Their action is to reduce the waste of the tissues When the amount of food is sufficient this is injurious acting like too much food The cheapest way of taking alcohol is in beer The cost of one oz of alcohol taken in different beverages is as follows in beer 2D. spirits 4D wines 18 6 D. 361 For the support of strength you can get an equal amount of nourishment from vegetables or animals. The character of men depends much on the food they take. It required 5oz. of flesh formers daily to do good day's work. To get this from potatoes, it is necessary to take 25 lbs, but even an Irishman's stomach can only take in half that quantity, so that an Irishman living on potatoes alone could only do half a day's work. The Irish famine caused new material for food to be introduced* wh being more nourishing than potatoes *And spread his work over the whole year instead of only 2ce a year 362 enough for a good days work could be taken without inconvenience. Who gave us trouble in the Indian mutiny? Not the rice eaters of Bengal but the pulse eaters We may sum up the general conclusions in the words of Prior. Was ever Tartar fierce or cruel Upon the strength of water gruel. Balance between animal & vegetable life The functions of animals & vegetables are precisely opposite in a chemical sense. A vegetable is a reducing apparatus, reducing CO2 An animal is an apparatus for oxidation. 363 Vegetables are fixed Animals have the power of locomotion A vegetable evolves O absorbs heat & electricity Decomposes CO2 - HO - NH3 Produces organic substances Transforms inorganic matter into organic Derives its elements from earth & air An animal absorbs o evolves heat & electricity Produces CO2 - HO - NH3 Consumes organic substances. Transforms organic matter into inorganic Restores its elements to earth & air Functions of vegetables. Animals find their substance in vegetables. The vegetable kingdom is 364 the great laboratory of organic life. They are powerful reducing agents. For every cubic foot of CO2 they reduce 1 cubic foot of O is restored to the atmosphere. The vital force of a plant growing in the dark is unable to reduce CO2, light is required for this. Nitrate of ammonia is formed by lightning flashes. 365 Functions of animals. In animals we certainly find organic matter in its highest forms but for a limited time only Then function is not to create organic matter but to transform it into inorganic matter. They use the organic matter of vegetables & make it into organs wh have high functions to perform. Broken down from the complex molecule, into wh it was formed by vegetables it becomes less & less complex at every change. Every change of them is a degradation. they being finally converted into CO2 & NH3 The process of decay produces CO2 & NH3. 366 [illustration] The substances of dead animals passes thro' the same change as the non-nitrogenous substances in their bodies The animal stands midway between the vegetable & mineral kingdoms. It has nothing to do with forming organic bodies 367 Mutual relation of plants & animals. Animals derive nutrition from plants. Plants truly feed animals but animals as truly feed plants. It is certain that the atoms of wh. we are composed have passed thro' a succession of animals & men. Perhaps the brain with wh. I (Professor Playfair) am now thinking once formed part of the liver of the Emperor of China. There is the mineral kingdom as represented by air & soil. The vegetable elaborating organic matter from the mineral. The animal living on plants but breaking them 368 down to mineral matter. Index Absorption in animals Acetates 76 Acetic acid artificial production of 73 Acetification process of 74 Acetone 68 & 75 Acetyl 67 Aconitin 100 Acrolene 100 Acid acetic 72 - anhydrous 70 - glacial 75 aconitic 134 acrylic 100 amido - acetic (glycocoll) angelic 101 benzoic 117 butyric 79 capric caproic Caprylic Carbazolic 113 Carbolic 111 Carminic Cerebric 285 Choleic [tairiochalic] 274 cholic 275 citraconic citric 132 cyanuric 159 dextroracemic 129 erythric 218 excretolic formic fulminic 158 fumaric 128 gallic 134 gallobaunic 136 glucic 198 glycocholic 273 glycolic 92 hippuric 315 humic hydrocyanic 142 hydroferrocyanic 149 hyocholic 276 hyoglycholic 276 hyofaurocholic 276 indigotic kinic (quinic) lactic 92 lauric licanoric leucic lithofellic malic 127 margaric meconic melanuric mesoxalic Mucic 199 Nitrobenzoic Nitrocinnanic Nitrococcussic Nitrophenic Oenanthic Oenanthylic Oleic oleophosphoric orsellesic oxaluric oxamic palmitic 82 parabanic 263 parellagic pectic pelargonic phenic picric 113 pinic propionic pyrogallic 135 pyroligneous quinic 132 quercitannic racemic 129 ruberythric 218 rutic 82 saccharic salicylic sebacic sorbic stearic 83 suberic succinic sulphobenzoic tannic 135 tartaric 128 taurocholic thionuric toluic ulmic uric 267 usnic vaccinic valeric xanthic Acids acetic group of - series of amidated 265 fatty oleic oxalic stearic dyective colours Albumen Albumenoid group pro- perties of. Albuminous urine Alcoates Alcohol, absolute - action of acids on allylic amylic - bases, mode of preparing butylic benzoin caproic cerotic caprylic cuminic ethylic hexylic (camoic) caurylic melissylic methylic oetylic price of propylic radicles synthesis of alkoliolic fermentation T.L. Brunton Edin. University Session 1861-2 Lecture notes Of lectures on Organic Chemistry by Professor Lyon Playfair [illegible] Contents [Inorganic] Table of Contents Table of organic substances wh may be formed from their elements without vital agency 1 Difference between organic & inorganic substances 4 Definitions of organic chemistry 6 Preparation of a higher from a lower alcohol 7 Empirical & rational formulas 8 Homologous series 10 Heterologous class 11 Qualitative examination of organic bodies 12 Quantitative analysis 15 Example of organic analysis 31 Olifines Ethylene series, Olefiant gas, Propylene, Butylene, Amylene, Hesylene &c 19 Marsh gas series, Hydricles of ethylene series 26 Alcohol radicals. Preparation 29 Table. Transformation of organic compounds by different ferments 32 Reduction of other series to olifines 33 Definition of radical 35 Ethers. 36 Substitution products of methylic ether 37 Haloid compounds of ether 41 Ethers as a class 42 Alcohols 44 Wines & spirits 48 Fermentation 51 Theory of the action of ferments 53 Brewing 55 Composition of malt liquors. Table 56 Homologues of the alcohols 57 General properties of alcohols 58 Compound ethers 59 Biatomic ethers & alcohols 62 Aldehyds 65 Ketones 68&74 Anhydrides or acids 69 Hydrated acids. Relation of these to alcohol & ether 71 Relation between the alcohols, aldehyds, & ketones 74 Acetates 76 Acids homologous to acetic acid 79 Fatty acids 82 Candles 84 Saponification 86 Candles from coal 88 Acids produced from bratomic alcohols 91 Oxalates 96 Negative radicals. Acetoyl. Allyl. Angelyl 98 Oxidized radicals of allyl 100 Table. Homologues of acrlylic acid 101 Glycerine 102 Glycerides on common fats 104 Soap 105 Chief fats 107 Aromatic series 109 Phenyl 109 & 117 Benzyl 115 Distillation of coal. Naphtha 118 Coal tar colours 122 Malic Tumaric, Tartaric, Racemic & Kainic Acids 127-132 Trebasic acids Citric, gallic, tanine &c 132 Tanning 137 Compound haloid radicals 139 Cyanogen 140 Hydrocyanic acid 142 Cyanides 145 Haloid ethers of cyanogen 146 Nitriles 147 Preparation of higher acids from nitriles 147 Double electronegative cyanides 148 Ferrocyanogen 148 Ferridcyanogen 152 Nitroferrocyanides or nitroprussides 153 Cyanates 155 Sulphocyanogen 156 Sulphocyanates & sulphocyanides 157 Bicyanogen 157 Fulminates 158 Tricyanogen 159 Characters of cyanogen 160 Organic bases representative of alkalis & metallic oxides in organic chemistry 160 Amines 161 Monameries 161 Production of these compound ammonias 162 Organic bases coal tar 164 Diamines. Urea. 164 Triamines 166 Organic alkaloids 166 alkaloids from hemlock, broom, tobacco, opium, chinchona bark, strychnine family, solinacia family. tea &c. 168-182 Hydrates of Carbon Action of dilute acids & oxidizing agents on them 182 Views of their chemical constitution 183 Cellulose-gum cotton-vegetable parchment 183 Starch. Starch in vegetables 186 British gum. Manufacture of starch 188 Special starches 189 Starch in the animal kingdom 190 Inulin Lichenin 190 Glycogen. Dextrin 191 Gums 193 Quantities of cellulose & gum in different vegetable substances 193 Arabin. Cerasine. Bassorin. Pectin 194 Sugars 195 Grape sugar or glucose 196 Test for diabetic sugar 197 Caramel. Saccharides. Glucic acid 198 Action of yeast & of nitrogenous ferments on grape sugar. mucic acid 199 Fruit sugar on fructose 200 Cane sugar or sucrose 200 Barley sugar. Caramel. Conversion of sucrose into glucose. Saccharides 201 Fermentation of sucrose 202 Manufacture of sugar 202 Refining of sugar 205 Sweetness & uses of sugar 206 Relation of H+O in sugar 207 Milk sugar 208 Lacto-carmel. Lactose 209 Trehulose. Megatose. Mellitose 210 Non fermentible sugars. Inosite 210 Seyllite. Sorbite 211 Glucosides. Salicin 212 Action of amulcin & acids on salicin 212 Saligenin. Populin. Quercitrin Convolvulin 213 Colouring matters 214 Isolation of colouring matters 214 Dyeing. Mordants. Printing 215 Madder. Ruberithric acid 218 Aliyacin. Lakes. Resemblance to 219 naphthalin. Production of Chloralizarin from naphthalin Purpurine. Rubiacine 219 Logwood Hematoxylin. Brazilwood 221 yellow dyes 221 Indigo 222 Topical dyeing 223 Colouring matters of lichens 224 Cochineal. Carminic acid 225 Volatile oils, resins & caoutchouc Essential oils 226 Stereoptines 227 Preparation of essential oils 227 Classification of these oils. Central formula 228 Essences isomeric with camphine 229 Turpentine 229 Essences not isomeric with camphine 231 Oxygenized essences Camphors 231 Resins, Copal. Mastic. Sandarac. Lac. 232 Sealing wan Lacquers 234 Guayacum. Jalaps. Amber 235 Caoutchouc. Gutta-percha 236 Asphalt & bitumen 238 Ozokerite. Sheerite. Fichtilite. Hartite Idualite 239 Animal chemistry Vital agency 240 Histogenetic substances 241 Existence of some both in animals & vegetables 242 Soluble & insoluble states Action of acids & alkalis on them 243 Putrefaction 244 Test for any of these nitrogenous bodies 245 Protein 245 Albumen albumen of blood 246 Insoluble albumen 248 Fibrin 248 Syntonine 249 Casein Vitellin 250 Globulin 252 Hemato crystalline 253 Derivatives from the albumenous group 253 Ossein Glutin 254 Glue confectionary gelatine 256 Theory of the formation of nitrogenous substances occuring as derivatives in the animal body 257 Kreatin. Kreatinine Sarkosine 258 Methyluramine. Sarkin. Guanine 260 Kanthin Cystin 261 Allantoin Tyrosine 262 Alloxan Parabanic acid 263 Thyanicric acid Alloxantin. Cerebrin. 264 Amide acids. Taurin. Leucin 265 Uric acid. Action of peroxide of Plouit. 267 Urates 268 Derivatives of uric acid 269 Murexide. Guanocolours. Purpuric acid. 270 Compounds from uric acid 271 Cyanuric acid. Inosic acid 272 Acids of bile 272 Glycocholic acid 273 Taurocholic acid 274 Cholic acid 275 Hyoglycholic acid 276 Hyocholic acid. Hyotaurcholic acid 276 Lithofellinic acid 276 Action of acids on cholic acid. Cholordic acid 277 Cholosterin 277 Solid constituents of animals. Bones 278 Teeth. Dentin. 279 Muscular Tissues Composition 280 Sapid constituents of flesh 281 To make strong soup. To boil meat 281 & 2 Extract of flesh 283 Relative values of meat 283 Salting of meat 283 Components of the brain 284 Cerebric acid, Oleophosphoric acid 285 Glands & their juices 286 Digestive fluids Saliva, Ptyalin, Froth, Tartar 287 Functions of saliva 289 Pancreatic fluid 290 Gastric juice, Pepsin. 291 Intestinal juice. Bile. 294 Excrement 296 Intestinal gases 297 Blood 298 Blood corpuscles. Lymph corpuscles 299 Composition of blood 300 Composition of blood corpuscles & liquor sanguinis 301 Hematin, Hematocrystallin 301 Gases in blood 302 Coagulum. Serum 303 Relation of dropsy to the quantity of albumen in serum 304 Chyle 305 Lymph 306 Fluids of generation & developement. 307 Milk 308 Urine 310 Urea 312 Uric acid 314 Hippuric acid 315 Extractive matter, what it is. 315 Mineral ingredients 316 Abnormal ingredients 318 Urine of animals 320 Urinary sediments 321 Urinary calculi 324 Respiration 325 Difference in volume between air inspired & expired 326 Cause of difference in colour between venous & arterial blood 326 N1 NH3 & CO2 in air expired 327 Effects of air richer or poorer in O than usual on respiration 329 Effect of air containing CO2 on respiration. Cause of CO2 acting as a poison 330 Differences in the expiration of CO2 331 Effect of fasting on the quantity of CO2 332 Influence of sex & age 332 Effect of exercise. Influence of food 333 Respiratory equivalents 333 Exciters & nonexciters of respiration 334 Cause of sleep 335 Sleep of hybernating animals 336 Conditions in wh we are most prone to sleep 337 Respiration of the lower animals 337 Origin of the co2 338 General conclusions 339 Animal nutrition 340 Classes of food. Flesh formers & heat givers 341 Flesh formers 342 Use of gelatine 344 Non-nitrogenous substances or heat givers 345 Varying quantity of respiratory food. 347 Formation of fat. 350 Use of fat to hybernating animals 351 Proportion between flesh formers & heat givers in various foods 352 Mineral matter in food 353 Amount of several kinds of food required. Manner of finding uses 354 Pauper & prison diets 357 Action of alcoholic beverages 360 Cost of 1 oz of alcohol in different beverages 360 Relation between character of men & their food 361 Balance between animal & vegetable life 362 Functions of animals 365 Mutual relation of plants & animals 367 [illegible] 13 1 Organic Chemistry Table of the most of important bodies capable of being formed from their elements without vital agency. Cyanogen (C2 N)=Cy Hydrocyanic acid CyH. Ferrocyanide of Fe2 Cy6 Potassium 4k+6HO. Ferricyanide of K. Fe2 Cy6 3K. Urea NH3 CyO } Ho } Marsh gas C2 H4 Oxalic acid C2 O3 HO } C2 O3 HO } Formic acid C2 HO3 } HO } Chloroform C2 H Cl3 Acetic acid C4 H3 O3 } HO } Alcohol C4 H5 O } HO } 2 Ether C4 H5 O } C4 H5 O } Olefiant gas C4 H4 Acetic Ether C4 H5 O } C4 H3 O3 } Oil of garlic C6 H5 S } C6 H5 S } Oil of mustard C6 H5 S } Cy S } Glycerine C6 H8 O6 Butyric acid C8 H7 O3 } HO } Oil of pine apples C4 H5 O } C8 H7 O3 } Oil of pears C10 H11 O } C4 H3 O } Oil of apples C10 H11 O } C10 H9 O3 } Valerianic acid C10 H9 O3 } HO } Grape sugar C12 H12 O12 Lactic acid C12 H12 O12 3 Caproic acid C12 H11 O3 } HO } Benzole C12 H6 Nitrobenzol C12 H5 NO4 C12 H5 O } HO } Picric acid C12 H2 (NO4)3 O } HO } Salicylate of methyl C14 H5 O5 } Oil of Wintergreen C2 H3 O } Naphth C20 H8 4 Organic chemistry is that part of the science wh relates to living bodies. Organic substances are either those with build up living bodies or are produced by living bodies or by submitting these products to different processes in the laboratory. If you compare alcohol an organic base with KO an inorganic base you perceive a great difference between them. Place alcohol in contact with an acid & it does not combine with it while KO does forming a salt. If you add chloroform an organic substance rich in Cl to acetate of Pb you get no precipitate of Pb.Cl. while if you add NaCl an inorganic substance containing Cl. you get a precipitate 5 precipitate If you take a solution of a salt & try reactions with it to-day & then try the same reactions with it to-morrow you will get the same result. If you can do this with an organic compound you may very probably get a different result. If you break up an organic compound you get C, O, H, & N but if you put these together in a flask you cannot make them combine. If you place Na, O & P together you will get NaOPO5 Place C, H & O together & you will not get an organic body. It was supposed at the beginning of the century that there were two different sciences. 6 It was sought to give a definition & in order to do this it was sought whether there was not some element common to organic chemistry & peculiar to it. It was proposed to call it the chemistry of carbon. But CO2, cyanogen & cyanide of K can be made without vital agency. There are bodies not organic wh contain carbon. Liebig defined it as the chemistry of compound radicals you deal in it, not with elements but with little systems. We have however as much right to consider SO2 as a compound 7 compound radical as many of the organic. The last definition was, In organic chemistry combination is ternary or quaternary in inorganic chemistry it is binary. A chemical definition could not be got. It was shown that many products of vital action could be obtained in the laboratory Wöhler made urea & acetic acid artificially. Any alcohol, can be made from a lower one by making a cyanide of an alcohol radical & from this a compound ammonium by acting on it by nascent H The alcohol can be made from this. 8 We see then that the laws of transformation are the same & why then is it necessary to break up the science? The division is empirical. The compounds of C have been farther investigated than the compounds of any other element. These compounds of C occur in living beings & for this reason we call it organic chemistry. The compounds of C are particularly complex. It is important to distinguish between empirical or rational formulæ. The empirical formula is merely the translation of the analysis. Some chemists believe that the rational formula expresses the mode in wh the atoms 9 are arranged. The chemists who hold this doctrine seldom come to an agreement regarding the rational formula of a body. The empirical formula is a fact, the rational is a conjecture. When two chemists were arguing about the formula, it resolved itself into an enumeration of what could be got from the body ; & when one chemist was hard pressed he said "although you show that a certain body" can be taken from this body you cannot show that it exists in the body. Gerhardt proposed that you should make the formula indicate the transformations wh a body could undergo. 10 Thus alcohol C4 H5 } O2 H } Meaning that H & O could be replaced by other substances & that ethers could be got from it in wh C4 H5 exists. The importance of rational formulae is apparent when we consider isomeric bodies Acetate of methyl C4 H3 O2 } O2 = C6 H6 O4 C2 H3 } Formiate of ethyl C2 HO2 } O2 = C6 H6 O4 C4 H5 } These bodies have the same empirical formula but different properties. In organic chemistry the notion of homologous series is important. A homologous series is a series of bodies differing from one 11 another by n times C2 H2. The members represent one another in function, if you apply the same reagents you get the same result. C4 H6 O2 act on it by C4 H5 I C6 H8 O2 C6 H7 I C10 H12 O2 C10 H11 I Heterologous Class. If you compare the bodies you derive from common alcohol you get bodies said to be heterologous. Alcohol C4 H6 O2 C6 H8 O2 Ether C4 H5 O C6 H7 O Aldehyd C4 H4 O2 C6 H6 O2 In the horizontal line the bodies are heterologous & in the vertical lines homologous The boiling pt of alcohol uses 19 degrees Centigrade for every addition of C2 H2. 12 The qualitative examination of organic bodies is peculiar. Examination of bodies for C. When you heat a body rich in C decomposition takes place CO2 being given off & some residual C deposited Organic bodies when heated, as a rule deposit C. Heat sugar in a tube Organic matter when heated either deposits carbonaceous matter or gives off a peculiar smell due to empyreumatic oils. This is the test for C. We seldom test for it. Organic bodies frequently contain N. the testing for which is very important. When a body containing N is burned a peculiar smell is given off. Burns a feather. 13 When a body containing N is heated to redness with a mixture of soda & lime called soda-lime NH3 on a compound NH4 is given off. Another method. When you heat an organic body to redness with Na. you can get the N transformed into Cy or NaCy. Dissolve the residue in HO & add a mixture of per & proto salts of Fe & HCl, if N be present you get prussian blue. The detection of Br. S. & c in organic bodies is attended with difficulty. When organic bodies contain Cl & the like the properties of the Cl are masked & you must heat to redness or with some strongly oxidizing body. Cause the organic body to come 14 into contact with red hot NaOCO2 the Cl combines with the Na & you get Na Cl from which you may calculate the Cl. In place of heating to redness you may heat it to 150°C with strong No5. If you seal up an organic body containing Cl with NO5 & Ag O No5. you get the Cl as AgCl. Detection of S. Not to miss the S you must effect complete destruction of the body. 15 Quantitative Analysis. When organic bodies are heated to redness with great excess of O all the C becomes CO2 & all the H becomes HO. This is universally true. Organic analysis is founded on this fact As certain how much CO2 & HO a given weight of the substance will yield. Several methods may be employed. Bring the body into contact with red hot Cu O. The apparatus consists of 2 parts the combustion & absorption parts. Previously to using the Cu O must be heated red hot since anything exposed to the air takes up dust wh is often organic. You may conveniently heat the Cuo in a Cu crucible. [illustration] The absorption part consists of a 16 Ca Cl Tube + KO bulls. The solution of the KO is made by dissolving 1 part of stick caustic KO in 2 1/2 parts HO. The connections must be light. To test this warm the bulbs so as to expel some air & if the liquid keeps its level afterward for 2 or 3 minutes the joints are tight. In place of CuO, PbO CrO3 is often used. It fuses at a red heat & buries the substance to be burned. Oils are burned by PbO CrO3 O must be passed thro' the tube at the end of the operation, either from a gas holder or from some KO Cl O5 in the tube. When a substance contains N a little alteration is necessary in this arrangement. When a body containing N is heated to redness with CuO, the 17 C Becomes CO2 & the Hi HO, the N appears partly as N & partly as NO2. The NO2 would interfere with the CO2. To remedy this you introduce clean Cu turnings NO2 when slowly passed over Cu turnings is decomposed. Cu turnings prevent NO2 from becoming NO. When a substance contains Cl it is essential to make the combustion with PbOCrO3. If it contains I you must place a long layer of Cu turnings in the front of the tube, these at a red heat absorb the I. To make combustion of liquids make a small glass bulb & seal one end [illustration], weigh it, fill it with liquid by warming it, seal it & weigh again. 18 The difference of the wts is the wt of the liquid taken up. You allow the liquid to distil very slowly over the CuO. When gas ceases to escape the operation is finished. Then pass o over it. Determination of N. Most organic bodies when heated to redness with a caustic alkali yield NH3, the HO of the caustic alkali being decomposed, the C taking the O & forming CO2 & the N taking H & forming NH3 thus– { CN } = NH3 { C1/2 } { O H } { O H } CO2 = { O H } Will & Varrenhapp's method. [illustration] In this case you use a mixture of NaO + CaO for combustion The N is converted into NH3 & absorbed 19 by the HCl with wh the bulbs are filled If you were to operate on KoNo5 you would get no NH3 You would only get traces if you were working with indigo. Where the N is present in the oxidized or nitrous state you get no NH3. Mix a body with CuO, heat to redness, cause the products to pass over Cu turnings & collect the gas in a mercurial trough All the C is got as CO2 the H as HO & you measure the N. General formula of Olefines C2n H2n. Olefiant gas was described in the inorganic part of the course Olefiant gas or Ethylene C4 H4 atomic wt 28 S.G. 9784 20 When HOSO3 is heated with alcohol C4 H6 is produced. [illustration] Alcohol C4 H6 O2 C4 H6 O2 = C4 H6 & H2 O2 taken by HOSO3 . C6 H4 is a colourless gas, has a faint smell, is poisonous, produces headache if much gets into the atmosphere, burns with a very luminous flame. It is contained in a small quantity in common illuminating gas. The name of the gas is got from the fact that when it brought into contact with Cl an oily liquid is formed. [illustration] B is a gas holder containing C4 H4 & C a bottle containing Cl. Pass the C46H4 into C & an oily liquid is seen on the sides C4 H4 readily unites with Br [illustration] 21 C is a glass stopcock fitting tightly into the mouth of the vessel B, into wh some Br is put, C4 H4 is then passed thru it & B is gently heated, & afterwards the liquid formed is poured out of B The Brome liquid is not miscible with HO. C6 H4 takes up 2 equivalents of Cl, Br or I forming Dutch liquid C4 H4 Cl2 C6 H4 Br2 C6 H6 I2 C6 H4 unites with hydracids C4 H4 + HCl = C4 H4 Chloride of ethyl C4 H4 + HBr = Bromide C4 H4 + HI = Iodide C4 H4 unites with HOSO3 C4 H4 HOSO3 sulphurinic acid. HOSO3 These reactions require time To get the reaction with HOSO3 22 Seal up C4 H4 with HOSO3 & Hg & shake up. Berthelot the discoverer of the process shook it 5000 times. If Cl be made to act on C4 H4 Cl2 substitution products are obtained. Act in the sunshine on C4 H4 Cl2. by Cl & you may get C4 Cl4 Cl2. Dutch liquid is not attacked by aqueous caustic KO but when digested for some time with an alcoholic solution of KO it yields C4 H3 Cl + HCl wh the alcohol takes away. Monochloride of ethylene is acted on by Cl yielding C4 H3 Cl, Cl2 . If you act on this by a solution of caustic KO in alcohol you get C4 H3 Cl2 + H CL. 23 Ethylene C4 H6 C4 H3 Cl2 C4 H2 Cl2 C4 H Cl3 C4 Cl4 C4 H4 Cl2 C4 H3 Cl Cl2 C4 H2 Cl2 Cl2 C4 H Cl3 Cl2 C4 Cl4 Cl2 A similar set of reactions can be got with every [oliferic] Propylene. C6 H6 A gas having a very disagreeable smell, very noxious C6 H5 I + 2Hg + HCl = C6 H6 + HgI + HgCl C6 H6 exists in many mixtures it represents C4 H4 exactly. It combines with Br I & hydracids With HCl it forms chloride of propyl. HI - iodide HoSo3 Butylene C8 H8. 24 C8 H8 occurs in small quantity in coral gas, it is colourless. slightly soluble in HO, soluble in alcohol, combines with Br & I. Amylene C10 H10. A A colourless liquid, boils at a temp. very little above the ordinary one of the atmosphere has a disagreeable smell, very volatile. Distil potato spirit with Zn Cl Potato spirit = C10 H12 O2 C10 H12 O2 + Zn Cl = C10 H10 It is a liquid heavier than HO. Readily combines with Cl & Br producing much heat. [illustration] Pours some Br from a pipette into some C10 H10 in a flask. Violent action takes place. Combines with hydracids. With H CL it forms chloride of amyl. 25 Unites with NO4 forming a beautiful crystalline compound. C10 H10 (NO4)2 The higher olifines are very little known Hexylene C12 H12 Distil oleic acid. May be got pure from mannite It is a colourless liquid boils at 60°C . resembles amylene. Unites with Cl violently with Br. C14 H14 Caprylene C16 H16 Elaene C18 H18 Paramylene C20 H20 Cetylene C32 H32 got from spermaceti The composition of olifines above C12 H12 is little known 26 Marsh gas C2 H4 = 16.S.G.5596 Marsh gas is derived from C2 H2 by adding 2 equivalents. Add H2 to any olifine & you get corresponding member of the marsh gas family C2 H4 occurs native, bubbles up in marshy places, exists in considerable quantity in coal mines, & in common gas Prep. Heat acetate of KO with HO KO Acetate of KO = C2 O2 C2 H3 K/O2 HOKO=H/K/O2 C2 O2 C2 H3 K/O2 + H K / O2 = C2 O2 K K/O4 + H C2 H3 Marsh gas = hydride of ethyl Zinc ethyl is a colourless liquid of enimense energy, as great as that of K. It unites with great energy with Ho. ZN C2 H3 + Ho = ZnO + C2 H3 H. 27 [illustration] Break the end off a small bulb of Zn methyl under HO. You may collect & measure the gas produced. Break the end of a glass bulb & the liquid will take fire depositing ZnO & metallic Zn C2 H4 burns without much smoke, it is inert, Br does not act on it Expose C2 H4 + CL to sunlight & you get action Members of the olifine family may be absorbed by fuming HOSO3. You may make this by adding anhydrous SO3 to HOSO3 There are not many members of the marsh gas family well known. C2 H4 Marsh gas C4 H6 hydride of Ethyl. C6 H8 } exist but not C8 H10 } well examined 28 C10 H12 hydride of amyl C12 H16 - hexyl. Hydride of Ethyl atomic wt 30 S.G. Place Zn Ethyl in HO. Take propionate of KO + HOKO heat together & you get hydride of ethyl. It is a colourless gas. It closely resembles hydride of methyl in its properties Hydride of Amyl. Boils at about 30°c, has a smell like chloroform [illustration] Iodide of amyl Zn + HO are sealed up in a table & heated in the water bath for some time Zn amyl forms first & then acts on the HO. It is very light, the lightest liquid known, has a pleasant smell. 29 Hydride of Hexyl C6 H14 May be got from mannite Colourless, very light boils at 60°C. It is very probable that it is the H representative of the sugar family. Very little certain is known of the higher families Family of alcohol radicals. Methyl C2 H3 C2 H3 Ethyl C4 H5 Propyl Butyl Amyl C10 H11 C10 H11 Amyl boils at a very high temp. is a colourless mobile liquid with a peculiar smell 30 When an iodide of an alcohol radical is heated strongly with Zn you get Zn I & the radical. C4 H5 } I } C4 H5 } I } + Zn2 = Zn } I } Zn } I } + C4 H5 C4 H5 Alcohol radicals may be got from fatty acids If you electrolyse acetic acid you get CO2 & methyl. Acetic acid = C2 O2 C2 H3 } H } O2 C2 O2 C2 H3 } H } O2 + O = C2 O2 O2 + HO + C2 H3 Take any other fatty acid of the series & you get an alcohol radical having C2 less than the acid is an extremely indifferent body The alcohols have not yet been 31 got from alcohol radicals Example of organic analysis Analysis of mannite. .3532 grams mannite gave .5069 - CO2 diff. of wt of KO bulb .2505 - HO - of CaCl tube Since 22 grams of CO2 contain 6C you multiply the co2 by 3 & divide by 11. .5069 x 3 = 1.5207 ÷ 11 = .1382 C To find the H divide the HO by 9 .2505 ÷ 9 = .0277 .3512 : .1382 :: 100 : 39.13 Percentage of C .3512 : .0277 :: 100 : 7.8 - H The diff between the wts of C + H & of the mannite is 0. 39.1C ÷ 6 = 6.5C = 65 7.8H ÷ 1 = 7.8H = 78 53.1O ÷ 8 = 6.60 = 66 100. To find the formula divide the percentage by the equivalents 32 of the bodies. The percentage of C should not be 2/10 ° below the theoretical quantity of the percentage of H 1/10 above it. Transformation of organic compounds by different ferments. Diatase Starch { C12 H10 O10 + 4HO = Grape sugar { C12 H14 O14 2 yeast Grape sugar { C12 H14 O14 = alcohol { 2C4 H6 O2 + 4CO2 + 2HO 3 Casein Milk sugar { C24 H24 O24 = Lactic acid { 2(C12 H10 O10, 2HO) Lactic acid { C12 H12 O12 = Butyric acid { C8 H8 O4 + 4CO2 + 4H 33 4 Synaptase Amygdalin { C40 H27 NO22 = Hydrocyanic acid { HC2 N + Oil of bitter almonds { 2C14 H6 O2 + Formic acid 2C2 H4 O6+3HO + Grape sugar { C12 H14 O14 /2 Salicin C26 H18 O14 + 4HO = Salicenin { C14 HO + Grape sugar We have considered the olifines the homologues of marsh gas & the alcohol radicals. We can reduce nearly all the others to the olifines Methyline C2 H2 supposed to exist in wood spirit, not known in a separate state. Ethylene C4 H4 Propylene C6 H6 Butylene C8 H8 Amylene C10 H10 These are distinctly radicals in themselves they unite 34 with Cl. They are biatomic. This is expressed by two dots thus C6 H6,, They unite with 2 atoms Cl, Br &c. Homologous of marsh gas These are olifines having their biatomicity gratified by 2 atoms, H. C2 H4 C4 H6 &c There are some instances where the biatomicity is not fully gratified having only 1 atom of H & 1 atom to be filled up by something else. These are the alcohol radicals. C2 H2 , H = C2 H3 methyl C4 H4 , H = C4 H5 ethyl C6 H6 , H = C6 H7 propyl C8 H8 , H = C8 H9 butyl C10 H10 , H = C10 H11 amyl. These are olifines stepping towards 35 the gratification of their biatomicity Suppose you add 1 atom Cl to C2 H3 you get chloride of methyl C2 H3 Cl or to C4 H5 you get chloride of ethyl C4 H4 HCl = C4 H5 Cl Suppose instead of Cl you substitute O, thus, C4 H6 HO You get ethers, of wh common ether is the type General formula of ethers Cn Hn HO corresponding to marsh gas Cn Hn HH. A radical is merely a body wh moves about Act on PbO by HCl. PbO + HCl = PbCl + H O. What is the radical ? The body you can move about viz., Pb. In the same way C4 H4 H O + H Cl = C4 H5 CL + HO. Instead of C4 H4 H you write 36 C4 H5. the radical because you move it about. What are the ethers wood spirit n methylic common propylic butylic amylic Methylic ether C2 H3 O = 23. Or when free it is doubled, as instead of C4 H5 to get a four volume formula you have C8 H10 (C4 H4 ) H this is lob sided having H on one pole & not on the other H (C4 H4) (C4 H4) H When doubled it is symmetrical. Why does ether double itself. O(C4 H4) H. The symmetry is not quite complete, tho' it is thus when in combination H O H (C4 H4) (C4 H4) H H O When free it doubles its combining vol. 37 wh is 2 Methylic ether vap. density Prep. Heat wood spirit with 4 parts HOSO3 & pass thro HOKO. It is a colourless etherial gas not condensible at 60°C, burn, with a pale blue flame, very soluble in HO to the extent of soluble in alcohol. Combines readily with HOSO3 & HCl. Act on KO by HCl. KO + HCl = KCl + HO. - C2 H3 O - C2 H3 O + HCl = C2 H3 Cl + HO. You may get chloride, iodide & bromide of methyl. Substitution products of Chloride of methyl, C2 H3 Cl. Chloroform. Two equivalents of H are substituted by Cl. (C2 H Cl2) Cl. The arbitrary formula is C2 H Cl3. 38 s.g of liquid chloroform 1.48 boils at 60.8°C Put 20 lbs Ca Cl in 120 lbs HO place in a Cu retort 1/3 full add 4 lbs alcohol. Heat quickly to 80°c & then withdraw the fire. You get 2 fluids the heavier is chloroform, wash with It is a colourless liquid, of an etherial sweet odour, sharp & sweetish taste. It is inflamed with difficulty. Place some on cotton wool it burns & gives off HCl. It falls thro' HO without dissolving. It is a good solvent of india rubber, P. Vinic ether, C4 H5 0 combining formula. & C8 H10 O2 its free formula. 39 formula. s.g of liquid .03736 at 0°C & .0724 at 16°C or 257. Boils at 35.5°C or 957. Vap. den. 2.586 Prep. Act on common alcohol with HOSO3 [illustration] C4 H6 O2 common alcohol HO - C4 H5 O = ether. you may suppose alcohol to be the hydrate of ether. There have been many treatises on this reaction. The HOSO3 has an affinity for HO & takes it away. Seal up anhydrous MgOSO3 & alcohol in a tube, the MgOSO3 takes away the HO & you get ether. There is no difficulty 40 in this case. But in distilling alcohol & HOSO3 , the HOSO3 does not combine with the HO. In the receiver you get HO & ether equal in bulk to the alcohol. There are many like instances in catalyses. The HOSO3 takes the HO but the heat drives it off. There are other theories. One is that a body called sulphorinic acid is formed. first. There is reason to suppose that HOSO3 is S2 O6 = HO/ HO/ S2 O6 Ho | C4 H5 O | S2 O6 sulphorinic acid KO | C4 H5 O | S2 O6 sulphorinate of Ko. They say that the sulphorinic 41 sulphorinic acid is decomposed, Haloid compounds of ether. Hydrochloric ether, C4 H5 Cl Pass HCl thro' ether or better thro' alcohol, you get C4 H5 Cl, chloride of ethyl. S.g of liquid 0.874 boils at 11°C A colourless, very volatile liquid & has a penetrating etherial odour. Slightly soluble in HO, soluble in alcohol. Analogous to an oxide KO + HCl = KCl + HO C4 H5 O + HCl = C4 H5 Cl+ HO. Iodide of ethyl. C4 H5 I. s.g boils at 72°C Colourless of an etherial smell. Much used to get radicals Act on hydrochloric ether by Cl & you get chlorinated ether. Act on it with Cl in sunlight 42 sunlight & you get Dichlorinated ether. Act with Cl by sunlight & heat & you get Trichlorinated ether. Ethers as a class. They represent the protoxides of metals Ko when free is probably not KO but KKO2 or K2 02. Ether when separate is not C4 H4 O but C8 H10 O2. Two atoms of radical united with 2 of O. What happens to KO when it is hydrated? KH/O2 = KO1 HO. one atom k going out & one of H going in. Take 1 atom of radical from ether & add 1 of H. (C4 H5) O2 alcohol is one of the H radicals of the double 43 ether taken out & 1 atom H put in its place. That the ethers are really duplicated in their separate state follows from the fact that you are able to substi- tute one radical by another C4 H5 } C4 H5 } O2 C4 H5 } C2 H3 } O2 C2 H3 } C2 H3 } O2 C2 H3 } C4 H5 } O2 When not in a free state they halve themselves & unite with a base. KO + NO5 = KONO5 C4 H5 O + NO5 = C4 H5 O NO5 you can form a whole set of ethers. The ethers are to be considered as the protoxides of the metals & the alcohols as the 44 hydrates of the protoxides KO (C4 H5 O) HO KO. (C4 H5 O) HO. Alcohols = 4 vols. S.G liquid vap. Boiling point Wood spirit C2 H4 O2 0.798 1.12 150° Spirit of wine C4 H6 O2 0.796 1.61 173 Propylic alcohol C6 H8 O2 - 2.02 206 Butylic C8 H10 O2 0.803 2.59 233 Amylic C10 H12 02 0.818 3.14 270 Caproic C12 H16 O2 0.830 3.53 304 Caprylic C16 H18 02 0.820 4.5 356 Lauric C24 H26 O2 Cetylic C32 H34 O2 Cerylic C54 H56 O2 Melissic C60 H62 O2 Aldehydes. Formic aldehyd Acetic Propionic Butyric 45 Valerianic aldehyd Caproic Oenauthylic Capric Euodic Ethers form a homologous series corresponding to the alcohols. The general formula of an alcohol is that of an ether + 1HO Ether = Cn Hn,, Ho1 + HO = Cn Hn an alcohol. The alcohols belong to a different class from the ethers, as a hydrate does not represent a protoxide but a peroxide. O | O | K2 O | O | (CnHn)2 | O | | O | K O | HO | K O | HO | C4 H5 O | NO5 | K O | NO5 | C4 H5 Alcohol is a hydrate of ether & is a salt. 46 Wood spirit on methylic alcohol C2 H6 O2 = O| HO | C2 H3. equals 32. s.g of liquid 0.818 at 32°, at 65° 0.798 vap. density 1.12 boils at 150° F Prep Distil wood, acetic acid & wood spirit are given off it is purified by lime & distilled from Ca Cl. When pure, it is colourless has the odour of acetic ether is a good solvent for resins when oxidized it forms formic acid. Vinic alcohol or spirit of wine. C4 H6 O2. O| HO| C4 H5 = 46. s.g when free at 60° is 0.794 vap. den. 1.613 boils at 173°F or 78°C. Alcohol has been made synthetically. We believe it contains C4 H4 47 add 2 atoms HO & you alcohol. C4 H4 " H2 O2 - C4 H6 O2 Pass C4 H4 into HOSO3 add HO & distil, alcohol comes over. [illustration] Prep. Distil from fermented add KOCO2 wh has been heated & the KOCO2 takes the HO & falls to the bottom. you distil again from Ca Cl or dried CuO. It is a colourless, volatile mobile liquid of an aromatic smell & burning taste It has a strong affinity for HO, & the mixture contracts. burns without smoke. It has never been solidified by cold, at -166° F it becomes viscid, is a good solvent for Br, I, S, Na & bodies containing H. In using it as a fuel it is 48 completely burnt. C4 H6 O2 + 120 = 4CO2 + 6HO. It unites with salts as HO does & forms alcoates instead of hydrates. Wines & spirits. Proof spirit 50.76 P.C. alcohol & 49.74 HO [illustration] Proof used to be -set some gunpowder on a tile pour spirit over it. & set the spirit on fire. If the spirit be above proof the gunpowder should go off when the spirit is burned. if under proof the HO it contains wets the powder so that it does not go off. Distilled spirits. Brandy contains 55 P.C. alcohol in its ordinary state it is coloured with burnt sugar 49 & peach kernels are added during distillation to flavour it. gin is got from fermented grain & flavoured by juniper berries. Whisky is distilled from grain & has a slightly smoky taste. Rum is got from sugar Arrack from fermented rice betel nuts or palm juice Potato brandy is get by converting potato starch into glucose & distilling it. Wines are the fermented fluid without distilling. When all the sugar is converted into alcohol they are called dry. when much sugar remains they are called fruity. The bouquet is due 1st,, to the completion or 50 non completion of these actions 2nd to the deposition of cream of tartar 3d to the formation of fragrant ethers by the action of vegetable acids on the strength of wines Port or Madeira 15-20 P.C alcohol Sherry 15-17 Lisbon 16 Malmsey 13 Champagne 12 French clarets 9-10 Rhenish wines 10-12 Cider 4-8 Perry 6-8 Ale 6-8 Porter 5 Small beer 1 1/2 The market value of wines depends on their flavour 51 One imperial pint of the following wines contains HO oz alcohol oz sugar grs Tartaric acid grs. Port 16 4 1-2 80 Brown sherry 4 1/2 360 90 Claret 2 none 161 Burgundy 12 1/2 2 1/2 160 Fermentation It is the process by wh sugar is converted into alcohol. Grape sugar in honey C12 H12 O12 Act by yeast = 4Co2 + 2(C4 H6 O2) Yeast does not appear in the final product Conditions for fermentation The temperature must be 50°-60° F HO must be present to keep the sugar in solution Air must be present to make the yeast live & effect the transformation Nitrogenized substances 52 must be present & a body capable of fermenting. There is spontaneous fermentation as in crushed grapes the air acts on the nitrogenous matter in the cells. When we add a ferment to sugar, & the ferment disappears or forms a heavy substance wh falls to bottom. The yeast is a vegetable growing body, & consists of cells wh when placed in a warm saccharine fluid increase, one cell giving off many others, about 1/250th of an inch in diameter. They finally cease to produce gas. 53 Composition Before fermentation after C 47.71 p.c 48.31 H 6.7 7.33 N 10.15 5.07 O 35.44 39.29 SoP Traces Traces. The N is only one half of what it was when the operation commenced. When yeast is active it is acid if you add an alkali to it, it stops its action & the fermentation. Weak acids favour fermentation, strong acids destroy it. Some poisons destroy it others do not. Theory of action of ferments Liebig's view is that the ferment is in a state of internal change & that it communicates this change to the other body 54 wh is in a state of statical equilibrium. Pasteur considers that it is an action not correlative with the death of the plant but with its life. He burnt yeast & added the ashes & an ammonia salt to sugar. The NH3 disappeared from the solution. The result of fermentation is complex. Glycerin & butylic acid are produced as well as alcohol & CO2. Suppose you put a piece of putrid cheese or casein into sugar, you get a different action & lactic acid is produced If the cheese is very putrid the lactic acid becomes butyric 55 acid. C12 H12 O12 The brewing of beer is a reproductive fermentation A certain quantity of yeast is added to the fermenting liquid & grows so much that much more yeast is obtained. Malting is the germination of barley. When the young sprout is about 1/2 inch in length & begins to bifurcate, its life is destroyed by roasting. The barley in malting contains diastase. Diastase can convert starch into dextrin, it then changes the dextrin into grape sugar. One part diastase can convert 4000 parts of starch into sugar malt contains 1/500th of its weight of diastase, so there is enough 56 diastase left to An infusion of the malt is made & 4 or 5 parts of fresh barley added It converts the barley into sugar you then add say 1 part yeast wh produces 2 parts of alcohol 4CO2 + 2HO In the barley there is gluten a body of the same composition as the muscle of our bodies. The yeast acts on the gluten & it receives so much food from the gluten that it grows with great rapidity & produces much new yeast. Composition of 1 imperial pint HO oz ale oz sugar grs acetic acid grs London stout 18 1/2 1 1/2 281 54 - porter 19 1/4 3/4 267 45 pale ale 17 1/2 2 1/2 240 40 mild - 18 3/4 1 1/4 280 38 strong - 18 2 2.136 54 57 Homologues of the alcohols. Propylic alcohol. C6 H8 O2. Found in the product of the fermentation of grape skins. It is a colourless liquid with an agreeable fruity smell, lighter than HO. Prepared by synthesis from propylene. Propylene is passed into HOSO3 HO is added & it is distilled. Butylic alcohol C8 H10 O2 Found in small quantity in fusel oil. It is a colourless liquid, smelling like fusel oil & wine, soluble in HO but separates on the addition of salt. Amylic alcohol. C10 H12 O2 S.G of the liquid 0.818 vap. density 3.147 boils at 58 Has a higher boiling pt than the previous ones. Brandy contains a little fusel oil & whiskey a good deal. Test pour some of the spirit thought to contain it on your hand & allow it to evaporate you can then smell the fusel oil. It is though a colourless, mobile liquid, of a disagreeable odour burning taste, slightly soluble in HO, soluble in alcohol & ether when strong it is poisonous & produces a cough & spasm of the glottis Caproic alcohol. Formed in the fermentation of grape skins, Refracts light strongly: insoluble in HO General properties of alcohols. The chemical reactions of alcohols 59 alcohols are nearly all the same. If we act on them by acids you get ethers. C4 H5 O HO + NO5 = C4 H5 O NO5 + HO KO HO + NO5 = KONO5 + HO. The compound ethers are on the same type as alcohols, but acids replacing the HO. Boiling pts Vinic alcohol 78°C } difference Propylic 96C } 18°C Butylic 112° } 16°C Amylic 132 } 20°C Caproic 150°} 18°C Compound ethers are derived from the alcohols, & are salts of the ethers, the HO of the alcohol being replaced by acid. Sulphuric ether, not that of shops wh is common ether but that of chemists C4 H5 OSO3 Prep. Act on ether by anhydrous 60 anhydrous SO3 in the cold, Colourless, aromatic liquid not miscible with HO. Nitric ether. C6 H5 ONO5. Used in pharmacy. S.G of liquid 1.11 boils at 85°C. Distil HONO5 with alcohol & a little urea. When pure it is a colourless aromatic liquid, with a faint smell of apples, explodes when quickly heated. Nitrous ether C4 H5 ONO3 s.g of liq boils at 16.4°C Distil spirit of wine with HONO5 It is yellow, inflammible insoluble in HO soluble in alcohol. Decomposed in heating with the evolution of N. Even the feeble acids have 61 been made to unite with ether. C4 H5 O CO2 C4 H5 O Sc O2 a proposition was made for covering the houses of Parliament with a coating of silica by means of C4 H5 OSiO2. Sulphovenates, are salts of ether in wh one of the equivalents of HO in HOSO3 viewed as a bibasic acid is replaced by ether. HO | HO | S2 O6 HO | C4 H5 O | S2 O6 add KO KO | C4 H5 O | S2 O6 Sulphovenate of Ko It is not HOSO3 alone wh acts in this way, PO5 does it also HO | HO | HO | PO5 HO | HO | C4 H5 O | PO5 Phosphovenic acid As every ether has its alcohol & every alcohol can form a compound ether you might 62 go on in the series but when you know the properties of one in a series the others much resemble it. Nitrite of amyl. It is amylic alcohol with HO displaced & NO3 added C10 H11 O HO C10 H11 O NO3 It has properties the very reverse of chloroform. It increases the action of the heart, & produces acute headache. In cases of long suspended syncope it might be useful. Biatomic ethers & alcohols. An ether is monoatomic when it unites with 1 atom acid or with of HO to form alcohol. C4 H4 " HH. marsh gas. C4 H4 ClCl C4 H4 HO ether. 63 C4 H4 O O Cn Hn" O O biatomic ether Cn Hn OO + 2HO - alcohol Why should those be biatomic? KOHO it has one of O in the base KONO5 Sn O2, 2HO it has 2 of O in the base Sn O2, 2NO5 The same with biatomic alcohol. Ethylene ether C4 H4 O2 corresponding to dutch liquid Has been imperfectly studied. 2b hydrate or ethylene alcohol C4 H4 O2 + 2HO generally called glycol is better known. Empirical formula C4 H6 O4 Obtained by the action of HOKO on acetate of ethylene. C4 H4 O2, 2C4 H3 O3 + 2KO HO = 2(KOC4 H3 O3) + C4 H4 O2 + 2HO. A clear thick sweet liquid 15 64 Soluble in HO & alcohol, the vapour burn & is converted into acid by oxidation. Acetate of ethylene. Act on Bromide of ethylene a dutch liquid by acetate of KO. C4 H4 I2 + 2KOC4 H3 O3 = 2 KI + C4 H4 O2, 2C4 H3 O3 Acetic ether is a colourless liquid, at a high temp. it smells feebly of acetic acid. We can produce the homologues of glycol thro the whole series. C4 H4 HO common ether C6 H6 OO biatomic - . C4 H4 HO + HO common alcohol. C4 H4 OO + 2HO biatomic - Cn Hn HO + HO common Cn Hn OO + 2HO biatomic Cn Hn OO, 2HO Cn Hn OO, 2A C6 H6 OO 2(C4 H3 O3) binacetate of ether of olifine 65 Every homologous olifine has an ether & alcohol belonging to it. We now consider a stepping stone between the alcohols & acids, the aldehydes. Alcohol Aldehyde Acids of alcohols. Cn Hn + 1. +1 means that there is 1 atom of H more than the number of C. alcohol Cn Hn +1 O, HO = HO + ether General way of forming aldehydes from alcohols. Cn Hn +1 HO - 2H = aldehyde. It is simply by oxidation that you do this. [illustration] Put a heated Pt wire into a glass in wh is a little ether. Aldehyde vapours form round the Pt. You are forcing the H to combine with the O by the action 66 of the Pt. [illustration] Distil alcohol, HOSO3 & Mn O2 in a capacious retort & aldehyde is produced. Add 2 atoms of H to an aldehyde & you get an alcohol. Vinic or acetic aldehyde C4 H6 O2. s.g of liq 0.79. vapour density 1.53 4 volume formula boils at 21°C. Distil in a capacious retort 6 parts HOSO3, 4 alcohol of 85 P.C.. 4HOO 6 MnO2. The loss is considerable. you get a colourless liquid of an irritating pungent odour, burns with a white flame, with alkaline bisulphides it forms a white solid compounds. It is singularly unstable, if you seal it up in a tube it changes after a time to porcelain 67 like substance, it is then probably C12 H12 O6 There are several of these varieties. General process to get aldehydes. Suppose you wish acetic aldehyde. Distil acetate of lime with one equivalent of formiate of lime acetic aldehyde. Ca O C4 H3 O3 + Ca O C2 HO3 = 2Ca O CO2 + C6 H4 O2 General view of the constitution of aldehydes There are several views. Gerhardt thinks they are constituted on the type of H. H = H } H } C4 H3 O2 } H } = acetic aldehyde. That one H is replaced by C4 H3 O2 a radical he calls acetyle. Liebig thinks that they are alcohols of unknown radicals 68 & that the radicals are negative or are Cn Hn -1 having 1 atom less H than C. C4 H3 O HO = aldehyde = hydrate of oxide of acetyle. He calls C4 H3 O acetyle. In our view we view aldehyde as the alcohols of oxidized olifines C4 H4 " HO common ether C4 H3 O, " HO aldehyde 1 H being replaced by O. Every alcohol has its ether - aldehyde - ketone. If you take the acid salt of any as Acetate of Pt + distil you get a tarry liquid wh when purified is a acetone the ketone of the ketone the aldehyde in wh 1 H is substituted by the alcohol radical below it in the series 69 C2 H3 methyl is the radical below C4 H5 ethyl in the series. C4 H5 O, HO substitute the H by methyl C4 H5 O (C2 H3) O. Ketone of the series. Acetone C6 H8 O2 = C4 H5 O2 C2 H3/ C6 H8 O2 Heat chloride of acetyle with Zn methyl. It is a clear colourless liquid of an etherial smell, soluble in HO but separates readily on the addition of salt, readily soluble in alcohol & ether. Absorbs H Cl readily & polymerizes Anhydrides or acids. When monoatomic alcohols homologous with methylic are fully oxidized they are changed into aldehydes & then into 70 acids. All the acids are derived from corresponding alcohols by oxidation It was long supposed that there was no anhydrous acid in the organic series. KOSO3 = KSO4 There is a great disposition among chemists to reduce to the binary type. They have got anhydrous acids mode. General reaction. By acting on a salt such as an acetate with a body wh is oxichloride of P, P Cl3 O2. Example. To get anhydrous acetic acid. Take acetate of KO. C4 H3 O3, HO, From chloride of P. you can get chloride of acetyle C4 H3 O2 Cl, = anhydrous acetic 71 acid in wh 1 of O is replaced by Cl. C4 H3 O3 KO + C4 H3 O2 Cl = 2(C4 H3 O3)+ KCl. Anhydrous acetic acid. Its formula is doubled C8 H6 O6 liquid s.g 1.073 vapour density 3.47 boils at 140°C. It is a colourless mobile, highly refracting liquid. It sinks thro HO like oil but gradually unites with it & forms vinegar All other anhydrous acids could be prepared. Hydrated acids Relation of these acids to alcohol & ether. Ether C4 H6 " HO Ethylene ether C4 H6 " OO - Alcohol or glyeds C4H4 OO HO HO Oxydized series Aldehyde C4 H3 O " HO Anhydride C4 H3 O " OO Acetic acid C4 H3 O OO/HO 72 Formic Acid. empirical formula C2 H2 O4 s.g of liquid 1.235 vapour density 1.554. Occurrence. Called formic acid because it occurs in the red ant Formica rufa: occurs in the stinging nettle urtica urens & in various animal secretions. Obtained by synthesis. By passing CO over HO KO KO HO + 2CO = KOC2 H3 O3. Distil starch with HOSO3 + MnO2 This is not the best way. Mix syrupy glycerine with oxalic acid & heat. It was formerly got by crushing & distilling ants. It forms many salts wh crystallize readily & form definite & permanent compounds. Acetic acid. HO C4 H3 O3 or C4 H4 O4 s.g of liquid 1.063 vapour density 73 2.08 boils at 119°C. Occurs as acetates in various vegetable juices in the perspiration of animals, in the juice of flesh Prepared by synthesis. By the action of CO2 on Zn methyl. C2 H3 Na + C2 O4 = Na C6 H3 O3. you get acetate of Na Commercially. Distil wood & you get pyroligneous acid & pyroxylic spirit. The ash, oak & beech are preferred. Add lime & you get acetate of lime, distil over & you get glacial acetic acid, it is so called because it becomes solid when exposed to cold. If you pass alcohol over spongy Pt in presence of air you get acetic acid Oxidize alcohol. A large cask is 74 taken, wh allows air to pass thro it, & filled with beech wood shavings & alcohol [illustration] poured over it, it is done two or three times & in its passage is oxidized to acetic acid. 1 part alcohol + 6 HO + 1/1000 th part of honey are taken. Relation between the alcohols aldehydes & ketones. alcohol C4 H4 H1 O1 HO double ether C4 H4 " H1 O1 (C2 H3)O Aldehyd C4 H3 O " H1 O. Acetone C4 H3 O " (C2 H3)O. is not a common alcohol in wh the H is replaced by the radical neat lower in the series it is the aldehyd in wh the H is replaced by the radical 1 below it in the series. Thus, Butyrone, C8 H7 O " (C6 H7)O. 75 16 [illustration] Prep of acetone C is a Cu retort in wh Acetic acid. C4 H4 O2 At 55° it is solid & crystalline melts at 62°, has a pungent peculiar smell, burning taste, acid taste, miscible with HO, ether & alcohol, it dissolves camphor & essential oils, the strongest acetic acid forms aromatic vinegar & is generally flavoured with essence of camphor or bergamot. It is used in medicine as a rubefacient, when too strong it blisters the skin. Most acetates are soluble. Vinegar is dilute acetic acid is is made from bad wine The temp necessary to produce oxidation is 70-80°F. Malt vinegar is now largely 76 used, it contains about 5 P.C of acetic acid. Acetic acid may be acted on by Cl & forms a very complete substitution acid. KO C4 H3 O3 acetate of KO. KO C4 Cl3 O3 chloracetate of KO. Acetates. Acetate of KO. KO C4 H3 O3 Prep. Dissolve KO CO2 in acetic acid Prep. Anhydrous. foliated, deliquescent. Acetate of NaO. NaOC6 H3 O3 + 6HO. Colourless transparent effloresent cooling taste. Acetate of ammonia. NH4 OC6 H3 O3. White crystalline easily solube decomposes when heated. distilled. Nh4 OC6 H3 O3 = 4HO + C4 H3 N = C2 H3 C2 N or cyanide of methyl. The cyanide of the radical below that from wh acid is derived. 77 another example propionate of ammonia. NH4 OC6 H5 O3 = 4HOC6 H5 N = C6 H5 C2 N NH4 OC2 H3 O3 is used in medicine as a refrigerent & to act on the kidneys Acetate of PG. PGOC4 H3 O3 + 3HO this is neutral acetate. Prep. Dissolve PGO in acetic acid & crystallize. It is often called sugar of PG. It crystallizes in transparent rhombic prisms, has a sweet taste, soluble in twice its wt of HO & alcohol, it is used as a lotion is poisonous. There are some subacetates. 3PbO, 1C4 H3 O3 6PbO 1 C4 H3 O3. Acetates of Cu. There are several. Neutral acetate 1 CuO 5 acetic acid 78 & 5HO. There are various insoluble subacetates. Verdigris. Expose sheets of Cu in alternate layers with fermented grape skins. The crust is scraped off & made into a paste with vinegar & made into moulds. Glycocol is connected with acetic acid. Occurs in the transformation of many animal substances in the decomposition of hippuric acid &c. It is crystalline sweet, fusible at 78°C soluble in HO & hydrated alcohol, insoluble in ether & absolute alcohol. It is a very weak acid acting partly as an acid & partly as a base. 79 It is acetic acid in wh 1 atom H ionical is substituted by amidoger NH2 . Acetic acid (C4 H2 HO)"OO Glycolic -- (C4 H2 OO)"OO Glycocol C4 H2 (NH2)O) OO NH3 thought to be (NH2) H hydride of amidogen Acids homologous to acetic acid Propionic acid. HOC6 H5 O3 liquid s.g 0.991 boils at 140°C Its synthesis has been effected by Na ethyl . C4 H5 Na + C2 O4 = NaOC6 H5 O3 proprionate of NaO. Butyric acid C8 H8 O4 = HOC8 H7 O3 liquid s.g 0.978 Occurs ready formed in certain fruits, in sourkrout. In the animal organism it is found sometimes in sweat, in gastric juice, in 80 certain diseases in wh the expectorations have a bad smell. In the bad smelling juices of certain animals. In the oxidation of casein & fibrin By fermenting sugar by poor cheese or curd in presence of chalk. you get butyrate of lime, lactate of lime is first formed. Add HCl & distil & you get butyric acid. It is a colourless liquid, with a very disgusting odour. Crystallized by intense cold. Slightly soluble in HO. Butyrates crystallize & have no disagreeable smell when dry, tho when wet the CO2 of the air liberates some 81 butyric acid & causes a smell. They have more the character of soaps than any salts we have yet dealt with. Butyrate of lime. It is much more soluble in than Butyric ether C4 H5 OC8 H7 O3. liquid s.g .901 boils at 119°C, a clear, mobile, liquid, & fragrant ether It occurs in the pineapple, melon strawberry & other fruits Some fragrant ethers are got from acids having an abominable smell A strong alcoholic solution of butyric ether is sold under the name of essence of pineapples, & more diluted as essence of strawberries. Amylic or valeric acid C10 H10 O6 = HO1 C10 H9 O3 82 liquid s.g 0.937 vapour density 3.66 boiling point 347° Occurs in valerian & angelica root, in putrid cheese in train & sperm oil Prep. Distil valerian root with HO. Or Distil fusel oil with HOSO3 + KO2CrO3 It is limpid, has an odour like cheese floats on HO. Forms valeriates wh are soapy substances. Fatty acids Rutic is the first true fatty acid or oil when melted. It occurs in the fat of goats. Palmitic acid C32 H32 O4 or Ho C32 H31 O3 Melts at 62°C. All the fats vegetable & animal are compound ethers, the ether they contain is that of Glycerin united with a fatty acid Palmitic acid in combination 83 with glycerin is in almost all fats especially human & pigs It is obtained by saponification Fat = Glycerin } Fatty acid } + KO = KO } fatty acid } = soap. Act on soap by alcohol & you get the acid in a free state. Prep. Tasteless white fat crystallizes in tufts insoluble in HO soluble in alcohol & ether. Palmitates are soaps insoluble when the bases are earths, soluble when they are fats. Stearic acid C36 H36 O4 melts at 69.2°C occurs in combination with glycerine in most fats, in all animal fats the richer the fat in stearic acid the harder it is. It is got from stearate of KO by HCl insoluble in HO. 84 When distilled it is converted into palmitic acid. Stearates of alkalis are soluble Neutral stearates are decomposed by HO into alkalis & Lamps were used before candles were introduced. Torches were the first candles & were probably used with lanterns. Pling alludes to candles wh were probably of wax. The only cheap candles in this country were the fats themselves. They had a low fusing point & ran & the wick did not burn away and required snuffing. [illustration] Palmers candlestick was meant to remedy this. The candle was kept at the level of the candlestick by a spiral spring & the 85 wick wh was double turned outwards so that the end was always exposed to the air & thus burned away. Improvements in candles. It was discovered that tallow consisted of stearine & oleine & that by heating tallow to the fusing pt of oleine but not to that of stearine the oleine might be pressed out & stearine left. Tallow melts at 102° Stearine 144 Stearic acid 15° Candles of stearic acid would thus be better than those of stearine The stearine was saponified & the soap acted on by HCl. There were many objections to the use of stearic acid candles The wick got clogged up. This was found to be owing to the wick 86 leaving alkaline ashes & forming a soap with the stearic acid This was remedied by dipping the wick in HOSO3. C6 H5 O3"' Glycerine ether (C6 H5 O3"') 3HO Glycerine (C6 H5 O3"') 3A A fat. Tallow is a mixture of fats, as, oleine. palmitine & stearine glycerine itself is not combustible. In the stearic acid candles, the oleine & glycerine are both removed. Stearic acid candles so called, are generally palmitic acid & are got from palm oil. The improvements in candle making depend chiefly on Chevreuls researches on fats. Saponification. The fat is boiled with lime, & HOSO3 added. 87 to the lime salt of the fatty acid thus obtained. the acid is then got in free state (C6 H5 O3"') 3a + CaO = lime salt 3HO = glycerine 3SO3 Another difficulty in the use of stearic acid candles is that it has a tendency to crystallize. The crystalline flakes often broke off the candles. By putting a little arsenic into the acid the crystallization was stopped, but fumes of as were given off while the candle was burning & hurt the health of those who used it. This nearly put a stop to the manufacture but after some time it was found that a small percentage of wax served the same purpose as the As. The saponification was next 58 effected by HOSO3 instead of lime. Mix the fat with HOSO3 & heat by blowing steam thro' them C6 H5 O3"' 3A + 6HOSO3 = C6 H5 O3"', 3SO3 + 3A,3S03. Pass superheated steam at about 600° thro' the fat. it splits it up into the acid & the ether. C6 H5 O3"' | 3A. The glycerin & acid both distil, separately. Candles from Coal. Coal when distilled produces various gases. among others olefiant gas C4 H4 & other higher homologues. C8 H8 C10 H10 Cn Hn 89 If you distil at a low temperature Cn Hn comes over chiefly in a solid state. if at a higer temp. you get liquid products; & higer still gaseous products Boghead coal is distilled at as low a temp. as possible & an oil comes over. wh. is called paraffin because it possesses almost no affinities This when cooled from 40° to 32° deposits solid paraffine. In 1852 L. Playfair thought that paraffine could be got from the oil, but the maker of the oil would not try it, so Playfair obtained a quantity from him & by experimenting succeeded in getting it. Paraffine contains the conditions of illumination in the highest degree. The illuminant in coal gas is C4 H4 & its homologues 90 Paraffine is C4 H4 in a condensed state. All the paraffine is burned. It is not fat wh burns in a candle it is gas. The pores of the carbonized part of the wick act as so many retorts. Acids heterologous Melissic HOC62 H59 O3 Cerotic HOC34 H53 O3 Arachidic Stearic Palmitic Myristic Lauric Rutic Pelargonic Caprylic Ænanpylic Caproic Valeric 91 Butyric Propionic Acetic Formic Acids produced from biatomic alcohols. C4 H4 " HOHO monoatomic alcohol. C4 H4 "OO2HO bi -. In examining the oxidation of monoatomic alcohols we found that aldehydes were first produced & then acids.. C4 H4 "HO C4 H4 O"HO C4 H3 O"OO. Products of the oxidation of Glycol. We find two acids result. In the first 2 atoms of H in C4 H4 are replaced by O. In the second all the H is replaced by O. 92 Glycol ether C4 H4 "OO glycolic acid C4 H2 O2"OO Oxalic - C4 O4 "OO. What would be the acid for methylene C2 H2 if it were fully oxidized? C2 O2 OO = C2 O4 = 2CO2 . Formic acid C2 HO"OO Carbonic C2 O2 "OO Acetic C4 H3 O"OO Glycolic C4 H2 O3 "OO Glycolic acid. Got by the slow oxidation of glycol. It is a syrupy acid liquid The anhydride is got by distilling tartaric acid Lactic acid C6 H6 O6 = 2HOC6 H4 O4 Occurrence. It is extensively distributed in the animal kingdom it is found free in the gastric juice, found in muscle, in 93 the pancreas, in milk, in the brain & lungs & abnormally in urine blood & saliva. It is supposed to be the acid wh dissolves out the mineral matter in bones & produces rickets. It stands in the same relation to propylic wh the latter bears the glycol. Glycol or ethylene alcohol C4 H6 O41 - 2H + 2O = C4 H4 O6 Glycolic acid. Propylene alcohol C6 H8 O4 - 2H + 2O = C6 H6 O6 Lactic acid. Prep. 8 parts of sugar are dissolved in 50 parts HO, 1 part of poor cheese & 8 of chalk are added, & fermented at 80°. Lactate of lime is thus got & by adding HOSO3 you get the acid. It is a transparent, uncrystalline liquid, of a sharp taste It is not volatile & can displace volatile acids, when heated it 94 loses HO & becomes lactic anhydride. Lactates of alkalies do not crystallize - earths & metallic oxides do. Lactate of Zn unites with 3HO. Flesh juice lactates all contain 1 equivalent less of HO than those of that got by fermenting sugar. Fully oxidized olifine acids in wh the H is substituted by O. Formic acid C2 HO"OO Carbonic C2 OO"OO Carbonic oxide C2 O2 is a radical. Sulphocarbonic C2 O2 S2 acid Chloro - C2 O2 Cl2 Oxalic C4 H2 O8 C6 H4 O8 Succinic C8 H6 O8 Lupinic C10 H8 O8 Sebacic C20 H18 O8 Oxalic acid 2HOC4 O6 Occurs in vegetable juices, as acid 95 oxalates, in common sorrel, in lichens in rhubarb, sometimes free. Rarely in the animal kingdom as oxalates of lime in calculi & in urine in an abnormal state. Prep. Heat starch gently with HONO5. It has been obtained by another method. Heat sawdust with caustic Ko & NaO. The H is removed & the O goes You get a mixture of oxalates of NaO & KO. Add CaO & you get insoluble oxalate of lime. Add HOSO3 & you get oxalic acid free. 2Nao, C4 O6 + 2CaO = 2CaOC4 O6 2CaO, C4 O6 + 2SO3 = 2CaOSO3 + C4 O6. It is a crystalline acid crystallizes in colourless transparent like Epsom salts, for wh 96 it is sometimes mistaken. The remedy is chalk, CaOCO2 or magnesia It forms a numerous class of salts, the oxalates, the principal are those of KO & NH3 . Oxalate of KO. 2KO1 C4 O6 + 2HO. Soluble in HO. crystallizes in There is a bin- & quadroxalate wh is is found in sorrel & cress. Neutral Ko| Ko| C4O6 Binoxalate Ho| Ko| C4O6 Quadroxalate Ho| Ko| C4O6 + Ho| Ho| C4O6 + 4HO. Oxalate of ammonia . Prep. Saturate oxalic acid with NH3 & crystallize. It is largely used for testing, as for salts of lime, with wh it gives a white precipitate of 97 neutral oxalate of lime. Oxalate of lime Occurs native in the animal & vegetable kingdoms. Succinic acid 2HOC8 H4 O6 It is homologous with acetic acid It occurs in amber in various fossil resins. in turpentine in the animal kingdom, in the spleen of oxen. It is formed by the oxidation of some organic substances, by the putrefaction of plants of the asparagus kind & by the fermentation of malate of lime. Prop. It is a white brilliant, crystalline acid, crystallizes in rhombic prisms, not easily soluble in cold alcohol, soluble in hot alcohol soluble in HO. From 175 to 180° C it sublimes 98 It is a fixed acid not easily acted on by reagents. Like most bilasic acids it forms neutral & acid succinates. Negative radicals. We have been considering positive radicals. the radicals of the alcohols, the general formula for wh is Cn Hn +1 as for example ethyl C4 H5 = C4 H4 + H The general formula of negative radicals is Cn Hn -1 as for example Acetoyl C4 H3 Allyl C6 H5 Angelyl C10 H9 How can we consider these as olifines? C has a great tendency to unite with itself. Allyl C6 H5 ={(C4 {(C2 H4)"H. C2 having united with the C in the olifine. & the biatonicty of the radical thus formed not being fully 99 gratified by uniting with 1 of H as ethyl C4 H5 = C4 H4 H. It is not mere speculation that C unites with itself. It may be so in the case of allyl but it is known in the case of naphthalene C20 H8 a body wh chokes up gas pipes & wh has all the characters of an olifine. Allyl C6 H5 or in the separate state C12 H10. liquid s.g 0.58 boils at 59ºC. It has the synonym acryl. It has been got in a separate state. Got by the action of Na on iodide of allyl. It is a volatile ethereal liquid burns with an illuminating flame unites with Br & I & forms compounds. Sulphide of allyl or oil of garlic C6 H5 S. boils at 140ºC. 100 occurs in garlic & may be distilled from it & then forms sulpo of allyl. Oil of mustard is the sulphocyanide of allyl. Oil of garlic C6 H5 S. - mustard C6 H5 CyS. It may be got artificially. Act on iodide of allyl by KS. C6 H5 I + KS Allyl ether C6 H5. - alcohol C6 H5 OHO. When oxidized it forms an acid corresponding to acetic, acrylic acid, Oxidized radicals of allyl. Alcohol C4 H6 O2 - 2H = C4 H4 O2 aldehyde. - C4 H6 O2 - 2H + 2O = C4 H4 O4 acetic acid Allyl alcohol C6 H6 O2 - 2H = C6 H4 O4 acryl aldehyd - C6 H6 O2 - 2H + 2O = C6 H4 O4 acrylic acid. Allyl or acryl aldehyde synonym acrolene. It is the nasty smell you perceive when you blow out a candle 101 candle In this case it is got from glycerin wh is distilled in the red hot part of the wick. It has a frightful smell, extremely pungent. attacks the eyes, & if concentrated burns the skin. Oxidized allyl alcohol. Homologues of acrylic acid (with 2C added Acrylic acid C6 H4 O4 same as acetic acid series Angelic C10 H8 O4 from angelica root Damaluric C14 H12 O4 in urine of cows Hypogaic C32 H30 O4 in earth nuts Oleic C36 H34 O6 in most fats C38 H36 O4 C in mustard seed Oleic acid C36 H34 O4 = HOC36 H33 O3 Occurs in most oils & fats as a glyceride. May be got from almond oil by saponifying & converting it 102 into a lead soap & acting on this by HCl. It is tasteless has no smell, does not act on vegetable colours It is solid below 14° C, is insoluble in HO. soluble in alcohol & ether. With NO4 it forms a solid substance. Pass NO4 thro castor oil wh contains much oleic acid Glycerine. The basis of fats. It appears to contain the same radical as allyl. C6 H5 OHO allyl alcohol C6 H5 O3 3HO Glycerin The atoms cannot be arranged in the same way (C4 H4") (C2 ) HO (C4 H4) (C2 O2) HO in Glycerine ether. Glycerin C6 H8 O6 liquid s.g 1.97. 103 Prep. Distil fats with super- heated steam. It is a colourless, syrupy, liquid does not crystallize, has no smell, sugary sweet taste, not volatile except in the vapour of steam. When distilled by itself it is decomposed. When acted on by yeast it yields propionic, acetic & formic acid When heated with KO C6 H8 O6 + 2KO = Acetate of KO KOC4 H3 O3 + Formeate of KO KOC2 HO3 + 4H Made by synthesis. Make iodide of allyl C6 H5 I. Act on it by 3Br. C6 H5 I + 3Br = C6 H5 Br3 + I. C6 H5 "'Br3 + 3KOC4 H3 O3 = 3KBr + C6 H5 O3 , 3C4 H3 O3 Decompose with HOKO or HOBaO. C6 H5 O3 . 3C4 H3 O3 + 3BaO1 HO Saponification Making soaps from glycerides 104 All ordinary fats are glycerides the 3 atoms of HO in glycerine being replaced by 3 atoms of a fatty acid. C6 H5 O3, 3HO C6 H5 O3, 3 acetic acid C6 H5 O3, 3F F = fatty acid. Glycerides or common fats. Occur in the animal & vegetable kingdoms, embracing all the fats we know. Fats may be prepared artificially. Seal glycerin & stearic acid up in a tube & expose to high temp. These fatty glycerides are easily decomposed. They are generally mixed with other fats. To get stearine heat mutton fat with cold ether wh dissolves out palmitine & oleine 105 Stearine C114 H110 O12 = tristearate of glycerin C6 H5 O3 | C36 H35 O3 C36 H35 O3 C36 H35 O3 It is a colourless pearly fat, melts at 63° C. Insoluble in HO, slightly in cold alcohol & ether. Saponification is decomposing this fat, taking away the glycerin & putting in 3KO instead. Glycerine is triatomic so you put ?.=s of a monoatomic body instead KO| C36 H35 O3 KO| C36 H35 O3 KO| C36 H35 O3 Mix hot alcoholic solutions of KO & of stearine and on cooling you get a soap, the glycerine remaining dissolved in the alcohol. Glycerine | Acid A A 3KO In making soap. take a 106 glyceride & potash ley & pass steam thro' it [illustration] When the heat is great enough to melt the tallow a soap is formed. In ordinary soap making a soft soap is made when KO is employed, with NaO a hand soap is obtained. It is easier to make a KO than a NaO soap because it saponifies more easily. It is afterwards made into a NaO soap by salting. KOS + NaCl Yellow soap. Boil tallow or palm- oil with an alkali & add rosin & salt out. Mottled is got from tallow or palm oil, an Fe soap makes the mottling Castile or Marseilles soap is 107 got from olive oil & mottled with FeS. & alkaline sulphides. Chief fats. Palmitine Tripalmitate of glycerin ether. Exists in most fats, especially the softer kinds, in palm & cocoa nut oils May be got from olive oil by cooling Margarine. Supposed formerly to contain margaric acid wh is now known to be a mixture of palmitic & stearic acids. Oleine. Trioleate of glycerine ether Expose olive oil to cold to separate the palmitine & the oleine remains. Natural fats are of 3 kinds 1st solid like tallow 2nd,, semisolid like butter 3d,, liquid like oil They are all lighter than & insoluble in HO, all soluble 108 in ether many in alcohol They occur in the animal & vegetable kingdoms, in all animal fluids except urine Vegetable fats. Cocoa nut oil melts at 20ºC, contains various acids glyceride of coccinic Palm oil. Melts at 27ºC is a yellow butter like substance, 20000 tons of it as imported annually from Africa, it soon becomes rancid, contains palmitine & oleine Vegetable oils may be divided into drying & non drying. Non drying. Colza Drying Linseed croton & castor oils Animals fats. Suet. Fat of oxen & sheep, melted & freed from nitrogenous matter. consists of oleine, stearine & palmitine 109 palmitine Lard contains stearine & palmitine. Human fat is like lard melts at 25° C. Spermaceti. When pure contains cetine, not glycerine but a substance corresponding to it. Cetine C64 H64 O4 = ethal ether C32 H33 O, palmitic acid C32 H31 O3 Sperm & codliver oil are examples of liquid animal fats. Aromatic series. There are several of these radicals Phenyl C12 H5 Benzyl C14 H7 Xylyl C16 H9 Cumenyl C18 H11 Cymyl C20 H13 Phenyl. It is an important series. It contains benzole used in making coal tar colours Phenyl ether C12 H5 O It is got by distilling benzoate 110 of Cu. It is colourless, smells slightly like a geranium it soluble in alcohol. Chloride of Phenyl. C12 H4 Cl. Hydride of Phenyl or Benzol sometimes called Benzine C12 H5 H corresponds to C4 H5 H. Prep. Distil coal tar. [illustration] A vessel filled with HO surrounding the neck of the retort is kept at a temp. of 170° , the temp. at wh benzole distils other substances wh distil at a higher temp. are cooled & fall back into the retort while the benzole distils over. It is used for cleaning white kid gloves & for taking out grease spots. To use it rub the benzole all round the spot without touching it & bring it [illustration] 111 gradually over the spot. It is a colourless, thin oil, of an agreeable odour when pure, solid at 0ºC melts at 5ºC, burns with a smoky illuminating flame increases the illuminating power of gas. It is a good solvent for fats & camphors, it dissolves S.I. & Br readily possibly uniting to some extent with them. Benzyl C12 H5 H Benzyl ether - alcohol C12 H5 OHO When pure & free from HO it is a white crystalline solid substance. Kreosote consists of carbolic, cressylic & probably of some higher acid Phenyl alcohol or carbolic acid. C12 H6 O2. Boils at 185º 112 Found in cows urine, in coal tar. Solid when quite dry & crystallizes in needles, wh melt at 35ºC. It has a disagreeable smell, burning taste, is heavier than HO, in wh it is slightly soluble, it is soluble in alcohol & ether. It is an active poison to animals & plants. It is a strong antiseptic. A coffin filled with carbolate of lime preserved a body for 2 months. Carbolate of lime & sulphite of lime form Macdougal's disinfecting powder. Nitrophenyl ether C12 H5 NO4 Usually called nitrobenzol. It is C12 H5 H having the H replaced by NO4. Prep. Act on benzol by fuming HONO5. It is a yellow oily liquid, solid at 3ºC, smells like oil of bitter 113 almonds, for wh it is used in perfumery & confectionery with advantage since it is not poisonous while oil of bitter almonds often contains hydrocyanic acid. It has a sweet taste insoluble in HO, soluble in alcohol & ether. Used in making anilene. Anilene is NH3 in wh 1 equivalent of H is replaced by phenyl. N |H |H |H N |C12 H5 | H | H To obtain aniline act on nitrobenzol by some deoxidizing agent. That usually employed is acetate of KO. C12 H5 NO4 + 2HO + 47e = C12 H7 N + 27e2 O3 Or by acting with HS. C12 H5 NO4 + 6HS = C12 H7 N + 4HO + 6S Nitrophenyl alcohol C12 H2 (NO4)3 OHO. It is carbolic acid in wh part of the H is replaced by NO4 & has 114 the synonym of carbosotic acid Prepared by the prolonged action of HONO5 on kresote or carbolic acid. It is formed by oxidizing silk, salicin, indigo, alves, gum benzoate & resins. Prep. It crystallizes in brilliant yellow plates, maybe sublimed with care, soluble in alcohol & cold HO, more readily in hot HO soluble in hot HOSO3, is an active poison. May be used in small doses instead of quinine but makes the patients skin yellow. Used to dye silk & woolen. It has been proposed to mix it with As. before selling it in shops as it has an intensely bitter taste, & would be detected. In cases of slow poisoning it would make the skin yellow & thus draw 115 attention Carbosotates crystallize in well defined salts. The acid characted is due to the electronegative character of the radical. Benzyl C14 H7 - ether C14 H7 O. It is an oily liquid & is got by the action of BO2 on benzyl alcohol. Toluol. Hydride of Benzyl, C14 H7 H Obtained from liquid coal tar + tolubalsam. It is colourless & resembles benzol in it properties, is insoluble in HO soluble in alcohol & ether. HONO5 act on it in the same way as on benzol. Benzyl alcohol C14 H7 O, HO It is an oily colourless liquid insoluble in HO soluble in alcohol 116 alcohol & ether. By oxidation it becomes the oil of bitter almonds In the olifine view Benzyl alcohol C16 H6 " HO HO - ether C16 H6 " HO oil of bitter almonds = biatomic ether C14 H6 " OO benzoine is the aldehyd C14 H5 O " HO Benzoic acid C14 H5 O"OO. Oil of bitter almonds: general formula C14 H6 O2. liquid s.g l.043 boils at 180° C. Obtained when almonds are macerated & distilled with HO. It is fragrant oil, transparent very refractive, has a powerful smell is used in perfumery, is not poisonous in itself but often contains hydrocyanic acid When it contains this & is put in contact with lime it is 117 Changed into benzoin Benzoic acid. Occurs in putrid horses urine Obtained by sublimation from gum benzoate. It is volatile, slightly soluble in HO soluble in alcohol & ether. When taken as a medicine it is converted into hippuric & is found as such in the urine. Benzoates are crystalline, when heated they are decomposed into benzoin naphthaline Let us now go back to the phenyl series & consider the coal tar colours. The phenyl series differs from the benzyl by C2 H2 Phenyl C12 H5 or as olifine C12 H4 "H Benzyl C14 H7 Manufacture of benzol. Nitrobenzol 118 Nitrobenzol &c. When coal is distilled for gas it produces various substances, HO & tar distil over along with the gas. Ten to 12 gallons distil over of oil of from 1 ton of coal. It was formerly a waste product & even yet it is sold at a penny to three halfpence the gallon. [illustration] To get naphtha pass steam thro' the tar On a large scale 100 part tar yield Naphtha 9 parts Lead oil 60 - Pitch 31 - Naphtha is nearly the only thing wh comes over with the steam the pitch & dead oil 119 remain in the retort, & the is a afterwards distilled by a common fire. Naphtha is a rough commercial term & signifies a great variety of substances Roughly purified it is used for many purposes. Crude naphtha contains 3 substances. Basic oils Acid oils Neutral hydrocarbons. Basic oils may be got from the naphtha by agitating with HOSO3. They are all compound ammonias. Aniline exists in the basic oils but is not got from them. Acid oils. 120 Take naphtha & shake it with caustic NaO or KO the acid oils dissolve in the NaO or KO & are separated by adding HCl. When separated they form kreosote wh is carbolic acid C12 H6 O2 & cressilic acid C14 H8 O2 Carbolic acid is used in toothache & to preserve timber When acted on by NO5 it forms carbosotic acid. Carbolic acid C12 H6 O2 Carbosotic - C12 H3 (NO4)3 O2 Carbosotic acid is a strong dying agent. Dissolve a little in a little hot HO & then add some cold, you get a solution excellent for dying silk yellow. Wet the silk in HO & rinse in the carbosotic acid. This is the first use of coal tar in colouring substances. 121 Neutral hydrocarbons. Chiefly benzol & its homologues. The benzol is distilled by passing it thro a cistern of HO at 177°. Benzol is very volatile, & it is possible to burn air charged with it [illustration] Dried air is passed over heated asbestos B to heat the air, & thro' some benzol in A the air then may be burned as at C. It may be used for setting enemy's ships on fire by pouring it on the HO & throwing some K on it wh takes fire & inflames the benzol. Nitrobenzol. C12 H5 NO4 Benzal acted on by NO3. It is used in perfumery. To get colours from it, it is first 122 made into aniline C12 H5 NO4 + 2HO + 4Fe = aniline C12 H7 N + 2Fe2 O3 Aniline C12 H7 N It is a compound ammonia A short time ago 1/2 lb aniline would have been thought very valuable in a laboratory & probably none possessed so much as except perhaps who was making researches upon it It was a short time ago sold for a few shillings per gallon but has now risen in price in consequence of the demand for it & is now a few shillings per pound. From aniline are made Mauve or purple Violine Rosein Magenta or Rosaniline Azuline 123 These tar compounds are capable of producing colours [illustration] Put 2 drops of pyroline in a jar & shakes up- moistens a piece of pine wood in the shape of a dagger with HCl & put it into the jar, the moistened point becomes red. Mauve. [illustration] Put some aniline ( a very little will do ) into a bottle & add a little acetic acid to assist its solubility. you get a solution of acetate of aniline, pour into HO & add chloride of lime- [illustration] it becomes brown at first but afterwards becomes purple. On a large scale it is prepared by acting on sulpate of aniline by KO, 2CrO3 in equivalent quantities. You get a dark powder, wash 124 this with coal tar & dissolve it in alcohol The alcoholic solution is evaporated to dryness & you get a green powder wh is soluble in alcohol. It is from the alcoholic solution that we dye the colours. Pour a little tartaric acid into some hot HO & pour in a small quantity of alcoholic solution of mauve. Wet the silk to be dyed & put it in. The chemistry of the colour is not well understood. It is easily tested by HOSO3. Add a little strong HOSO3 to a little mauve & you get a dirty green solution. Add a little HO & you get a fine blue. Add a good deal of HO & it becomes mauve again 125 Magenta. The true red colouring matter is rosaniline. In making it take a weak deoxidizing agent instead of a strong as with mauve. [illustration] Take a small quantity of anhydrous bichloride of In as that in the sealed tube A, pour it into the flask B, add aniline cautiously, it forms a solid compound, gradually add more aniline till you have an excess Heat cautiously over a lamp The action is violent. Any weak anhydrous Acetic acid & As O5 are also used. It is necessary to boil off the excess of aniline. Blue de Paris a azuline Is got from carbolic acid 126 Put a very little mauve or magenta on a sheet of paper hanging up & spout alcohol from a washing bottle on it, the colour dissolves running over the paper. The chemistry of some of these colours is known Rosaniline is a triammonia 3 atoms of H coalescing into one. NH3 x 3 = N3 H9. The compounds radical substituting H is unknown. Let R signify rosaniline. R unites with 1 or 3 atoms of acid. R + 1A gives the strongest colour R + 3A - a less strong -. R is colourless by itself, but when dissolved in alcohol or acid it has a strong colour. Magenta is acetate of R. In the case of the purples we must use hot HO in dying but in the case of carbosotic 127 acid & magenta, cold will do. All animal fibres take up these colours readily. Cotton does not & you must treat it with tannic acid. Purple & violine are not true ammonias, they seem to be neutral In cotton printing, albumen is put on the place wh is desired to be coloured & exposed to steam & dried. It is then rinsed in a solution of the dye as silk is the vegetable fibres do not take it up but the albumen does. Malic acid 2HOC8 H4 O8 It is bibasic. It occurs frequently in unripe fruits, in the apple but is got most easily from the berries of the mountain ash. It has a strong acid, agreeable taste 128 When heated it is changed into fumaric acid fumaric acid. 2HOC8 H2 O6 . It is readily obtained from Iceland moss or malic acid. It forms micaceous scales wh require 200 parts of cold HO for solution. Tartaric acid. General formula C8 H6 O12 = 2HOC8 H4 O10. Occurs in the tamarinds & mountain ash berries, but is got chiefly from grapes. The substance called argol found in wine casks is bitartrate of KO. It is obtained in rather a curious way from this by converting it into neutral tartrate of lime. Argol Ko } Ho } T Add CaCl & lime if you added CaCl alone you would get CaO } HO } T but by adding lime too you get CaO} CaO} T 129 add HOSO3 to this CaO} CaO} T + 2HOSO3 = Ho} Ho } T + 2CaOSO3 . It crystallizes in oblique prisms is colourless transparent, of an acid agreeable taste, soluble in HO alcohol & wood spirit, its solution especially when hot exerts a right-handed rotation on polarized light There are two different crystalline forms. Sometimes, especially in the grapes of the Vosges, an acid of the same formula as tartaric acid called racemic. Racemic acid is rather difficult to get as it only appears sometimes. Racemates crystallize differently from tartrates & have a different number of atoms of 130 HO of crystallization. It was supposed to be an isomer of T & to have its atoms arranged differently. T produces a right-handed rotation of polarized light Racemic acid a left handed one. The crystals were unsymmetrical but in different directions. Pasteur showed that when put together they are symmetrical It is thus the same acid in different crystalline forms. Tartrates are used largely in medicine & the arts. Used in calico is printing. If in calico printing you wish a part to remain white you use tartaric acid as a resist to the mordant wh is always used. The mordant forms a very soluble 131 soluble tartrate & does not remain on that place, & so the dye does not adhere to that place. In all cases of bibasic acids as tartaric acid where you have 2 HO thus HO } HO } T you may replace 1 HO or both. HO } HO } T KO } HO } T KO } KO } T NaO } KO } T. Argol is cream of tartar or bitartrate of KO HO } KO } T. It is hard white & crystalline difficultly soluble in cold HO, more soluble in hot HO, has a sour taste & feels gritty to teeth. When heated it forms black flux. Bitartrate of KO is extensively used in medicine as a diuretic. Neutral tartrate. It is deliquescent. All acids even tartaric acid, convert it into cream of tartar. Rochelle salts KO,Na OT + 8HO. 132 KO } NaO } T crystallizes with 8Ho, in large clean, rhombic prisms, is used in medicine. forms the basis of seidlity powders. Tartar emetic. It is a double salt corresponding to cream of tartar. KO } SbO3 } T + aqua. Mix 3 parts SbO with 4 cream of tartar, make into a paste, digest It is soluble in 15 parts HO, is a violent emetic in larger doses acts as cathartic poison. Kinic Occurs in chinchona bark. Crystallizes in colourless prisms wh melt at 155°C. Solid on cooling at a higher temperature it is decomposed. Tribasic acids. Citric acid C12 H8 O14 . 133 Occurs in the lemon, gooseberry cherry & tamarind. As citrates in the tumours of the Jerusalem artichoke. Only the fruits wh contain acid united with alkali become sweet on ripening the acid being converted into sugar. Where acid is free as in the lemon, it does not become sugar. It is prepared like tartaric acid but is more easily made since it has no tendency to become uncrystalline as tartaric acid is apt to do. It crystallizes in large colourless prisms, very soluble in HO & alcohol, not in ether. It is used in calico printing both as a resist & to heighten the colours. Heated to 175° it is decomposed & becomes 134 C12 H8 O14 - 2HO = C12 H6 O12 Fused with lime it forms oxalate & acetate of lime. C12 H8 O14 + 2HO from the HOCaO = C4 H2 O8 + 2(C4 H4 O4). Citrates are necessarily a large class. Citric is tribasic acid. HO | HO | HO | C12 H5 O11 . Aquinitic acid. Found in aconitum Forms warty crystals easily soluble in HO. It is the acid in opium, it is a white silvery acid, loses its HO of crystallization at Gallic acid 2HOC14 H6 O10 It is bibasic, is contained in gull nuts in mango seeds in sumach. 135 It is got artificially by the splitting up of tannin when it is boiled. It is white silky crystalline. soluble in 3 parts of boiling HO & 100 cold HO, with a salt of Fe it forms ink. When heated to 210° it is decomposed, it loses C2 O6 & becomes pyrogallic acid. Pyrogallic acid C12 H6 O6 = Used for estimating O. With a little alkali it absorbs O completely. Tannic acid. Tannic acid is a general name for organic substances wh precipitate gelatine & form leather. It is contained in the leaves & bark of most forest trees, especially the oak, elm in the whortleberry, tea, coffee. Tannic acid except that from coffee. Precipitates protosalts 136 of Fe a blue black, or in acid solutions of a dark green. Some like tannic acid from catechu precipitate it a dark green. Gallotannic acid C54 H22 O34 Obtained from gall nuts. Take an ethereal solution of gall nuts, it divides into two parts the upper part is gallic & the lower tannic acid. Obtained thus it is a white, crystalline body soluble in HO, soluble in weak alcohol & ether. The aqueous solution absorbs O Gallotannic acid should be called tannin, it is a glucoside. Act on it by acid wt brings HO into play. 137 C54 H22 O34 + 8HO = 3(C14 H6 O10) + C12 H12 O12. Boil tannic acid with HCl, It is not certain whether it is a bi or tri [crossed out] basic acid. It is used in medicine as an astringent. Ink. Gallotannate of Fe. Take 3/4 lb of bruised gall nuts, dissolve them in 1 gallon of cold HO, add 6 oz of FeOSO3 . 6oz of gum arabic 5 drops of kreosote to prevent it moulding, digest at common temps. for 2 or 3 weeks, shaking frequently. Ink stain = Fe2 O3 To take it out heat with a little oxalic acid. it forms soluble oxalate of Fe. Gallotannate or tannate of gelatine. The object in tanning is to unite the skin with acid to prevent putrefaction, & yet leave the 138 skin supple. The time required varies, as, the hippopotamus skin is 2 inches thick & required nearly a year. While the kid's skin is only a fraction of an inch thick & requires only a few weeks. The processes are, 1st. Place the skin in lime, the root of the hair is attacked by it Remove the hair with a knife & open the pores by placing in a pit of HOSO3 & HO. Layers of skins & oak bark are laid in pits for 3 months, they are then taken out & fresh bark is added, the skins are then placed in again so that the one wh had been at the top is now at the bottom & allowed to remain there for some time. It is strange that no quicker 139 process can be employed The use of hydraulic presses to force the liquor into the pores, & of stronger solutions does not make such good leather If Simon the tanner of Joppa came back to this world he would find the trade precisely as he left it. In white kid gloves no tannic acid is used, it is protected by aluming Tawed leather The skins are cleaned & treated with Al2 Cl3 made by mixing alum & NaCl, & then rubbed with oily substances. In chamois leather as much oil is put in as possible. Compound haloid radicals. The chief representative is cyanogen C2 N. 140 It has perfectly parallel characters with any other haloid. Cl} 4 Cl} hyrdo Cl} chloride Cl} Cl} Cl} vols H} chloric acid K} of k I} O} C2N} 4 C2N} hydro C2N} cyanide C2N} C2N} cyanic C2N} vols H} cyanic K} of k I} O} acid acid Cl} Cl} 4 vols Cl} H} hydrochloric acid Cl} K} chloride of K Cl} I} Cl} O} C2 N} C2 N} 4 vols C2 N} H} hydrocyanic acid C2 N} K} Cyanide of K C2 N} I} C2 N} O} Cyanic acid Cyanogen was the 1st,, compound radical clearly established in organic chemistry. Cyanogen C2 N. = 26. if it has 2 vols 52 if 4 vols. S.G of gas 1.806. Symbol. Cy. It is monoatomic. The reason for this is that though N is pentatomic but is joined to 2 of C wh is biatomic & has thus 4 atoms filled up & only 1 left. N,,,,, - C2,,, = C2 N, Cy has the power of doubling itself & forming other radicals. Cy C2 N Bicy. C4 N2 Tricy C6 N3 Mellan C18 N13. 141 Cy is best got by heating cyanide of Hg in a tube. This corresponds to the method of getting O. [illustration] HgO2 heat = Hg + 2O HgCy2 - = H8 + 2Cy. A black substance is left in the tube wh has the same composition as Cy. Prop. It is colourless, has a peculiar prussic acid & odour at a pressure of 3 atmospheres it becomes liquid & the liquid solidifies at -35°C, it burns with a purple flame, producing CO2 & N, it is soluble in HO & alcohol the latter takes up 22 vols. of it The solutions decompose & urea is formed. Urea is an anomalous cyanate of NH4 . NH4 O C2 N K unites with Cy as it does with Cl. 142 Hydrocyanic or prussic acid. HCy= 27 s.g of the gas 0.9476. 4 vol vap. formula. Acc. Probably never found free but various seeds give it by distillation owing to the action of ferments on it. Almonds, peaches apricots, the leaves of peaches & the kernels of plums yield it. Mode of preparing it. Distil K Cy with HOSO3. pass over CaCl & condense by ice. s.g of liquid 0.967 boiled at 26ºC solid at -15ºC Has a smell like bitter almonds is an intense poison is soluble in all proportions in HO & alcohol. Does not keep well, after a while perhaps 2 or 3 years it becomes black & is apt to explode, you then break it under HO to prevent this, 143 Aqueous solution of HCy. Prep. Distil yellow prussiate of [illustration] KO & HOSO3. you get a solution of unknown strength. The medical strength is 2 percent of prussic acid. The London pharmacopia process for getting a solution of known strength, is. - Suspend 48 1/2 grams of cyanide of Ag in 1 oz HO & add 39 1/2 of HCl. An extemporaneous solution of HCy may be made by adding KCy to T & stirring, you get bitartrate of KO & a solution of HCy. The aqueous solution is more permanent if you add a little mineral acid. Solution of HCy under the action of strong acids or alkalis decomposes 144 decomposes into formiate of NH4 . C2 NH + 4HO = NHOC2 HO3 HCy is easily tested. Test. Take FeOSO3 wh has been a little rusted in air. If not rusted add a few drops of a persalt of Fe. Add HOKO to precipitate the oxide of Fe. Add HCl to neutralize the KO & take up the Fe. Add these to the suspected solution & if HCy be present prussian blue is produced. The rationale of this process is HCy, KO & a salt of Fe make yellow prussiate of KO, if you add HCl to make a solution of Fe prussian blue is produced. Another test. Put the suspected solution in a watch glass & add a drop or 2 of sulphide of NH4 to neutralize it, put over it another watch glass & [illustration] 145 evaporate it to dryness in a hot water bath. Add perchloride of Fe. You are producing sulphocyanide of K wh has the property of striking a blood red colour with perchloride of Fe. When used as a poison it quickly escapes from the system on account of its volatility so that 3 days after you cannot detect it in the body. Cyanides resemble the haloid salts of Cl & are got in the same way. To get KCl HCl + KO = KCl + HO - KCy HCy + KO = KCy + HO. On a large scale KCy is got by heating yellow prussiate of KO with KOCO2 . yellow prussiate of Ko. K4 Fe2 Cy6 K4 Fe2 Cy6 + 2KOCO2 = 5KCy + KoCyO + 2Fe + 2CO2 . You can prevent the 146 formation of KOCyO by adding a little C. K4 Fe2 Cy6 + 2KOCO2 + 2C = 6KCy + 2FeO + 2CO2 + 2CO. Dissolve it out & evaporate it down. It is use largely in electrotyping to dissolve Ag + Au, & as a reducing agent. Bicyanide of H8 - H8 Cy2 . Boil 4 parts prussian blue 3 of peroxide of H8 & 4O of HO. It crystallizes in prisms, soluble in HO more difficultly soluble in alcohol, very poisonous. Alkalis do not precipitate H8 O from it. Cyanide of Ag. AgCy. Prep. Add KCy to a salt of Ag. It unites with KCy & readily forms double salts. Haloid ethers of Cyanogen. Cy unites with ethyl as Cl does. 147 Prep of cyanide of ethyl. Add KCy to C4 H5 I. C4 H5 I + KCl = C4 H3 Cl + KI prep of chloride of ethyl C4 H5 I + KCy = KI + C4 H5 Cy cyanide of ethyl. We find the Cy has gone in more intimately to the ethyl than we would suppose On this account These compounds are called nitriles. Cyanide of ethyl. C4 H4 C2 N. It is a colourless liquid, mobile of an agreeable but garlicky odour Does not comport itself with alkalis like ordinary ether. It is soluble in alcohol & ether. C4 H5 Cl + KOHO = KCl + C4 H6 O2 propionate of KO C4 H5 C2 N + KOHO + 2HO = KOC6 H5 O3 + NH3 Propionic acid one above C4 H5 in the series. Act on a nitrile by an alkali & you get the acid one above it in the series. 148 Double electro negative cyanides. The cyanides form a remarkable series of salts when certain metals combine with them, especially Fe 4KCy + 2FeCy = yellow prussiate of KO. If you get an insoluble cyanide of Fe by adding FeOSO3 to KCy & add excess of KCy to the insoluble salt it gradually dissolves & you get a solution of yellow prussiate of KO. Suppose the Fe has a formed a compound radical with Cy. Fe2 Cy6 called Ferrocyanogen. Yellow prussiate of KO is this + 4K & crystallizes with 6HO. Add HCl to this Fe2 Cy6 + 4K + 4HCl = 4KCl + Fe2Cy6 4H. [illustration] Has a solution of yellow prussiate of KO in the tube add HCl & ether 149 Fe2 Cy6 4H = hydroferrocyanic acid is insoluble in ether. A bluish white compound is formed. Occurs in crystalline plates, soluble in HO, is readily precipitated by ether. The solution quickly becomes blue, when boiled HCy is evolved. When the 4H are substituted by 4K you get yellow prussiate of KO. Yellow prussiate of KO. It is used in the arts largely. Prep. Cast off woolen garments, horns & hoofs of cattle, flesh & blood any thing that contains N are mixed with scrap Fe & Montreal pearl ashes & heated. Fe2 Cy6 4H = Hydroferrocyanic acid 150 Fe2 Cy6 4K = yellow prussite of KO. It is formed when a substance containing N is fused with KOCO2 & Fe or allowed to digest on Fe. Occurs in lemonyellow tabular crystals soluble in HO not soluble in alcohol, of a bitter taste & purgative but not poisonous, If you take away 1 of K & make red prussiate it becomes intensely poisonous Yellow prussiate is tetrabasic. Fe2 Cy6 { 2Ba { 2K Fe2 Cy6 { 3Cu { K. We have doubled the formula on this account. [illustration] Add yellow prussiate to CuOSO3 & a mahogany red is produced. Ferrocyanide of NaO. Na4 Cy6 + 10HO. Ferrocyanide of Fe. Take a solution of Fe OSo3 & add yellow prussiate, you get a 151 a precipitate, while at first but wh absorbs o from the HO & becomes blue. It has this composition. Fe2 Cy6 {3Fe {K. Add yellow prussiate to a persalt of Fe & you get prussian blue at once Fe7 Cy9 . Prussian blue Prop. It is a beautiful blue of a coppery lustre when dry, after being washed in HO it may be dissolved in oxalic acid. This when thickened with gum forms steven's blue ink. It is readily decomposed by alkalis. Add caustic NaO or KO to prussian blue, it produces a reddish colour & forms oxide of Fe. Put a cloth dipped in a salt of Fe into prussiate of KO & it is dyed blue. 152 Ferridcyanogen. It has the same composition as ferrocyanogen but is tribasic instead of tetrabasic Fe2 Cy6,,,, radical of yellow prussiate Fe2 Cy6,,, - red - Pass Cl this is a solution of yellow prussiate. Fe2 Cy6 4K + Cl = KCl + Fe2 Cy6 3K. Hydroferridcyanic acid. Is got in the same way & has much the same properties as Hydroferrocyanic acid. Add HCl to red prussiate of KO & add ether. Or add HOSO3 to Ferricyanide of Pb. Crystallizes in brown needles, better easily decomposed. Ferridcyanides are generally red. They are distinguished from ferrocyanides by giving no precipitate with perchloride of Fe. 153 yellow prussiate with Protosalt of Fe gives a white precipitate Red prussiate - blue yellow- persalt - blue Red- dark brown. Ferridcyanide of K. Is generally called red prussiate of potash. Crystallizes in ruby red right rhombic prisms, soluble in HO insoluble in alcohol, gives a precipitate with metallic salts in wh all 3 of K are replaced by metal. K3 Fe2 Cy6 + 3AgONO5 = 3AgFe2 Cy6 + 3KONO5. Turnbulls prussian blue, is prussian blue got from red prussiate & FeOSO3. Nitroferrocyanides or nitroprussides Fe2 Cy6,,,, Fe2 Cy6,,, Fe2 Cy5 NO,, Nitroprusside of Na. 154 Made by the action of NO5 on Nitroprusside of K. When you add sulphide of NH4 to this a beautiful purple colour is produced wh is very transitory. It is the best test for S. Put a lock of hair into a test tube & dissolve it in caustic NaO or KO. heating it to aid the solution. You must always convert the S into an alkaline sulpide. Adds a good deal of HO so as not to act on the filter & filters it. Adds nitroprusside of Na & a deep purple is produced showing the presence of S in the hair. The nitroprussides give a salmon coloured precipitate with salts of Fe. Oxides chlorides & sulpides of Cy. It must be recollected that there are 3 sorts of Cy. Cy Cy2 & Cy3 . 155 Cyanic acid CyO. Cyanates are easily got by heating a cyanide with an oxide such as of Pb. CyO is not so easily got. Distil cyanuric acid & collect the product in a freezing mixture. It is colourless mobile A drop on the skin produces a sore. Above 0°C it changes into a procelain like mass. Cyanates. General formula MOCyO corresponding to MOClO. They bear heating to redness without decomposition. You do not obtain CyO by acting on them by acids Cyanate of KO. KOCyO. Prep. Heat prussiate of KO with 156 an oxidizing agent such as MNO2 . It is soluble in HO, the solution is decomposed when heated. KOC2 NO + 3HO = NH3 + HO} KO} C2 O4 Cyanite of NH4 . NH4 OCyO. Prep. Act on cyanate of KO by NH6 OSO3 It is white crystalline, soluble in HO & alcohol, it is not urea, wh is an anomalous cyanate of ammonia NH4 OC2 NO. Chloride of Cy. NCO2 Cl. vap. density 2.124 Act on cyanide of H8 by Cl. Colourless, very poisonous gas, of a disagreeable pungent small, at -53°C it becomes liquid. In closed tubes it becomes double CyCl = Cy2 Cl2 . Sulphocyanogen Sulphocyanates correspond to cyanates S playing the part of O. 157 CyO CyS . It has never been got in a separate state. A yellow compound got, has been called CyS but does not behave as such. It forms sulphocyanates wh are interesting because NaCyS at least exists in the saliva man & the sheep. Put some saliva in a watch glass & add perchloride of Fe. Sulphocyanide of K. KSCyS. Prep. Heat together yellow prussiate of KO1 KOCO2 & Bicyanogen Cy2 C4 N2 . Not known in its separate state Bicyanic acid Cy2 O2. It has the synonym fulminic acid . 158 2 HOCy2 O2 Fulminic acid Not known free. Fulminate of Hg. 2HgOCy2 O2 Prep. Heat HgONO5 & alcohol together It crystallizes in white needles very explosive not soluble in cold HO but soluble in hot. Add Zn to the solution & Hg is deposited & fulminate of Zn remains. Act on fulminate of Zn by Cl, & it becomes chloride of Cy & C2 (NO4 ) Cl3 chlor-carbasotic acid. It is possible that 1/2 the N in fulminic acid may not be present as Cy. It is closely allied to Cy. Persulphocyanic acid. Little soluble in alcohol & ether With alkalis it forms soluble 159 & with heavy metals insoluble salts. Bichloride of Cy It is formed when CyCl is left in a sealed tube. It is a colourless liquid boils at 15ºC. Tricyanogen. Cy3 . Forms cyanuric acid Cy3 O3 3HO. Got by the action of terchloride of Cy on HO. CyCl3 + 6HO = 3HOCy3 O3 + 3HCl Transparent crystals, no smell or taste, reacts acid. Cyanurates Cy3 Cl Expose anhydrous Crystallizes in brilliant needles wh melt at 140ºC boil at 190ºC Smells like the excrements 160 of mice, difficulty soluble in HO readily soluble in alcohol & ether. Characters of Cy. Cy has the character of a radical closely resembles Cl but has the power of duplicating & triplicating itself & forming other radicals Unites so intimately with metals as to appear to form radicals Polymerizes itself. Mellone C18 N13 Organic bases representative of alkalis & metallic oxides in organic chemistry. The bases resemble NH3 They act like NH3 on hydracids without expelling the H. They almost all unite with PtCl2 to form double salts. It is believed that they are all constituted on the NH3 type. 161 The general name is amines. NH3 N | | H | H | H Primary N | | A | H | H Secondary N | | A | B | H Tertiary N | | A | B | C Monamines Example N | | C4 H5 | H | H N | | C4 H5 | C2 H3 | H N | | C4 H5 | C2 H3 | C10 H11 All these are true ammonias, form salts with hydracids & take up HO when they unite with oxyacids. They are volatile alkalis & have a peculiar odour generally resembling NH3 . The replacing radicals are generally the common compound radicals. C12 H3 Cl2 | H | | N Chlorphenylamine C12 H3 ( NO4 )2 | H | | N dinitrophenylamine When you have such substitutions as these, electro negative 162 bodies replacing H, the basic power of the body is much impaired & in some cases destroyed. Glycocol C4 H3 O4 | H | H | | N neutral Benzamic acid C4 H5 O4 | H | H | | N Production of these compound ammonias. They are produced by the action of an iodide of an alcohol radical on NH3 . N | | H | H | H + C4 H5 I = N | | C4 H5 + I | H [cross out] | H Or by deoxidizing a nitro compound as in aniline* Ethylamine s.g 0.696 boils at 18.7°C It is a colourless liquid of an ammonaical odour, its causticity is nearly equal to that of KO. It blues red litmus, neutralizes powerful acids, raises a blister * C12 H5 ( NO4 ) + 6HS = N | | C12 H5 | H | H + 4HO + 6S. 163 on the tongue, drives NH3 from its salts Tri It is colourless liquid, inflammible slightly soluble in HO less so than ethylamine. Act on this with C4 H5 I, & you get iodide of ethylammonium a compound corresponding to NH4 I. N | | C4 H5 | C4 H5 | C4 H5 + C4 H5 I = N( C4 H5 )4 I. Act on the last body by AgO & you get AgI + N( C4 H5 )4 O corresponding to NH4 O. Oxide of tetrethylammonium You cannot distinguish it from KO in its chemical characters It acts as a caustic & forms a soap with fats. It precipitates metallic oxides like KO Add it to CuOSO3 & CuO is precipitated & sulpate of tetrethylammonium 164 tetrethylammonium formed In coal tar there is a remarkable set of organic bases You get them by treating with HOSO3, decomposing by KO & distilling Pyridine C10 H5,,, N Picoline C12 H7,,, N Lutidine C14 H9,,, N Lecoline C18 H7 N Lepidine C20 H9 N Put a mixture of Lutidine into a sealed tube into hot HO they being less soluble in hot than cold HO float on the top of the liquid on the tube Diamines. Where 2 atoms of NH3 have coalesced unto one. N2 | | H2 | H2 | H2 you may have primary, secondary & tertiary diamines N2 | | A2 | B2 | C2 165 Urea belongs to this class. Common urea. N2 | | C2 O2 | H2 | H2 Urea forms from 77 to percent of human urine Prep. Evaporate urine till it becomes syrupy & add an equal volume of colourless NO5 of s.g 1.35. It forms nitrate of urea, separate the acid by BaO & the urea by alcohol & crystallize. Artificial urea. KOC2 NO + NH4 OSO3 = KOSO3 + NH4 OC2 NO. Prop. It crystallizes in 4 sided prisms like KONO5 Soluble in HO & alcohol, when heated it is converted in great part into NH3 & Cyanuric acid. Unites with acids & forms salts. N2 | | C2 O2 | H2 | H2 N | | C2 O2 | C4 H5 | H2 Triamines. N3 | | H3 | H3 | H3 Organic alkaloids. It was long the opinion of chemists that vegetables only produce neutral & acid substances. In 1803 got an alkali from opium & in 1804 got another alkali. yet it was 12 years after, that the opinion became prevalent that alkalis were produced by vegetables. General properties. They behave like NH3 . They neutralize acids & form salts. They are all solid or liquid, generally fixed a few 167 are volatile. Some are soluble in HO some in alcohol. The sulphates, nitrates, chlorides & acetates are soluble. The tartrates They are generally violent poisons or active remedial agents. They may be divided into 3 classes A. Volatile alkalis free from O. B. Bases readily soluble in alcohol sparingly in HO. C. Bases soluble both in HO & alcohol. A. Example. Nicatine. Prep. Macerate tobacco in HO. The malate of nicotine dissolves Ni = nicotine. M = malic acid NiOM + KO = Ni + HO The Ni distils over. B. Prep. These bases are united 168 with acids such as Kinic acid or meconic acid. Add HCl the chlorides are dissolved out, add lime wh. forms CuCl & precipitates the alkali. Take it up by & crystallize from alcohol C. Dissolve in HCl & form chlorides. Neutralize the chlorides by NH3 & precipitate by oxalate of ammonium. Decompose by BaO & crystallize. Conia is a secondary monamine N | | C16 H14 | H. It is prepared from hemlock chiefly from the seed. It is a colourless oil of penetrating odour & burning taste it is strong poison, in presence of HO it acts strongly alkaline, difficultly soluble in HO. 169 especially when warm, readily soluble in alcohol & ether. Act on it by C4 H5 I & you get ethyl conia. Sparteia. A tertiary monamine N | C16 H13,,, Got from broom, heavier than HO, the liquid boils at 287°C. Alkaline & narcotic poison, has an odour like aniline nicotine, it is a diamine C20 H14 | N2 Occurs in tobacco chiefly in combination with malic It is a colourless liquid, absorbs O readily & becomes brown, has a burning taste, slight-odour of tobacco, is intensely poisonous There is from 2 to 7 Percent in tobacco. The mild kinds of tobacco as 170 Havannah used for smoking contain the least quantity, those sorts used for snuff contain most. The strength of snuff is due to nicotine, its pungency to ammonia salts. Snuff. The leaves of tobacco are allowed to ferment for 18 months. During this time there is a considerable absorption of O & the temp. often rises to 100°. They are then ground & sifted. In fermenting 2/3? of the nicotine is destroyed, NH4OCO2 is formed & a volatile oil to wh the aroma is due & 2 P.C. of nicotine remains. Alkaloids in opium. They are numerous. Morphia C34 H19 O6 N probably a monamine. 171 Codeia C36 H21 O6 N Thebeia C38 H21 O6 N Papaverin C40 H21 O6 N Narcotin C46 H25 O14 N. Narcein C46 H29 O18 N Opianine Pseudomorphine & phorphyroxine Morphine In crystallizing it takes 2HO. Occurs in opium in combination with mechonic & sometimes sulphuric acid. It is present in from 6 to 12 PC. Smyrna opium contains most, Crystallizes in brilliant prisms, taste slightly bitter, has a slight alkaline reaction when heated it parts with its HO of crystallization & at a higher heat is decomposed. HO dissolves 1/1000th part of its wt of it it is readily soluble in 172 alcohol slightly in ether It is a strong narcotic poison when heated with soda lime it becomes methylamine. Muriate of morphia. It crystallizes with 6HO in fine silky prisms, soluble in HO & alcohol. When impure it crystallizes in large crystals, the purer it is, it is more difficultly crystallizable. It forms double salts with PT Cl2 . Acetate of morphia It is a deliquescent salt, crystallizes in thin needles. Sulphate of morphia Salts of morphia are largely used in medicine. 173 5 grains to the ounce are administered like laudanum in small doses. Though less powerful than laudanum. Test. salts of Fe2 O3 3SO3 give a blue colour with it, concentrated NO5 a red colour at first fading to yellow. Conine Crystallizes with 2HO. Occurs in opium to the extent of 1 P.C.. Though homologous with morphia it is not analogous to it in its properties. Soluble in 8 parts cold HO & 17 hot. Melts at 150°C. Decomposes at higher temperatures is poisonous, produces tetanic convulsions like strychnine. 174 Papaverin Is not poisonous. Narcotin Is present from 6 to 8 PC in opium Crystallizes in small rhombic prisms, little soluble in alcohol or ether. Has very feeble alkaline properties many of its salts are decomposed by HO. Is poisonous. 2O grains will kill a dog. There are 3 homologues of narcotine in opium. Alkaloids in chinchona bark There are four. Quinine C40 H24 O4 | N2 Cinchonin C40 H24 O2 | N2 Chinidin C36 H22 O2 | N2 Arcin C46 H26 O8 | N2 They are all diamines. They are found united in cinchona bark with kinic & kinotannic acid. 175 Quinine Found chiefly in the yellow bark in about 3 1/2 P.C. Crystallizes in silky needles from ether, as a white curdy precipitate from its salts, soluble in ether, in 200 parts boiling HO, more soluble in lime water. Readily soluble in alcohol & ether. Intensely bitter, alkaline, melts at 120°C. Unites with acids so as to form 2 classes of salts. The pill used by Dr Livingston in cases of African fever & wh. never fails if the patient be removed to a higher district. 3 to 4 grains resin of julap 3 to 4 - calomel. 3 to 4 - quinine A drop or two of tincture of cardamums to dissolve the resin & 176 form the bolus. It ought not to purge but to occasion gentle movement Sulphate of quinine It unites with 1 atom of HOSO3 , crystallizes with 7 HO in long brilliant prisms, easily loses 5 HO, difficultly soluble in pure HO. Acid salt Q HO SO3 . Used in medicine, add a drop or 2 of HOSO3 to assist its solubility. It is often adulterated with CaOSO3 sugar, calomel, fats, starch, & salicin. To detect adulteration, burn a portion if CaOSO3 is in it, the CaOSO3 remains. If with calomel or sugar you can smell them. If not completely soluble in dilute HOSO3 it contains fats or starch. If salicin be mixed with it. 177 dissolve in 6 times its wt of HOSO3 add 12 parts HO, salicin will be precipitated. Cinchonine. Found chiefly in the grey bark Crystallizes in large anhydrous prisms, soluble in alcohol & ether The salts are intensely bitter, precipitated by gall nuts, heated with KO it becomes Chinodin or quinidine [crossed out] Brilliant prisms soluble in alcohol difficulty in ether Aracin. Found in China cusco. Alkaloids of strychnine family. found in seeds & bark of nux vomica in the 178 Ignata bean. Contains 2 alkaloids Strychnine C42 H22 O4 N2 Brucin C46 H26 O8 N2 Colourless 4 sided prisms, scarcely soluble in alcohol or HO, intensely bitter, soluble in aqueous alcohol when boiling, frightful poison Nitrate. have been used in medicine Tests. Add to the suspected solution Ko2CrO3 & HOSO3, it it produces a violet blue, passing to red. Brucin With 8HO. Crystallizes in colourless prisms 4 sided insoluble in HO & ether 179 readily in alkalis with strong oxidizing agents it forms methylic ether. Alkaloids of the solinacia family. There are 3. Nicotin Hyocyanin. - Atropin C34 H23 O6 N. Occurs in atropa. White, sharp bitter taste soluble in HO & alcohol. Fuses, & decomposes at higher temps. Salts decompose readily. Violent poison, dilates the pupil of the eye. Salts are soluble but difficulty crystallizable Hyocyanin. Has properties similar to atropin. Veratrin C64 H52 N2 O10 18 180 Found in veratrum, produces sneezing is a violent poison. Dervin. C60 H46 N2 O6 Delphinine C64 H32 N2 O4 Colchecine Aconitin Alkal Caffeine or theine. Found in tea & coffee & paraguay tea. In 3 quarters of the globe men have derived a beverage wh they take about the same time of the day. From plants not only of the same species but of a different order They all contain the same alkaloid theine or caffeine call it caffeine. Caffeine C16 H10 O4 N4 tetramine you may view diamines or tramines as monamines. N2 | | H2 | H2 | H2 maybe = N | | NH4 | H | H N | | NH3. | H | H | H In wh the radicals of compound 181 ammonias replace the H Theine or Caffeine. Occurs in tea & coffee. Prepared from tea by subliming it. Crystallizes in thin brilliant needles 177°C sublimes at a higher temp. Difficulty soluble in cold HO, is a weak base its salts are decomposed by HO. In large doses it produces increased action of the heart. irritability of temper If you take 3 grains of theine a day about 2 cups night & morning you [crossed out] may retain you usual temper & state of nerves. If you take 4 or 5 grains it produces irritability of temper & nervousness. If you feel in a nervous state 182 without being able to account for it, it us very probably from this cause. To cure it, take chocolate instead of tea or coffee for some days when it will most probably be cured. Theobromine Occurs in cocoa. It is methyl theine. Hydrates of Carbon Under this head are included all bodies wh have the genera formula CmHnOn Such bodies are starches, sugars gums, bodies wh have a neutral or indifferent character. Dilute acids convert most of them to grape sugar Acts on sawdust by HOSO3 & it is converted into grape sugar. Oxidizing agents convert them to oxalic acid. 183 The views of their chemical constitution are not certain They are at present supposed to be alcohols If the H & O be not present as HO it is in a form nearly approaching it. Take grape sugar for instance C12 H14 O14 It has the same volume as 14 atoms HO frozen to ice the C occupying no appreciable bulk When dissolved it occupies the same volume as 14 atoms of liquid HO. The H8-O comport themselves in solution as HO & when solid as ice. Cellulose C36 H30 O30. It is the basis of vegetable structures. You have it nearly pure in cotton wool. Occurs in the sap of growing vegetables. It is the same in composition from whatever source derived 184 Is nearly pure in the pith of elder rice paper, linen & cotton. Prop. It is a white, solid, sometimes parent Its s.g is a little higher than that of Ho. Its composition is the same but its physical characters differ according to the source whence it has been derived. It is compact in the branches of trees hard & dense in the shells of the filbert & cocoa nut. It is digested or not digested by animals according to its physical condition. It is easily transformed HOSO3 boiled with it converts it into dextrin & then to grape sugar. These all being the same in percentage composition. Digested with HONO3 it forms guncotton. 185 guncotton. [Illustration] Puts cotton in a mixture of HOSO3 & HONO5 washes & drys it. Part of the H has been substuted by NO4. There are several kinds according to the length of time it remains in the acid. Cellulose C36 H30 O30 Gun cotton A C36 H21 (NO4)9 O30 B C36 H22 (NO4)8 O30 C C36 H23 (NO6)7 O30 D C36 H24 (NO4)6 O30 Common paper is cellulose or lignin in another form . A curious transformation is effected by HOSO3 wh converts it into vegetable parchment. Take 2 volumes of the strongest oil of vitriol & one volume of HO carefully measured. 186 Dip ordinary unsized paper, which blotting paper into it & wash well the last HO should have a little NH3 in it to remove all traces of HOSO3. Wash again to remove the NH3 & dry it. The strength of the paper is much increased, a slip of paper that would have before broken by 5lbs will afterwards require 72lbs to break it. Starch. C12 H10 O10 Is very extensively distributed in nature. It varies in its forms according to the source from wh it is obtained Grains of starch in Tous les Moïs are 1/260th in. in diameter. Those in wheat are 1/1000th in. & in rice 1/3000th. in. Starch exist in various quantities in vegetables used for 187 food. There is in Wheat flour 57 to 67 P.C. of starch Rice 85-86 Barley 39 40 Oats 30 40 Rye 54 61 Lentiles 39 40 Maize 65 66 - flour 77 Buck Wheat 43 44 Beans 37 Peas 38 Potatoes 23. Prop. It is white tasteless, insoluble in cold HO & ether, when put in hot HO it swells up & forms a jelly. This is not a true solution for freezing separates it into grains of starch. The youngest grains separate first Test. Put a little Cl into a mixture 188 mixture of the starch solution & KI. The Cl is liberate I. Dilute acids convert starch into dextrin Heated with dilute HOSO3 it becomes grape sugar NO5 dissolves starch & HO precipitates it as an explosive compound as gun cotton in fact. By carefully heating it from 160° to 200°C it becomes dextrin. British gum is made in this way. Manufacture of starch. It exists with gluten in flour. To get rid of the gluten, subject starch to fermentation by wh. the gluten is destroyed, this causes a very bad smell. A new process has been proposed Dissolve the gluten by alkalis & then the starch remains. To get it from potatoes. 189 Grate the potatoes & put them on [illustration] a sieve, pour HO on them stirring them all the time The starch passes thro' the sieve & settles at the bottom of vessel placed below it. Wash the starch once or twice Special Starches. Several are sold for food. Sago is got from the pith of the sago palm. It is made into a paste & pressed thro' a perforated metallic plate & then exposed to the heat of steam to dry it. Tapioca. Is got from the root of the manioc. This root contains HCy wh is separated in the process of making. Arrowroot. Is got from the root stocks of various plants. Salep Is made from the root of the male orchis. 190 Starch in the animal kingdom Sometimes in healthy animals tissues, granules of starch have been found in the brain. The waxy appearance of the liver Inulin C26 H20 O20 + 3HO. Distinguished from starch by not giving a blue with I. Exists in chicory, dandelion Becomes yellow with I. Long boiling converts it into dextrin & then to grape sugar. Lichenin Found in Iceland moss, soluble in hot HO. Irish moss contains another kind C10 H10 O10 + 3HO. Peculiarly distinguished by forming a precipitate with gelatin. 191 Take a solution of Irish moss. & add it to a solution of gelatin no precipitate is formed Add a drop or two of alum & you get a stringy precipitate. Glycogen. Got from mans liver. I produces a dark red colour with it. It has no taste or smell forms a paste with HO Found in the saliva, pancreatic juice Diastase & dilute acids Its formula is given as C12 H10 O10 C12 H12 O12, & as C12 H16 O14. Dextrin C12 H10 O10. It is a product of the transformation of starch Got by roasting starch. 192 10 parts of starch are moistened with 3 of HO, the HO is to contain 1/150th of its weight of HONO5. The paste is allowed to dry spontaneously. It is a colourless transparent body like gum, deviates the plane of polarized light to the right hand, there seems to be an intermediate compound between starch & dextrin, soluble in HO wh starch is not & blued by I wh dextrin is not. Distinguished from gum by forming a beautiful blue solution with Cu OSO3 & KO. When this is heated suboxide of [illustration] Cu is deposited. Dextrin is used as a gum for 193 machinery as in calico printing To prepare glutinous bandages to reduce fractures. Gums. They have the same composition as starch, form a mucilaginous solution with HO. They all give mucic acid with HONO5 instead of oxalic acid as starch does. Quantities of cellulose & gum In one lb of the following substances there are. In Potatoes 327 grs cellulose 27 grs gum Rice 218 87 Wheat 109 109 Barley 2oz 146 Oats 2oz 218. Gums have the same percentage composition wherever 194 obtained but seem to have different combining proportions Gum arabin or arabic C12 H11 O11 Unites with bases as acetate of Pb. Is soluble in cold HO A solution of 18 P.C is so thick that it cannot be filtered, it is insoluble in alcohol. Cerasin The gum from cherry trees. Bassorin. Found in gum tragacanth seems to be a modification of pectin or vegetable jelly Pectin The gelatinous principle of fruits carrots, turnips &c. It is probably identical with Bassorine. It only swells in HO without dissolving. It seems to be a feeble acid. 195 It is rendered soluble by long boiling & passes into ordinary gum. Sugars Cane C12 H11 O11 Fruit C12 H12 O12 Grape C12 H12 O12 + 2HO Milk C24 H19 O19 + 5HO Mellitose C24 H24 O24 + 4HO Eucalyn C12 H12 O12 + 2HO Sorbin C12 H12 O12 Inosite C12 H12 O12 + 4HO Under the name of sugars are included all vegetable substances wh have a sweet taste They are formed during the life of the plant but are perfectly definite chemical compounds & crystallize They are so distinctive in their characters that they may be divided into 2 classes. 196 Sugars susceptible of vinous fermentation by yeast. Sugars not susceptible. Grape sugar or glucose C12 H12 O12 + 2HO is in crystallized state really C12 H14 O14. Occurs in the juice of grapes, in plums, cherries & dried fruits. Occurs in many of those as fructose. Fructose is uncrystallizable. Honey becomes crystalline after some time from the fructose in it becoming grape sugar. It occurs in the animal kingdom as a normal constituent of the liver. Occurs in diabetic urine. It is formed very quickly in the body under certain circumstances. If the fourth ventricle of 197 the brain is irritated by a needle diabetic sugar appears in the urine a few minutes after. Test. Heat a solution suspected of containing it with CuOSO3 & a few drops of KO. Cu2 O is formed. It first appears as a yellowish hydrate but afterwards reddish It is prepared on a large scale by allowing starch & HO at 130° F to flow into a vat containing HO & 1PC of HOSO3. It is boiled for 1/2 an hour when all the starch is converted into grape sugar. Neutralize by CaO & crystallize. Prop. It crystallizes with difficulty in warty concretions Tastes less sweet than cane 198 sugar, is soluble in HO & alcohol. Turns the plane of polarized light to the right. At 100°C it melts & loses 2HO at a higher heat it becomes brown does not taste sweet & is then called caramel, whose formula is C12 H9 O9 & is used for colouring Grape sugar unites with bases & forms saccharides 2(C12 H12 O12) 3 Pbo sesquisaccharate of Pb. Unites with NaCl & forms a crystalline compound It is also said to combine with organic acids. It is easily oxidized With HOSO3 it forms conjugate acids, act on that by strong bases & it forms glucic acid C8 H5 O5. 199 When a solution of grape sugar is acted on by yeast it is converted into alcohol & CO2. C12 H12 O12 acted on by yeast = 2eq. alc. 4 - CO2. When cheese, muscle or other nitrogenous ferment acts on sugar the change is quite different. Lactic acid C12 H12 O12 = (C6 H6 O6)2. If you carry this farther & the putrid cheese acts more on it. C12 H12 O12 = 1 Eq Butyric acid C8 H8 O4 4 - CO2 4 - H C4 O8 H4 C12 H12 O12. Ultimately sugar is converted into mucic acid or rather into a slimy acid whose composition is not well known. 200 Fruit sugar or fructose Has the same composition as grape sugar & only differs from it in not being crystallizable. Is found in honey & fruits. Cane sugar C12 H11 O11. Introduced into Europe some centuries before the Christian era but did not come into general use till the discovery of America. Occurs in sugar cane, beet root, sugar maple. Readily crystallizes in 3 forms. in the crystalline form as sugar candy, in the vitreous state as barley sugar. Barley sugar gives out much heat in passing into the crystalline form. The same thing takes place 201 with AsO3. Readily crystallizes in 4 sided rhomb The taste is sweeter & purer than that of grape sugar. Is soluble in 1/3 its wt of HO less soluble in alcohol than glucose. Heated to 160° it melts to a colourless liquid & cools in the vitreous state as barley sugar. Barley sugar after a time becomes crystalline. By a strong heat sugar becomes [crossed out] caramel. When a solution is boiled with dilute acid it becomes fructose & if for 2 hours longer grape sugar. With strong bases it forms saccharides. C12 H11 O11 BaO. Cane sugar cannot be fermented 202 fermented by yeast without becoming grape sugar. If you take equal wts of cane & grape sugar, the cane sugar will require more yeast than the glucose to ferment it, the extra yeast being employed in converting into glucose. Manufacture of sugar. It exists in various substances but that used in this country is chiefly obtained from cane. The sugar cane is cut before flowering & the juice expressed. The juice contains a good deal of albumen wh would act as a ferment & wh is separated by coagulating the albumen This is called defication. You put in a certain quantity of lime or as lately practised of CaOSO2. Boil & the 203 albumen is coagulated. The syrup is then evaporated. If you evaporate at too high a temp. it is converted into fructose, to prevent this it is boiled in vacuum pans in wh it boils at instead of 220°. It is then transferred to wooden cylinders & crystallized. It is drained from molasses by means of an extremely rapidly rotating perforated cylinder called the Jim Crow & sometimes the devil. The best canes contain about 18 PC of sugar but only 7 to 10 PC is got On the continent sugar is got from beet root. The roots are pulled in October They are rasped & the juice 204 expressed. The juice contains 10 PC of sugar but the manufacture is so much better conducted than that of cane sugar that 7 PC is obtained. In one manufactory in Belgium they got 8 1/2 P.C. There is the same defacation & evaporation as in cane sugar It is filtered thro animal charcoal. The crystals are longer & flatter than those of cane sugar, & its taste not so sweet maple sugar Holes from 1/4 to 1/2 an inch deep are made in the wood of the maple & the juice collected from them by reeds or spoub wh are stuck into them. The juice is collected in March April & May. 205 Each tree yields 3 lbs of sugar in a season & continues to do so for 30 years The juice is concentrated & crystallized every 24 hours. Refining of sugar. Raw sugar is dissolved in lime HO & mixed with bone charcoal & steam blown thro' it & if very impure bullock's blood is added. It is filtered thro bags of twilled cotton, & thro animal charcoal (burned bones). It is evaporated in vacuum pans. The syrup if evaporated in air may rise to 230° wh converts it into fructose, while if evaporated in vacuum pans 140° to 150° is sufficient. It is evaporated till the syrup is so strong that a thread 206 drawn from the finger will return to it without breaking. It is heated to 170° F run into conical moulds. Sweetness & uses of sugar. The sweetness of sugar is definite. 1 lb of cane sugar is equal to 2 1/2 lbs of grape on 3 lbs of milk sugar in sweetness. It is chiefly useful as a food in supporting active respiration, useful in keeping up the animal heat. It is good for infants for this purpose since being soluble it is more easily assimilated to the system. For this reason it exists in large quantity in milk. In the United States the consumption of sugar per 207 head of the population is [crossed out] 40 lbs. In France 4 lbs in Belgium 6 in Austria 2 1/2 in Russia 2 1/2 in the united kingdom 28 in Benzuela 110. Cane sugar is found in plants during the germination of seeds & previous to the unfolding of their buds. The bark of birch contains a good deal Grasses & palms contain most when about to blossom. Jaggery, cocoa nut & wine palms In America sugar is got from the stalks of maize. Relation of H & O in sugar. The H & O stand in the proportion necessary to form HO In such a state also as if it were present in the form of HO. 9 atoms of HO in the state of ice is equal in volume w 9.8 atoms of HO. 208 C12 H11 O11 = 171/3p.SM.1.6 = 106 atomic vol. 9.8 x 11 = 107.8- of 11 atoms of HO in the state of ice. The bulk of an atom of sugar is the same as that of the HO in it in the state of ice the C occupying no sensible space. Milk sugar = 180/1.543 = 116.6 at vol 9.8 x 12 = 117.6 at vol of HO in it. If you dissolve sugar in HO you only increase the HO by the bulk of the HO in the sugar the C occupying no sensible space. Sugar of milk. C12 H11 O11 + HO or more usually C24 H22 O22 + 2HO. milk sugar is only found in the animal kingdom Prep. Evaporate whey after the separation of the curd & crystallize 209 crystallize on twigs. Crystallizes in 4 sided prisms terminated by 4 sided pyramids. The crystals are hard & gritty, feebly sweet, soluble in HO, more difficulty than other sugars, in 6 parts of cold HO & 3 to 4 of hot. It does not become syrupy, on account of its small solubility & does not deliquesce in air. At 130°C it loses its HO of crystallization at higher temps. it becomes brown & is called Lacto caromel C12 H10 O12 It forms saccharides. Precipitates Cu2 O from solutions even in cold but less readily than glucose. Dilute acids convert it into lactose wh has the same formula as grape sugar but does not 210 form a compound with NaCl Although milk sugar does not ferment the Tartars ferment mares milk & make cumase Other fermentible sugars. Trehalose C12 H11 O11 Found in a substance called Trehala a substance used in the East for food a product of insects. Megatose. C12 H12 O12 + 2HO. Got from the twigs of the larch Mellitose C12 H12 O12 + 2HO. From the manna of Eucaliptas Non fermentable sugars. Inosite C12 H12 O12 + 4HO. This is muscle sugar Found in the muscle of the heart in the brain & nerves in unripe common beans & in the cells of the lung & the liver 211 Prep. Crystallizes in small crystals efflorescing in air. Soluble in HO & weak alcohol insoluble in alcohol & ether. At 210° it melts to a clear liquid. Dilute acids do not change it. It does not reduce Cu It does not suffer vinous fermentation, by cheese it suffers lactic or butyric fermentation. Scyllite Is found in the liver of shark If you evaporate Inosite nearly to dryness & add CaCl Sorbite is Is got from the berries of the mountain ash. Its taste is sweet It does not ferment & does not produce grape sugar when boiled with acids 212 Sugars unite with various organic substances. Salicin is one of these. They are called glucosides . Salicin C26 H18 O14. It is an antipyriodic like quinine When boiled with sugar it breaks up into sugar Occurs in willow, poplar Crystallizes in small brilliant colourless prisms, intensely bitter, melts at 120°c Soluble in hot HO, difficultly in cold, soluble in alcohol not in ether. Concentrated HOSO3 dissolves it with a purple red colour. By the action of amulcin, the ferment of almonds* it splits up into saligenin & grape sugar. C26 H18 O14 + 2HO taken up by the action of the amulcin = salignen C14 H8 O4 + glucose C12 H12 O12 x Or by the action of ptyalin the ferment in saliva. 213 Heated with acids it breaks up in a similar way but loses 2HO C26 H18 O14 = C14 H6 O2. salintene + C12 H12 O12 grape sugar.x Saligenin is the alcohol & salintene the ether of the alcohol. There is a large number of glucosides. Populene C40 H26 O20 Obtained from poplars. By the action of amulcin it is converted into glucose saligenin & benzoic acid. C40 H26 O20 = C12 H12 O12 + C14 H8 O4 + C14 H6 O4 Quercitrene Got from the quercus & the bark of the horse chestnut Convolvulene Obtained from jalap roots. Tannine. Is tannic acid & glucose. *Salicin distilled over CaO gives carbolate of lime. 214 Colouring matters These are associated together more by technical use than by chemical relations. They are unlike bodies. They are found in all parts of different plants. They are difficult of isolation Method of doing so. Boil with Ho, alcohol & ether according to their solubility; agitate with PbO wh takes up the colouring matter. Decompose the Pb compound by HS & evaporate in vacuo. Sometimes the colouring matter does not exist in the plant but is formed by oxidation or by the action of a ferment. Thus, madder root does not contain the colouring matter in it, till it has been acted on 215 by a ferment wh the root itself contains. It yields a whole series of colouring matters. Most of these colours attach themselves to an animal substance much more readily than to a vegetable one. Puts a little white of egg wh has been coagulated by heat in the bottom of a vessel into a colouring matter wh dyes it while a vegetable substance is not much affected unless a mordant is put on it. Silks & woolens are dyed directly by these colouring matters. To dye calico print a pattern on it by an acetate. To produce red with madder print with acetate of alumina 216 For purple with acetate of alumina & acetate of Fe. For black with acetate of Fe alone The cloth is hung up & the acetic acid flies off. Puts a cloth printed with alumina in logwood Mordants act more by their acid than basic characters they are sesquioxides. Protoxides are not good mordants. One method of dying is if you can put into the pores of the cloth a colour naturally insoluble & render it insoluble in the cloth itself. This is done in the case of indigo. Mix FeO & KO or CaO with indigo blue, this gives indigo white. Indigo blue differs from indigo 217 white by 1 H. Indigo blue C16 H5 NO2 white C16 H6 NO2 When indigo white is poured from one vessel to another the H is oxidized to HO & it becomes insoluble indigo blue. [illustration] It is large jar in wh is indigo while the sediment is at the bottom. It is called an indigo beck. Dips a cloth printed with an oxidizing substances (CuOSO3) into indigo white. The printed parts are left white, because the CuOSO3 oxidized the indigo white & rendered it insoluble on the surface of the cloth so that it could not penetrate. Adds some alum & a little NH3 to a solution of cochineal. The A2 O3 precipitates it as a 218 Lake. It is this property wh enables the mordant to take down the colour with it & fix it. Madder. Madder is got from the root of the Rubia tinctorum found in Turkey, Holland & the south of France. Fresh madder does not contain colouring matter but contains a resin called rubio erithric acid C32 H18 O18. By the action of a natural ferment within itself it becomes alizarin the colouring principle of madder & glucose. C32 H18 O18 = C20 H6 O6 + C12 H12 O12 The is a large number of colouring matters in madder Alizarin subliming is orange 219 it is red. Alizarin C20 H6 O6 Crystallizes in fine red prisms orange red after subliming. Sparingly soluble in cold HO readily soluble in alcohol, ether & hot HO. Alkalies dissolve it CaO & Bao give blue lakes. Al a deep red. Fe2 O3 a purple It has very much the composition of naphthalin. If you replace some of the H in naphthalin by Cl you get a chlor-alizarin. It is alleged that alizarin is obtained in France from naphthalin. Purpurin C18 H6 O6 Occurs in old madder not in 220 new. Prepared from alizarin acted on by yeast Crystallizes in yellow red prisms Fuses easily & sublimes. Alkalis dissolve it yellow. BaO + CaO give purple lakes. Rubiacine C32 H11 O10 A yellow colouring matter. Is a product of the natural fermentation of the original resin Crystallizes in yellow needles gives the yellow shades in madder dyeing When madder has been used in dyeing one half of the colouring matter is taken up the other half used to be thrown away. The spent madder is now digested with very dilute HOSO3 & steam blown 221 thro it. It is then produces dyes as good & perhaps even of more brilliant shades than the original did. Logwood It contains a honey yellow [crossed out] substance wh is called Hœmitoxalyn wh has no relation to the colouring matter of the blood. Its formula is C32 H14 O2 It forms a red with Al -black - Fe. Crystallizes in violet microscopic crystals wh dissolve red. By a nitrogenenous ferment especially by ammonia if produced it becomes much more powerfully tinctorial Brazil wood. None of the yellow dyes have been much examined Quercitron C. 222 Indigo. It is got from plants of the genus Indig ofera from is atus tinctoria or woad, found in the urine of cows & in that of men in some diseases. Sometimes occurs in milk to wh it gives the blue colour. Prep. The leaves of the indigo plant are macerated & CaO added & allowed to ferment; the indigo white is formed wh soon becomes insoluble indigo blue. Add a per salt of fe to indigo white & it becomes indigo blue. Indigo blue as it occurs in commerce has S.G 1.35. Crystallizes when quite pure in crystals wh have a coppery lustre. 223 HOSO3 dissolves it completely Pure indigo blue may be fused. You may suppose indigo blue to be the radical & indigo white the hydrate. Indigo blue C16 H5 NO2 - White C16 H5 NO2 H. There is one other method of dyeing. Topical dyeing. It is the means by wh you can get an insoluble powder on the surface of the cloth Albumen from blood & casein from cheese is sold for this. Casein is dissolved in NH3 mixed with the colouring matter & heated so as to allow the NH3 to evaporate. Very often these topical applications 224 applications are arsenic green. Or take albumen & colouring matter such as ultramarine expose to steam to coagulate the albumen. [Illustration] This method has enabled many styles of printing to be employed. Cu or As colours should not be employed as they occasion great injury to the health. Many colouring matters are glucosides. They seem to be weak bases. The best mordants are those oxides on the verge of being acids. Mordants are the metallic oxides Chemically they are called lakes. Colouring matter of lichens. They readily split themselves up into several acids, some of wh readily give colouring 225 matters with NH3. Erythric acid C46 H22 O20 Orsellenic C16 H8 O8 Orsellic C32 H14 O14 Evernic C34 H16 O14 Some when treated with stronger acids as HOSO3 or HONO5 break up into new compounds & produce colouring matters [Illustration.] adheres to albumen Albumen is printed on the cloth & coagulated by steam & dyed by the the archil colour. One or two animal colours are employed in the arts. Cochineal. It consists of the dried bodies of insects wh feed on a certain kind of fig. This dye contains carminic acid C28 H14 O14 226 This unites readily with bases. Another insect forms the lac dye used for dying cloth red. Volatile oils, resins & caoutchoue. Essential oils. They are occasionally found ready formed in plants as in the orange & lemon. In other cases it is made by the action of HO on seed as in bitter almond & mustard oil. In the animal kingdom These are rare, altho' they occur in ants. The general classification of essential oils is more pharmaceutical than chemical. They are either solid or liquid When solid they are easily fusible & are volatile Though the boiling points of some are high they generally 227 ally go over readily in steam. They produce a temporary stain on paper, fixed acids produce a permanent one. They have a peculiar penetrating odour generally agreeable. They are rarely pure in commerce They contain a solid substance wh is the oil oxidized or hydrated & wh are called stereoptenes. The oils are prepared in some cases as from the orange & lemon by pressure. More usually as from aromatic plants by hanging the plants in bags & passing steam thro' them & condensing it. They are prepared for perfumery by a peculiar process. A cake of tallow is taken & the flowering plants spread over it. It is then gently 228 heated not enough to melt the tallow. The tallow gradually extracts the oil. The tallow is then treated with alcohol wh dissolves out the oils. They may be divided into different classes. 1st Essential or volatile oils free from O. 2nd - containing O. 3d - S. 4th - wh suffer change by distillation. The central formula around wh they all turn is that of camphine C20 H16 for a 4 vol. formula. Some have only half that C10 H8. Some have these two formulas united C30 H24 229 Essences isomeric with camphine. Essence of bergamot - lemons - orange - birch - camomile - juniper - copaiba C30 H24 - carraway - cloves - ginger - cubebs - thyme - valerian Turpentine. By this is meant camphine C20 H16. Boils at 160°c S.G. 0.864. Got by wounding pines, when it flows out, this is distilled & gives essence of turpentine 230 In this state it is colourless transparent oil with a peculiar disagreeable odour & burning taste. Insoluble in HO, difficulty in common alcohol readily in absolute alcohol & ether concentrated acids dissolve it. It converts O into ozone. If you shake some up in a bottle with air you may detect the presence of the ozone formed applying the test. It contains so much H that if you moisten some cotton wool with it & having warmed it put it into some Cl, HCl fumes are formed & it takes fire. It combines with HO & forms solid stearoptines C20 H16 + 4 HO 231 C20 H16 + 3HO, C20 H16 + 2HO & C20 H16 + HO. These are called camphors of turpentine. Essences not isomeric with camphine. Oil of peppermint C20 H18 Contained as a solid hydrate in certain oils C20 H18 + 2HO. Essence of cedar wood C32 H26 C32 H20 + 2HO is a solid hydrate. Oxygenized essences. Camphors Common Camphor True laurel camphor C20 H16 O2 Obtained from camphor wood by chopping the wood in branches & distilling in HO. Fuses at 175°C boils at 205°C. Vap. density 5.32. Difficult to pound from its elasticity, but may be done 232 easily by putting a drop or two of alcohol on it & then pounding it. Borneo camphor C20 H18 O2. Got by puncturing the tree. Crystallizes in 6 sided prisms colourless & transparent Other camphors. Stearoptines of many plants are really camphors. In peppermint & cedar oil C20 H20 O2 C32 H26 O2 Resins These are exudations from They appear to be formed by the oxidation of the essential oils more oxidized than the camphors. Camphors C20 H16 O2 Resins C20 H16 O2 - n H + n O. 233 They are used for varnishes by mixing pounded glass with pounded resin & treating with alcohol or wood spirit Copal, Mastic, Sandarac Common varnish for maps 24 parts Mastic 3 - Venice turpentine 1 - Camphor 10 - pounded glass Mixed with 72 parts of oil of turpentine & filtered. Lac. Sold in 3 forms. Stick lac. An insect perforates certain trees & the lac It is sold in commerce on the twigs. This is pounded & heated with NaOCO2 wh dissolves out the colouring matter wh is used 234 for dye. The lac is melted in canvass bags & is squeezed on bamboos. & is then called shell lac. Got on ficus indigus or ficus religiosa. Used for sealing wax & for stiffening hats for wh purpose it is dissolved in wood spirit. Sealing wax 48 parts lac 12 venice turpentine 1 Balsam of Peru 36 Vermilion stirred up with it. For making lacquers of wh there are several kinds the usual one is, Lac is mixed with 1/2 its wt of sandarac & a little venice turpentine, dissolved in 10 to 12 parts alcohol. The brass is heated before it is applied. 235 Guayacum. Obtained from guayacum officinalis It is bluish green or brown The alcoholic solution is a good test for ozone wh makes it blue Jalaps. Contain glucosides Jalapin is a glucoside. Amber It is a fossil resin found in coal but chiefly thrown up on the shores of the Baltic between Memel Often contains insects of extinct species but related to present species. Seems to have been an exudation S.G 1.065. Insoluble in alcohol & ether, soluble in essential oils. After having been 236 once fused it is soluble in turpentine & then forms amber varnish By dry distillation it yields succinic acid & amber oil. With HONO5 it forms artificial camphor having a smell like musk. Caoutchouc. It is a resinous substance suspended in the milky juice of various plants. In its ordinary state in commerce it is impure. When separated from its impurities its formula shows it to be a hydrocarbon nC8 H7 Soluble in chloroform but is precipitated by alcohol, melts at 120°C & at 200°C it beings to decompose. Insoluble in HO & alcohol Soluble in turpentine, benzol 237 naphtha & chloroform. The solution in naphtha is used for water proofing cloths. Unites with S & forms vulcanized india rubber. Got by treating with sulphide of C or usually with chloride of S. S2 Cl . Gutta percha. Is like india rubber in its composition & many characters except its want of elasticity at common temps. Is the concrete juice of percha. Scarcely elastic at common temps. but becomes elastic at 212°f. Is worked at a high temp.; welds when soft is soluble in the same reagents as caoutchoue. Is not attacked by HFl. Vulcanized india rubber gradually 238 gradually loses its S & becomes brittle especially if kept in contact with metal wh takes the S. Asphalt & bitumen Occurs extensively in nature as springs some of wh contain the asphalt in solution The salt of the earth spoken of in the Bible probably means bitumen & when it is spoken of as having lost its savour it means that it had lost some of its volatile hydrocarbons. It was ordered to be used in burnt sacrifices & was probably smeared over the bodies & thus rendered them more combustible. Asphalt is the residue of mineral oils wh have lost their volatile hydrocarbons. 239 Occurs in Turkey Persia Egypt & even in our own country There was a spring near Edinburgh & there are in the Industrial Museum several black candles made from it. There is one near Alfreton in Derby from wh paraffine was first made. There are many mineral hydrocarbons like asphalt. Ozokerite C2 H2 n. Sheerit Found in brown coal in Germany Fichtilite C8 H7 Found in fossil pines. Hartit C6 H5. Idrialit C80 H28 O2 Found with cinnabar in Idria. 240 Animal Chemistry. We could make urea & grape sugar waste products of vital agency but chemistry has yet made but small progress in producing the The ruling agency in vegetable & animal life is vital agency. When we see plants growing on the same soil, nourished by the same substances, watered by the same rain & stimulated by the same manure & yet producing substances as different as starch & morphia we cannot tell what the hidden force wh produces these transformations is. Latterly we have got a more exact idea of force & know that, heat, electricity, chemical affinity &c 241 are all resolvable into motion. But although our ideas of force are extending & we can compare the animal body to a steam engine yet one force is left of wh we known nothing viz., vital force. We know the engine but not the engineer. Histogenetic substances. All those wh build up the frame- work of the animal body are termed histogenetic. They are the substances of wh the organs consist. Fat is not an organic, is not a histogenetic substance. Albumen Fibrin Casein Syntonin Fibrin in muscle Globulin found in the eye. 242 Hemato crystallin. Most of them, the first three at least are found indifferently in the animal & vegetable kingdoms. If you stir fresh blood with twigs fibrin coagulates on them. Whip fresh juice of cauliflower with twigs & you get fibrin Boil cabbage juice & you get albumen. You can get it from blood Add an acid such as HCl to casein & cheese is formed Add HCl to solution of peas & you get the same casein These substances exist both in plants & animals. General properties whence soever derived. Uncrystallizable translucent of a yellowish colour: tough 245 when dry, adhesive or jelly like when moist. Brittle gelatinous plates when dry. Exist in 2 forms In the soluble state as fibrin in the blood In the insoluble state as when the blood is out of the body. The exact cause of the transformation from the soluble to the insoluble state is not known They part with 2P.C of some proximate constituent* when they become insoluble. insoluble varieties They seem to dissolve unchanged in acetic & phosphoric acid. Mineral acids decompose them All are transformed by long boiling in HO When oxidized by HONO5 or *As soda or potash generally alkalies 244 other oxidizing acid they produce acids of the alcohol series beginning at formic & going up to caproic acid They also produce aldehydes. Some in oxidizing produce oil of bitter almonds & acids of benzyl series Digested with HOSO3 or strong HCl. they produce almost invariably Leucine & Tyrosine & commonly Glycine, besides NH3 salts under the influence of caustic alkalis When moistened they putrefy the elements dividing themselves according to their greatest affinities. Putrefaction thus differs from decay wh is a combustion. Among the products of their putrefaction are the carbonate butyrate & valerate of NH3 , NH4 S 245 Common test for these; for any of these nitrogenous bodies. Moisten with a salt of H8 having an excess of Hg & heat to [Illustration.] 212°. They become red on the surface. Do not heat too violently. This is a test for all histogenetic substances. Mulder argued that they all contained a substance called protein wh was the basis of them all. According to Mulder it has the formula C36 H25 N4 O10 + 2HO wh can be driven off by heat. Percentage composition of protein according to this formula. C = 54.7 N = 14.2 H = 6.8 O = 24.3 He supposed other bodies to be 246 protein combined with P & S. Though his views are no longer held by chemists the nomenclature is retained & they are called protein compounds. Probably they are all the same as regards organic composition & the ground work is the same in all & they differ merely in form. Albumen Is the chief type of the group. Exists in various states probably owing to the amount of alkali with wh it is united.* Occurs in vegetable juices in blood, chyle & lymph in all serous liquids, in the juice of flesh & cellular tissues, in white of egg. Prop. 1st. Soluble albumen As obtained from white of egg it is transparent, yellowish, *Thus its reactions are not always the same 247 soluble body of a glairy consistence. S.G 1.261. When put in HO it swells & dissolves, the solution reacts alkaline from the NaO it contains. Remove this by acetic acid & add HO & it becomes insoluble Metallic salts precipitate albumen Add HgCl to albumen & it forms an insoluble coagulum, on this account albumen is used in cases of poisoning by HgCl. When heated to 63°C it becomes opaline at 75°C it coagulates entirely. It is then insoluble in Tannic acid precipitates albumen. Albumen of blood. is not coagulated by dilute HOSO3 248 Insoluble albumen When albumen is acted on by heat it appears to be the first form from wh all the other nitrogenous substances are formed. It requires very little change to become muscle or the contents of nerve tubes Fibrin Occurs chiefly in blood, lymph & chyle in a state of solution Prop. Separates in an insoluble state in delicate filaments. We know nothing of pure soluble fibrin Coagulated fibrin is opaque yellowish fibrous mass hard & brittle when dry Swells in HO but is insoluble in it, dissolves in solution of KONO5 at 40°C but is coagulated by boiling & acetic acid 249 Digested at 150°C with HO under pressure, by sealing it up with HO in a tube. The fibrin is apparently converted into albumen. It becomes soluble & is coagulated by acids & behaves exactly like albumen. Vegetable fibrin is prepared by putting flour in a muslin bag & kneading it in a stream of HO. The starch is carried thro' the pores & the fibrin remains behind. Gluten of wheat is identical with fibrin Syntonine. Is fibrin of muscle Is the chief constituent of the striated muscles, is in smaller quantity in the smooth muscles & in the arterial coat & spleen When first taken from the body it is snow white. 250 Soluble in HO containing 1 PC of HCl, insoluble in KONO5. Is precipitated from its solutions in alkalis by KCl. or NaCl The solution in lime water is coagulated by heat. Casein. Occurs in the milk of mammals, in small quantity in blood under the name of serum casein. It exists in yolk of egg so intimately mixed with albumen that it used to be thought a separate substance & was called vitellin Exists in the juice of flesh in the juice of the thymous gland. In the vegetable kingdom in the seeds of leguminosæ Prop. Chiefly differs from the other allied substances in its mode of coagulating. Maybe got from milk by adding HCl or rennet 251 Acetic & Lactic acid precipitate it from solutions. Strong acetic acid however dissolves it. Rennet coagulates it. It is not precipitated by heat. The skin formed on the top of boiled milk is caused by the oxidation & not by the coagulation of casein. If boiled with CaCl or Mg OSO3 it is precipitated but the base goes down along with it. On account of this property it is used for cement for glass & earthenware. A poor cheese is made into a paste with lime. Vegetable casein of leguminosae or Legumin Occurs in leguminosae from 20 to 25 P.C. They are even too nutritive The casein is obtained by coagulating 252 coagulating their infusion by rennet or by adding acids. Casein of animals & vegetables is exactly the same Cheese is sold in China made from beans. Its solution when heated forms a skin on the top like milk heated. Globulin. Forms 36 P.C of the crystalline lens of the eye, & got its name from being supposed to be identical with the coagulable part of the corpuscles of the blood. Differs from albumen by coagulating at 93°C. The solution is not coagulable by acetic acid or NH3 . It becomes turbid when the acetic acid solution is heated. Is precipitated by CO2 253 Hemato crystalline It is albumen in a state in wh it can be crystallized Got from the blood of the guinea pig from wh it crystallizes in tetrahedra. Is in the blood of rats & mice. It is difficult to get from man's blood but from it & from the blood of carnivora it is in prisms From the hamster in rhombohedrous Differs from all other albuminous bodies by not being precipitated by metallic salts & Cl2 ONO5 It is obviously a glucoside* The characteristic of all histogenetic substances is that they all contain 15 P.C of N. B Derivatives from the albumenous group * the substance wh remains beside glucose has like same composition as albumen 254 They closely resemble albumenous bodies but contain rather less C. They differ in physical characters They do not form cells but form organic bases of certain tissues With strong HCl, HONO5, & prussiate of KO they are not precipitated Ossein. Prep. But a piece of bone in dilute HCl, & treat with alcohol & ether to take out the fat. Insoluble in HO, is converted into glutin by boiling *Glutin It is a transformed condition of ossein. Is called gelatin in commerce. It is colourless transparent & horny Brittle, heavier than HO, *Different form gluten wh is in wheat, Glutin is the general name for gelatine 255 tasteless insoluble in cold HO soluble in hot Water with 1 P.C of glutin is gelatinous. Long digestion in HO or destroys its gelatinous property Forms a precipitate with tannic acid. Dry distillation produces various bases from it as methytannin Glutin does not appear to be in the body except in the spleen. Chondrin Prep. Boil the permanent & articulate cartilages It much resembles glutin. It is precipitated by acetic acid, per salts of Fe, HCl alum Treated with Many albumenous bodies pass into glutin when boiled 256 Glutin & elasticin are known to us as common glue Glue is made from the parings of ox hides boiled in a coarse cloth cut into blocks & dried. Size is a less strong glue made from the parings of parchment & used in liquid state. Confectionery gelatine Made from the swimming bladders of fish & the parings of fine hides. Abroad it is made from the tendons of rats. In the abattoirs where horses are slaughtered, the carcases are put into rooms plastered so that the rats cannot make holes in them & two or three bricks are left wh can be removed & replaced at pleasure. The rats are allowed to enter at night to clean the bones of the 257 horses before the bones are sold to the P. makers. In the morning the bricks are replaced & a man having a mask & thick gloves & armed with a bludgeon enters & kills the rats, their skins are made into kid gloves & their thigh bones cleaned & made into toothpicks for the London clubs; the rest of the body is boiled down for gelatine. Leather is a tannate of gelatin There are various nitrogenous substances wh occur as derivatives in the animal body These substances are formed probably by the transformation of histogenetic substances arrested in their passage to complete oxidation. They are probably amides Amides contain their N as 258 amidogen NH2 . Kreatin C8 H9 N3 O4 + 2HO . Occurs in the striped & smooth muscles in urine in the brain in blood. It is best got from the flesh of fowls or skate fish in wh there are 3 parts of kreatin to 1000 parts of flesh. It is a clear, transparent colourless, brilliant body crystallizes in rhombic columns loses 2HO at 100°C. Insoluble in strong alcohol but soluble in dilute spirits of wine. Has a bitter taste, neutral in reactions. When heated with strong acids it becomes converted into kreatinin a substance wh also occurs in urine. C8 H9 N3 O4 = C8 H7 N3 O2 + 2HO. When heated with BaO it takes up 2HO, & becomes urea & sarkosine 259 C8 H9 N3 O4 + 2HO = Urea C2 H4 N4 O2 + sarkosine C6 H7 NO4 kreatinine Occurs in blood muscle & urine is is formed by the action of acids on kreatin Crystallizes in colourless rhombic prisms, soluble in HO + hot alcohol, the solution reacts alkaline & is a feeble base, when concentrated it tastes like dilute NH3 . By long keeping it becomes kreatin, especially in presence of lime water Kreatin & kreatinine are products of the oxidation of the tissues on their way to urea. Sarcosin. C6 H7 NO4 Although to be expected, yet it is not perfectly certain that it exists in the urine Prep. Act on kreatin by alkalis. BaOH5 It crystallizes in rhombic 260 prisms soluble in HO Seems to be ami When kreatin 2(C8 H9 N3 O4 ) + 10H8 O = 10Hg + 2HO + 4CO2 + (2C4 H7 N3, C4 H2 O8) Methyluramine C4 H7 N3. It is probably a triamine It is a strong base precipitates oxides, drives NH3 from salts, its constitution is unknown. Sarkin C10 H4 N4 O2 Occurs in the flesh of horses, oxen & men. Crystallizes in colourless transparent needles readily soluble in HO difficultly in alcohol Fuming NO5 converts it into Guanin Guanin C10 H5 N5 O2 . Occurs in guano & spider's 261 excrements in the liver & cavities of pancreas White or yellowish isomorphous mass without taste or smell Insoluble in HO alcohol & ether, soluble in alkalis. Unites with salts as ZnCl. By NO5 or HOSO3 & MnO2 it becomes xanthin. Guanin C10 H5 N5 O2 Xanthin C10 H4 N4 O4 Xanthin occurs in urine occasionally, forms calculi has been found in flesh & salivary ducts An amorphous white mass Soluble in acids & alkalis, little soluble in HO. Resembles sarkosin & in less decidedly basic then they. Cystin C6 H6 NS2 O4 Is a rare constituent of urinary 262 calculi. Has been lately found in nerves & liver Crystallizes in colourless transparent- 6 sided [crossed out] tables. Neutral, insoluble in HO & alcohol soluble in acids & alkalis. Allantoin C8 H6 N4 O6 Occurs in cows, [illegible] & in the urine of calves & dogs Is got by the oxidation of uric acid Is most easily got from calf's urine. Crystallizes in colourless brilliant prisms, tasteless having no smell neutral, soluble in hot HO & alcohol insoluble in ether soluble in alkalis but is decomposed when boiled with them taking up 10HO. C8 H6 N4 O6 + 10HO + 2(C4 H2 O8) + 4NH3 Tyrosin C18 H11 NO6 Occurs in the liver, pancreas in cochineal in root of 263 & is a general product of the decomposition of albuminous bodies by acids & alkalis. Prop. Occurs in white silky crystals. Soluble in hot HO insoluble in alcohol & ether Dissolves without change in alkalis & acids forms conjugate bodies with HOSO3. Aloxan C8 H2 N2 O8 + {2HO or 8HO} Made from guano. By the oxidation of uric acid by NO5. Occurs in octahedral crystals Soluble in HO, the solution colours the skin red. It reddens litmus paper. At 100°C it loses HO. Forms like alkalis HONO5 oxidizes it & forms parabanic acid. 264 Reducing agents as HS convert it into aloxantin. Aloxantin is readily changed Thyanuric acid is C8 H5 N3 O2 S2 Formed when aloxane is treated with SO2 & saturated with NH3. Aloxantin C8 H5 N2 O10 Got by acting on aloxan by reducing agents Crystallizes in colourless prisms dissolves in NH3 with a purple colour. The solution is acid. it gives a violet precipitate with BaO. Its products of oxidation are similar to those of alloxan. Cerebrin C34 H33 NO5 Occurs in the brain. It is a white porous powder, tasteless 265 tasteless, having no smell, insoluble in HO, soluble in alcohol & ether neutral. Decomposed by boiling acids at 80°C Amide acids. Taurin C4 H7 NO5 S2. Occurs in the muscles of all mollusca, in the lungs, sometimes in the kidneys & often in the liver of higher animals. Produced by the action of acids on Taurocholic acid a constituent of bile. Prep. Heat or bile with HCl. Evaporate & exhaust with alcohol. It has been got artificially by heating isotinate of ammonia C4 H9 O8 NS2 it loses 2HO H2 O2 C4 H7 O6 NS2 Taurin It is thus the amide of isatinic 266 acid. It forms colourless transparent 6 sided prisms dissolves easily in HO, insoluble in alcohol & ether. dissolves in acids, is neutral. Leucin C12 H13 NO4 Exists in blood vascular glands spleen, in thymous gland In liver & bile, the pancreas & salivary glands & thin secretions. In the contents of small intestines in the lungs & kidneys* It is always produced by the action of strong acids & alkalis on albumenous bodies Prepared synthetically by heating valeric anhydride with HCy. Valeric anhydride C10 H10 O2 + HC2 N + 2HO = C12 H13 NO4 Leucin is the amide of caproic acid. Caproic acid C12 H11 O3, HO Leucin C12 H10 (NH2 )O3 , HO * has been found in diseased brain 267 Prop. When quite pure it crystallizes in colourless brilliant plates, Freely soluble in HO less so in alcohol & insoluble in ether. The solutions are neutral. With HONO5 it gives various products among others Leucic & Lactic acid. Uric acid. C10 H4 N4 O6 It is biatomic = 2HO C10 H2 N4 O4 . Occurs in small quantity in the urine of man & carnivora, scarcely at all in that of herbivora. The urine of birds & serpents chiefly consists of this & also that of tortoises. Largely in the excrements of butterflies & beetles Traces of it in healthy blood Increases in gout & Brights disease Is in excess in cholera, bronchitis & pneumonia Is a frequent substance in calculi. 268 Prep. Urates in serpents excrements are urate of amonia principally. Treat with alkalis (KO) & add HCl & the sparinly soluble uric acid is precipitated. It is a white crystalline powder difficultly soluble in HO insoluble in alcohol & ether. When heated it is converted into urea, cyamuric acid, NH4 oeo2 HCy. Peroxide of Pb makes it into alantoin, urea, oxalic acid & CO2. This is important. It is only a feeble acid but is bibasic & forms acid & neutral salts. Urates. General formula MO} HO} = Uric Urate of NaO. NaO HO /U 1 eq of HO in uric acid is replaced by 1 of NaO. 269 Difficulty soluble in cold HO, more so in hot. This is the reason that urine sometimes though clear when ejected becomes turbid on cooling. Acid urate of ammonia NHO HO /U Crystallizes in fine needles or an amorphour precipitate scarcely soluble in cold HO Urate of lime CaO HO /U Occurs in calculi & sometimes as a urinary sediment Forms chalk stones in the joints of gouty persons. White amorphous & difficultly soluble in cold HO. Derivatives of Uric acid. When HONO5 acts on uric acid, it is dissolved with a yellow colour & various products are formed. By careful evaporation to dryness & treating with NH3, it becomes purple. 270 Bestway. Take 4 grs. aloxantin & 7 of hydrated alloxan, dissolves in 1/2 an oz. of HO by boiling. Add to 1/6 oz. by measure of saturated solution of NH4 OCO2, & murexide is formed. It must be boiling before adding to NH4 OCO2 . Murexide C16 H8 N6 O12 Has the synonym of precipitate of ammonia. Is used in dyeing. Its owing to the formation of murexide that the guano colours are formed. Guano consists of the excrements of sea fowl It is treated with KO to dissolve the uric acid. The uric acid when treated with NH3 forms murexide. It is then treated with salts of PbO & Hg. Properties of murexide 271 Crystallizes in 4 sided prisms, of a golden green beautiful metallic lustre. Difficultly soluble in HO readily in KO with a purple colour. Test for uric acid. Dissolve uric acid in HONO5 & alloxan is formed It is supposed that murexide contains a compound called purpuric acid & that it is a NH3 compound of this. NH4O} HO} purpuric acid C16 H3 N5 O10 No substance has yielded so many compounds to organic chemistry as uric acid. Some of the chief are, Uric acid & nitric acid form alloxan C10 H4 N4 O6 + 2HO +20 = alloxan C8 H2 N2 O8 + Urea C2 H4 N2 O2 Act on alloxan by a feebly oxidizing agent as KO. 272 C8 H2 N2 O8 + 4HO = mesoxalic acid C6 H2 O10 + Urea C2 H4 N2 O2 Cynuric acid Seems to take the place of uric acid in the urine of the dog. Crystallizes in 4 sided prisms Melts when heated & exhales the odour of hemp nitrile Dissolves in acids & alkalis & has all the charactes of a feeble acid. Inosic acid. HO, C10 H6 N2 O10 . Found in the juice of flesh in small quantity. Forms a solid white uncrystalline mass, soluble in HO, insoluble in alcohol & ether. Reddens litmus, tastes like flesh forms salts. Acids of bile. Bile besides less essential constituents contains NaO salts of 2 nitrogenous acids. 273 These acids are like glucosides They do not contain grape sugar but bodies corresponding to it. The one contains glycin the other taurin instead of glucose. Both contain the same acid. viz, cholic acid. Cholic acid with taurin & glycin forms conjugate acids. Glycocholic acid HOC52 H42 NO11 Occurs as glycocholate of NaO in bile. Is the main constituent of ox gall & is in small quantity in that of other animals except the pig. Glycocholic acid crystallizes in very delicate needles, soluble in hot HO & alcohol, difficulty in ether. The solution tastes sweet & then intensely bitter, reddens litmus With HOSO3 & sugar it gives 274 an intense purple red. Soluble in concentrated acids, without colour at first but absorbs O & becomes coloured. When long boiled with BaO it is decomposed C52 H43 NO12 + 2HO = cholic acid C48 H40 O10 + glycin C4 H5 NO4 glycin is the amide of acetic acid & is a product of the action of acids on gelatin Hence glycocholic acid is a conjugate acid. Taurocholic acid C52 H45 NO14 S2 So called because it contains taurin instead of glycin. It is the second chief acid in bile Occurs as the NaO salt in the bile of man, ox, dog, goat frog boar, anaconda &c. In certain fresh water fishes. Has been detected in the blood in transudations *In the boar is is apparently alone not accompanied by other acid 275 & in urine in cases of suppressed excretion of bile. White amorphous bitter powder soluble in HO Easily decomposed by heating Is decomposed by boiling with BaO taking 2HO. cholic acid taurin C52 H45 NO14 S2 + 2HO = C48 H40 O10 + C4 H7 NO6 S2 Taurin is the amide of isithionic acid. With HOSO3 & sugar it gives the same reaction as glycocholic acid. With ferments the taurs & glycocholic acids are broken up as with [ferment] alkalis. Cholic acid C48 H40 O10 . Crystallizes in transparent colourless tetrahedral crystals Has a bitter but sweet taste, readily soluble in alcohol & ether, difficulty in HO. Its alcoholic solution reddens litmus & dries CO2 from its salts. 276 With alkalis it forms crystalline salts. With HOSO3 & sugar it gives the purple reaction of bile. Hyoglycholic acid C54 H43 NO10 . Substitutes these other acids in the bile of the pig. Not found in that of any other animal. A white resinous substance melts in boiling HO. Insoluble in HO & ether It is a conjugate acid & contains glycin & Hyocholic acid Hyocholic acid C50 H40 O8 . There is another corresponding to it in the bile of the pig. Hyotaurocholic acid C54 H45 NO12 S2 . Lithofellinic acid C40 H36 O8. Exists in oriental. in the biliary concretions of antelopes & goats, of wh it forms the chief part. 277 It belongs to the same class as these others When cholic acid is acted on by acids it forms several substances one of wh is called choloidic acid. Cholic C48 H40 O10 - 2HO = choloidic C48 H33 O8 Amorphous mass melts on boiling readily soluble in alcohol. Cholosterin C52 H44 O2. It is a crystalline fatty substance found in bile but generally in biliary concretions. It is like a monoatomic alcohol Found in the brain blood, lungs It is neutral melts at 145°C sublimes at 360° Gives an aromatic oil by distilling having a smell like the geranium Insoluble in cold alcohol, soluble in boiling alcohol & ether. * Found abundantly in biliary concretions 278 Solutions of bile dissolve it readily It unites with one equivalent of acetic acid with displacement of one eq. of HO. Compound ethers may begot from it as from cedernal C52 H44 O2 C4 H3 O3. All bile of animals is coloured by a substance wh forms a bile pigment. Originally brown in man but, becomes green by oxidation Solid constituents of animals Bones. Those of vertebrate animals are tolerably constant in composition When dried at 212° they have 1/3d. of their weight of organic matter & 2/3ds of mineral matter. Large bones & those wh have much work have more mineral matter General average of the composition of bones taken from various analyses. 279 3CaO, PO5 57 parts. CaO CO2 8 Ca Fl 1 3MgO, PO5 1- mineral matter 67 Cartilage 33 The mineral matter in bones increases with age. The teeth resemble the bones in composition. Dentin is like dense bone. Organic matter in it 28 P.C. The enamel contains no cartilage. Mineral matter in teeth 3CaO PO5 81-88 P.C CaO CO2 7-8 Ca Fl 3-4 3MgO, PO5 1-1 1/2 Muscular tissues. They are extremely complicated & contain many substances but may be on an average. HO 74-80 P.C Solid ingredients 26-20 PC. Among the solid ingredients 280 There are in the 26 parts. Syntonin 15.4-17.7 Gelatinous substances 0.6-1.9 Albumen 2.2 -3.0 Kreatin } Kreatinine } Inosite } Inosic acid } Hypoxanthin } Traces Fat 1.50-2.30 Lactic acid 0.60-0.68 PO5 0.66-.70 NaO 0.07-0.09 KO 0.50-0.54 Mgo } ZnO 0.02-0.03 } Traces. NaO is chiefly confined to the blood & KO is in the flesh. Many of these are dissolved in the fluid surrounding the fibres of the muscles. Healthy muscles have an alkaline reaction but after the rigour of death an acid reaction. Contraction of muscle is always accompanied by oxidation CO2 being evolved 281 In this the sapid constituents of the meat reside & the bodies wh. are so important for nutrition as the phosphates. If you take the flesh of the fox & venison & express the juice & dip the flesh of the fox in the juice of the venison & cook it, you cannot distinguish it from venison. If you take away these juices Supposing you wish to make soup you wish to get out the sapid constituents, in boiling meat you want to keep in these. To make the strongest soup. Mince the meat, put it in cold HO & gradually raise the temperature. You must go beyond 150°F before you coagulate the blood & till this is done the soup 282 has a red colour. To boil meat plunge it at once into boiling HO on about 1/4 hour & then reduce the temp. to 160° by adding cold HO. x The boiling HO at once coagulates the albumen on the surface & the sort of crust thus formed keeps in the sapid & nourishing constituents. To make the strongest possible soup for invalids Take one lb of lean beef mince it & mix with 1lb of HO, heat it very slowly till it boils & all the soluble & gelatinous matters are extracted. You then strain it thro' a cloth The effect on the patient is very different if you leave it with its straw colour or colour it with burnt sugar or burnt onion. If you colour it they think it is much stronger. * Keep simmering & about the end of the operation you may raise to [illegible] again 283 Evaporate this to dryness & you get the true extract of flesh. That sold in shops is only glue. In boiling beef the albumen coagulates at 140°F but the blood globules do not coagulate before 158°F. On this account in roast meat although it is perfectly cooked, the inside sometimes appears raw, the heat there having never been up to 158°. Relative values of meat In 1 lb of each. Veal Beef Mutton Pork HO 10oz-0grs. 8oz-0grs 7oz 16.6.69 3 grs Gelatine 1-2 1-62 1-52 0.385 Fibrin & albumen 1-199 1-122 0-385 0-315 Fat 2-281 4-340 6.176 8-0 Mineral matter 0-312 0-350 0-245 0-105. Salting of meat. When meat is placed in salt a curious action goes on. 284 From its affinity for HO the salt takes the HO from the outside of the meat & dries it. The juice from the inside of the meat is then diffused into this & thence into the brine. But the brine does not easily penetrate into the meat. The sapid constituents & the mineral salts come out. A great part of its nutriment is thus removed from salted meat. When it is long used scurvy & other diseases arising from defective nourishment make their appearance. Components of the brain. They are not satisfactorily made out. Among them are oleine, oleic acid, leucin, margaric acid Cholesterine, stearic & palmitic acid 285 The two characteristic ingredients are cerebric acid & oleophosphoric acid. Cerebric acid. It is a phosphorized fatty acid. & is found partly free & partly in combination with NaO. Insoluble in HO but swells like starch when the HO is heated. Oleophosphoric acid. It is a greasy oily liquid partly found free & partly in combination. Found also in the yolk of egg. When long boiled it is decomposed into oleine & phosphoric acid. Mineral ingredients are of very small amount. They amount in the human brain to 0.027 PC of these 3KO, PO5 55 P.C 286 3NaOPO5 23 PC 3MgOPO5 3FeOPO5 3CaOPO5 There is also PO5 either as stronly acid phosphates of free also SiO2 Glands & their juices Leucin is in the pancreas & spleen, in thymous gland in thyroid body & in living ox. Lyrosin Hypoxanthin in the spleen thymous gland Uric acid in spleen. Formic, acetic, succinic & lactic acid are found in these glands. Inosite in the spleen, liver, kidney Thymous gland pancreas & lungs. Cystin. Taurin Guanin in the pancreas of ox. The mineral ingredients in glands vary much In the liver the KO salts predominate 287 predominate over those of NaO. The reverse is the case in the spleen. Cl forms 2 1/2 P.C. of the ash of the spleen & 3/10 PC of the spleen PO5 forms 33.5 PC of ash of liver & 18.5 P.C of ash of spleen. CaOMgO in small quantity In spleen Fe is abundant, forming 7 to 16 PC of the ash. Mn, Cu & Pb are commonly but not always found both in the liver & spleen. In occasionally Digestive fluids Saliva S.g 1.004 to 1.006 It is always alkaline but more so during meals than when fasting. The saliva of the pyrotid gland contains ptyalin as a marked ingredient It has the same power as diastase of converting starch first into [illegible] & then into sugar It is an albuminous matter in a state of change 288 Ptyalin It is an albumenate of NaO. Forms 1/3 of the whole sold residue of saliva. It is very prone to decomposition or putrefaction. It is a strong ferment. The conversion is almost instantaneous. Composition of saliva of pyrotid gland. In 1000 parts from the dog. HO 995.3 Solid residue 4.7 Of the residue Organic matter 1.7 Alkaline chlorides & sulphocyanides 2.1 CaOCo2 1.2 In certain animals the sulphocyanides exist more than in others. Add a per salt of Fe to saliva & a red color is produced showing the presence of sulphocyanogen. The composition of human saliva is like that of the dog's. 289 HO 994.10 solid residue 5.90 The presence of sulphocyanide of NaO is characteristic. The daily secretion of saliva by an adult man is about 48oz. but differs according to his food. Mineral matter in it consists of KO, NaO & CaO salts. The last when acted on by the air & converted into CaOCo2 forms the solid encrustration froth on horses mouths. CaOCo2, 3CaOPO5 & mucus form tartar. The sulphocyanide of K on the teeth is a medicine The function of saliva is partly chemical & partly mechanical. Healthy saliva is frothy & carries down 0 into the stomach * The KSCy exists chiefly in saliva of man & sheep 290 stomach wh aids the digestion Its chief function is to convert the starch of food into sugar. The [crossed out] saliva from the pyrotid gland alone has not this power. Various nations have found out this power of saliva. The formation of diastase is the use of malting. In South America there is a fermented drink made from maize. Old women chew it & spit it into jars, it is then fermented. The pancreatic fluid is like saliva. It is alkaline like it & converts starch into sugar It is a colourless clear, frothy, tenacious substance S.G 1.008. Coagulates only slightly when gives 1.36 P.C of solid matter Contains a solid substance, like albumenate of NaO but not identical 291 identical with it is prone to decomposition Ptyalin An adult man secrets 10lbs of pancreatic juice daily. Pancreatic juice of dogs. HO 980.45 solid residue 19.55 pancreatic ferment 12.71 Mineral bodies 6.84 Its chief juice is to convert into sugar the starchy matters wh have escaped the action of the saliva. Bernard of Paris asserts that it acts as amulcin & breaks up fats* Pancreatic juice does this out of the body It is possible that the pancreatic juice may reform the NaCl broken up in the process of digestion. Gastric juice It is the fluid poured out from Into glycerin & fatty acids 292 the lining membrane of the stomach. It is neutral in the empty stomach. acid when food has been recently taken in. S.G 1.0023. The acid is generally lactic acid. Shmidt's analysis HO 994.4 solid ingredients 5.596 peculiar ferment pepsin 3.195 free HCl 0.2 CCl 0.06 NaCl 1.46 Lactic acid is with it in varying quantity. The saliva is mixed with it in analysis. Marked ingredients. Pepsin & free acid. Pepsin. It is an albumenous body soluble in HO insoluble in alcohol. The HO solution is precipitated by [illegible] H8, Pb. 293 Converts coagulated albumen into the soluble form only does so in presence of free acid, The fresh gastric juice of the dog dissolve 1/20th of its wt of coagulated albumen. Its function is to render the nitrogenous parts of the food soluble but to accomplish this it must have free acid. Bile immediately suspends the action of pepsin. * The quantity of gastric juice secreted by animals is almost incredible about 1/4 of their wt daily. In the case of Katharine Cutt a person who had a fistula thro' wh the stomach could be observed it was about 30 lbs daily. Yet it is not sufficient to dissolve all the albumenous bodies introduced as food. *Thus the gastric juices has no effect on food after it has passed into the intestine 294 The stomach is protected from the action of the gastric juice by the epithelium & not by its vitality for the hand legs of a frog introduced into the stomach thro' a fistula were digested, the vitality of the frog not preventing it. The intestinal juice seems to combine the effects of the pancreatic & gastric juice. About 10oz one secreted daily Bile is the liquid produced from venous blood by the liver. It is a viscid tenacious fluid of a brown or green colour & musty odour & bitter taste S.G 1.02. It putrefies readily but if freed from mucus it does not change. Sometimes alkaline often neutral. Composition. HO [crossed out] 90.44 Biliary bodies 8. 295 Aqueous extract, alkaline salts. phosphates chlorides & lactates 0.85 Mucus 0.30 NaO & KO 0.41 Characteristic bodies Resinous matter. Cholic acid. Tauro & Glyco-cholic. It unites with alkalis like resins Cholosterine is always in healthy bile in small quantity 1 part in 10000 parts of bile. Retention of bile concentrates it. A man of 10 stone secrets 5 lbs daily. Its main use is to promote the digestion of fatty matters. Lehman considers the bile as the waste matter of formation of blood corpuscles If you moisten one capillary tube with HO & the other with bile & put them in a fatty substance the fat rises higher in the tube wetted with bile than in that wetted with HO. 296 It probably neutralizes the acid chyme from the stomach. Excrement It consists of undigested particles of food of epithelium & mucus decomposed biliary constituents. Its smell is due to decomposed biliary constituents or the imperfect combustion of albumen. If you distil albumen with KOHO you get essence of excrements. When the diet is mixed the colour is yellow brown on a flesh diet it is darker & on a milk diet it is yellow. Its action is generally alkaline In an adult man there are about 5oz daily. It contains 73 PC HO 27 PC solid constituents. The N in the fœces & in the urine 297 correspond closely to the N introduced in the food. There are few soluble salts in the foeces these having passed out in the urine. There is more MgO than CaO in proportion to the food, showing that some CaO has been taken into the system. The foecal ash gives 31 P.C. of tribasic PO5 . Taurin is always found & a peculiar crystalline body very unpleasant to prepare called excretin C78 H78 O2 S. Intestinal gases They owe their origin partly to air conveyed to the stomach & partly to the decomposition of the intestinal contents The O has disappeared in the large & middle of the small intestine The chief gases are CO2 & N. 298 H sometimes appears & when it does so in large quantity to extent of 25 PC Carbonetted H sometimes appears. HS rarely exceeds 1-2 P.C. Blood. General properties. It is a thick viscid fluid S.G 1.055 in human blood, usually of a bright cherry red, arterial blood is lighter coloured than venous when removed from the body it changes & separates into the clot or cross amentum & serum. When warm it has a peculiar odour stronger in the blood of man than women. If you add HOSO3 to blood it gives a stronger smell If you add HOSO3 to the blood of the horse & heat the smell of the stable becomes perceptible, or if to cows blood, the smell of the cow 299 house. The S.G of women's blood especially during pregnancy is less than that of men's. Blood is not only a solution but an emulsion holding solid particles suspended in it. It contains blood corpuscles, lymph corpuscles fat globules Blood corpuscles. They are thick circular slightly biconcave discs. In human blood they about 1/3200 th of an inch in diameter. In most mammals except the elephant they are smaller than in man. In amphibia they are very large. Lymph corpuscles. They are lighter than blood. The fluid in wh they float is called the liquor sanguinis 300 & contains fibrin in addition to the solid constituents of the serum The clot is coagulated fibrin & contains the blood corpuscles & some serum. The composition of living & dead blood is different Living blood Blood corpuscles Liquor sanguinis Dead blood 2 minutes after being taken from body. clot = fibrin & corpuscles Serum. Average of 22 analysis of healthy human blood. HO 781.60 } solid constituents 218.40 } in 1000 parts. Of the solid constituents Blood corpuscles 135.0 Albumen in serum 70.0 Fibrin 2.50 Fats 1.55 Soluble salts 6.0 Earthy phosphates 0.35 301 Fe 0.55 Extracted matter 2.45 Various analyses have been given of blood corpuscles & liquor sanguinis. The blood corpuscles contain 16.75 hæmatin } 241.07 hematocrystalline } in 1000 parts Liquor sanguinis contains neither of these but contains 4.05 fibrin 78.84 Albumen. The two characteristic constituents are hematin & hematocrystalline. Hematocrystallin is a glucoside Prep. of Hemat Mix defibrinated blood with a saturated solution of NaOSO3 & wash with alcohol & ether. C44 H22 N3 O6 Fe. Hæmatin Occurs in blood in the soluble form. 302 It is got also as a brownish black substance without smell or taste On ignition it leaves a considerable quantity of Fe2 O3 Dissolves in alkalis but is precipitated by acids. If you add KONO5 to blood the fibrin does not coagulate. HCl, NaCl, KOSO3, acid phosphate of KO & of NaO, bibasic phosphate of CaO & MgO are the mineral constituents of blood. In the liquor sanguinis NaCl, phosphate of NaO & HCl in small quantity are found. Gases in blood. CO2, N & O. They are found almost entirely in the blood corpuscles & hardly in the serum. If you shake up serum with gases it does not absorb them, but the blood corpuscles 303 corpuscles do to a considerable extent. In arterial blood there is relatively but not positively more O than in venous blood. Ratio of O to CO2 in arterial blood is as 6 to 16 & as 4 to 16 in venous blood. Coagulum. The clot is produced by the coagulation of fibrin. The cause of this is due to a considerable extent to the escape of NH3. 1 part NH3 keeps 3000 parts of blood fluid in a close vessel at 98°F. Agitation hastens coagulation & free access of air also Dilute solution of salts retard coagulation. In inflammatory diseases there is a constant increase of fibrin in the blood. In inflammatory blood it is covered with free corpuscles. In dysentery the fibrin also increases & albumen diminishes 304 Serum After the separation of the blood corpuscles & fibrin the serum is sometimes turbid owing to fat globules in drunkards & pregnant women's blood It is usually a straw coloured liquid The serum of womens blood contains 1 P.C. more of HO than men's. In mans blood 90.71 PC -women's- 91.71 The serum of arterial contains more HO than that of venous blood. Albumen in serum 7.9-9.8 - in collective blood 6.3-7.1 Albumen decreases in most diseases especially scurvy Bright's disease In intermittent fever & cholera it increases & after drastic purgatives Dropsy begins when the albumen in the serum is below 6 PC. 305 Various salts in small quantity are found in the serum. Analysis of ash serum. KCl 4.054 P.C NaCl 61.087 NaOCO2 28.78 acid phosp. NaO. 3.195 KOSO3 2.784 NaOCO2 & KOSO3 probably exist in the blood as lactates of NaO & KO. Chyle It is the liquid into wh the nutritious portion of the blood is converted. Its composition varies according to the food. It is an opalescent fluid, has a feebly alkaline reaction. & maukish taste When boiled it deposits a small quantity of floculent albumen. That from the lacteals does not coagulate. The fibrin in chyle seems to be less elaborated than in blood 306 Casein, fat, lactic acid & sugar are said to occur in chyle. There have been few opportunities of examining healthy human chyle. That of animals seems to be a dilute kind of blood. When exposed to air it becomes red. There is 12 P.C. of mineral residue in the solid residue. NaCl is abundant & alkalis combined with albumen. Lymph. It is a colourless or yellowish fluid got from the lymphatic. The ingredients seem to be the same as those of blood It coagulates in from 5 to 20 minutes after being taken out. Analysis of lymph. HO 957.6} Solid ingredients 42.4} in 1000 parts. Fibrin & lymph corpuscles 0.37 307 Albumen & extractive matter 34.72 Mineral matter 7.31 It is supposed that 22 lbs of lymph are formed in the body of an adult man in 24 hours. Fluids of generation & development The seminal fluid has been mixed with secretions of prostate & other glands before analyzed. It is commonly heavier than HO slightly alkaline, is coagulated by alcohol but not by heating. Characteristic ingredient Seminal filaments The motions of these are arrested by various solutions, as of kreosote.* Fluids of the egg. Generally consist of 2 parts the yolk & the white. The yolk contains fat globules & corpucles surrounded by fluid The corpuscles are phosphorized *And neutral salts &c. 308 fat probably glycerophosphoric acid The molecular granules are casein They form 14 P.C. of yolk. Albumen 3 . Collective fats 30. Glucose is always in the yolk. There are two pigments yellow & red. Mineral of constituents 15 P.C. White of egg contains 12 1/2 PC of albumenous ingredients, & ale Margarine oleine & glucose. The mineral ingredients are soluble & consist in a great measure of NaCl. The shell contains 97 PC. of CaOCO2 . & a little phosphate of CaO, MgO & organic matter Milk. It is an opaque fluid, of a white, bluish white or yellow colour. It is generally alkaline, sometimes acid.* s.g of women's milk 1.032. *as in carnivores 309 Under the microscope it is a clear liquid with fat globules wh have a fibrous covering. When this cover is broken in churning it allows the butter to gather These globules floating to the top produce cream. It does not coagulate but on heating it forms a scum from oxidation. Average of 89 analyses of human milk. HO 889.08} solid ingredients 110.92} in 1000 Milk sugar 43.64 P.C. Casein 39.24 P.C. Butter 26.66 Salts. 1.38 The quantity of casein increases with animal food During suckling the milk becomes changed. The butter remains tolerably constant 310 The casein increases as the child becomes developed Milk of dark haired women is better than of blondes & is richer in fats. The composition of asses milk is nearer that of women than any other animal. Composition of Cows Milk. HO 86.2 P.C Casein 4.2 Butter 5. Milk sugar 4.1 Mineral matter Urine. The urine is a liquid secreted by the kidneys from the blood. It removes the nitrogenous parts of decomposed tissues. Human urine is a clear fluid of a bitter saltish taste & bright amber colour 311 S.G 1.015 to 1.025. In a state of health it never exceeds 1.03. It has an acid reaction. In clean vessels it has no great tendency to putrefy but if there is any decaying organic matter present it does so readily. As it cools it often deposits a cloudy sediment, especially morning urine. On standing crystals of uric acid appear The composition of urine varies according to the food & exercise. In an experiment a man of 11 stone passed 52 oz of urine in the 24 hours. In this Urea 520 grs Uric acid 8 Hippuric acid 15 Kreatin 7 Kreatinine 4.5 Xanthin & Hypoxanthin Traces *Found after eating green [illegible] & fruits containing benzoic acid 21 312 Mineral matter 376 grs. Of wh NaCl forms 266 grs. The chief characteristic ingredient is urea. It is a product of the oxidation of the tissues. It is said that when albumen is oxidized by MnO2 urea is produced but this is doubtful. It is however certainly produced in the system from the oxidation of the tissues It is also got by the oxidation of uric acid & by the action of alkalis on kreatin & [crossed out] alloxan. NH4 O CyO when heated becomes urea Urea has the same empirical formula as NH4 OCyO though it is arranged in a different way N2} } H2 } H2 } H2 Na} } C2 O2 } H2 } H2 313 Crystallizes in 4 sided prisms like KONO5 soluble in alcohol & HO forms salts. It forms 77 to 82 P.C of urine evaporated There are about 25 parts of urea in 1000 parts of common urine. A man of 10 stones wt excretes daily 442 grs urea. - " - 520 grs. From 58 observations on young men the average is 549 grs per day. The average of 58 observations on young women is 425 grs. If the same weight of children from 6 to 3 years old & of old men. The children secrete 3 times as much as the old men. The average of urea is 244 Adult man on mixed diet 518 grs - vegetable - 389 - 314 Adult woman on mixed diet 412 grs - vegetable - 309 Professor Fry of Trinity College Dublin made various experiments on the students. Well fed flesh eating wine drinking students yeilded 576 grs daily Well fed water drinking vegetarians 394 grs Certain diseases influence the quantity of urea. it is increased in typhoid fever, in pneumonia pleurisy & rheumatic fever. Uric acid in urine. In urine it is generally combined with NaO. It is rarely more than 1/10 P.C in urine. From 7-8 grs in an adult man. In perfect health there ought to be no uric acid. In Professor experiments on students he found 315. Beef eating wine drinking students 4 1/2 grs daily HO drinking vegetarians 1 1/2 grs - Hippuric acid. Occurs chiefly in the urine of herbivora. If you become a vegetarian, hippuric acid takes the place of uric acid in the urine. A large amount of HO taken into the system lessens the uric acid as also sulphate of quinine taken as a medicine. Xanthin & Hypoxanthin Kreatin 5-7 grs in 24 hours Kreatinine is a product of the metamorphosis of kreatine. Extractive matters are less abundant in the urine of the child than of adults. Extractive matters are uncrystallizable bodies wh we do not 316 know. In starvation the exceed the ureaic in quantity. Among them are damaluric, carbolic & other acids & some volatile acids. Urine pigments. Indican the glucoside of indigo blue. Mineral ingredients. Of these NaCl is far the largest in amount Daily average in 8 students. .269 grams in 24 hours The average is generally taken as 200 grs for an adult male & less for women & children In acute diseases of the febrile sort the chlorides rapidly diminish, but when convalescence begins the chlorides increase rapidly. 317 The chlorides are carried off in the watery stools & in perspiration Sulphates. They occur in varying quantity The HOSO3 excreted daily as sulphates is 32 grs. The proportion rises in the afternoon & during digestion Animal food & active exercise increases the amount of the sulphates Phosphates PO5 is found in the urine partly as NaO PO5 & partly as phosphates of MgO & CaO In an adult man 50 to 60 grs of PO5 are excreted daily as phosphates. The maximum & minimum is the same as with the sulphates. Animals food increases the phosphates. Earthy phosphates excreted daily 318 are 15 grs. Fe in minute quantity is in urine. SiO2 & Fl in very minute traces. Secreted daily by an adult man. NaCl 266 grs HOSO3 (as sulphates) 32 PO5 (as phosphates) 55 Alkalis, CaO MgO & other salts. Undetermined. Abnormal ingredients. The presence of albumen in the urine often indicates Bright's disease, but it may be due to accidental causes. The urine may sometimes coagulate in health. Taking cantharides or a stimulant diuretic & pressure of blood in the kidney as in heart disease produces albumen in the urine. In boiling urine always add a 319 drop of NO5 after the operation When albumen remains persistently in the urine it is dangerous symptom. Fibrin sometimes occurs in urine Sugar does not exist in healthy urine but in diabetes & gout When the flow of 4th ventricle of the brain is punctured sugar appears in the urine & remains for some hours Sugar appears to be in the foetal urine. Fat does not occur in healthy urine but does in Bright's disease & chronic insanity. fatty degeneration of kidneys in in rapid emaciation but generally from Biliary compounds are found in jaundice. NH3 never occurs in healthy urine unless it has been accidentally 320 changed in the kidneys as by too long retention. In scarlatina it appears even though the urine be acid. When urine is alkaline NH3 generally is present, urea being very readily decomposed. Urine of animals The composition of that of the carnivora most nearly approaches to the human. It is light yellow & nasty odour bitter taste Has an acid reaction It contains much urea, little or no uric acid & much pigment. Dogs urine contains cyanuric acid That of the herbivora is yellow turbid. Contains hippuric but no uric acid. oxalate of lime & only a small amount 321 amount of phosphates relatively to man When they are fed on animals diet as the calf while suckling they give urine like that of the carnivora. The urine of birds forms a white coating to the solid excrement consists chiefly of urates of NH3 & CaO The urine of frogs is liquid & contains urea NaCl & phosphates. That of serpents is at first pulpy but soon dries & consists mainly of urates of alkalis, with a little urea Urinary sediments The occurrence of sediment in fresh urine as soon as cooled may sometimes show disease. It consists either of organized or unorganized substances. Inorganic sediment Uric acid Urates Organized Mucus & epithelial scales. 322 Inorg. Hippuric acid Oxalate of lime Earthy phosphates Cystin Org. Blood corpuscles Pus corpuscles Cancerous & tubercular matter Fibunous coats of the tubes of the kidneys Spermatozoa fungous bodies and infusoria Uric acid. Only occurs in strongly acid urine in any quantity; may be deposited after fermentation from decomposition of urates When free lactic acid is voided it decomposes urates & deposits uric acid. Uric acid sediment is always coloured, generally yellow or brown. Test. With HONO5 & NH3 it forms murexide. The urates are the most common of the sediments all occur in acid urine except that of NH3 Their colour varies from greyish white 323 to brownish red or purple. Urate of NaO. The cause of the sediments is partly their greater solubility in hot than cold HO. Sometimes from the HO in the bladder having exuded & left too little to dissolve them. Hippuric acid rarely occurs as a sediment. If a fruit like greengages containing benzoic acid be taken freely or if benzoic acid be taken as medicine or otherwise, hippuric acid appears in the urine Oxalate of lime It is sometimes produced by changes in old urine so it is not to be confounded with that deposited from fresh urine Earthy phosphates always appear when the urine is alkaline. 324 Urinary Calculi. They are formed in the kidneys or bladder by deposition or retention of urinary sediment. Around a nucleus more matter gradually accumulates. Sometimes the matter is not all of one kind The composition of the calculi is generally the same as that of the sediment. Uric acid or urates Kanthin Cystin Oxalate of lime CaOCO2 . Phosphate of lime Phosphates of MgO & NH3 . Fibrin & mucous compound Phosphate of MgO may be formed by throwing MgOSO3 into urine & allowing it to stand. The substances valuable as manure 325 manure may thus be removed, Fibrin & mucous compounds Respiration. The act of respiration consists essentially in the interchange of gases existing in the blood with those in the air. In animals low in the scale it takes place on the surface of the body but most animals have definite respiratory organs. The gases given out from the body are in the venous blood, but this does not come in the direct contact with the air. The lung tubes branch out into small ramifications & thus present an immense surface in small space. The air & blood are separated by a thin moist membrane thro wh the gases interchange by exismosis. The O is changed for CO2. 326 The change of colour in the venous blood from dark to light red is due not so much to the absorption of O as to the expulsion of CO2. If the CO2 be expelled & H substituted the same change takes place. The O taken in is in greater volume than the CO2 given out. The reason of this is that the O has to oxidize the tissues & convert them into urea & to make H into HO. When O is converted into CO2 it occupies the same volume so the interchange would be volume for volume if the O had not more work to perform in the body. For each volume of O absorbed in the lungs, there is only 0.8516 vol. of CO2 evolved. Hence there is 1/7th more O taken into the body than what is required for conversion into CO2 327 When we examine the volume of air expired after it has cooled & dried it is less than that inspired. The aqueous vapour expired in 24 hours is from 11 to 14 oz. Some of this is due to the HO taken as drink as well as to that formed in the system. The N in the air is little affected by respiration. A very slight increase of N in the air expired may be due to that dissolved in the HO we drink. The air expired is 0.402 ricer in O than that inspired. There is a very small quantity of NH3 to be detected in the air expired. The most important gas is CO2. The expired air of a healthy man contains 4.334 P.C of CO2. 328 Only a small part of the O of the air is taken up. Weight of gases expired by an adult man taking a general average during 24 hours. CO2 27.8 oz N in excess that inhaled .5 Aqueous vapour 14. Inhaled. O. 23.3 So that about 3 oz of O are retained in the system or go out in other excretions. The amount of CO2 in expired air depends on the frequency of respiration In Gerhardts' experiments Acts of respiration per minute 6 12 24 CO2 in 100 vols of air expired 5.528 4.262 3.355 329 48 2.984 96 2.662 When the breathing is undisturbed 30.5 cub. in. are expired in one respiration. But the rhythm of the respiration is Not all the CO2 in the pulmonary vessels is removed as it passes thro' the lungs. The respiration of air richer in O than common air produces no marked difference in the CO2. An animal breathes undisturbed though the O be increased to 3 times its normal amount. When decreased by one third they show no change but when decreased by two thirds they show great distress & if reduced to 3 P.C they rapidly 330 die. CO2 if added gradually to air does not impede respiration up to 12 P.C. When the animal has absorbed about 1/3 of their bodily volume of CO2 they show symptoms of poisoning tho' the O supplied along with the CO2 [illegible] The CO2 cannot escape by diffusion The largest portion of inhaled air goes back unchanged, only 1/5 th of the air in the lungs is changed in one respiration. Gases have no tendency to diffuse into themselves & when the air is charged with CO2 that in the system does not diffuse out. It is this wh renders CO2 a poison. A rabbit may breathe in an atmosphere of 20 P.C. CO2 for 20 hours if there be a constant supply. 331 CO in minute quantity will produce death if there be no ready method of diffusion. An atmosphere of 1 P.C. CO2 has been known to produce death especially if mixed with CO. According to Dr. Edward Smith's experiments the expiration of CO2 is less in hot parts of the season than in the cold. In the middle of August the CO2 is 30 P.C less than in the cold season. The maximum is in April & May & begins to fall at the end of May or in the beginning of June. It ascends in October & is high in December. Moisture in the air increases When there is change of barometric pressure in either direction there is an increased amount of CO2. 332 The effect of fasting is to diminish the amount of CO2. Some cats experimented on at first converted 80 P.C.O into CO2. 77 P.C the 2nd day & when they died of starvation 73 P.C. Dr E. Smith fasted for 27 hours & expired 0.25 P.C less CO2. There was a remarkable uniformity in the composition of the expired air but the number of respirations was less. Influence of sex & age. The male expires more CO2 than the female. Boys of like age expire more than girls. Charling's experiments age weight in kilograms CO2 per hour in grams CO2 per hour for every 1000 grams of wh Man 35 65.5 33.53 0.5119 youth 16 57.75 34.28 0.5887 soldier 28 82. 36.62 0.446 girl 17 55.75 25.34 0.454 333 Boy 10 22. 20.338 0.924 Girl 10 23. 19.162 0.883 Effect of exercise Exercise increases the CO2. Influence of food. The food influences the CO2 evolved. More O is absorbed to form CO2 when starch is used than when animal food is used. Less N is evolved on a vegetable than on an animal diet. In dogs fed on suet 6g P.C of the absorbed O was evolved as CO2. Fats contain a good deal of H as well as as C & O is required to oxidize this. In starch the H is combined with O.* Respiratory equivalents or amounts of food required to produce the animal heat in the body itself. 100 parts fat require 292.14 Oxygen *Animal food requires much O to oxidize albuminates & form urea 334 100 Starch 118.52 100 Sugar 106.67 Malic acid 82.78 Albumenous bodies 153.31 Dr E. Smith has drawn some conclusions wh however require farther confirmation. He says that food may be divided into 2 classes, those wh excite respiration & those wh do not. Exciters. Nitrogenous foods, milk sugar rum, beer, stout, the cereals Nonexciters. Starch, fat, certain alcoholic compounds, volatile elements of urine & spirits & coffee leaves. Pure alcohol, rum, ale & porter generally increased the respiration. Sherry lessened the air inspired but increased the CO2. Tea, coffee, chicory, & cocoa are respiratory exciters. Tea is the most *Brandy lessened it 335 powerful*, next coffee, next cocoa & lastly chicory. The addition of sugar & milk increases the respiratory effect. Its influence is immediate, its maximum is in about 20 minutes its duration is from 1 to 2 hours. Cause of sleep When trying to sleep the first thing we do is to take away the pressure, of the column of blood on the heart, wh we do by getting into a horizontal position. We lessen the respiration by lying in a fixed posture. The amount of O dissolved in the blood in the system is lessened. At every vital act there is change of matter. They are only destroyed in the act of oxygenation. *Therefore recommends tea to be given in suspended animation as a respiratory waiter 336 In every thought a portion of the brain is destroyed & as we get the O diminished in the blood the brain finds more difficulty in manifesting itself to the external world. In the case of the drunkard the O unites with the alcohol & the brain refuses to manifest itself & he becomes dead drunk. Sleep of hybernating animals During summer they accumulate fat round the heart & gradually push up the diaphragm against the lungs, this prevents the O being inspired readily & it falls asleep. Some wh do not accumulate so much fat as the tortoise take a roll of grass to push up the diaphragm. They are like a lamp slowly 337 burning the fat being the fuel. When this is consumed the diaphragm falls down the lungs begin to play the brain becomes active & the animal awakes. The conditions in wh we are most prone to sleep are when we have taken a large dinner wh pushes up the diaphragm. As there will be less combustion during sleep & so less animal heat we draw near the fire to compensate for this. Respiration of the lower animals. Carnivora living on ordinary food exhale more N & CO2 in proportion to their wt than herbivora Active birds consume 10 times more O than sluggish birds. Frogs & lizards convert 75 P.C & the salamander 82 P.C of O into 338 CO2. The wakeful ones consume 9 times & the half torpid ones 3 times as much as those wh are entirely rigid in winter. Origin of the CO2 It was once supposed that the CO2 was produced in the lungs. There seems to be no combustion at all in the lungs, for if there were the blood should be warmer there. This is not the case, as the blood is cooled in the lungs the blood of the left side of the heart is 2° colder than that on the right side: It seems to be produced in the tissues Every vital tissue of animals yields CO2 to the air pump. Gustave Liebig says that the muscles of the frog possess irritability * so long as the exhale *So long as they absorb O. If placed in H their irritability stops. 339 CO2. The changes are produced in the muscles . General conclusions That 8 1/2 oz of C are converted into CO2. in 24 hours, for wh. 22.66 of O would be necessary, but as only 85 P.C of O is used for CO2, 26.7 oz of O or 1 1/2 lb are daily consumed by an adult man. He destroys daily 117 oz of air wh. is equal to 164900 cub. in. In the course of the year he destroys 7 hundred weight of O. 1/5 is made into the body. It is an old tradition that the body of an animal changes once in 7 years, but this is not true as all the C would be burned in 3 days*. A man of 11 stones has 4 lbs albumenous bodies in blood. 27.5 in tissues *If there were no supply of Co you may calculate the rate of concrete from the N in the urine & excrement. 340 5lbs in bones The whole body would be changed in 18 weeks supposing that they were all changed at the same rate. Animal Nutrition Plants live on mineral food, wh they find in the atmosphere, CO2 HO & NH3. They assimilate the C from the CO2 into their system & give out the O. They get their N from NH3 & sometimes though rarely from NO5 but not from the N of the air. They get their H from HO. They have nothing to do with volition & on this account they have the property of moulding inorganic substances into organic forms. Animals have the function of volition to preform & so have not this property. 341 All animals are essentially herbivorous, even carnivora being so although indirectly. All food may be divided into 2 classes characterized by one essential difference. Those wh contain N. Those wh are destitute of it. Nothing destitute of N can build up the muscle of an animal. Those wh contain N are the histogenetic substances, casein, albumen &c, whether got from plants or animals We may call the one sort wh contain N flesh formers & the other heat givers. There is necessity for a mixture of food of both classes* It was long supposed that gelatine was an extremely nourshing substance but a commision both *If only one kind be given the animal dies just as if it received no food as only one part of its nut is supplied 342 of France & Holland appointed to examine into this found that when animals were fed entirely on it they died. In milk there is an admirable admixture of both kinds of food. Casein flesh formers Butter, sugar heat givers There is also mineral matter in it In all cookery we try to obtain this mixture. We eat beef with potatoes mutton with rice & pork with peas or beans Nitrogenous food or flesh formers. All the tissues wh form any part of an organ of an animal contain 15 P.C of N. Animals are certainly unable to take N from the atmosphere. There is one apparent exception: when an animal takes benzoic acid containing, no N it voids hippuric acid wh does. This is however in question of excretion; not of nutrition. There is no ground to suppose *and also the blood 343 that flesh can be formed from nonnitrogenous substances by assimilating N from any other source. The nutrition of a carnivorous animal is very simple. It takes the flesh & blood wh it finds ready formed & appropriates them to its own system. That of a sucking animal is equally simple. It is like a carnivorous animal eating its mother. It finds casein in the milk & appropriates it. The nutrition of every animal is equally simple. We find the histogenetic substances in plants. Thus the juice of the cauliflower contains fibrin assitedd of blood. Animals do not form the components of their flesh & blood out of unlike matters but they find 344 them ready formed in vegetables The process of nutrition consist in extracting them & giving them a place & form in the organism. This is the great law of animal nutrition Plastic elements { {Flesh animal Fibrin {Blood Albumen {Casein This excludes gelatine Gelatine may indirectly act as food by supplying food for the cellular tissue & thus saving the other food. Gelatine may thus in the case of a very weak person be of use when administered along with some other food, not alone, by supplying material for the cellular tissue wh has been much wasted by illness. & thus allowing the other food to be applied to the purpose of building up the organs. 348 Non nitrogenous substances. Fat, starch, gum, cane sugar, grape sugar, milk sugar, pectin bassarin, wine beer & spirits Since they are wholly free from N they cannot build up the frame work of the body yet they fulfil a very important function viz. supporting the animal heat. The temp. of fishes and amphibia is only a few degrees above the medium in wh they live. That of quadrupeds is 99-100° F birds 105 man 98-99 child 102 In lower animals even in health the temp. is to a certain degree regulated by the medium in 103 they been In the higher animals there is always a fixed temp. in health. Depression of this temp is attended 346 attended with a depression of the functions of an animal. There must be some means of regulating this temp. since the temp. of a man at sunny Palermo or of a traveller in the polar regions is the same. The appetite of the man is the regulator. Non-nitrogenous substances are usually the fuel. though the tissues of the body are sometimes as in the carnivora. The hyena moves about in order to burn his tissues to keep up the animal heat. From the known composition of food it is easy to calculate how much food is required to keep up the same temp. on different kinds of food. The heat giving equivalents 347 or the quantity of food required to keep the animal heat the same. Weights of different bodies requires to produce the same amount of heat. Fat 40.2 Cane sugar 100 Alcohol 53.8 Grape - 106 Starch 97.2 Flesh 309.7 Flesh has 8 times less respiratory value than fat. After deducting the heat necessary to evaporate HO as vapour in the breath we find that the rest taken in diet is sufficient to raise 143 lbs of HO from 32° to 99° & the specific heat of the substances wh compose the body is less than that of HO. Varying quantity of respiratory food. The body of a man may be represented as a chamber to be kept at the same temp in 348 summer & winter & in different climates. If you transport a man from India to the poles the temp. of his body remains the same but you must put in more food to sustain it. In extreme cold man takes enormous quantities of food. Sir John Franklin says that during the whole of the march they found that no clothing could keep them warm as long as they were fasting but when they could go to bed with full stomachs they could sleep comfortably. Parry took an Esquimaux lad not full grown & set him down to a weighed repast. the quantities he devoured are the following., 349 lbs oz Sea horse flesh hard frozen 4 - 4 -boiled 4 - 4 Bread & bread dust 1 - 12 Rich gravy soup 1 1/4 pints Spirit 3 glasses Strong grog 1 tumbler Water 1 gallon 1 pint Ross says that an Esquimaux eats daily on an average 20 lbs of flesh & oil Admiral Sarcheff says that a yacot took in 24 hours the hindquarter of an ox & 20 lbs of fats. [illegible] proportionate quantity of melted butter for drink. These accounts are not more astonishing than the difference between the coal we burn in summer & winter. The character of the food is made to suit the climate. Fruits & rice contain 20-30 PC of C. Blubber 80-90 In India beer & butter are freely 350 taken but apparently less as food than to unctuate the body & prevent excessive perspiration. Ordinary food contains fat In Cocoa 50 PC In coffee 12 PC A man inhales daily to consume these about 3000 gallons of air, much of the O of wh is burned by the food. The starchy matters & fat in the food produce fat in the body. In a grate where there is a free access of air the fuel is converted into CO2 , but in a gas retort where there is only a very limited supply of air various tarry matters distil over. Thus in the muscular arm of an Arab who is almost constantly in the open air & taking exercise 351 exercise there is no fat, but in a man leading a sedentary life & taking little exercise the fat accumulates. If there is a free introduction of air the starch is converted into CO2. In hybernating animals the fat is formed by imperfect combustion of the food in summer & in winter they live on it. There was a very fat pig weighed to be sent to an agricultural show, but just before being sent a slip of land from a neighbouring hill overwhelmed it. It was thought to be dead & no farther trouble was taken about it. About 120 days after the slip was removed for the purpose of building & the pig was found alive but it had decreased 352 140 lbs in weight. Proportion between flesh formers & heat givers. Plastic Cow's milk 10 30 Woman's - 10 40 Lentiles 10 21 Beans 10 22 Peas 10 23 Fat mutton 10 27 - pork 10 30 Beef 10 17 Hare 10 2 Veal 10 1 Wheat flour 10 46 Oatmeal 10 50 Rye - 10 57 Barley 10 57 White potatoes 10 86 Blue - 10 115 Rice 10 123 353 Buck wheat meal 10 130 Mineral matter in food The body of a man weighing 150 lbs contains Phosphate of lime 5lbs 13oz 0 grs Carbonate - 1 - 0 - 0 CaFe 0 - 3 - 0 NaCl 0 - 3 - 376 NaOCO2 acid phosphate of soda 0 - 0 - 400 KoSO3 0-0-400 Feo 0-0-150 KCl 0-0-12 Phosphate of potash 0-0-100 3MgOPO5 0-0-75 SiO2 0 - 0 - 3 The different organs exercise a selection, thus, P is taken to the brain,* Ca Fl to the teeth, SiO2 to the hair & nails, S is generally distributed but is taken especially *3CaOPO5 354 especially to the hair, phosphates of MgO & KO to the flesh, phosphate of NaO to the blood & cartilages. NaCl may act by facilitating absorption of HO by diffusion or by aiding the solubility of albumen or by affording HCl to the gastric juice & NaO to bile & pancreatic fluid. Fe is an essential ingredient of blood, gastric juice, hair & the black colouring matter of the eyes. To find the proportion of flesh formers in the food estimate the N in it & multiply by 6 3/10ths. Amount of the several kinds of food required The circumstances of age variation of climate &.c. influence this. There are two ways of finding how much food is required. We might find how much C was expired as CO2 & how much C & N 355 are in the foeces & urine, An adult man Expires as CO2 8.8oz C daily in urine & foeces 2.2oz C N in urine foeces & mucus 334 grams The C excreted daily is thus about 11 oz & the N is equal to 4 8/10 oz of flesh formers. Average diet 4 oz flesh formers 3 oz fat. 10 1/2 oz amylceous food 1 oz injested salts. 84 oz HO. 33 oz O. Another mode is take the experience of public dietaries We find by these on an average that for an adult man, daily 5 oz flesh formers 10 oz C *The amount of N in excrements in health indicates the amount of urine wasted in the day, By multiplying it by 6.25 you get the amount of tissues 356 are required When we contrast the diet of the aged with this we find that with them the flesh formers have sunk to 40oz but that the C is the same The proportion of C in the heat givers to that in the flesh formers is now as one to five. In children form 10 to 12 years of age flesh formers 2 1/2 oz C 8 oz In the young the process of supply is greater than that of waste. In the adult it is equal & in the aged less. It is during sleep that the body is built up. An adult spends 17 waking hours & in mechanical labour & 7 in sleep. An infant spends 4 waking 357 hours & 20 in sleep during wh its growth takes place. An old man spends 20 waking hours & 4 in sleep. In an adult the waste is to the supply as 100 to 100 In an infant as 25 to 250 In the aged as 125 to 50 In an infant there would not be ptyalin enough to convert its [illegible] food into sugar & so it finds the sugar ready formed in the milk. The casein is also in a soluble state. in the milk so the gastric juice has not to convert it into a soluble state. In cooking we try to get the same proportion of the different kinds of food as in milk. Pauper & prison diets. Prison diets were & still are by no means well regulated. 358 It was thought that a man on long confinement required much more food than one on short confinement. The question however is what is the waste if the tissues. Work-house diet is about 3 1/2 oz of flesh formers daily. The hard labour diet is no more than this & is quite insufficient for hard labour. Besides they are on the system of alteration according to the time of excrement. 1st Cerials yield nutritious meals of varying composition. The finest flour is not the most nutritious on an average they contain 14.6 PC flesh formers 69. heat givers Mineal matter 1.6 P.C 359 Oats contain 5 PC. of fat 17 flesh formers 66.4 heat givers 3.0 mineral matters Probably half the human race partake of tea Tea leaves contain 5 P.C. HO 3 Theine 15 Casein 6.7 aromatic oil The casein does not come out unless you put in soda. 360 The peculiar aroma of coffee is due to an essential oil wh it contains Action of alcoholic beverages. Their action is to reduce the waste of the tissues When the amount of food is sufficient this is injurious acting like too much food The cheapest way of taking alcohol is in beer The cost of one oz of alcohol taken in different beverages is as follows in beer 2D. spirits 4D wines 18 6 D. 361 For the support of strength you can get an equal amount of nourishment from vegetables or animals. The character of men depends much on the food they take. It required 5oz. of flesh formers daily to do good day's work. To get this from potatoes, it is necessary to take 25 lbs, but even an Irishman's stomach can only take in half that quantity, so that an Irishman living on potatoes alone could only do half a day's work. The Irish famine caused new material for food to be introduced* wh being more nourishing than potatoes *And spread his work over the whole year instead of only 2ce a year 362 enough for a good days work could be taken without inconvenience. Who gave us trouble in the Indian mutiny? Not the rice eaters of Bengal but the pulse eaters We may sum up the general conclusions in the words of Prior. Was ever Tartar fierce or cruel Upon the strength of water gruel. Balance between animal & vegetable life The functions of animals & vegetables are precisely opposite in a chemical sense. A vegetable is a reducing apparatus, reducing CO2 An animal is an apparatus for oxidation. 363 Vegetables are fixed Animals have the power of locomotion A vegetable evolves O absorbs heat & electricity Decomposes CO2 - HO - NH3 Produces organic substances Transforms inorganic matter into organic Derives its elements from earth & air An animal absorbs o evolves heat & electricity Produces CO2 - HO - NH3 Consumes organic substances. Transforms organic matter into inorganic Restores its elements to earth & air Functions of vegetables. Animals find their substance in vegetables. The vegetable kingdom is 364 the great laboratory of organic life. They are powerful reducing agents. For every cubic foot of CO2 they reduce 1 cubic foot of O is restored to the atmosphere. The vital force of a plant growing in the dark is unable to reduce CO2, light is required for this. Nitrate of ammonia is formed by lightning flashes. 365 Functions of animals. In animals we certainly find organic matter in its highest forms but for a limited time only Then function is not to create organic matter but to transform it into inorganic matter. They use the organic matter of vegetables & make it into organs wh have high functions to perform. Broken down from the complex molecule, into wh it was formed by vegetables it becomes less & less complex at every change. Every change of them is a degradation. they being finally converted into CO2 & NH3 The process of decay produces CO2 & NH3. 366 [illustration] The substances of dead animals passes thro' the same change as the non-nitrogenous substances in their bodies The animal stands midway between the vegetable & mineral kingdoms. It has nothing to do with forming organic bodies 367 Mutual relation of plants & animals. Animals derive nutrition from plants. Plants truly feed animals but animals as truly feed plants. It is certain that the atoms of wh. we are composed have passed thro' a succession of animals & men. Perhaps the brain with wh. I (Professor Playfair) am now thinking once formed part of the liver of the Emperor of China. There is the mineral kingdom as represented by air & soil. The vegetable elaborating organic matter from the mineral. The animal living on plants but breaking them 368 down to mineral matter. Index Absorption in animals Acetates 76 Acetic acid artificial production of 73 Acetification process of 74 Acetone 68 & 75 Acetyl 67 Aconitin 100 Acrolene 100 Acid acetic 72 - anhydrous 70 - glacial 75 aconitic 134 acrylic 100 amido - acetic (glycocoll) angelic 101 benzoic 117 butyric 79 capric caproic Caprylic Carbazolic 113 Carbolic 111 Carminic Cerebric 285 Choleic [tairiochalic] 274 cholic 275 citraconic citric 132 cyanuric 159 dextroracemic 129 erythric 218 excretolic formic fulminic 158 fumaric 128 gallic 134 gallobaunic 136 glucic 198 glycocholic 273 glycolic 92 hippuric 315 humic hydrocyanic 142 hydroferrocyanic 149 hyocholic 276 hyoglycholic 276 hyofaurocholic 276 indigotic kinic (quinic) lactic 92 lauric licanoric leucic lithofellic malic 127 margaric meconic melanuric mesoxalic Mucic 199 Nitrobenzoic Nitrocinnanic Nitrococcussic Nitrophenic Oenanthic Oenanthylic Oleic oleophosphoric orsellesic oxaluric oxamic palmitic 82 parabanic 263 parellagic pectic pelargonic phenic picric 113 pinic propionic pyrogallic 135 pyroligneous quinic 132 quercitannic racemic 129 ruberythric 218 rutic 82 saccharic salicylic sebacic sorbic stearic 83 suberic succinic sulphobenzoic tannic 135 tartaric 128 taurocholic thionuric toluic ulmic uric 267 usnic vaccinic valeric xanthic Acids acetic group of - series of amidated 265 fatty oleic oxalic stearic dyective colours Albumen Albumenoid group pro- perties of. Albuminous urine Alcoates Alcohol, absolute - action of acids on allylic amylic - bases, mode of preparing butylic benzoin caproic cerotic caprylic cuminic ethylic hexylic (camoic) caurylic melissylic methylic oetylic price of propylic radicles synthesis of alkoliolic fermentation T.L. Brunton Edin. University Session 1861-2 Lecture notes Of lectures on Organic Chemistry by Professor Lyon Playfair [illegible] Contents [Inorganic] Table of Contents Table of organic substances wh may be formed from their elements without vital agency 1 Difference between organic & inorganic substances 4 Definitions of organic chemistry 6 Preparation of a higher from a lower alcohol 7 Empirical & rational formulas 8 Homologous series 10 Heterologous class 11 Qualitative examination of organic bodies 12 Quantitative analysis 15 Example of organic analysis 31 Olifines Ethylene series, Olefiant gas, Propylene, Butylene, Amylene, Hesylene &c 19 Marsh gas series, Hydricles of ethylene series 26 Alcohol radicals. Preparation 29 Table. Transformation of organic compounds by different ferments 32 Reduction of other series to olifines 33 Definition of radical 35 Ethers. 36 Substitution products of methylic ether 37 Haloid compounds of ether 41 Ethers as a class 42 Alcohols 44 Wines & spirits 48 Fermentation 51 Theory of the action of ferments 53 Brewing 55 Composition of malt liquors. Table 56 Homologues of the alcohols 57 General properties of alcohols 58 Compound ethers 59 Biatomic ethers & alcohols 62 Aldehyds 65 Ketones 68&74 Anhydrides or acids 69 Hydrated acids. Relation of these to alcohol & ether 71 Relation between the alcohols, aldehyds, & ketones 74 Acetates 76 Acids homologous to acetic acid 79 Fatty acids 82 Candles 84 Saponification 86 Candles from coal 88 Acids produced from bratomic alcohols 91 Oxalates 96 Negative radicals. Acetoyl. Allyl. Angelyl 98 Oxidized radicals of allyl 100 Table. Homologues of acrlylic acid 101 Glycerine 102 Glycerides on common fats 104 Soap 105 Chief fats 107 Aromatic series 109 Phenyl 109 & 117 Benzyl 115 Distillation of coal. Naphtha 118 Coal tar colours 122 Malic Tumaric, Tartaric, Racemic & Kainic Acids 127-132 Trebasic acids Citric, gallic, tanine &c 132 Tanning 137 Compound haloid radicals 139 Cyanogen 140 Hydrocyanic acid 142 Cyanides 145 Haloid ethers of cyanogen 146 Nitriles 147 Preparation of higher acids from nitriles 147 Double electronegative cyanides 148 Ferrocyanogen 148 Ferridcyanogen 152 Nitroferrocyanides or nitroprussides 153 Cyanates 155 Sulphocyanogen 156 Sulphocyanates & sulphocyanides 157 Bicyanogen 157 Fulminates 158 Tricyanogen 159 Characters of cyanogen 160 Organic bases representative of alkalis & metallic oxides in organic chemistry 160 Amines 161 Monameries 161 Production of these compound ammonias 162 Organic bases coal tar 164 Diamines. Urea. 164 Triamines 166 Organic alkaloids 166 alkaloids from hemlock, broom, tobacco, opium, chinchona bark, strychnine family, solinacia family. tea &c. 168-182 Hydrates of Carbon Action of dilute acids & oxidizing agents on them 182 Views of their chemical constitution 183 Cellulose-gum cotton-vegetable parchment 183 Starch. Starch in vegetables 186 British gum. Manufacture of starch 188 Special starches 189 Starch in the animal kingdom 190 Inulin Lichenin 190 Glycogen. Dextrin 191 Gums 193 Quantities of cellulose & gum in different vegetable substances 193 Arabin. Cerasine. Bassorin. Pectin 194 Sugars 195 Grape sugar or glucose 196 Test for diabetic sugar 197 Caramel. Saccharides. Glucic acid 198 Action of yeast & of nitrogenous ferments on grape sugar. mucic acid 199 Fruit sugar on fructose 200 Cane sugar or sucrose 200 Barley sugar. Caramel. Conversion of sucrose into glucose. Saccharides 201 Fermentation of sucrose 202 Manufacture of sugar 202 Refining of sugar 205 Sweetness & uses of sugar 206 Relation of H+O in sugar 207 Milk sugar 208 Lacto-carmel. Lactose 209 Trehulose. Megatose. Mellitose 210 Non fermentible sugars. Inosite 210 Seyllite. Sorbite 211 Glucosides. Salicin 212 Action of amulcin & acids on salicin 212 Saligenin. Populin. Quercitrin Convolvulin 213 Colouring matters 214 Isolation of colouring matters 214 Dyeing. Mordants. Printing 215 Madder. Ruberithric acid 218 Aliyacin. Lakes. Resemblance to 219 naphthalin. Production of Chloralizarin from naphthalin Purpurine. Rubiacine 219 Logwood Hematoxylin. Brazilwood 221 yellow dyes 221 Indigo 222 Topical dyeing 223 Colouring matters of lichens 224 Cochineal. Carminic acid 225 Volatile oils, resins & caoutchouc Essential oils 226 Stereoptines 227 Preparation of essential oils 227 Classification of these oils. Central formula 228 Essences isomeric with camphine 229 Turpentine 229 Essences not isomeric with camphine 231 Oxygenized essences Camphors 231 Resins, Copal. Mastic. Sandarac. Lac. 232 Sealing wan Lacquers 234 Guayacum. Jalaps. Amber 235 Caoutchouc. Gutta-percha 236 Asphalt & bitumen 238 Ozokerite. Sheerite. Fichtilite. Hartite Idualite 239 Animal chemistry Vital agency 240 Histogenetic substances 241 Existence of some both in animals & vegetables 242 Soluble & insoluble states Action of acids & alkalis on them 243 Putrefaction 244 Test for any of these nitrogenous bodies 245 Protein 245 Albumen albumen of blood 246 Insoluble albumen 248 Fibrin 248 Syntonine 249 Casein Vitellin 250 Globulin 252 Hemato crystalline 253 Derivatives from the albumenous group 253 Ossein Glutin 254 Glue confectionary gelatine 256 Theory of the formation of nitrogenous substances occuring as derivatives in the animal body 257 Kreatin. Kreatinine Sarkosine 258 Methyluramine. Sarkin. Guanine 260 Kanthin Cystin 261 Allantoin Tyrosine 262 Alloxan Parabanic acid 263 Thyanicric acid Alloxantin. Cerebrin. 264 Amide acids. Taurin. Leucin 265 Uric acid. Action of peroxide of Plouit. 267 Urates 268 Derivatives of uric acid 269 Murexide. Guanocolours. Purpuric acid. 270 Compounds from uric acid 271 Cyanuric acid. Inosic acid 272 Acids of bile 272 Glycocholic acid 273 Taurocholic acid 274 Cholic acid 275 Hyoglycholic acid 276 Hyocholic acid. Hyotaurcholic acid 276 Lithofellinic acid 276 Action of acids on cholic acid. Cholordic acid 277 Cholosterin 277 Solid constituents of animals. Bones 278 Teeth. Dentin. 279 Muscular Tissues Composition 280 Sapid constituents of flesh 281 To make strong soup. To boil meat 281 & 2 Extract of flesh 283 Relative values of meat 283 Salting of meat 283 Components of the brain 284 Cerebric acid, Oleophosphoric acid 285 Glands & their juices 286 Digestive fluids Saliva, Ptyalin, Froth, Tartar 287 Functions of saliva 289 Pancreatic fluid 290 Gastric juice, Pepsin. 291 Intestinal juice. Bile. 294 Excrement 296 Intestinal gases 297 Blood 298 Blood corpuscles. Lymph corpuscles 299 Composition of blood 300 Composition of blood corpuscles & liquor sanguinis 301 Hematin, Hematocrystallin 301 Gases in blood 302 Coagulum. Serum 303 Relation of dropsy to the quantity of albumen in serum 304 Chyle 305 Lymph 306 Fluids of generation & developement. 307 Milk 308 Urine 310 Urea 312 Uric acid 314 Hippuric acid 315 Extractive matter, what it is. 315 Mineral ingredients 316 Abnormal ingredients 318 Urine of animals 320 Urinary sediments 321 Urinary calculi 324 Respiration 325 Difference in volume between air inspired & expired 326 Cause of difference in colour between venous & arterial blood 326 N1 NH3 & CO2 in air expired 327 Effects of air richer or poorer in O than usual on respiration 329 Effect of air containing CO2 on respiration. Cause of CO2 acting as a poison 330 Differences in the expiration of CO2 331 Effect of fasting on the quantity of CO2 332 Influence of sex & age 332 Effect of exercise. Influence of food 333 Respiratory equivalents 333 Exciters & nonexciters of respiration 334 Cause of sleep 335 Sleep of hybernating animals 336 Conditions in wh we are most prone to sleep 337 Respiration of the lower animals 337 Origin of the co2 338 General conclusions 339 Animal nutrition 340 Classes of food. Flesh formers & heat givers 341 Flesh formers 342 Use of gelatine 344 Non-nitrogenous substances or heat givers 345 Varying quantity of respiratory food. 347 Formation of fat. 350 Use of fat to hybernating animals 351 Proportion between flesh formers & heat givers in various foods 352 Mineral matter in food 353 Amount of several kinds of food required. Manner of finding uses 354 Pauper & prison diets 357 Action of alcoholic beverages 360 Cost of 1 oz of alcohol in different beverages 360 Relation between character of men & their food 361 Balance between animal & vegetable life 362 Functions of animals 365 Mutual relation of plants & animals 367 [illegible] 13 1 Organic Chemistry Table of the most of important bodies capable of being formed from their elements without vital agency. Cyanogen (C2 N)=Cy Hydrocyanic acid CyH. Ferrocyanide of Fe2 Cy6 Potassium 4k+6HO. Ferricyanide of K. Fe2 Cy6 3K. Urea NH3 CyO } Ho } Marsh gas C2 H4 Oxalic acid C2 O3 HO } C2 O3 HO } Formic acid C2 HO3 } HO } Chloroform C2 H Cl3 Acetic acid C4 H3 O3 } HO } Alcohol C4 H5 O } HO } 2 Ether C4 H5 O } C4 H5 O } Olefiant gas C4 H4 Acetic Ether C4 H5 O } C4 H3 O3 } Oil of garlic C6 H5 S } C6 H5 S } Oil of mustard C6 H5 S } Cy S } Glycerine C6 H8 O6 Butyric acid C8 H7 O3 } HO } Oil of pine apples C4 H5 O } C8 H7 O3 } Oil of pears C10 H11 O } C4 H3 O } Oil of apples C10 H11 O } C10 H9 O3 } Valerianic acid C10 H9 O3 } HO } Grape sugar C12 H12 O12 Lactic acid C12 H12 O12 3 Caproic acid C12 H11 O3 } HO } Benzole C12 H6 Nitrobenzol C12 H5 NO4 C12 H5 O } HO } Picric acid C12 H2 (NO4)3 O } HO } Salicylate of methyl C14 H5 O5 } Oil of Wintergreen C2 H3 O } Naphth C20 H8 4 Organic chemistry is that part of the science wh relates to living bodies. Organic substances are either those with build up living bodies or are produced by living bodies or by submitting these products to different processes in the laboratory. If you compare alcohol an organic base with KO an inorganic base you perceive a great difference between them. Place alcohol in contact with an acid & it does not combine with it while KO does forming a salt. If you add chloroform an organic substance rich in Cl to acetate of Pb you get no precipitate of Pb.Cl. while if you add NaCl an inorganic substance containing Cl. you get a precipitate 5 precipitate If you take a solution of a salt & try reactions with it to-day & then try the same reactions with it to-morrow you will get the same result. If you can do this with an organic compound you may very probably get a different result. If you break up an organic compound you get C, O, H, & N but if you put these together in a flask you cannot make them combine. If you place Na, O & P together you will get NaOPO5 Place C, H & O together & you will not get an organic body. It was supposed at the beginning of the century that there were two different sciences. 6 It was sought to give a definition & in order to do this it was sought whether there was not some element common to organic chemistry & peculiar to it. It was proposed to call it the chemistry of carbon. But CO2, cyanogen & cyanide of K can be made without vital agency. There are bodies not organic wh contain carbon. Liebig defined it as the chemistry of compound radicals you deal in it, not with elements but with little systems. We have however as much right to consider SO2 as a compound 7 compound radical as many of the organic. The last definition was, In organic chemistry combination is ternary or quaternary in inorganic chemistry it is binary. A chemical definition could not be got. It was shown that many products of vital action could be obtained in the laboratory Wöhler made urea & acetic acid artificially. Any alcohol, can be made from a lower one by making a cyanide of an alcohol radical & from this a compound ammonium by acting on it by nascent H The alcohol can be made from this. 8 We see then that the laws of transformation are the same & why then is it necessary to break up the science? The division is empirical. The compounds of C have been farther investigated than the compounds of any other element. These compounds of C occur in living beings & for this reason we call it organic chemistry. The compounds of C are particularly complex. It is important to distinguish between empirical or rational formulæ. The empirical formula is merely the translation of the analysis. Some chemists believe that the rational formula expresses the mode in wh the atoms 9 are arranged. The chemists who hold this doctrine seldom come to an agreement regarding the rational formula of a body. The empirical formula is a fact, the rational is a conjecture. When two chemists were arguing about the formula, it resolved itself into an enumeration of what could be got from the body ; & when one chemist was hard pressed he said "although you show that a certain body" can be taken from this body you cannot show that it exists in the body. Gerhardt proposed that you should make the formula indicate the transformations wh a body could undergo. 10 Thus alcohol C4 H5 } O2 H } Meaning that H & O could be replaced by other substances & that ethers could be got from it in wh C4 H5 exists. The importance of rational formulae is apparent when we consider isomeric bodies Acetate of methyl C4 H3 O2 } O2 = C6 H6 O4 C2 H3 } Formiate of ethyl C2 HO2 } O2 = C6 H6 O4 C4 H5 } These bodies have the same empirical formula but different properties. In organic chemistry the notion of homologous series is important. A homologous series is a series of bodies differing from one 11 another by n times C2 H2. The members represent one another in function, if you apply the same reagents you get the same result. C4 H6 O2 act on it by C4 H5 I C6 H8 O2 C6 H7 I C10 H12 O2 C10 H11 I Heterologous Class. If you compare the bodies you derive from common alcohol you get bodies said to be heterologous. Alcohol C4 H6 O2 C6 H8 O2 Ether C4 H5 O C6 H7 O Aldehyd C4 H4 O2 C6 H6 O2 In the horizontal line the bodies are heterologous & in the vertical lines homologous The boiling pt of alcohol uses 19 degrees Centigrade for every addition of C2 H2. 12 The qualitative examination of organic bodies is peculiar. Examination of bodies for C. When you heat a body rich in C decomposition takes place CO2 being given off & some residual C deposited Organic bodies when heated, as a rule deposit C. Heat sugar in a tube Organic matter when heated either deposits carbonaceous matter or gives off a peculiar smell due to empyreumatic oils. This is the test for C. We seldom test for it. Organic bodies frequently contain N. the testing for which is very important. When a body containing N is burned a peculiar smell is given off. Burns a feather. 13 When a body containing N is heated to redness with a mixture of soda & lime called soda-lime NH3 on a compound NH4 is given off. Another method. When you heat an organic body to redness with Na. you can get the N transformed into Cy or NaCy. Dissolve the residue in HO & add a mixture of per & proto salts of Fe & HCl, if N be present you get prussian blue. The detection of Br. S. & c in organic bodies is attended with difficulty. When organic bodies contain Cl & the like the properties of the Cl are masked & you must heat to redness or with some strongly oxidizing body. Cause the organic body to come 14 into contact with red hot NaOCO2 the Cl combines with the Na & you get Na Cl from which you may calculate the Cl. In place of heating to redness you may heat it to 150°C with strong No5. If you seal up an organic body containing Cl with NO5 & Ag O No5. you get the Cl as AgCl. Detection of S. Not to miss the S you must effect complete destruction of the body. 15 Quantitative Analysis. When organic bodies are heated to redness with great excess of O all the C becomes CO2 & all the H becomes HO. This is universally true. Organic analysis is founded on this fact As certain how much CO2 & HO a given weight of the substance will yield. Several methods may be employed. Bring the body into contact with red hot Cu O. The apparatus consists of 2 parts the combustion & absorption parts. Previously to using the Cu O must be heated red hot since anything exposed to the air takes up dust wh is often organic. You may conveniently heat the Cuo in a Cu crucible. [illustration] The absorption part consists of a 16 Ca Cl Tube + KO bulls. The solution of the KO is made by dissolving 1 part of stick caustic KO in 2 1/2 parts HO. The connections must be light. To test this warm the bulbs so as to expel some air & if the liquid keeps its level afterward for 2 or 3 minutes the joints are tight. In place of CuO, PbO CrO3 is often used. It fuses at a red heat & buries the substance to be burned. Oils are burned by PbO CrO3 O must be passed thro' the tube at the end of the operation, either from a gas holder or from some KO Cl O5 in the tube. When a substance contains N a little alteration is necessary in this arrangement. When a body containing N is heated to redness with CuO, the 17 C Becomes CO2 & the Hi HO, the N appears partly as N & partly as NO2. The NO2 would interfere with the CO2. To remedy this you introduce clean Cu turnings NO2 when slowly passed over Cu turnings is decomposed. Cu turnings prevent NO2 from becoming NO. When a substance contains Cl it is essential to make the combustion with PbOCrO3. If it contains I you must place a long layer of Cu turnings in the front of the tube, these at a red heat absorb the I. To make combustion of liquids make a small glass bulb & seal one end [illustration], weigh it, fill it with liquid by warming it, seal it & weigh again. 18 The difference of the wts is the wt of the liquid taken up. You allow the liquid to distil very slowly over the CuO. When gas ceases to escape the operation is finished. Then pass o over it. Determination of N. Most organic bodies when heated to redness with a caustic alkali yield NH3, the HO of the caustic alkali being decomposed, the C taking the O & forming CO2 & the N taking H & forming NH3 thus– { CN } = NH3 { C1/2 } { O H } { O H } CO2 = { O H } Will & Varrenhapp's method. [illustration] In this case you use a mixture of NaO + CaO for combustion The N is converted into NH3 & absorbed 19 by the HCl with wh the bulbs are filled If you were to operate on KoNo5 you would get no NH3 You would only get traces if you were working with indigo. Where the N is present in the oxidized or nitrous state you get no NH3. Mix a body with CuO, heat to redness, cause the products to pass over Cu turnings & collect the gas in a mercurial trough All the C is got as CO2 the H as HO & you measure the N. General formula of Olefines C2n H2n. Olefiant gas was described in the inorganic part of the course Olefiant gas or Ethylene C4 H4 atomic wt 28 S.G. 9784 20 When HOSO3 is heated with alcohol C4 H6 is produced. [illustration] Alcohol C4 H6 O2 C4 H6 O2 = C4 H6 & H2 O2 taken by HOSO3 . C6 H4 is a colourless gas, has a faint smell, is poisonous, produces headache if much gets into the atmosphere, burns with a very luminous flame. It is contained in a small quantity in common illuminating gas. The name of the gas is got from the fact that when it brought into contact with Cl an oily liquid is formed. [illustration] B is a gas holder containing C4 H4 & C a bottle containing Cl. Pass the C46H4 into C & an oily liquid is seen on the sides C4 H4 readily unites with Br [illustration] 21 C is a glass stopcock fitting tightly into the mouth of the vessel B, into wh some Br is put, C4 H4 is then passed thru it & B is gently heated, & afterwards the liquid formed is poured out of B The Brome liquid is not miscible with HO. C6 H4 takes up 2 equivalents of Cl, Br or I forming Dutch liquid C4 H4 Cl2 C6 H4 Br2 C6 H6 I2 C6 H4 unites with hydracids C4 H4 + HCl = C4 H4 Chloride of ethyl C4 H4 + HBr = Bromide C4 H4 + HI = Iodide C4 H4 unites with HOSO3 C4 H4 HOSO3 sulphurinic acid. HOSO3 These reactions require time To get the reaction with HOSO3 22 Seal up C4 H4 with HOSO3 & Hg & shake up. Berthelot the discoverer of the process shook it 5000 times. If Cl be made to act on C4 H4 Cl2 substitution products are obtained. Act in the sunshine on C4 H4 Cl2. by Cl & you may get C4 Cl4 Cl2. Dutch liquid is not attacked by aqueous caustic KO but when digested for some time with an alcoholic solution of KO it yields C4 H3 Cl + HCl wh the alcohol takes away. Monochloride of ethylene is acted on by Cl yielding C4 H3 Cl, Cl2 . If you act on this by a solution of caustic KO in alcohol you get C4 H3 Cl2 + H CL. 23 Ethylene C4 H6 C4 H3 Cl2 C4 H2 Cl2 C4 H Cl3 C4 Cl4 C4 H4 Cl2 C4 H3 Cl Cl2 C4 H2 Cl2 Cl2 C4 H Cl3 Cl2 C4 Cl4 Cl2 A similar set of reactions can be got with every [oliferic] Propylene. C6 H6 A gas having a very disagreeable smell, very noxious C6 H5 I + 2Hg + HCl = C6 H6 + HgI + HgCl C6 H6 exists in many mixtures it represents C4 H4 exactly. It combines with Br I & hydracids With HCl it forms chloride of propyl. HI - iodide HoSo3 Butylene C8 H8. 24 C8 H8 occurs in small quantity in coral gas, it is colourless. slightly soluble in HO, soluble in alcohol, combines with Br & I. Amylene C10 H10. A A colourless liquid, boils at a temp. very little above the ordinary one of the atmosphere has a disagreeable smell, very volatile. Distil potato spirit with Zn Cl Potato spirit = C10 H12 O2 C10 H12 O2 + Zn Cl = C10 H10 It is a liquid heavier than HO. Readily combines with Cl & Br producing much heat. [illustration] Pours some Br from a pipette into some C10 H10 in a flask. Violent action takes place. Combines with hydracids. With H CL it forms chloride of amyl. 25 Unites with NO4 forming a beautiful crystalline compound. C10 H10 (NO4)2 The higher olifines are very little known Hexylene C12 H12 Distil oleic acid. May be got pure from mannite It is a colourless liquid boils at 60°C . resembles amylene. Unites with Cl violently with Br. C14 H14 Caprylene C16 H16 Elaene C18 H18 Paramylene C20 H20 Cetylene C32 H32 got from spermaceti The composition of olifines above C12 H12 is little known 26 Marsh gas C2 H4 = 16.S.G.5596 Marsh gas is derived from C2 H2 by adding 2 equivalents. Add H2 to any olifine & you get corresponding member of the marsh gas family C2 H4 occurs native, bubbles up in marshy places, exists in considerable quantity in coal mines, & in common gas Prep. Heat acetate of KO with HO KO Acetate of KO = C2 O2 C2 H3 K/O2 HOKO=H/K/O2 C2 O2 C2 H3 K/O2 + H K / O2 = C2 O2 K K/O4 + H C2 H3 Marsh gas = hydride of ethyl Zinc ethyl is a colourless liquid of enimense energy, as great as that of K. It unites with great energy with Ho. ZN C2 H3 + Ho = ZnO + C2 H3 H. 27 [illustration] Break the end off a small bulb of Zn methyl under HO. You may collect & measure the gas produced. Break the end of a glass bulb & the liquid will take fire depositing ZnO & metallic Zn C2 H4 burns without much smoke, it is inert, Br does not act on it Expose C2 H4 + CL to sunlight & you get action Members of the olifine family may be absorbed by fuming HOSO3. You may make this by adding anhydrous SO3 to HOSO3 There are not many members of the marsh gas family well known. C2 H4 Marsh gas C4 H6 hydride of Ethyl. C6 H8 } exist but not C8 H10 } well examined 28 C10 H12 hydride of amyl C12 H16 - hexyl. Hydride of Ethyl atomic wt 30 S.G. Place Zn Ethyl in HO. Take propionate of KO + HOKO heat together & you get hydride of ethyl. It is a colourless gas. It closely resembles hydride of methyl in its properties Hydride of Amyl. Boils at about 30°c, has a smell like chloroform [illustration] Iodide of amyl Zn + HO are sealed up in a table & heated in the water bath for some time Zn amyl forms first & then acts on the HO. It is very light, the lightest liquid known, has a pleasant smell. 29 Hydride of Hexyl C6 H14 May be got from mannite Colourless, very light boils at 60°C. It is very probable that it is the H representative of the sugar family. Very little certain is known of the higher families Family of alcohol radicals. Methyl C2 H3 C2 H3 Ethyl C4 H5 Propyl Butyl Amyl C10 H11 C10 H11 Amyl boils at a very high temp. is a colourless mobile liquid with a peculiar smell 30 When an iodide of an alcohol radical is heated strongly with Zn you get Zn I & the radical. C4 H5 } I } C4 H5 } I } + Zn2 = Zn } I } Zn } I } + C4 H5 C4 H5 Alcohol radicals may be got from fatty acids If you electrolyse acetic acid you get CO2 & methyl. Acetic acid = C2 O2 C2 H3 } H } O2 C2 O2 C2 H3 } H } O2 + O = C2 O2 O2 + HO + C2 H3 Take any other fatty acid of the series & you get an alcohol radical having C2 less than the acid is an extremely indifferent body The alcohols have not yet been 31 got from alcohol radicals Example of organic analysis Analysis of mannite. .3532 grams mannite gave .5069 - CO2 diff. of wt of KO bulb .2505 - HO - of CaCl tube Since 22 grams of CO2 contain 6C you multiply the co2 by 3 & divide by 11. .5069 x 3 = 1.5207 ÷ 11 = .1382 C To find the H divide the HO by 9 .2505 ÷ 9 = .0277 .3512 : .1382 :: 100 : 39.13 Percentage of C .3512 : .0277 :: 100 : 7.8 - H The diff between the wts of C + H & of the mannite is 0. 39.1C ÷ 6 = 6.5C = 65 7.8H ÷ 1 = 7.8H = 78 53.1O ÷ 8 = 6.60 = 66 100. To find the formula divide the percentage by the equivalents 32 of the bodies. The percentage of C should not be 2/10 ° below the theoretical quantity of the percentage of H 1/10 above it. Transformation of organic compounds by different ferments. Diatase Starch { C12 H10 O10 + 4HO = Grape sugar { C12 H14 O14 2 yeast Grape sugar { C12 H14 O14 = alcohol { 2C4 H6 O2 + 4CO2 + 2HO 3 Casein Milk sugar { C24 H24 O24 = Lactic acid { 2(C12 H10 O10, 2HO) Lactic acid { C12 H12 O12 = Butyric acid { C8 H8 O4 + 4CO2 + 4H 33 4 Synaptase Amygdalin { C40 H27 NO22 = Hydrocyanic acid { HC2 N + Oil of bitter almonds { 2C14 H6 O2 + Formic acid 2C2 H4 O6+3HO + Grape sugar { C12 H14 O14 /2 Salicin C26 H18 O14 + 4HO = Salicenin { C14 HO + Grape sugar We have considered the olifines the homologues of marsh gas & the alcohol radicals. We can reduce nearly all the others to the olifines Methyline C2 H2 supposed to exist in wood spirit, not known in a separate state. Ethylene C4 H4 Propylene C6 H6 Butylene C8 H8 Amylene C10 H10 These are distinctly radicals in themselves they unite 34 with Cl. They are biatomic. This is expressed by two dots thus C6 H6,, They unite with 2 atoms Cl, Br &c. Homologous of marsh gas These are olifines having their biatomicity gratified by 2 atoms, H. C2 H4 C4 H6 &c There are some instances where the biatomicity is not fully gratified having only 1 atom of H & 1 atom to be filled up by something else. These are the alcohol radicals. C2 H2 , H = C2 H3 methyl C4 H4 , H = C4 H5 ethyl C6 H6 , H = C6 H7 propyl C8 H8 , H = C8 H9 butyl C10 H10 , H = C10 H11 amyl. These are olifines stepping towards 35 the gratification of their biatomicity Suppose you add 1 atom Cl to C2 H3 you get chloride of methyl C2 H3 Cl or to C4 H5 you get chloride of ethyl C4 H4 HCl = C4 H5 Cl Suppose instead of Cl you substitute O, thus, C4 H6 HO You get ethers, of wh common ether is the type General formula of ethers Cn Hn HO corresponding to marsh gas Cn Hn HH. A radical is merely a body wh moves about Act on PbO by HCl. PbO + HCl = PbCl + H O. What is the radical ? The body you can move about viz., Pb. In the same way C4 H4 H O + H Cl = C4 H5 CL + HO. Instead of C4 H4 H you write 36 C4 H5. the radical because you move it about. What are the ethers wood spirit n methylic common propylic butylic amylic Methylic ether C2 H3 O = 23. Or when free it is doubled, as instead of C4 H5 to get a four volume formula you have C8 H10 (C4 H4 ) H this is lob sided having H on one pole & not on the other H (C4 H4) (C4 H4) H When doubled it is symmetrical. Why does ether double itself. O(C4 H4) H. The symmetry is not quite complete, tho' it is thus when in combination H O H (C4 H4) (C4 H4) H H O When free it doubles its combining vol. 37 wh is 2 Methylic ether vap. density Prep. Heat wood spirit with 4 parts HOSO3 & pass thro HOKO. It is a colourless etherial gas not condensible at 60°C, burn, with a pale blue flame, very soluble in HO to the extent of soluble in alcohol. Combines readily with HOSO3 & HCl. Act on KO by HCl. KO + HCl = KCl + HO. - C2 H3 O - C2 H3 O + HCl = C2 H3 Cl + HO. You may get chloride, iodide & bromide of methyl. Substitution products of Chloride of methyl, C2 H3 Cl. Chloroform. Two equivalents of H are substituted by Cl. (C2 H Cl2) Cl. The arbitrary formula is C2 H Cl3. 38 s.g of liquid chloroform 1.48 boils at 60.8°C Put 20 lbs Ca Cl in 120 lbs HO place in a Cu retort 1/3 full add 4 lbs alcohol. Heat quickly to 80°c & then withdraw the fire. You get 2 fluids the heavier is chloroform, wash with It is a colourless liquid, of an etherial sweet odour, sharp & sweetish taste. It is inflamed with difficulty. Place some on cotton wool it burns & gives off HCl. It falls thro' HO without dissolving. It is a good solvent of india rubber, P. Vinic ether, C4 H5 0 combining formula. & C8 H10 O2 its free formula. 39 formula. s.g of liquid .03736 at 0°C & .0724 at 16°C or 257. Boils at 35.5°C or 957. Vap. den. 2.586 Prep. Act on common alcohol with HOSO3 [illustration] C4 H6 O2 common alcohol HO - C4 H5 O = ether. you may suppose alcohol to be the hydrate of ether. There have been many treatises on this reaction. The HOSO3 has an affinity for HO & takes it away. Seal up anhydrous MgOSO3 & alcohol in a tube, the MgOSO3 takes away the HO & you get ether. There is no difficulty 40 in this case. But in distilling alcohol & HOSO3 , the HOSO3 does not combine with the HO. In the receiver you get HO & ether equal in bulk to the alcohol. There are many like instances in catalyses. The HOSO3 takes the HO but the heat drives it off. There are other theories. One is that a body called sulphorinic acid is formed. first. There is reason to suppose that HOSO3 is S2 O6 = HO/ HO/ S2 O6 Ho | C4 H5 O | S2 O6 sulphorinic acid KO | C4 H5 O | S2 O6 sulphorinate of Ko. They say that the sulphorinic 41 sulphorinic acid is decomposed, Haloid compounds of ether. Hydrochloric ether, C4 H5 Cl Pass HCl thro' ether or better thro' alcohol, you get C4 H5 Cl, chloride of ethyl. S.g of liquid 0.874 boils at 11°C A colourless, very volatile liquid & has a penetrating etherial odour. Slightly soluble in HO, soluble in alcohol. Analogous to an oxide KO + HCl = KCl + HO C4 H5 O + HCl = C4 H5 Cl+ HO. Iodide of ethyl. C4 H5 I. s.g boils at 72°C Colourless of an etherial smell. Much used to get radicals Act on hydrochloric ether by Cl & you get chlorinated ether. Act on it with Cl in sunlight 42 sunlight & you get Dichlorinated ether. Act with Cl by sunlight & heat & you get Trichlorinated ether. Ethers as a class. They represent the protoxides of metals Ko when free is probably not KO but KKO2 or K2 02. Ether when separate is not C4 H4 O but C8 H10 O2. Two atoms of radical united with 2 of O. What happens to KO when it is hydrated? KH/O2 = KO1 HO. one atom k going out & one of H going in. Take 1 atom of radical from ether & add 1 of H. (C4 H5) O2 alcohol is one of the H radicals of the double 43 ether taken out & 1 atom H put in its place. That the ethers are really duplicated in their separate state follows from the fact that you are able to substi- tute one radical by another C4 H5 } C4 H5 } O2 C4 H5 } C2 H3 } O2 C2 H3 } C2 H3 } O2 C2 H3 } C4 H5 } O2 When not in a free state they halve themselves & unite with a base. KO + NO5 = KONO5 C4 H5 O + NO5 = C4 H5 O NO5 you can form a whole set of ethers. The ethers are to be considered as the protoxides of the metals & the alcohols as the 44 hydrates of the protoxides KO (C4 H5 O) HO KO. (C4 H5 O) HO. Alcohols = 4 vols. S.G liquid vap. Boiling point Wood spirit C2 H4 O2 0.798 1.12 150° Spirit of wine C4 H6 O2 0.796 1.61 173 Propylic alcohol C6 H8 O2 - 2.02 206 Butylic C8 H10 O2 0.803 2.59 233 Amylic C10 H12 02 0.818 3.14 270 Caproic C12 H16 O2 0.830 3.53 304 Caprylic C16 H18 02 0.820 4.5 356 Lauric C24 H26 O2 Cetylic C32 H34 O2 Cerylic C54 H56 O2 Melissic C60 H62 O2 Aldehydes. Formic aldehyd Acetic Propionic Butyric 45 Valerianic aldehyd Caproic Oenauthylic Capric Euodic Ethers form a homologous series corresponding to the alcohols. The general formula of an alcohol is that of an ether + 1HO Ether = Cn Hn,, Ho1 + HO = Cn Hn an alcohol. The alcohols belong to a different class from the ethers, as a hydrate does not represent a protoxide but a peroxide. O | O | K2 O | O | (CnHn)2 | O | | O | K O | HO | K O | HO | C4 H5 O | NO5 | K O | NO5 | C4 H5 Alcohol is a hydrate of ether & is a salt. 46 Wood spirit on methylic alcohol C2 H6 O2 = O| HO | C2 H3. equals 32. s.g of liquid 0.818 at 32°, at 65° 0.798 vap. density 1.12 boils at 150° F Prep Distil wood, acetic acid & wood spirit are given off it is purified by lime & distilled from Ca Cl. When pure, it is colourless has the odour of acetic ether is a good solvent for resins when oxidized it forms formic acid. Vinic alcohol or spirit of wine. C4 H6 O2. O| HO| C4 H5 = 46. s.g when free at 60° is 0.794 vap. den. 1.613 boils at 173°F or 78°C. Alcohol has been made synthetically. We believe it contains C4 H4 47 add 2 atoms HO & you alcohol. C4 H4 " H2 O2 - C4 H6 O2 Pass C4 H4 into HOSO3 add HO & distil, alcohol comes over. [illustration] Prep. Distil from fermented add KOCO2 wh has been heated & the KOCO2 takes the HO & falls to the bottom. you distil again from Ca Cl or dried CuO. It is a colourless, volatile mobile liquid of an aromatic smell & burning taste It has a strong affinity for HO, & the mixture contracts. burns without smoke. It has never been solidified by cold, at -166° F it becomes viscid, is a good solvent for Br, I, S, Na & bodies containing H. In using it as a fuel it is 48 completely burnt. C4 H6 O2 + 120 = 4CO2 + 6HO. It unites with salts as HO does & forms alcoates instead of hydrates. Wines & spirits. Proof spirit 50.76 P.C. alcohol & 49.74 HO [illustration] Proof used to be -set some gunpowder on a tile pour spirit over it. & set the spirit on fire. If the spirit be above proof the gunpowder should go off when the spirit is burned. if under proof the HO it contains wets the powder so that it does not go off. Distilled spirits. Brandy contains 55 P.C. alcohol in its ordinary state it is coloured with burnt sugar 49 & peach kernels are added during distillation to flavour it. gin is got from fermented grain & flavoured by juniper berries. Whisky is distilled from grain & has a slightly smoky taste. Rum is got from sugar Arrack from fermented rice betel nuts or palm juice Potato brandy is get by converting potato starch into glucose & distilling it. Wines are the fermented fluid without distilling. When all the sugar is converted into alcohol they are called dry. when much sugar remains they are called fruity. The bouquet is due 1st,, to the completion or 50 non completion of these actions 2nd to the deposition of cream of tartar 3d to the formation of fragrant ethers by the action of vegetable acids on the strength of wines Port or Madeira 15-20 P.C alcohol Sherry 15-17 Lisbon 16 Malmsey 13 Champagne 12 French clarets 9-10 Rhenish wines 10-12 Cider 4-8 Perry 6-8 Ale 6-8 Porter 5 Small beer 1 1/2 The market value of wines depends on their flavour 51 One imperial pint of the following wines contains HO oz alcohol oz sugar grs Tartaric acid grs. Port 16 4 1-2 80 Brown sherry 4 1/2 360 90 Claret 2 none 161 Burgundy 12 1/2 2 1/2 160 Fermentation It is the process by wh sugar is converted into alcohol. Grape sugar in honey C12 H12 O12 Act by yeast = 4Co2 + 2(C4 H6 O2) Yeast does not appear in the final product Conditions for fermentation The temperature must be 50°-60° F HO must be present to keep the sugar in solution Air must be present to make the yeast live & effect the transformation Nitrogenized substances 52 must be present & a body capable of fermenting. There is spontaneous fermentation as in crushed grapes the air acts on the nitrogenous matter in the cells. When we add a ferment to sugar, & the ferment disappears or forms a heavy substance wh falls to bottom. The yeast is a vegetable growing body, & consists of cells wh when placed in a warm saccharine fluid increase, one cell giving off many others, about 1/250th of an inch in diameter. They finally cease to produce gas. 53 Composition Before fermentation after C 47.71 p.c 48.31 H 6.7 7.33 N 10.15 5.07 O 35.44 39.29 SoP Traces Traces. The N is only one half of what it was when the operation commenced. When yeast is active it is acid if you add an alkali to it, it stops its action & the fermentation. Weak acids favour fermentation, strong acids destroy it. Some poisons destroy it others do not. Theory of action of ferments Liebig's view is that the ferment is in a state of internal change & that it communicates this change to the other body 54 wh is in a state of statical equilibrium. Pasteur considers that it is an action not correlative with the death of the plant but with its life. He burnt yeast & added the ashes & an ammonia salt to sugar. The NH3 disappeared from the solution. The result of fermentation is complex. Glycerin & butylic acid are produced as well as alcohol & CO2. Suppose you put a piece of putrid cheese or casein into sugar, you get a different action & lactic acid is produced If the cheese is very putrid the lactic acid becomes butyric 55 acid. C12 H12 O12 The brewing of beer is a reproductive fermentation A certain quantity of yeast is added to the fermenting liquid & grows so much that much more yeast is obtained. Malting is the germination of barley. When the young sprout is about 1/2 inch in length & begins to bifurcate, its life is destroyed by roasting. The barley in malting contains diastase. Diastase can convert starch into dextrin, it then changes the dextrin into grape sugar. One part diastase can convert 4000 parts of starch into sugar malt contains 1/500th of its weight of diastase, so there is enough 56 diastase left to An infusion of the malt is made & 4 or 5 parts of fresh barley added It converts the barley into sugar you then add say 1 part yeast wh produces 2 parts of alcohol 4CO2 + 2HO In the barley there is gluten a body of the same composition as the muscle of our bodies. The yeast acts on the gluten & it receives so much food from the gluten that it grows with great rapidity & produces much new yeast. Composition of 1 imperial pint HO oz ale oz sugar grs acetic acid grs London stout 18 1/2 1 1/2 281 54 - porter 19 1/4 3/4 267 45 pale ale 17 1/2 2 1/2 240 40 mild - 18 3/4 1 1/4 280 38 strong - 18 2 2.136 54 57 Homologues of the alcohols. Propylic alcohol. C6 H8 O2. Found in the product of the fermentation of grape skins. It is a colourless liquid with an agreeable fruity smell, lighter than HO. Prepared by synthesis from propylene. Propylene is passed into HOSO3 HO is added & it is distilled. Butylic alcohol C8 H10 O2 Found in small quantity in fusel oil. It is a colourless liquid, smelling like fusel oil & wine, soluble in HO but separates on the addition of salt. Amylic alcohol. C10 H12 O2 S.G of the liquid 0.818 vap. density 3.147 boils at 58 Has a higher boiling pt than the previous ones. Brandy contains a little fusel oil & whiskey a good deal. Test pour some of the spirit thought to contain it on your hand & allow it to evaporate you can then smell the fusel oil. It is though a colourless, mobile liquid, of a disagreeable odour burning taste, slightly soluble in HO, soluble in alcohol & ether when strong it is poisonous & produces a cough & spasm of the glottis Caproic alcohol. Formed in the fermentation of grape skins, Refracts light strongly: insoluble in HO General properties of alcohols. The chemical reactions of alcohols 59 alcohols are nearly all the same. If we act on them by acids you get ethers. C4 H5 O HO + NO5 = C4 H5 O NO5 + HO KO HO + NO5 = KONO5 + HO. The compound ethers are on the same type as alcohols, but acids replacing the HO. Boiling pts Vinic alcohol 78°C } difference Propylic 96C } 18°C Butylic 112° } 16°C Amylic 132 } 20°C Caproic 150°} 18°C Compound ethers are derived from the alcohols, & are salts of the ethers, the HO of the alcohol being replaced by acid. Sulphuric ether, not that of shops wh is common ether but that of chemists C4 H5 OSO3 Prep. Act on ether by anhydrous 60 anhydrous SO3 in the cold, Colourless, aromatic liquid not miscible with HO. Nitric ether. C6 H5 ONO5. Used in pharmacy. S.G of liquid 1.11 boils at 85°C. Distil HONO5 with alcohol & a little urea. When pure it is a colourless aromatic liquid, with a faint smell of apples, explodes when quickly heated. Nitrous ether C4 H5 ONO3 s.g of liq boils at 16.4°C Distil spirit of wine with HONO5 It is yellow, inflammible insoluble in HO soluble in alcohol. Decomposed in heating with the evolution of N. Even the feeble acids have 61 been made to unite with ether. C4 H5 O CO2 C4 H5 O Sc O2 a proposition was made for covering the houses of Parliament with a coating of silica by means of C4 H5 OSiO2. Sulphovenates, are salts of ether in wh one of the equivalents of HO in HOSO3 viewed as a bibasic acid is replaced by ether. HO | HO | S2 O6 HO | C4 H5 O | S2 O6 add KO KO | C4 H5 O | S2 O6 Sulphovenate of Ko It is not HOSO3 alone wh acts in this way, PO5 does it also HO | HO | HO | PO5 HO | HO | C4 H5 O | PO5 Phosphovenic acid As every ether has its alcohol & every alcohol can form a compound ether you might 62 go on in the series but when you know the properties of one in a series the others much resemble it. Nitrite of amyl. It is amylic alcohol with HO displaced & NO3 added C10 H11 O HO C10 H11 O NO3 It has properties the very reverse of chloroform. It increases the action of the heart, & produces acute headache. In cases of long suspended syncope it might be useful. Biatomic ethers & alcohols. An ether is monoatomic when it unites with 1 atom acid or with of HO to form alcohol. C4 H4 " HH. marsh gas. C4 H4 ClCl C4 H4 HO ether. 63 C4 H4 O O Cn Hn" O O biatomic ether Cn Hn OO + 2HO - alcohol Why should those be biatomic? KOHO it has one of O in the base KONO5 Sn O2, 2HO it has 2 of O in the base Sn O2, 2NO5 The same with biatomic alcohol. Ethylene ether C4 H4 O2 corresponding to dutch liquid Has been imperfectly studied. 2b hydrate or ethylene alcohol C4 H4 O2 + 2HO generally called glycol is better known. Empirical formula C4 H6 O4 Obtained by the action of HOKO on acetate of ethylene. C4 H4 O2, 2C4 H3 O3 + 2KO HO = 2(KOC4 H3 O3) + C4 H4 O2 + 2HO. A clear thick sweet liquid 15 64 Soluble in HO & alcohol, the vapour burn & is converted into acid by oxidation. Acetate of ethylene. Act on Bromide of ethylene a dutch liquid by acetate of KO. C4 H4 I2 + 2KOC4 H3 O3 = 2 KI + C4 H4 O2, 2C4 H3 O3 Acetic ether is a colourless liquid, at a high temp. it smells feebly of acetic acid. We can produce the homologues of glycol thro the whole series. C4 H4 HO common ether C6 H6 OO biatomic - . C4 H4 HO + HO common alcohol. C4 H4 OO + 2HO biatomic - Cn Hn HO + HO common Cn Hn OO + 2HO biatomic Cn Hn OO, 2HO Cn Hn OO, 2A C6 H6 OO 2(C4 H3 O3) binacetate of ether of olifine 65 Every homologous olifine has an ether & alcohol belonging to it. We now consider a stepping stone between the alcohols & acids, the aldehydes. Alcohol Aldehyde Acids of alcohols. Cn Hn + 1. +1 means that there is 1 atom of H more than the number of C. alcohol Cn Hn +1 O, HO = HO + ether General way of forming aldehydes from alcohols. Cn Hn +1 HO - 2H = aldehyde. It is simply by oxidation that you do this. [illustration] Put a heated Pt wire into a glass in wh is a little ether. Aldehyde vapours form round the Pt. You are forcing the H to combine with the O by the action 66 of the Pt. [illustration] Distil alcohol, HOSO3 & Mn O2 in a capacious retort & aldehyde is produced. Add 2 atoms of H to an aldehyde & you get an alcohol. Vinic or acetic aldehyde C4 H6 O2. s.g of liq 0.79. vapour density 1.53 4 volume formula boils at 21°C. Distil in a capacious retort 6 parts HOSO3, 4 alcohol of 85 P.C.. 4HOO 6 MnO2. The loss is considerable. you get a colourless liquid of an irritating pungent odour, burns with a white flame, with alkaline bisulphides it forms a white solid compounds. It is singularly unstable, if you seal it up in a tube it changes after a time to porcelain 67 like substance, it is then probably C12 H12 O6 There are several of these varieties. General process to get aldehydes. Suppose you wish acetic aldehyde. Distil acetate of lime with one equivalent of formiate of lime acetic aldehyde. Ca O C4 H3 O3 + Ca O C2 HO3 = 2Ca O CO2 + C6 H4 O2 General view of the constitution of aldehydes There are several views. Gerhardt thinks they are constituted on the type of H. H = H } H } C4 H3 O2 } H } = acetic aldehyde. That one H is replaced by C4 H3 O2 a radical he calls acetyle. Liebig thinks that they are alcohols of unknown radicals 68 & that the radicals are negative or are Cn Hn -1 having 1 atom less H than C. C4 H3 O HO = aldehyde = hydrate of oxide of acetyle. He calls C4 H3 O acetyle. In our view we view aldehyde as the alcohols of oxidized olifines C4 H4 " HO common ether C4 H3 O, " HO aldehyde 1 H being replaced by O. Every alcohol has its ether - aldehyde - ketone. If you take the acid salt of any as Acetate of Pt + distil you get a tarry liquid wh when purified is a acetone the ketone of the ketone the aldehyde in wh 1 H is substituted by the alcohol radical below it in the series 69 C2 H3 methyl is the radical below C4 H5 ethyl in the series. C4 H5 O, HO substitute the H by methyl C4 H5 O (C2 H3) O. Ketone of the series. Acetone C6 H8 O2 = C4 H5 O2 C2 H3/ C6 H8 O2 Heat chloride of acetyle with Zn methyl. It is a clear colourless liquid of an etherial smell, soluble in HO but separates readily on the addition of salt, readily soluble in alcohol & ether. Absorbs H Cl readily & polymerizes Anhydrides or acids. When monoatomic alcohols homologous with methylic are fully oxidized they are changed into aldehydes & then into 70 acids. All the acids are derived from corresponding alcohols by oxidation It was long supposed that there was no anhydrous acid in the organic series. KOSO3 = KSO4 There is a great disposition among chemists to reduce to the binary type. They have got anhydrous acids mode. General reaction. By acting on a salt such as an acetate with a body wh is oxichloride of P, P Cl3 O2. Example. To get anhydrous acetic acid. Take acetate of KO. C4 H3 O3, HO, From chloride of P. you can get chloride of acetyle C4 H3 O2 Cl, = anhydrous acetic 71 acid in wh 1 of O is replaced by Cl. C4 H3 O3 KO + C4 H3 O2 Cl = 2(C4 H3 O3)+ KCl. Anhydrous acetic acid. Its formula is doubled C8 H6 O6 liquid s.g 1.073 vapour density 3.47 boils at 140°C. It is a colourless mobile, highly refracting liquid. It sinks thro HO like oil but gradually unites with it & forms vinegar All other anhydrous acids could be prepared. Hydrated acids Relation of these acids to alcohol & ether. Ether C4 H6 " HO Ethylene ether C4 H6 " OO - Alcohol or glyeds C4H4 OO HO HO Oxydized series Aldehyde C4 H3 O " HO Anhydride C4 H3 O " OO Acetic acid C4 H3 O OO/HO 72 Formic Acid. empirical formula C2 H2 O4 s.g of liquid 1.235 vapour density 1.554. Occurrence. Called formic acid because it occurs in the red ant Formica rufa: occurs in the stinging nettle urtica urens & in various animal secretions. Obtained by synthesis. By passing CO over HO KO KO HO + 2CO = KOC2 H3 O3. Distil starch with HOSO3 + MnO2 This is not the best way. Mix syrupy glycerine with oxalic acid & heat. It was formerly got by crushing & distilling ants. It forms many salts wh crystallize readily & form definite & permanent compounds. Acetic acid. HO C4 H3 O3 or C4 H4 O4 s.g of liquid 1.063 vapour density 73 2.08 boils at 119°C. Occurs as acetates in various vegetable juices in the perspiration of animals, in the juice of flesh Prepared by synthesis. By the action of CO2 on Zn methyl. C2 H3 Na + C2 O4 = Na C6 H3 O3. you get acetate of Na Commercially. Distil wood & you get pyroligneous acid & pyroxylic spirit. The ash, oak & beech are preferred. Add lime & you get acetate of lime, distil over & you get glacial acetic acid, it is so called because it becomes solid when exposed to cold. If you pass alcohol over spongy Pt in presence of air you get acetic acid Oxidize alcohol. A large cask is 74 taken, wh allows air to pass thro it, & filled with beech wood shavings & alcohol [illustration] poured over it, it is done two or three times & in its passage is oxidized to acetic acid. 1 part alcohol + 6 HO + 1/1000 th part of honey are taken. Relation between the alcohols aldehydes & ketones. alcohol C4 H4 H1 O1 HO double ether C4 H4 " H1 O1 (C2 H3)O Aldehyd C4 H3 O " H1 O. Acetone C4 H3 O " (C2 H3)O. is not a common alcohol in wh the H is replaced by the radical neat lower in the series it is the aldehyd in wh the H is replaced by the radical 1 below it in the series. Thus, Butyrone, C8 H7 O " (C6 H7)O. 75 16 [illustration] Prep of acetone C is a Cu retort in wh Acetic acid. C4 H4 O2 At 55° it is solid & crystalline melts at 62°, has a pungent peculiar smell, burning taste, acid taste, miscible with HO, ether & alcohol, it dissolves camphor & essential oils, the strongest acetic acid forms aromatic vinegar & is generally flavoured with essence of camphor or bergamot. It is used in medicine as a rubefacient, when too strong it blisters the skin. Most acetates are soluble. Vinegar is dilute acetic acid is is made from bad wine The temp necessary to produce oxidation is 70-80°F. Malt vinegar is now largely 76 used, it contains about 5 P.C of acetic acid. Acetic acid may be acted on by Cl & forms a very complete substitution acid. KO C4 H3 O3 acetate of KO. KO C4 Cl3 O3 chloracetate of KO. Acetates. Acetate of KO. KO C4 H3 O3 Prep. Dissolve KO CO2 in acetic acid Prep. Anhydrous. foliated, deliquescent. Acetate of NaO. NaOC6 H3 O3 + 6HO. Colourless transparent effloresent cooling taste. Acetate of ammonia. NH4 OC6 H3 O3. White crystalline easily solube decomposes when heated. distilled. Nh4 OC6 H3 O3 = 4HO + C4 H3 N = C2 H3 C2 N or cyanide of methyl. The cyanide of the radical below that from wh acid is derived. 77 another example propionate of ammonia. NH4 OC6 H5 O3 = 4HOC6 H5 N = C6 H5 C2 N NH4 OC2 H3 O3 is used in medicine as a refrigerent & to act on the kidneys Acetate of PG. PGOC4 H3 O3 + 3HO this is neutral acetate. Prep. Dissolve PGO in acetic acid & crystallize. It is often called sugar of PG. It crystallizes in transparent rhombic prisms, has a sweet taste, soluble in twice its wt of HO & alcohol, it is used as a lotion is poisonous. There are some subacetates. 3PbO, 1C4 H3 O3 6PbO 1 C4 H3 O3. Acetates of Cu. There are several. Neutral acetate 1 CuO 5 acetic acid 78 & 5HO. There are various insoluble subacetates. Verdigris. Expose sheets of Cu in alternate layers with fermented grape skins. The crust is scraped off & made into a paste with vinegar & made into moulds. Glycocol is connected with acetic acid. Occurs in the transformation of many animal substances in the decomposition of hippuric acid &c. It is crystalline sweet, fusible at 78°C soluble in HO & hydrated alcohol, insoluble in ether & absolute alcohol. It is a very weak acid acting partly as an acid & partly as a base. 79 It is acetic acid in wh 1 atom H ionical is substituted by amidoger NH2 . Acetic acid (C4 H2 HO)"OO Glycolic -- (C4 H2 OO)"OO Glycocol C4 H2 (NH2)O) OO NH3 thought to be (NH2) H hydride of amidogen Acids homologous to acetic acid Propionic acid. HOC6 H5 O3 liquid s.g 0.991 boils at 140°C Its synthesis has been effected by Na ethyl . C4 H5 Na + C2 O4 = NaOC6 H5 O3 proprionate of NaO. Butyric acid C8 H8 O4 = HOC8 H7 O3 liquid s.g 0.978 Occurs ready formed in certain fruits, in sourkrout. In the animal organism it is found sometimes in sweat, in gastric juice, in 80 certain diseases in wh the expectorations have a bad smell. In the bad smelling juices of certain animals. In the oxidation of casein & fibrin By fermenting sugar by poor cheese or curd in presence of chalk. you get butyrate of lime, lactate of lime is first formed. Add HCl & distil & you get butyric acid. It is a colourless liquid, with a very disgusting odour. Crystallized by intense cold. Slightly soluble in HO. Butyrates crystallize & have no disagreeable smell when dry, tho when wet the CO2 of the air liberates some 81 butyric acid & causes a smell. They have more the character of soaps than any salts we have yet dealt with. Butyrate of lime. It is much more soluble in than Butyric ether C4 H5 OC8 H7 O3. liquid s.g .901 boils at 119°C, a clear, mobile, liquid, & fragrant ether It occurs in the pineapple, melon strawberry & other fruits Some fragrant ethers are got from acids having an abominable smell A strong alcoholic solution of butyric ether is sold under the name of essence of pineapples, & more diluted as essence of strawberries. Amylic or valeric acid C10 H10 O6 = HO1 C10 H9 O3 82 liquid s.g 0.937 vapour density 3.66 boiling point 347° Occurs in valerian & angelica root, in putrid cheese in train & sperm oil Prep. Distil valerian root with HO. Or Distil fusel oil with HOSO3 + KO2CrO3 It is limpid, has an odour like cheese floats on HO. Forms valeriates wh are soapy substances. Fatty acids Rutic is the first true fatty acid or oil when melted. It occurs in the fat of goats. Palmitic acid C32 H32 O4 or Ho C32 H31 O3 Melts at 62°C. All the fats vegetable & animal are compound ethers, the ether they contain is that of Glycerin united with a fatty acid Palmitic acid in combination 83 with glycerin is in almost all fats especially human & pigs It is obtained by saponification Fat = Glycerin } Fatty acid } + KO = KO } fatty acid } = soap. Act on soap by alcohol & you get the acid in a free state. Prep. Tasteless white fat crystallizes in tufts insoluble in HO soluble in alcohol & ether. Palmitates are soaps insoluble when the bases are earths, soluble when they are fats. Stearic acid C36 H36 O4 melts at 69.2°C occurs in combination with glycerine in most fats, in all animal fats the richer the fat in stearic acid the harder it is. It is got from stearate of KO by HCl insoluble in HO. 84 When distilled it is converted into palmitic acid. Stearates of alkalis are soluble Neutral stearates are decomposed by HO into alkalis & Lamps were used before candles were introduced. Torches were the first candles & were probably used with lanterns. Pling alludes to candles wh were probably of wax. The only cheap candles in this country were the fats themselves. They had a low fusing point & ran & the wick did not burn away and required snuffing. [illustration] Palmers candlestick was meant to remedy this. The candle was kept at the level of the candlestick by a spiral spring & the 85 wick wh was double turned outwards so that the end was always exposed to the air & thus burned away. Improvements in candles. It was discovered that tallow consisted of stearine & oleine & that by heating tallow to the fusing pt of oleine but not to that of stearine the oleine might be pressed out & stearine left. Tallow melts at 102° Stearine 144 Stearic acid 15° Candles of stearic acid would thus be better than those of stearine The stearine was saponified & the soap acted on by HCl. There were many objections to the use of stearic acid candles The wick got clogged up. This was found to be owing to the wick 86 leaving alkaline ashes & forming a soap with the stearic acid This was remedied by dipping the wick in HOSO3. C6 H5 O3"' Glycerine ether (C6 H5 O3"') 3HO Glycerine (C6 H5 O3"') 3A A fat. Tallow is a mixture of fats, as, oleine. palmitine & stearine glycerine itself is not combustible. In the stearic acid candles, the oleine & glycerine are both removed. Stearic acid candles so called, are generally palmitic acid & are got from palm oil. The improvements in candle making depend chiefly on Chevreuls researches on fats. Saponification. The fat is boiled with lime, & HOSO3 added. 87 to the lime salt of the fatty acid thus obtained. the acid is then got in free state (C6 H5 O3"') 3a + CaO = lime salt 3HO = glycerine 3SO3 Another difficulty in the use of stearic acid candles is that it has a tendency to crystallize. The crystalline flakes often broke off the candles. By putting a little arsenic into the acid the crystallization was stopped, but fumes of as were given off while the candle was burning & hurt the health of those who used it. This nearly put a stop to the manufacture but after some time it was found that a small percentage of wax served the same purpose as the As. The saponification was next 58 effected by HOSO3 instead of lime. Mix the fat with HOSO3 & heat by blowing steam thro' them C6 H5 O3"' 3A + 6HOSO3 = C6 H5 O3"', 3SO3 + 3A,3S03. Pass superheated steam at about 600° thro' the fat. it splits it up into the acid & the ether. C6 H5 O3"' | 3A. The glycerin & acid both distil, separately. Candles from Coal. Coal when distilled produces various gases. among others olefiant gas C4 H4 & other higher homologues. C8 H8 C10 H10 Cn Hn 89 If you distil at a low temperature Cn Hn comes over chiefly in a solid state. if at a higer temp. you get liquid products; & higer still gaseous products Boghead coal is distilled at as low a temp. as possible & an oil comes over. wh. is called paraffin because it possesses almost no affinities This when cooled from 40° to 32° deposits solid paraffine. In 1852 L. Playfair thought that paraffine could be got from the oil, but the maker of the oil would not try it, so Playfair obtained a quantity from him & by experimenting succeeded in getting it. Paraffine contains the conditions of illumination in the highest degree. The illuminant in coal gas is C4 H4 & its homologues 90 Paraffine is C4 H4 in a condensed state. All the paraffine is burned. It is not fat wh burns in a candle it is gas. The pores of the carbonized part of the wick act as so many retorts. Acids heterologous Melissic HOC62 H59 O3 Cerotic HOC34 H53 O3 Arachidic Stearic Palmitic Myristic Lauric Rutic Pelargonic Caprylic Ænanpylic Caproic Valeric 91 Butyric Propionic Acetic Formic Acids produced from biatomic alcohols. C4 H4 " HOHO monoatomic alcohol. C4 H4 "OO2HO bi -. In examining the oxidation of monoatomic alcohols we found that aldehydes were first produced & then acids.. C4 H4 "HO C4 H4 O"HO C4 H3 O"OO. Products of the oxidation of Glycol. We find two acids result. In the first 2 atoms of H in C4 H4 are replaced by O. In the second all the H is replaced by O. 92 Glycol ether C4 H4 "OO glycolic acid C4 H2 O2"OO Oxalic - C4 O4 "OO. What would be the acid for methylene C2 H2 if it were fully oxidized? C2 O2 OO = C2 O4 = 2CO2 . Formic acid C2 HO"OO Carbonic C2 O2 "OO Acetic C4 H3 O"OO Glycolic C4 H2 O3 "OO Glycolic acid. Got by the slow oxidation of glycol. It is a syrupy acid liquid The anhydride is got by distilling tartaric acid Lactic acid C6 H6 O6 = 2HOC6 H4 O4 Occurrence. It is extensively distributed in the animal kingdom it is found free in the gastric juice, found in muscle, in 93 the pancreas, in milk, in the brain & lungs & abnormally in urine blood & saliva. It is supposed to be the acid wh dissolves out the mineral matter in bones & produces rickets. It stands in the same relation to propylic wh the latter bears the glycol. Glycol or ethylene alcohol C4 H6 O41 - 2H + 2O = C4 H4 O6 Glycolic acid. Propylene alcohol C6 H8 O4 - 2H + 2O = C6 H6 O6 Lactic acid. Prep. 8 parts of sugar are dissolved in 50 parts HO, 1 part of poor cheese & 8 of chalk are added, & fermented at 80°. Lactate of lime is thus got & by adding HOSO3 you get the acid. It is a transparent, uncrystalline liquid, of a sharp taste It is not volatile & can displace volatile acids, when heated it 94 loses HO & becomes lactic anhydride. Lactates of alkalies do not crystallize - earths & metallic oxides do. Lactate of Zn unites with 3HO. Flesh juice lactates all contain 1 equivalent less of HO than those of that got by fermenting sugar. Fully oxidized olifine acids in wh the H is substituted by O. Formic acid C2 HO"OO Carbonic C2 OO"OO Carbonic oxide C2 O2 is a radical. Sulphocarbonic C2 O2 S2 acid Chloro - C2 O2 Cl2 Oxalic C4 H2 O8 C6 H4 O8 Succinic C8 H6 O8 Lupinic C10 H8 O8 Sebacic C20 H18 O8 Oxalic acid 2HOC4 O6 Occurs in vegetable juices, as acid 95 oxalates, in common sorrel, in lichens in rhubarb, sometimes free. Rarely in the animal kingdom as oxalates of lime in calculi & in urine in an abnormal state. Prep. Heat starch gently with HONO5. It has been obtained by another method. Heat sawdust with caustic Ko & NaO. The H is removed & the O goes You get a mixture of oxalates of NaO & KO. Add CaO & you get insoluble oxalate of lime. Add HOSO3 & you get oxalic acid free. 2Nao, C4 O6 + 2CaO = 2CaOC4 O6 2CaO, C4 O6 + 2SO3 = 2CaOSO3 + C4 O6. It is a crystalline acid crystallizes in colourless transparent like Epsom salts, for wh 96 it is sometimes mistaken. The remedy is chalk, CaOCO2 or magnesia It forms a numerous class of salts, the oxalates, the principal are those of KO & NH3 . Oxalate of KO. 2KO1 C4 O6 + 2HO. Soluble in HO. crystallizes in There is a bin- & quadroxalate wh is is found in sorrel & cress. Neutral Ko| Ko| C4O6 Binoxalate Ho| Ko| C4O6 Quadroxalate Ho| Ko| C4O6 + Ho| Ho| C4O6 + 4HO. Oxalate of ammonia . Prep. Saturate oxalic acid with NH3 & crystallize. It is largely used for testing, as for salts of lime, with wh it gives a white precipitate of 97 neutral oxalate of lime. Oxalate of lime Occurs native in the animal & vegetable kingdoms. Succinic acid 2HOC8 H4 O6 It is homologous with acetic acid It occurs in amber in various fossil resins. in turpentine in the animal kingdom, in the spleen of oxen. It is formed by the oxidation of some organic substances, by the putrefaction of plants of the asparagus kind & by the fermentation of malate of lime. Prop. It is a white brilliant, crystalline acid, crystallizes in rhombic prisms, not easily soluble in cold alcohol, soluble in hot alcohol soluble in HO. From 175 to 180° C it sublimes 98 It is a fixed acid not easily acted on by reagents. Like most bilasic acids it forms neutral & acid succinates. Negative radicals. We have been considering positive radicals. the radicals of the alcohols, the general formula for wh is Cn Hn +1 as for example ethyl C4 H5 = C4 H4 + H The general formula of negative radicals is Cn Hn -1 as for example Acetoyl C4 H3 Allyl C6 H5 Angelyl C10 H9 How can we consider these as olifines? C has a great tendency to unite with itself. Allyl C6 H5 ={(C4 {(C2 H4)"H. C2 having united with the C in the olifine. & the biatonicty of the radical thus formed not being fully 99 gratified by uniting with 1 of H as ethyl C4 H5 = C4 H4 H. It is not mere speculation that C unites with itself. It may be so in the case of allyl but it is known in the case of naphthalene C20 H8 a body wh chokes up gas pipes & wh has all the characters of an olifine. Allyl C6 H5 or in the separate state C12 H10. liquid s.g 0.58 boils at 59ºC. It has the synonym acryl. It has been got in a separate state. Got by the action of Na on iodide of allyl. It is a volatile ethereal liquid burns with an illuminating flame unites with Br & I & forms compounds. Sulphide of allyl or oil of garlic C6 H5 S. boils at 140ºC. 100 occurs in garlic & may be distilled from it & then forms sulpo of allyl. Oil of mustard is the sulphocyanide of allyl. Oil of garlic C6 H5 S. - mustard C6 H5 CyS. It may be got artificially. Act on iodide of allyl by KS. C6 H5 I + KS Allyl ether C6 H5. - alcohol C6 H5 OHO. When oxidized it forms an acid corresponding to acetic, acrylic acid, Oxidized radicals of allyl. Alcohol C4 H6 O2 - 2H = C4 H4 O2 aldehyde. - C4 H6 O2 - 2H + 2O = C4 H4 O4 acetic acid Allyl alcohol C6 H6 O2 - 2H = C6 H4 O4 acryl aldehyd - C6 H6 O2 - 2H + 2O = C6 H4 O4 acrylic acid. Allyl or acryl aldehyde synonym acrolene. It is the nasty smell you perceive when you blow out a candle 101 candle In this case it is got from glycerin wh is distilled in the red hot part of the wick. It has a frightful smell, extremely pungent. attacks the eyes, & if concentrated burns the skin. Oxidized allyl alcohol. Homologues of acrylic acid (with 2C added Acrylic acid C6 H4 O4 same as acetic acid series Angelic C10 H8 O4 from angelica root Damaluric C14 H12 O4 in urine of cows Hypogaic C32 H30 O4 in earth nuts Oleic C36 H34 O6 in most fats C38 H36 O4 C in mustard seed Oleic acid C36 H34 O4 = HOC36 H33 O3 Occurs in most oils & fats as a glyceride. May be got from almond oil by saponifying & converting it 102 into a lead soap & acting on this by HCl. It is tasteless has no smell, does not act on vegetable colours It is solid below 14° C, is insoluble in HO. soluble in alcohol & ether. With NO4 it forms a solid substance. Pass NO4 thro castor oil wh contains much oleic acid Glycerine. The basis of fats. It appears to contain the same radical as allyl. C6 H5 OHO allyl alcohol C6 H5 O3 3HO Glycerin The atoms cannot be arranged in the same way (C4 H4") (C2 ) HO (C4 H4) (C2 O2) HO in Glycerine ether. Glycerin C6 H8 O6 liquid s.g 1.97. 103 Prep. Distil fats with super- heated steam. It is a colourless, syrupy, liquid does not crystallize, has no smell, sugary sweet taste, not volatile except in the vapour of steam. When distilled by itself it is decomposed. When acted on by yeast it yields propionic, acetic & formic acid When heated with KO C6 H8 O6 + 2KO = Acetate of KO KOC4 H3 O3 + Formeate of KO KOC2 HO3 + 4H Made by synthesis. Make iodide of allyl C6 H5 I. Act on it by 3Br. C6 H5 I + 3Br = C6 H5 Br3 + I. C6 H5 "'Br3 + 3KOC4 H3 O3 = 3KBr + C6 H5 O3 , 3C4 H3 O3 Decompose with HOKO or HOBaO. C6 H5 O3 . 3C4 H3 O3 + 3BaO1 HO Saponification Making soaps from glycerides 104 All ordinary fats are glycerides the 3 atoms of HO in glycerine being replaced by 3 atoms of a fatty acid. C6 H5 O3, 3HO C6 H5 O3, 3 acetic acid C6 H5 O3, 3F F = fatty acid. Glycerides or common fats. Occur in the animal & vegetable kingdoms, embracing all the fats we know. Fats may be prepared artificially. Seal glycerin & stearic acid up in a tube & expose to high temp. These fatty glycerides are easily decomposed. They are generally mixed with other fats. To get stearine heat mutton fat with cold ether wh dissolves out palmitine & oleine 105 Stearine C114 H110 O12 = tristearate of glycerin C6 H5 O3 | C36 H35 O3 C36 H35 O3 C36 H35 O3 It is a colourless pearly fat, melts at 63° C. Insoluble in HO, slightly in cold alcohol & ether. Saponification is decomposing this fat, taking away the glycerin & putting in 3KO instead. Glycerine is triatomic so you put ?.=s of a monoatomic body instead KO| C36 H35 O3 KO| C36 H35 O3 KO| C36 H35 O3 Mix hot alcoholic solutions of KO & of stearine and on cooling you get a soap, the glycerine remaining dissolved in the alcohol. Glycerine | Acid A A 3KO In making soap. take a 106 glyceride & potash ley & pass steam thro' it [illustration] When the heat is great enough to melt the tallow a soap is formed. In ordinary soap making a soft soap is made when KO is employed, with NaO a hand soap is obtained. It is easier to make a KO than a NaO soap because it saponifies more easily. It is afterwards made into a NaO soap by salting. KOS + NaCl Yellow soap. Boil tallow or palm- oil with an alkali & add rosin & salt out. Mottled is got from tallow or palm oil, an Fe soap makes the mottling Castile or Marseilles soap is 107 got from olive oil & mottled with FeS. & alkaline sulphides. Chief fats. Palmitine Tripalmitate of glycerin ether. Exists in most fats, especially the softer kinds, in palm & cocoa nut oils May be got from olive oil by cooling Margarine. Supposed formerly to contain margaric acid wh is now known to be a mixture of palmitic & stearic acids. Oleine. Trioleate of glycerine ether Expose olive oil to cold to separate the palmitine & the oleine remains. Natural fats are of 3 kinds 1st solid like tallow 2nd,, semisolid like butter 3d,, liquid like oil They are all lighter than & insoluble in HO, all soluble 108 in ether many in alcohol They occur in the animal & vegetable kingdoms, in all animal fluids except urine Vegetable fats. Cocoa nut oil melts at 20ºC, contains various acids glyceride of coccinic Palm oil. Melts at 27ºC is a yellow butter like substance, 20000 tons of it as imported annually from Africa, it soon becomes rancid, contains palmitine & oleine Vegetable oils may be divided into drying & non drying. Non drying. Colza Drying Linseed croton & castor oils Animals fats. Suet. Fat of oxen & sheep, melted & freed from nitrogenous matter. consists of oleine, stearine & palmitine 109 palmitine Lard contains stearine & palmitine. Human fat is like lard melts at 25° C. Spermaceti. When pure contains cetine, not glycerine but a substance corresponding to it. Cetine C64 H64 O4 = ethal ether C32 H33 O, palmitic acid C32 H31 O3 Sperm & codliver oil are examples of liquid animal fats. Aromatic series. There are several of these radicals Phenyl C12 H5 Benzyl C14 H7 Xylyl C16 H9 Cumenyl C18 H11 Cymyl C20 H13 Phenyl. It is an important series. It contains benzole used in making coal tar colours Phenyl ether C12 H5 O It is got by distilling benzoate 110 of Cu. It is colourless, smells slightly like a geranium it soluble in alcohol. Chloride of Phenyl. C12 H4 Cl. Hydride of Phenyl or Benzol sometimes called Benzine C12 H5 H corresponds to C4 H5 H. Prep. Distil coal tar. [illustration] A vessel filled with HO surrounding the neck of the retort is kept at a temp. of 170° , the temp. at wh benzole distils other substances wh distil at a higher temp. are cooled & fall back into the retort while the benzole distils over. It is used for cleaning white kid gloves & for taking out grease spots. To use it rub the benzole all round the spot without touching it & bring it [illustration] 111 gradually over the spot. It is a colourless, thin oil, of an agreeable odour when pure, solid at 0ºC melts at 5ºC, burns with a smoky illuminating flame increases the illuminating power of gas. It is a good solvent for fats & camphors, it dissolves S.I. & Br readily possibly uniting to some extent with them. Benzyl C12 H5 H Benzyl ether - alcohol C12 H5 OHO When pure & free from HO it is a white crystalline solid substance. Kreosote consists of carbolic, cressylic & probably of some higher acid Phenyl alcohol or carbolic acid. C12 H6 O2. Boils at 185º 112 Found in cows urine, in coal tar. Solid when quite dry & crystallizes in needles, wh melt at 35ºC. It has a disagreeable smell, burning taste, is heavier than HO, in wh it is slightly soluble, it is soluble in alcohol & ether. It is an active poison to animals & plants. It is a strong antiseptic. A coffin filled with carbolate of lime preserved a body for 2 months. Carbolate of lime & sulphite of lime form Macdougal's disinfecting powder. Nitrophenyl ether C12 H5 NO4 Usually called nitrobenzol. It is C12 H5 H having the H replaced by NO4. Prep. Act on benzol by fuming HONO5. It is a yellow oily liquid, solid at 3ºC, smells like oil of bitter 113 almonds, for wh it is used in perfumery & confectionery with advantage since it is not poisonous while oil of bitter almonds often contains hydrocyanic acid. It has a sweet taste insoluble in HO, soluble in alcohol & ether. Used in making anilene. Anilene is NH3 in wh 1 equivalent of H is replaced by phenyl. N |H |H |H N |C12 H5 | H | H To obtain aniline act on nitrobenzol by some deoxidizing agent. That usually employed is acetate of KO. C12 H5 NO4 + 2HO + 47e = C12 H7 N + 27e2 O3 Or by acting with HS. C12 H5 NO4 + 6HS = C12 H7 N + 4HO + 6S Nitrophenyl alcohol C12 H2 (NO4)3 OHO. It is carbolic acid in wh part of the H is replaced by NO4 & has 114 the synonym of carbosotic acid Prepared by the prolonged action of HONO5 on kresote or carbolic acid. It is formed by oxidizing silk, salicin, indigo, alves, gum benzoate & resins. Prep. It crystallizes in brilliant yellow plates, maybe sublimed with care, soluble in alcohol & cold HO, more readily in hot HO soluble in hot HOSO3, is an active poison. May be used in small doses instead of quinine but makes the patients skin yellow. Used to dye silk & woolen. It has been proposed to mix it with As. before selling it in shops as it has an intensely bitter taste, & would be detected. In cases of slow poisoning it would make the skin yellow & thus draw 115 attention Carbosotates crystallize in well defined salts. The acid characted is due to the electronegative character of the radical. Benzyl C14 H7 - ether C14 H7 O. It is an oily liquid & is got by the action of BO2 on benzyl alcohol. Toluol. Hydride of Benzyl, C14 H7 H Obtained from liquid coal tar + tolubalsam. It is colourless & resembles benzol in it properties, is insoluble in HO soluble in alcohol & ether. HONO5 act on it in the same way as on benzol. Benzyl alcohol C14 H7 O, HO It is an oily colourless liquid insoluble in HO soluble in alcohol 116 alcohol & ether. By oxidation it becomes the oil of bitter almonds In the olifine view Benzyl alcohol C16 H6 " HO HO - ether C16 H6 " HO oil of bitter almonds = biatomic ether C14 H6 " OO benzoine is the aldehyd C14 H5 O " HO Benzoic acid C14 H5 O"OO. Oil of bitter almonds: general formula C14 H6 O2. liquid s.g l.043 boils at 180° C. Obtained when almonds are macerated & distilled with HO. It is fragrant oil, transparent very refractive, has a powerful smell is used in perfumery, is not poisonous in itself but often contains hydrocyanic acid When it contains this & is put in contact with lime it is 117 Changed into benzoin Benzoic acid. Occurs in putrid horses urine Obtained by sublimation from gum benzoate. It is volatile, slightly soluble in HO soluble in alcohol & ether. When taken as a medicine it is converted into hippuric & is found as such in the urine. Benzoates are crystalline, when heated they are decomposed into benzoin naphthaline Let us now go back to the phenyl series & consider the coal tar colours. The phenyl series differs from the benzyl by C2 H2 Phenyl C12 H5 or as olifine C12 H4 "H Benzyl C14 H7 Manufacture of benzol. Nitrobenzol 118 Nitrobenzol &c. When coal is distilled for gas it produces various substances, HO & tar distil over along with the gas. Ten to 12 gallons distil over of oil of from 1 ton of coal. It was formerly a waste product & even yet it is sold at a penny to three halfpence the gallon. [illustration] To get naphtha pass steam thro' the tar On a large scale 100 part tar yield Naphtha 9 parts Lead oil 60 - Pitch 31 - Naphtha is nearly the only thing wh comes over with the steam the pitch & dead oil 119 remain in the retort, & the is a afterwards distilled by a common fire. Naphtha is a rough commercial term & signifies a great variety of substances Roughly purified it is used for many purposes. Crude naphtha contains 3 substances. Basic oils Acid oils Neutral hydrocarbons. Basic oils may be got from the naphtha by agitating with HOSO3. They are all compound ammonias. Aniline exists in the basic oils but is not got from them. Acid oils. 120 Take naphtha & shake it with caustic NaO or KO the acid oils dissolve in the NaO or KO & are separated by adding HCl. When separated they form kreosote wh is carbolic acid C12 H6 O2 & cressilic acid C14 H8 O2 Carbolic acid is used in toothache & to preserve timber When acted on by NO5 it forms carbosotic acid. Carbolic acid C12 H6 O2 Carbosotic - C12 H3 (NO4)3 O2 Carbosotic acid is a strong dying agent. Dissolve a little in a little hot HO & then add some cold, you get a solution excellent for dying silk yellow. Wet the silk in HO & rinse in the carbosotic acid. This is the first use of coal tar in colouring substances. 121 Neutral hydrocarbons. Chiefly benzol & its homologues. The benzol is distilled by passing it thro a cistern of HO at 177°. Benzol is very volatile, & it is possible to burn air charged with it [illustration] Dried air is passed over heated asbestos B to heat the air, & thro' some benzol in A the air then may be burned as at C. It may be used for setting enemy's ships on fire by pouring it on the HO & throwing some K on it wh takes fire & inflames the benzol. Nitrobenzol. C12 H5 NO4 Benzal acted on by NO3. It is used in perfumery. To get colours from it, it is first 122 made into aniline C12 H5 NO4 + 2HO + 4Fe = aniline C12 H7 N + 2Fe2 O3 Aniline C12 H7 N It is a compound ammonia A short time ago 1/2 lb aniline would have been thought very valuable in a laboratory & probably none possessed so much as except perhaps who was making researches upon it It was a short time ago sold for a few shillings per gallon but has now risen in price in consequence of the demand for it & is now a few shillings per pound. From aniline are made Mauve or purple Violine Rosein Magenta or Rosaniline Azuline 123 These tar compounds are capable of producing colours [illustration] Put 2 drops of pyroline in a jar & shakes up- moistens a piece of pine wood in the shape of a dagger with HCl & put it into the jar, the moistened point becomes red. Mauve. [illustration] Put some aniline ( a very little will do ) into a bottle & add a little acetic acid to assist its solubility. you get a solution of acetate of aniline, pour into HO & add chloride of lime- [illustration] it becomes brown at first but afterwards becomes purple. On a large scale it is prepared by acting on sulpate of aniline by KO, 2CrO3 in equivalent quantities. You get a dark powder, wash 124 this with coal tar & dissolve it in alcohol The alcoholic solution is evaporated to dryness & you get a green powder wh is soluble in alcohol. It is from the alcoholic solution that we dye the colours. Pour a little tartaric acid into some hot HO & pour in a small quantity of alcoholic solution of mauve. Wet the silk to be dyed & put it in. The chemistry of the colour is not well understood. It is easily tested by HOSO3. Add a little strong HOSO3 to a little mauve & you get a dirty green solution. Add a little HO & you get a fine blue. Add a good deal of HO & it becomes mauve again 125 Magenta. The true red colouring matter is rosaniline. In making it take a weak deoxidizing agent instead of a strong as with mauve. [illustration] Take a small quantity of anhydrous bichloride of In as that in the sealed tube A, pour it into the flask B, add aniline cautiously, it forms a solid compound, gradually add more aniline till you have an excess Heat cautiously over a lamp The action is violent. Any weak anhydrous Acetic acid & As O5 are also used. It is necessary to boil off the excess of aniline. Blue de Paris a azuline Is got from carbolic acid 126 Put a very little mauve or magenta on a sheet of paper hanging up & spout alcohol from a washing bottle on it, the colour dissolves running over the paper. The chemistry of some of these colours is known Rosaniline is a triammonia 3 atoms of H coalescing into one. NH3 x 3 = N3 H9. The compounds radical substituting H is unknown. Let R signify rosaniline. R unites with 1 or 3 atoms of acid. R + 1A gives the strongest colour R + 3A - a less strong -. R is colourless by itself, but when dissolved in alcohol or acid it has a strong colour. Magenta is acetate of R. In the case of the purples we must use hot HO in dying but in the case of carbosotic 127 acid & magenta, cold will do. All animal fibres take up these colours readily. Cotton does not & you must treat it with tannic acid. Purple & violine are not true ammonias, they seem to be neutral In cotton printing, albumen is put on the place wh is desired to be coloured & exposed to steam & dried. It is then rinsed in a solution of the dye as silk is the vegetable fibres do not take it up but the albumen does. Malic acid 2HOC8 H4 O8 It is bibasic. It occurs frequently in unripe fruits, in the apple but is got most easily from the berries of the mountain ash. It has a strong acid, agreeable taste 128 When heated it is changed into fumaric acid fumaric acid. 2HOC8 H2 O6 . It is readily obtained from Iceland moss or malic acid. It forms micaceous scales wh require 200 parts of cold HO for solution. Tartaric acid. General formula C8 H6 O12 = 2HOC8 H4 O10. Occurs in the tamarinds & mountain ash berries, but is got chiefly from grapes. The substance called argol found in wine casks is bitartrate of KO. It is obtained in rather a curious way from this by converting it into neutral tartrate of lime. Argol Ko } Ho } T Add CaCl & lime if you added CaCl alone you would get CaO } HO } T but by adding lime too you get CaO} CaO} T 129 add HOSO3 to this CaO} CaO} T + 2HOSO3 = Ho} Ho } T + 2CaOSO3 . It crystallizes in oblique prisms is colourless transparent, of an acid agreeable taste, soluble in HO alcohol & wood spirit, its solution especially when hot exerts a right-handed rotation on polarized light There are two different crystalline forms. Sometimes, especially in the grapes of the Vosges, an acid of the same formula as tartaric acid called racemic. Racemic acid is rather difficult to get as it only appears sometimes. Racemates crystallize differently from tartrates & have a different number of atoms of 130 HO of crystallization. It was supposed to be an isomer of T & to have its atoms arranged differently. T produces a right-handed rotation of polarized light Racemic acid a left handed one. The crystals were unsymmetrical but in different directions. Pasteur showed that when put together they are symmetrical It is thus the same acid in different crystalline forms. Tartrates are used largely in medicine & the arts. Used in calico is printing. If in calico printing you wish a part to remain white you use tartaric acid as a resist to the mordant wh is always used. The mordant forms a very soluble 131 soluble tartrate & does not remain on that place, & so the dye does not adhere to that place. In all cases of bibasic acids as tartaric acid where you have 2 HO thus HO } HO } T you may replace 1 HO or both. HO } HO } T KO } HO } T KO } KO } T NaO } KO } T. Argol is cream of tartar or bitartrate of KO HO } KO } T. It is hard white & crystalline difficultly soluble in cold HO, more soluble in hot HO, has a sour taste & feels gritty to teeth. When heated it forms black flux. Bitartrate of KO is extensively used in medicine as a diuretic. Neutral tartrate. It is deliquescent. All acids even tartaric acid, convert it into cream of tartar. Rochelle salts KO,Na OT + 8HO. 132 KO } NaO } T crystallizes with 8Ho, in large clean, rhombic prisms, is used in medicine. forms the basis of seidlity powders. Tartar emetic. It is a double salt corresponding to cream of tartar. KO } SbO3 } T + aqua. Mix 3 parts SbO with 4 cream of tartar, make into a paste, digest It is soluble in 15 parts HO, is a violent emetic in larger doses acts as cathartic poison. Kinic Occurs in chinchona bark. Crystallizes in colourless prisms wh melt at 155°C. Solid on cooling at a higher temperature it is decomposed. Tribasic acids. Citric acid C12 H8 O14 . 133 Occurs in the lemon, gooseberry cherry & tamarind. As citrates in the tumours of the Jerusalem artichoke. Only the fruits wh contain acid united with alkali become sweet on ripening the acid being converted into sugar. Where acid is free as in the lemon, it does not become sugar. It is prepared like tartaric acid but is more easily made since it has no tendency to become uncrystalline as tartaric acid is apt to do. It crystallizes in large colourless prisms, very soluble in HO & alcohol, not in ether. It is used in calico printing both as a resist & to heighten the colours. Heated to 175° it is decomposed & becomes 134 C12 H8 O14 - 2HO = C12 H6 O12 Fused with lime it forms oxalate & acetate of lime. C12 H8 O14 + 2HO from the HOCaO = C4 H2 O8 + 2(C4 H4 O4). Citrates are necessarily a large class. Citric is tribasic acid. HO | HO | HO | C12 H5 O11 . Aquinitic acid. Found in aconitum Forms warty crystals easily soluble in HO. It is the acid in opium, it is a white silvery acid, loses its HO of crystallization at Gallic acid 2HOC14 H6 O10 It is bibasic, is contained in gull nuts in mango seeds in sumach. 135 It is got artificially by the splitting up of tannin when it is boiled. It is white silky crystalline. soluble in 3 parts of boiling HO & 100 cold HO, with a salt of Fe it forms ink. When heated to 210° it is decomposed, it loses C2 O6 & becomes pyrogallic acid. Pyrogallic acid C12 H6 O6 = Used for estimating O. With a little alkali it absorbs O completely. Tannic acid. Tannic acid is a general name for organic substances wh precipitate gelatine & form leather. It is contained in the leaves & bark of most forest trees, especially the oak, elm in the whortleberry, tea, coffee. Tannic acid except that from coffee. Precipitates protosalts 136 of Fe a blue black, or in acid solutions of a dark green. Some like tannic acid from catechu precipitate it a dark green. Gallotannic acid C54 H22 O34 Obtained from gall nuts. Take an ethereal solution of gall nuts, it divides into two parts the upper part is gallic & the lower tannic acid. Obtained thus it is a white, crystalline body soluble in HO, soluble in weak alcohol & ether. The aqueous solution absorbs O Gallotannic acid should be called tannin, it is a glucoside. Act on it by acid wt brings HO into play. 137 C54 H22 O34 + 8HO = 3(C14 H6 O10) + C12 H12 O12. Boil tannic acid with HCl, It is not certain whether it is a bi or tri [crossed out] basic acid. It is used in medicine as an astringent. Ink. Gallotannate of Fe. Take 3/4 lb of bruised gall nuts, dissolve them in 1 gallon of cold HO, add 6 oz of FeOSO3 . 6oz of gum arabic 5 drops of kreosote to prevent it moulding, digest at common temps. for 2 or 3 weeks, shaking frequently. Ink stain = Fe2 O3 To take it out heat with a little oxalic acid. it forms soluble oxalate of Fe. Gallotannate or tannate of gelatine. The object in tanning is to unite the skin with acid to prevent putrefaction, & yet leave the 138 skin supple. The time required varies, as, the hippopotamus skin is 2 inches thick & required nearly a year. While the kid's skin is only a fraction of an inch thick & requires only a few weeks. The processes are, 1st. Place the skin in lime, the root of the hair is attacked by it Remove the hair with a knife & open the pores by placing in a pit of HOSO3 & HO. Layers of skins & oak bark are laid in pits for 3 months, they are then taken out & fresh bark is added, the skins are then placed in again so that the one wh had been at the top is now at the bottom & allowed to remain there for some time. It is strange that no quicker 139 process can be employed The use of hydraulic presses to force the liquor into the pores, & of stronger solutions does not make such good leather If Simon the tanner of Joppa came back to this world he would find the trade precisely as he left it. In white kid gloves no tannic acid is used, it is protected by aluming Tawed leather The skins are cleaned & treated with Al2 Cl3 made by mixing alum & NaCl, & then rubbed with oily substances. In chamois leather as much oil is put in as possible. Compound haloid radicals. The chief representative is cyanogen C2 N. 140 It has perfectly parallel characters with any other haloid. Cl} 4 Cl} hyrdo Cl} chloride Cl} Cl} Cl} vols H} chloric acid K} of k I} O} C2N} 4 C2N} hydro C2N} cyanide C2N} C2N} cyanic C2N} vols H} cyanic K} of k I} O} acid acid Cl} Cl} 4 vols Cl} H} hydrochloric acid Cl} K} chloride of K Cl} I} Cl} O} C2 N} C2 N} 4 vols C2 N} H} hydrocyanic acid C2 N} K} Cyanide of K C2 N} I} C2 N} O} Cyanic acid Cyanogen was the 1st,, compound radical clearly established in organic chemistry. Cyanogen C2 N. = 26. if it has 2 vols 52 if 4 vols. S.G of gas 1.806. Symbol. Cy. It is monoatomic. The reason for this is that though N is pentatomic but is joined to 2 of C wh is biatomic & has thus 4 atoms filled up & only 1 left. N,,,,, - C2,,, = C2 N, Cy has the power of doubling itself & forming other radicals. Cy C2 N Bicy. C4 N2 Tricy C6 N3 Mellan C18 N13. 141 Cy is best got by heating cyanide of Hg in a tube. This corresponds to the method of getting O. [illustration] HgO2 heat = Hg + 2O HgCy2 - = H8 + 2Cy. A black substance is left in the tube wh has the same composition as Cy. Prop. It is colourless, has a peculiar prussic acid & odour at a pressure of 3 atmospheres it becomes liquid & the liquid solidifies at -35°C, it burns with a purple flame, producing CO2 & N, it is soluble in HO & alcohol the latter takes up 22 vols. of it The solutions decompose & urea is formed. Urea is an anomalous cyanate of NH4 . NH4 O C2 N K unites with Cy as it does with Cl. 142 Hydrocyanic or prussic acid. HCy= 27 s.g of the gas 0.9476. 4 vol vap. formula. Acc. Probably never found free but various seeds give it by distillation owing to the action of ferments on it. Almonds, peaches apricots, the leaves of peaches & the kernels of plums yield it. Mode of preparing it. Distil K Cy with HOSO3. pass over CaCl & condense by ice. s.g of liquid 0.967 boiled at 26ºC solid at -15ºC Has a smell like bitter almonds is an intense poison is soluble in all proportions in HO & alcohol. Does not keep well, after a while perhaps 2 or 3 years it becomes black & is apt to explode, you then break it under HO to prevent this, 143 Aqueous solution of HCy. Prep. Distil yellow prussiate of [illustration] KO & HOSO3. you get a solution of unknown strength. The medical strength is 2 percent of prussic acid. The London pharmacopia process for getting a solution of known strength, is. - Suspend 48 1/2 grams of cyanide of Ag in 1 oz HO & add 39 1/2 of HCl. An extemporaneous solution of HCy may be made by adding KCy to T & stirring, you get bitartrate of KO & a solution of HCy. The aqueous solution is more permanent if you add a little mineral acid. Solution of HCy under the action of strong acids or alkalis decomposes 144 decomposes into formiate of NH4 . C2 NH + 4HO = NHOC2 HO3 HCy is easily tested. Test. Take FeOSO3 wh has been a little rusted in air. If not rusted add a few drops of a persalt of Fe. Add HOKO to precipitate the oxide of Fe. Add HCl to neutralize the KO & take up the Fe. Add these to the suspected solution & if HCy be present prussian blue is produced. The rationale of this process is HCy, KO & a salt of Fe make yellow prussiate of KO, if you add HCl to make a solution of Fe prussian blue is produced. Another test. Put the suspected solution in a watch glass & add a drop or 2 of sulphide of NH4 to neutralize it, put over it another watch glass & [illustration] 145 evaporate it to dryness in a hot water bath. Add perchloride of Fe. You are producing sulphocyanide of K wh has the property of striking a blood red colour with perchloride of Fe. When used as a poison it quickly escapes from the system on account of its volatility so that 3 days after you cannot detect it in the body. Cyanides resemble the haloid salts of Cl & are got in the same way. To get KCl HCl + KO = KCl + HO - KCy HCy + KO = KCy + HO. On a large scale KCy is got by heating yellow prussiate of KO with KOCO2 . yellow prussiate of Ko. K4 Fe2 Cy6 K4 Fe2 Cy6 + 2KOCO2 = 5KCy + KoCyO + 2Fe + 2CO2 . You can prevent the 146 formation of KOCyO by adding a little C. K4 Fe2 Cy6 + 2KOCO2 + 2C = 6KCy + 2FeO + 2CO2 + 2CO. Dissolve it out & evaporate it down. It is use largely in electrotyping to dissolve Ag + Au, & as a reducing agent. Bicyanide of H8 - H8 Cy2 . Boil 4 parts prussian blue 3 of peroxide of H8 & 4O of HO. It crystallizes in prisms, soluble in HO more difficultly soluble in alcohol, very poisonous. Alkalis do not precipitate H8 O from it. Cyanide of Ag. AgCy. Prep. Add KCy to a salt of Ag. It unites with KCy & readily forms double salts. Haloid ethers of Cyanogen. Cy unites with ethyl as Cl does. 147 Prep of cyanide of ethyl. Add KCy to C4 H5 I. C4 H5 I + KCl = C4 H3 Cl + KI prep of chloride of ethyl C4 H5 I + KCy = KI + C4 H5 Cy cyanide of ethyl. We find the Cy has gone in more intimately to the ethyl than we would suppose On this account These compounds are called nitriles. Cyanide of ethyl. C4 H4 C2 N. It is a colourless liquid, mobile of an agreeable but garlicky odour Does not comport itself with alkalis like ordinary ether. It is soluble in alcohol & ether. C4 H5 Cl + KOHO = KCl + C4 H6 O2 propionate of KO C4 H5 C2 N + KOHO + 2HO = KOC6 H5 O3 + NH3 Propionic acid one above C4 H5 in the series. Act on a nitrile by an alkali & you get the acid one above it in the series. 148 Double electro negative cyanides. The cyanides form a remarkable series of salts when certain metals combine with them, especially Fe 4KCy + 2FeCy = yellow prussiate of KO. If you get an insoluble cyanide of Fe by adding FeOSO3 to KCy & add excess of KCy to the insoluble salt it gradually dissolves & you get a solution of yellow prussiate of KO. Suppose the Fe has a formed a compound radical with Cy. Fe2 Cy6 called Ferrocyanogen. Yellow prussiate of KO is this + 4K & crystallizes with 6HO. Add HCl to this Fe2 Cy6 + 4K + 4HCl = 4KCl + Fe2Cy6 4H. [illustration] Has a solution of yellow prussiate of KO in the tube add HCl & ether 149 Fe2 Cy6 4H = hydroferrocyanic acid is insoluble in ether. A bluish white compound is formed. Occurs in crystalline plates, soluble in HO, is readily precipitated by ether. The solution quickly becomes blue, when boiled HCy is evolved. When the 4H are substituted by 4K you get yellow prussiate of KO. Yellow prussiate of KO. It is used in the arts largely. Prep. Cast off woolen garments, horns & hoofs of cattle, flesh & blood any thing that contains N are mixed with scrap Fe & Montreal pearl ashes & heated. Fe2 Cy6 4H = Hydroferrocyanic acid 150 Fe2 Cy6 4K = yellow prussite of KO. It is formed when a substance containing N is fused with KOCO2 & Fe or allowed to digest on Fe. Occurs in lemonyellow tabular crystals soluble in HO not soluble in alcohol, of a bitter taste & purgative but not poisonous, If you take away 1 of K & make red prussiate it becomes intensely poisonous Yellow prussiate is tetrabasic. Fe2 Cy6 { 2Ba { 2K Fe2 Cy6 { 3Cu { K. We have doubled the formula on this account. [illustration] Add yellow prussiate to CuOSO3 & a mahogany red is produced. Ferrocyanide of NaO. Na4 Cy6 + 10HO. Ferrocyanide of Fe. Take a solution of Fe OSo3 & add yellow prussiate, you get a 151 a precipitate, while at first but wh absorbs o from the HO & becomes blue. It has this composition. Fe2 Cy6 {3Fe {K. Add yellow prussiate to a persalt of Fe & you get prussian blue at once Fe7 Cy9 . Prussian blue Prop. It is a beautiful blue of a coppery lustre when dry, after being washed in HO it may be dissolved in oxalic acid. This when thickened with gum forms steven's blue ink. It is readily decomposed by alkalis. Add caustic NaO or KO to prussian blue, it produces a reddish colour & forms oxide of Fe. Put a cloth dipped in a salt of Fe into prussiate of KO & it is dyed blue. 152 Ferridcyanogen. It has the same composition as ferrocyanogen but is tribasic instead of tetrabasic Fe2 Cy6,,,, radical of yellow prussiate Fe2 Cy6,,, - red - Pass Cl this is a solution of yellow prussiate. Fe2 Cy6 4K + Cl = KCl + Fe2 Cy6 3K. Hydroferridcyanic acid. Is got in the same way & has much the same properties as Hydroferrocyanic acid. Add HCl to red prussiate of KO & add ether. Or add HOSO3 to Ferricyanide of Pb. Crystallizes in brown needles, better easily decomposed. Ferridcyanides are generally red. They are distinguished from ferrocyanides by giving no precipitate with perchloride of Fe. 153 yellow prussiate with Protosalt of Fe gives a white precipitate Red prussiate - blue yellow- persalt - blue Red- dark brown. Ferridcyanide of K. Is generally called red prussiate of potash. Crystallizes in ruby red right rhombic prisms, soluble in HO insoluble in alcohol, gives a precipitate with metallic salts in wh all 3 of K are replaced by metal. K3 Fe2 Cy6 + 3AgONO5 = 3AgFe2 Cy6 + 3KONO5. Turnbulls prussian blue, is prussian blue got from red prussiate & FeOSO3. Nitroferrocyanides or nitroprussides Fe2 Cy6,,,, Fe2 Cy6,,, Fe2 Cy5 NO,, Nitroprusside of Na. 154 Made by the action of NO5 on Nitroprusside of K. When you add sulphide of NH4 to this a beautiful purple colour is produced wh is very transitory. It is the best test for S. Put a lock of hair into a test tube & dissolve it in caustic NaO or KO. heating it to aid the solution. You must always convert the S into an alkaline sulpide. Adds a good deal of HO so as not to act on the filter & filters it. Adds nitroprusside of Na & a deep purple is produced showing the presence of S in the hair. The nitroprussides give a salmon coloured precipitate with salts of Fe. Oxides chlorides & sulpides of Cy. It must be recollected that there are 3 sorts of Cy. Cy Cy2 & Cy3 . 155 Cyanic acid CyO. Cyanates are easily got by heating a cyanide with an oxide such as of Pb. CyO is not so easily got. Distil cyanuric acid & collect the product in a freezing mixture. It is colourless mobile A drop on the skin produces a sore. Above 0°C it changes into a procelain like mass. Cyanates. General formula MOCyO corresponding to MOClO. They bear heating to redness without decomposition. You do not obtain CyO by acting on them by acids Cyanate of KO. KOCyO. Prep. Heat prussiate of KO with 156 an oxidizing agent such as MNO2 . It is soluble in HO, the solution is decomposed when heated. KOC2 NO + 3HO = NH3 + HO} KO} C2 O4 Cyanite of NH4 . NH4 OCyO. Prep. Act on cyanate of KO by NH6 OSO3 It is white crystalline, soluble in HO & alcohol, it is not urea, wh is an anomalous cyanate of ammonia NH4 OC2 NO. Chloride of Cy. NCO2 Cl. vap. density 2.124 Act on cyanide of H8 by Cl. Colourless, very poisonous gas, of a disagreeable pungent small, at -53°C it becomes liquid. In closed tubes it becomes double CyCl = Cy2 Cl2 . Sulphocyanogen Sulphocyanates correspond to cyanates S playing the part of O. 157 CyO CyS . It has never been got in a separate state. A yellow compound got, has been called CyS but does not behave as such. It forms sulphocyanates wh are interesting because NaCyS at least exists in the saliva man & the sheep. Put some saliva in a watch glass & add perchloride of Fe. Sulphocyanide of K. KSCyS. Prep. Heat together yellow prussiate of KO1 KOCO2 & Bicyanogen Cy2 C4 N2 . Not known in its separate state Bicyanic acid Cy2 O2. It has the synonym fulminic acid . 158 2 HOCy2 O2 Fulminic acid Not known free. Fulminate of Hg. 2HgOCy2 O2 Prep. Heat HgONO5 & alcohol together It crystallizes in white needles very explosive not soluble in cold HO but soluble in hot. Add Zn to the solution & Hg is deposited & fulminate of Zn remains. Act on fulminate of Zn by Cl, & it becomes chloride of Cy & C2 (NO4 ) Cl3 chlor-carbasotic acid. It is possible that 1/2 the N in fulminic acid may not be present as Cy. It is closely allied to Cy. Persulphocyanic acid. Little soluble in alcohol & ether With alkalis it forms soluble 159 & with heavy metals insoluble salts. Bichloride of Cy It is formed when CyCl is left in a sealed tube. It is a colourless liquid boils at 15ºC. Tricyanogen. Cy3 . Forms cyanuric acid Cy3 O3 3HO. Got by the action of terchloride of Cy on HO. CyCl3 + 6HO = 3HOCy3 O3 + 3HCl Transparent crystals, no smell or taste, reacts acid. Cyanurates Cy3 Cl Expose anhydrous Crystallizes in brilliant needles wh melt at 140ºC boil at 190ºC Smells like the excrements 160 of mice, difficulty soluble in HO readily soluble in alcohol & ether. Characters of Cy. Cy has the character of a radical closely resembles Cl but has the power of duplicating & triplicating itself & forming other radicals Unites so intimately with metals as to appear to form radicals Polymerizes itself. Mellone C18 N13 Organic bases representative of alkalis & metallic oxides in organic chemistry. The bases resemble NH3 They act like NH3 on hydracids without expelling the H. They almost all unite with PtCl2 to form double salts. It is believed that they are all constituted on the NH3 type. 161 The general name is amines. NH3 N | | H | H | H Primary N | | A | H | H Secondary N | | A | B | H Tertiary N | | A | B | C Monamines Example N | | C4 H5 | H | H N | | C4 H5 | C2 H3 | H N | | C4 H5 | C2 H3 | C10 H11 All these are true ammonias, form salts with hydracids & take up HO when they unite with oxyacids. They are volatile alkalis & have a peculiar odour generally resembling NH3 . The replacing radicals are generally the common compound radicals. C12 H3 Cl2 | H | | N Chlorphenylamine C12 H3 ( NO4 )2 | H | | N dinitrophenylamine When you have such substitutions as these, electro negative 162 bodies replacing H, the basic power of the body is much impaired & in some cases destroyed. Glycocol C4 H3 O4 | H | H | | N neutral Benzamic acid C4 H5 O4 | H | H | | N Production of these compound ammonias. They are produced by the action of an iodide of an alcohol radical on NH3 . N | | H | H | H + C4 H5 I = N | | C4 H5 + I | H [cross out] | H Or by deoxidizing a nitro compound as in aniline* Ethylamine s.g 0.696 boils at 18.7°C It is a colourless liquid of an ammonaical odour, its causticity is nearly equal to that of KO. It blues red litmus, neutralizes powerful acids, raises a blister * C12 H5 ( NO4 ) + 6HS = N | | C12 H5 | H | H + 4HO + 6S. 163 on the tongue, drives NH3 from its salts Tri It is colourless liquid, inflammible slightly soluble in HO less so than ethylamine. Act on this with C4 H5 I, & you get iodide of ethylammonium a compound corresponding to NH4 I. N | | C4 H5 | C4 H5 | C4 H5 + C4 H5 I = N( C4 H5 )4 I. Act on the last body by AgO & you get AgI + N( C4 H5 )4 O corresponding to NH4 O. Oxide of tetrethylammonium You cannot distinguish it from KO in its chemical characters It acts as a caustic & forms a soap with fats. It precipitates metallic oxides like KO Add it to CuOSO3 & CuO is precipitated & sulpate of tetrethylammonium 164 tetrethylammonium formed In coal tar there is a remarkable set of organic bases You get them by treating with HOSO3, decomposing by KO & distilling Pyridine C10 H5,,, N Picoline C12 H7,,, N Lutidine C14 H9,,, N Lecoline C18 H7 N Lepidine C20 H9 N Put a mixture of Lutidine into a sealed tube into hot HO they being less soluble in hot than cold HO float on the top of the liquid on the tube Diamines. Where 2 atoms of NH3 have coalesced unto one. N2 | | H2 | H2 | H2 you may have primary, secondary & tertiary diamines N2 | | A2 | B2 | C2 165 Urea belongs to this class. Common urea. N2 | | C2 O2 | H2 | H2 Urea forms from 77 to percent of human urine Prep. Evaporate urine till it becomes syrupy & add an equal volume of colourless NO5 of s.g 1.35. It forms nitrate of urea, separate the acid by BaO & the urea by alcohol & crystallize. Artificial urea. KOC2 NO + NH4 OSO3 = KOSO3 + NH4 OC2 NO. Prop. It crystallizes in 4 sided prisms like KONO5 Soluble in HO & alcohol, when heated it is converted in great part into NH3 & Cyanuric acid. Unites with acids & forms salts. N2 | | C2 O2 | H2 | H2 N | | C2 O2 | C4 H5 | H2 Triamines. N3 | | H3 | H3 | H3 Organic alkaloids. It was long the opinion of chemists that vegetables only produce neutral & acid substances. In 1803 got an alkali from opium & in 1804 got another alkali. yet it was 12 years after, that the opinion became prevalent that alkalis were produced by vegetables. General properties. They behave like NH3 . They neutralize acids & form salts. They are all solid or liquid, generally fixed a few 167 are volatile. Some are soluble in HO some in alcohol. The sulphates, nitrates, chlorides & acetates are soluble. The tartrates They are generally violent poisons or active remedial agents. They may be divided into 3 classes A. Volatile alkalis free from O. B. Bases readily soluble in alcohol sparingly in HO. C. Bases soluble both in HO & alcohol. A. Example. Nicatine. Prep. Macerate tobacco in HO. The malate of nicotine dissolves Ni = nicotine. M = malic acid NiOM + KO = Ni + HO The Ni distils over. B. Prep. These bases are united 168 with acids such as Kinic acid or meconic acid. Add HCl the chlorides are dissolved out, add lime wh. forms CuCl & precipitates the alkali. Take it up by & crystallize from alcohol C. Dissolve in HCl & form chlorides. Neutralize the chlorides by NH3 & precipitate by oxalate of ammonium. Decompose by BaO & crystallize. Conia is a secondary monamine N | | C16 H14 | H. It is prepared from hemlock chiefly from the seed. It is a colourless oil of penetrating odour & burning taste it is strong poison, in presence of HO it acts strongly alkaline, difficultly soluble in HO. 169 especially when warm, readily soluble in alcohol & ether. Act on it by C4 H5 I & you get ethyl conia. Sparteia. A tertiary monamine N | C16 H13,,, Got from broom, heavier than HO, the liquid boils at 287°C. Alkaline & narcotic poison, has an odour like aniline nicotine, it is a diamine C20 H14 | N2 Occurs in tobacco chiefly in combination with malic It is a colourless liquid, absorbs O readily & becomes brown, has a burning taste, slight-odour of tobacco, is intensely poisonous There is from 2 to 7 Percent in tobacco. The mild kinds of tobacco as 170 Havannah used for smoking contain the least quantity, those sorts used for snuff contain most. The strength of snuff is due to nicotine, its pungency to ammonia salts. Snuff. The leaves of tobacco are allowed to ferment for 18 months. During this time there is a considerable absorption of O & the temp. often rises to 100°. They are then ground & sifted. In fermenting 2/3? of the nicotine is destroyed, NH4OCO2 is formed & a volatile oil to wh the aroma is due & 2 P.C. of nicotine remains. Alkaloids in opium. They are numerous. Morphia C34 H19 O6 N probably a monamine. 171 Codeia C36 H21 O6 N Thebeia C38 H21 O6 N Papaverin C40 H21 O6 N Narcotin C46 H25 O14 N. Narcein C46 H29 O18 N Opianine Pseudomorphine & phorphyroxine Morphine In crystallizing it takes 2HO. Occurs in opium in combination with mechonic & sometimes sulphuric acid. It is present in from 6 to 12 PC. Smyrna opium contains most, Crystallizes in brilliant prisms, taste slightly bitter, has a slight alkaline reaction when heated it parts with its HO of crystallization & at a higher heat is decomposed. HO dissolves 1/1000th part of its wt of it it is readily soluble in 172 alcohol slightly in ether It is a strong narcotic poison when heated with soda lime it becomes methylamine. Muriate of morphia. It crystallizes with 6HO in fine silky prisms, soluble in HO & alcohol. When impure it crystallizes in large crystals, the purer it is, it is more difficultly crystallizable. It forms double salts with PT Cl2 . Acetate of morphia It is a deliquescent salt, crystallizes in thin needles. Sulphate of morphia Salts of morphia are largely used in medicine. 173 5 grains to the ounce are administered like laudanum in small doses. Though less powerful than laudanum. Test. salts of Fe2 O3 3SO3 give a blue colour with it, concentrated NO5 a red colour at first fading to yellow. Conine Crystallizes with 2HO. Occurs in opium to the extent of 1 P.C.. Though homologous with morphia it is not analogous to it in its properties. Soluble in 8 parts cold HO & 17 hot. Melts at 150°C. Decomposes at higher temperatures is poisonous, produces tetanic convulsions like strychnine. 174 Papaverin Is not poisonous. Narcotin Is present from 6 to 8 PC in opium Crystallizes in small rhombic prisms, little soluble in alcohol or ether. Has very feeble alkaline properties many of its salts are decomposed by HO. Is poisonous. 2O grains will kill a dog. There are 3 homologues of narcotine in opium. Alkaloids in chinchona bark There are four. Quinine C40 H24 O4 | N2 Cinchonin C40 H24 O2 | N2 Chinidin C36 H22 O2 | N2 Arcin C46 H26 O8 | N2 They are all diamines. They are found united in cinchona bark with kinic & kinotannic acid. 175 Quinine Found chiefly in the yellow bark in about 3 1/2 P.C. Crystallizes in silky needles from ether, as a white curdy precipitate from its salts, soluble in ether, in 200 parts boiling HO, more soluble in lime water. Readily soluble in alcohol & ether. Intensely bitter, alkaline, melts at 120°C. Unites with acids so as to form 2 classes of salts. The pill used by Dr Livingston in cases of African fever & wh. never fails if the patient be removed to a higher district. 3 to 4 grains resin of julap 3 to 4 - calomel. 3 to 4 - quinine A drop or two of tincture of cardamums to dissolve the resin & 176 form the bolus. It ought not to purge but to occasion gentle movement Sulphate of quinine It unites with 1 atom of HOSO3 , crystallizes with 7 HO in long brilliant prisms, easily loses 5 HO, difficultly soluble in pure HO. Acid salt Q HO SO3 . Used in medicine, add a drop or 2 of HOSO3 to assist its solubility. It is often adulterated with CaOSO3 sugar, calomel, fats, starch, & salicin. To detect adulteration, burn a portion if CaOSO3 is in it, the CaOSO3 remains. If with calomel or sugar you can smell them. If not completely soluble in dilute HOSO3 it contains fats or starch. If salicin be mixed with it. 177 dissolve in 6 times its wt of HOSO3 add 12 parts HO, salicin will be precipitated. Cinchonine. Found chiefly in the grey bark Crystallizes in large anhydrous prisms, soluble in alcohol & ether The salts are intensely bitter, precipitated by gall nuts, heated with KO it becomes Chinodin or quinidine [crossed out] Brilliant prisms soluble in alcohol difficulty in ether Aracin. Found in China cusco. Alkaloids of strychnine family. found in seeds & bark of nux vomica in the 178 Ignata bean. Contains 2 alkaloids Strychnine C42 H22 O4 N2 Brucin C46 H26 O8 N2 Colourless 4 sided prisms, scarcely soluble in alcohol or HO, intensely bitter, soluble in aqueous alcohol when boiling, frightful poison Nitrate. have been used in medicine Tests. Add to the suspected solution Ko2CrO3 & HOSO3, it it produces a violet blue, passing to red. Brucin With 8HO. Crystallizes in colourless prisms 4 sided insoluble in HO & ether 179 readily in alkalis with strong oxidizing agents it forms methylic ether. Alkaloids of the solinacia family. There are 3. Nicotin Hyocyanin. - Atropin C34 H23 O6 N. Occurs in atropa. White, sharp bitter taste soluble in HO & alcohol. Fuses, & decomposes at higher temps. Salts decompose readily. Violent poison, dilates the pupil of the eye. Salts are soluble but difficulty crystallizable Hyocyanin. Has properties similar to atropin. Veratrin C64 H52 N2 O10 18 180 Found in veratrum, produces sneezing is a violent poison. Dervin. C60 H46 N2 O6 Delphinine C64 H32 N2 O4 Colchecine Aconitin Alkal Caffeine or theine. Found in tea & coffee & paraguay tea. In 3 quarters of the globe men have derived a beverage wh they take about the same time of the day. From plants not only of the same species but of a different order They all contain the same alkaloid theine or caffeine call it caffeine. Caffeine C16 H10 O4 N4 tetramine you may view diamines or tramines as monamines. N2 | | H2 | H2 | H2 maybe = N | | NH4 | H | H N | | NH3. | H | H | H In wh the radicals of compound 181 ammonias replace the H Theine or Caffeine. Occurs in tea & coffee. Prepared from tea by subliming it. Crystallizes in thin brilliant needles 177°C sublimes at a higher temp. Difficulty soluble in cold HO, is a weak base its salts are decomposed by HO. In large doses it produces increased action of the heart. irritability of temper If you take 3 grains of theine a day about 2 cups night & morning you [crossed out] may retain you usual temper & state of nerves. If you take 4 or 5 grains it produces irritability of temper & nervousness. If you feel in a nervous state 182 without being able to account for it, it us very probably from this cause. To cure it, take chocolate instead of tea or coffee for some days when it will most probably be cured. Theobromine Occurs in cocoa. It is methyl theine. Hydrates of Carbon Under this head are included all bodies wh have the genera formula CmHnOn Such bodies are starches, sugars gums, bodies wh have a neutral or indifferent character. Dilute acids convert most of them to grape sugar Acts on sawdust by HOSO3 & it is converted into grape sugar. Oxidizing agents convert them to oxalic acid. 183 The views of their chemical constitution are not certain They are at present supposed to be alcohols If the H & O be not present as HO it is in a form nearly approaching it. Take grape sugar for instance C12 H14 O14 It has the same volume as 14 atoms HO frozen to ice the C occupying no appreciable bulk When dissolved it occupies the same volume as 14 atoms of liquid HO. The H8-O comport themselves in solution as HO & when solid as ice. Cellulose C36 H30 O30. It is the basis of vegetable structures. You have it nearly pure in cotton wool. Occurs in the sap of growing vegetables. It is the same in composition from whatever source derived 184 Is nearly pure in the pith of elder rice paper, linen & cotton. Prop. It is a white, solid, sometimes parent Its s.g is a little higher than that of Ho. Its composition is the same but its physical characters differ according to the source whence it has been derived. It is compact in the branches of trees hard & dense in the shells of the filbert & cocoa nut. It is digested or not digested by animals according to its physical condition. It is easily transformed HOSO3 boiled with it converts it into dextrin & then to grape sugar. These all being the same in percentage composition. Digested with HONO3 it forms guncotton. 185 guncotton. [Illustration] Puts cotton in a mixture of HOSO3 & HONO5 washes & drys it. Part of the H has been substuted by NO4. There are several kinds according to the length of time it remains in the acid. Cellulose C36 H30 O30 Gun cotton A C36 H21 (NO4)9 O30 B C36 H22 (NO4)8 O30 C C36 H23 (NO6)7 O30 D C36 H24 (NO4)6 O30 Common paper is cellulose or lignin in another form . A curious transformation is effected by HOSO3 wh converts it into vegetable parchment. Take 2 volumes of the strongest oil of vitriol & one volume of HO carefully measured. 186 Dip ordinary unsized paper, which blotting paper into it & wash well the last HO should have a little NH3 in it to remove all traces of HOSO3. Wash again to remove the NH3 & dry it. The strength of the paper is much increased, a slip of paper that would have before broken by 5lbs will afterwards require 72lbs to break it. Starch. C12 H10 O10 Is very extensively distributed in nature. It varies in its forms according to the source from wh it is obtained Grains of starch in Tous les Moïs are 1/260th in. in diameter. Those in wheat are 1/1000th in. & in rice 1/3000th. in. Starch exist in various quantities in vegetables used for 187 food. There is in Wheat flour 57 to 67 P.C. of starch Rice 85-86 Barley 39 40 Oats 30 40 Rye 54 61 Lentiles 39 40 Maize 65 66 - flour 77 Buck Wheat 43 44 Beans 37 Peas 38 Potatoes 23. Prop. It is white tasteless, insoluble in cold HO & ether, when put in hot HO it swells up & forms a jelly. This is not a true solution for freezing separates it into grains of starch. The youngest grains separate first Test. Put a little Cl into a mixture 188 mixture of the starch solution & KI. The Cl is liberate I. Dilute acids convert starch into dextrin Heated with dilute HOSO3 it becomes grape sugar NO5 dissolves starch & HO precipitates it as an explosive compound as gun cotton in fact. By carefully heating it from 160° to 200°C it becomes dextrin. British gum is made in this way. Manufacture of starch. It exists with gluten in flour. To get rid of the gluten, subject starch to fermentation by wh. the gluten is destroyed, this causes a very bad smell. A new process has been proposed Dissolve the gluten by alkalis & then the starch remains. To get it from potatoes. 189 Grate the potatoes & put them on [illustration] a sieve, pour HO on them stirring them all the time The starch passes thro' the sieve & settles at the bottom of vessel placed below it. Wash the starch once or twice Special Starches. Several are sold for food. Sago is got from the pith of the sago palm. It is made into a paste & pressed thro' a perforated metallic plate & then exposed to the heat of steam to dry it. Tapioca. Is got from the root of the manioc. This root contains HCy wh is separated in the process of making. Arrowroot. Is got from the root stocks of various plants. Salep Is made from the root of the male orchis. 190 Starch in the animal kingdom Sometimes in healthy animals tissues, granules of starch have been found in the brain. The waxy appearance of the liver Inulin C26 H20 O20 + 3HO. Distinguished from starch by not giving a blue with I. Exists in chicory, dandelion Becomes yellow with I. Long boiling converts it into dextrin & then to grape sugar. Lichenin Found in Iceland moss, soluble in hot HO. Irish moss contains another kind C10 H10 O10 + 3HO. Peculiarly distinguished by forming a precipitate with gelatin. 191 Take a solution of Irish moss. & add it to a solution of gelatin no precipitate is formed Add a drop or two of alum & you get a stringy precipitate. Glycogen. Got from mans liver. I produces a dark red colour with it. It has no taste or smell forms a paste with HO Found in the saliva, pancreatic juice Diastase & dilute acids Its formula is given as C12 H10 O10 C12 H12 O12, & as C12 H16 O14. Dextrin C12 H10 O10. It is a product of the transformation of starch Got by roasting starch. 192 10 parts of starch are moistened with 3 of HO, the HO is to contain 1/150th of its weight of HONO5. The paste is allowed to dry spontaneously. It is a colourless transparent body like gum, deviates the plane of polarized light to the right hand, there seems to be an intermediate compound between starch & dextrin, soluble in HO wh starch is not & blued by I wh dextrin is not. Distinguished from gum by forming a beautiful blue solution with Cu OSO3 & KO. When this is heated suboxide of [illustration] Cu is deposited. Dextrin is used as a gum for 193 machinery as in calico printing To prepare glutinous bandages to reduce fractures. Gums. They have the same composition as starch, form a mucilaginous solution with HO. They all give mucic acid with HONO5 instead of oxalic acid as starch does. Quantities of cellulose & gum In one lb of the following substances there are. In Potatoes 327 grs cellulose 27 grs gum Rice 218 87 Wheat 109 109 Barley 2oz 146 Oats 2oz 218. Gums have the same percentage composition wherever 194 obtained but seem to have different combining proportions Gum arabin or arabic C12 H11 O11 Unites with bases as acetate of Pb. Is soluble in cold HO A solution of 18 P.C is so thick that it cannot be filtered, it is insoluble in alcohol. Cerasin The gum from cherry trees. Bassorin. Found in gum tragacanth seems to be a modification of pectin or vegetable jelly Pectin The gelatinous principle of fruits carrots, turnips &c. It is probably identical with Bassorine. It only swells in HO without dissolving. It seems to be a feeble acid. 195 It is rendered soluble by long boiling & passes into ordinary gum. Sugars Cane C12 H11 O11 Fruit C12 H12 O12 Grape C12 H12 O12 + 2HO Milk C24 H19 O19 + 5HO Mellitose C24 H24 O24 + 4HO Eucalyn C12 H12 O12 + 2HO Sorbin C12 H12 O12 Inosite C12 H12 O12 + 4HO Under the name of sugars are included all vegetable substances wh have a sweet taste They are formed during the life of the plant but are perfectly definite chemical compounds & crystallize They are so distinctive in their characters that they may be divided into 2 classes. 196 Sugars susceptible of vinous fermentation by yeast. Sugars not susceptible. Grape sugar or glucose C12 H12 O12 + 2HO is in crystallized state really C12 H14 O14. Occurs in the juice of grapes, in plums, cherries & dried fruits. Occurs in many of those as fructose. Fructose is uncrystallizable. Honey becomes crystalline after some time from the fructose in it becoming grape sugar. It occurs in the animal kingdom as a normal constituent of the liver. Occurs in diabetic urine. It is formed very quickly in the body under certain circumstances. If the fourth ventricle of 197 the brain is irritated by a needle diabetic sugar appears in the urine a few minutes after. Test. Heat a solution suspected of containing it with CuOSO3 & a few drops of KO. Cu2 O is formed. It first appears as a yellowish hydrate but afterwards reddish It is prepared on a large scale by allowing starch & HO at 130° F to flow into a vat containing HO & 1PC of HOSO3. It is boiled for 1/2 an hour when all the starch is converted into grape sugar. Neutralize by CaO & crystallize. Prop. It crystallizes with difficulty in warty concretions Tastes less sweet than cane 198 sugar, is soluble in HO & alcohol. Turns the plane of polarized light to the right. At 100°C it melts & loses 2HO at a higher heat it becomes brown does not taste sweet & is then called caramel, whose formula is C12 H9 O9 & is used for colouring Grape sugar unites with bases & forms saccharides 2(C12 H12 O12) 3 Pbo sesquisaccharate of Pb. Unites with NaCl & forms a crystalline compound It is also said to combine with organic acids. It is easily oxidized With HOSO3 it forms conjugate acids, act on that by strong bases & it forms glucic acid C8 H5 O5. 199 When a solution of grape sugar is acted on by yeast it is converted into alcohol & CO2. C12 H12 O12 acted on by yeast = 2eq. alc. 4 - CO2. When cheese, muscle or other nitrogenous ferment acts on sugar the change is quite different. Lactic acid C12 H12 O12 = (C6 H6 O6)2. If you carry this farther & the putrid cheese acts more on it. C12 H12 O12 = 1 Eq Butyric acid C8 H8 O4 4 - CO2 4 - H C4 O8 H4 C12 H12 O12. Ultimately sugar is converted into mucic acid or rather into a slimy acid whose composition is not well known. 200 Fruit sugar or fructose Has the same composition as grape sugar & only differs from it in not being crystallizable. Is found in honey & fruits. Cane sugar C12 H11 O11. Introduced into Europe some centuries before the Christian era but did not come into general use till the discovery of America. Occurs in sugar cane, beet root, sugar maple. Readily crystallizes in 3 forms. in the crystalline form as sugar candy, in the vitreous state as barley sugar. Barley sugar gives out much heat in passing into the crystalline form. The same thing takes place 201 with AsO3. Readily crystallizes in 4 sided rhomb The taste is sweeter & purer than that of grape sugar. Is soluble in 1/3 its wt of HO less soluble in alcohol than glucose. Heated to 160° it melts to a colourless liquid & cools in the vitreous state as barley sugar. Barley sugar after a time becomes crystalline. By a strong heat sugar becomes [crossed out] caramel. When a solution is boiled with dilute acid it becomes fructose & if for 2 hours longer grape sugar. With strong bases it forms saccharides. C12 H11 O11 BaO. Cane sugar cannot be fermented 202 fermented by yeast without becoming grape sugar. If you take equal wts of cane & grape sugar, the cane sugar will require more yeast than the glucose to ferment it, the extra yeast being employed in converting into glucose. Manufacture of sugar. It exists in various substances but that used in this country is chiefly obtained from cane. The sugar cane is cut before flowering & the juice expressed. The juice contains a good deal of albumen wh would act as a ferment & wh is separated by coagulating the albumen This is called defication. You put in a certain quantity of lime or as lately practised of CaOSO2. Boil & the 203 albumen is coagulated. The syrup is then evaporated. If you evaporate at too high a temp. it is converted into fructose, to prevent this it is boiled in vacuum pans in wh it boils at instead of 220°. It is then transferred to wooden cylinders & crystallized. It is drained from molasses by means of an extremely rapidly rotating perforated cylinder called the Jim Crow & sometimes the devil. The best canes contain about 18 PC of sugar but only 7 to 10 PC is got On the continent sugar is got from beet root. The roots are pulled in October They are rasped & the juice 204 expressed. The juice contains 10 PC of sugar but the manufacture is so much better conducted than that of cane sugar that 7 PC is obtained. In one manufactory in Belgium they got 8 1/2 P.C. There is the same defacation & evaporation as in cane sugar It is filtered thro animal charcoal. The crystals are longer & flatter than those of cane sugar, & its taste not so sweet maple sugar Holes from 1/4 to 1/2 an inch deep are made in the wood of the maple & the juice collected from them by reeds or spoub wh are stuck into them. The juice is collected in March April & May. 205 Each tree yields 3 lbs of sugar in a season & continues to do so for 30 years The juice is concentrated & crystallized every 24 hours. Refining of sugar. Raw sugar is dissolved in lime HO & mixed with bone charcoal & steam blown thro' it & if very impure bullock's blood is added. It is filtered thro bags of twilled cotton, & thro animal charcoal (burned bones). It is evaporated in vacuum pans. The syrup if evaporated in air may rise to 230° wh converts it into fructose, while if evaporated in vacuum pans 140° to 150° is sufficient. It is evaporated till the syrup is so strong that a thread 206 drawn from the finger will return to it without breaking. It is heated to 170° F run into conical moulds. Sweetness & uses of sugar. The sweetness of sugar is definite. 1 lb of cane sugar is equal to 2 1/2 lbs of grape on 3 lbs of milk sugar in sweetness. It is chiefly useful as a food in supporting active respiration, useful in keeping up the animal heat. It is good for infants for this purpose since being soluble it is more easily assimilated to the system. For this reason it exists in large quantity in milk. In the United States the consumption of sugar per 207 head of the population is [crossed out] 40 lbs. In France 4 lbs in Belgium 6 in Austria 2 1/2 in Russia 2 1/2 in the united kingdom 28 in Benzuela 110. Cane sugar is found in plants during the germination of seeds & previous to the unfolding of their buds. The bark of birch contains a good deal Grasses & palms contain most when about to blossom. Jaggery, cocoa nut & wine palms In America sugar is got from the stalks of maize. Relation of H & O in sugar. The H & O stand in the proportion necessary to form HO In such a state also as if it were present in the form of HO. 9 atoms of HO in the state of ice is equal in volume w 9.8 atoms of HO. 208 C12 H11 O11 = 171/3p.SM.1.6 = 106 atomic vol. 9.8 x 11 = 107.8- of 11 atoms of HO in the state of ice. The bulk of an atom of sugar is the same as that of the HO in it in the state of ice the C occupying no sensible space. Milk sugar = 180/1.543 = 116.6 at vol 9.8 x 12 = 117.6 at vol of HO in it. If you dissolve sugar in HO you only increase the HO by the bulk of the HO in the sugar the C occupying no sensible space. Sugar of milk. C12 H11 O11 + HO or more usually C24 H22 O22 + 2HO. milk sugar is only found in the animal kingdom Prep. Evaporate whey after the separation of the curd & crystallize 209 crystallize on twigs. Crystallizes in 4 sided prisms terminated by 4 sided pyramids. The crystals are hard & gritty, feebly sweet, soluble in HO, more difficulty than other sugars, in 6 parts of cold HO & 3 to 4 of hot. It does not become syrupy, on account of its small solubility & does not deliquesce in air. At 130°C it loses its HO of crystallization at higher temps. it becomes brown & is called Lacto caromel C12 H10 O12 It forms saccharides. Precipitates Cu2 O from solutions even in cold but less readily than glucose. Dilute acids convert it into lactose wh has the same formula as grape sugar but does not 210 form a compound with NaCl Although milk sugar does not ferment the Tartars ferment mares milk & make cumase Other fermentible sugars. Trehalose C12 H11 O11 Found in a substance called Trehala a substance used in the East for food a product of insects. Megatose. C12 H12 O12 + 2HO. Got from the twigs of the larch Mellitose C12 H12 O12 + 2HO. From the manna of Eucaliptas Non fermentable sugars. Inosite C12 H12 O12 + 4HO. This is muscle sugar Found in the muscle of the heart in the brain & nerves in unripe common beans & in the cells of the lung & the liver 211 Prep. Crystallizes in small crystals efflorescing in air. Soluble in HO & weak alcohol insoluble in alcohol & ether. At 210° it melts to a clear liquid. Dilute acids do not change it. It does not reduce Cu It does not suffer vinous fermentation, by cheese it suffers lactic or butyric fermentation. Scyllite Is found in the liver of shark If you evaporate Inosite nearly to dryness & add CaCl Sorbite is Is got from the berries of the mountain ash. Its taste is sweet It does not ferment & does not produce grape sugar when boiled with acids 212 Sugars unite with various organic substances. Salicin is one of these. They are called glucosides . Salicin C26 H18 O14. It is an antipyriodic like quinine When boiled with sugar it breaks up into sugar Occurs in willow, poplar Crystallizes in small brilliant colourless prisms, intensely bitter, melts at 120°c Soluble in hot HO, difficultly in cold, soluble in alcohol not in ether. Concentrated HOSO3 dissolves it with a purple red colour. By the action of amulcin, the ferment of almonds* it splits up into saligenin & grape sugar. C26 H18 O14 + 2HO taken up by the action of the amulcin = salignen C14 H8 O4 + glucose C12 H12 O12 x Or by the action of ptyalin the ferment in saliva. 213 Heated with acids it breaks up in a similar way but loses 2HO C26 H18 O14 = C14 H6 O2. salintene + C12 H12 O12 grape sugar.x Saligenin is the alcohol & salintene the ether of the alcohol. There is a large number of glucosides. Populene C40 H26 O20 Obtained from poplars. By the action of amulcin it is converted into glucose saligenin & benzoic acid. C40 H26 O20 = C12 H12 O12 + C14 H8 O4 + C14 H6 O4 Quercitrene Got from the quercus & the bark of the horse chestnut Convolvulene Obtained from jalap roots. Tannine. Is tannic acid & glucose. *Salicin distilled over CaO gives carbolate of lime. 214 Colouring matters These are associated together more by technical use than by chemical relations. They are unlike bodies. They are found in all parts of different plants. They are difficult of isolation Method of doing so. Boil with Ho, alcohol & ether according to their solubility; agitate with PbO wh takes up the colouring matter. Decompose the Pb compound by HS & evaporate in vacuo. Sometimes the colouring matter does not exist in the plant but is formed by oxidation or by the action of a ferment. Thus, madder root does not contain the colouring matter in it, till it has been acted on 215 by a ferment wh the root itself contains. It yields a whole series of colouring matters. Most of these colours attach themselves to an animal substance much more readily than to a vegetable one. Puts a little white of egg wh has been coagulated by heat in the bottom of a vessel into a colouring matter wh dyes it while a vegetable substance is not much affected unless a mordant is put on it. Silks & woolens are dyed directly by these colouring matters. To dye calico print a pattern on it by an acetate. To produce red with madder print with acetate of alumina 216 For purple with acetate of alumina & acetate of Fe. For black with acetate of Fe alone The cloth is hung up & the acetic acid flies off. Puts a cloth printed with alumina in logwood Mordants act more by their acid than basic characters they are sesquioxides. Protoxides are not good mordants. One method of dying is if you can put into the pores of the cloth a colour naturally insoluble & render it insoluble in the cloth itself. This is done in the case of indigo. Mix FeO & KO or CaO with indigo blue, this gives indigo white. Indigo blue differs from indigo 217 white by 1 H. Indigo blue C16 H5 NO2 white C16 H6 NO2 When indigo white is poured from one vessel to another the H is oxidized to HO & it becomes insoluble indigo blue. [illustration] It is large jar in wh is indigo while the sediment is at the bottom. It is called an indigo beck. Dips a cloth printed with an oxidizing substances (CuOSO3) into indigo white. The printed parts are left white, because the CuOSO3 oxidized the indigo white & rendered it insoluble on the surface of the cloth so that it could not penetrate. Adds some alum & a little NH3 to a solution of cochineal. The A2 O3 precipitates it as a 218 Lake. It is this property wh enables the mordant to take down the colour with it & fix it. Madder. Madder is got from the root of the Rubia tinctorum found in Turkey, Holland & the south of France. Fresh madder does not contain colouring matter but contains a resin called rubio erithric acid C32 H18 O18. By the action of a natural ferment within itself it becomes alizarin the colouring principle of madder & glucose. C32 H18 O18 = C20 H6 O6 + C12 H12 O12 The is a large number of colouring matters in madder Alizarin subliming is orange 219 it is red. Alizarin C20 H6 O6 Crystallizes in fine red prisms orange red after subliming. Sparingly soluble in cold HO readily soluble in alcohol, ether & hot HO. Alkalies dissolve it CaO & Bao give blue lakes. Al a deep red. Fe2 O3 a purple It has very much the composition of naphthalin. If you replace some of the H in naphthalin by Cl you get a chlor-alizarin. It is alleged that alizarin is obtained in France from naphthalin. Purpurin C18 H6 O6 Occurs in old madder not in 220 new. Prepared from alizarin acted on by yeast Crystallizes in yellow red prisms Fuses easily & sublimes. Alkalis dissolve it yellow. BaO + CaO give purple lakes. Rubiacine C32 H11 O10 A yellow colouring matter. Is a product of the natural fermentation of the original resin Crystallizes in yellow needles gives the yellow shades in madder dyeing When madder has been used in dyeing one half of the colouring matter is taken up the other half used to be thrown away. The spent madder is now digested with very dilute HOSO3 & steam blown 221 thro it. It is then produces dyes as good & perhaps even of more brilliant shades than the original did. Logwood It contains a honey yellow [crossed out] substance wh is called Hœmitoxalyn wh has no relation to the colouring matter of the blood. Its formula is C32 H14 O2 It forms a red with Al -black - Fe. Crystallizes in violet microscopic crystals wh dissolve red. By a nitrogenenous ferment especially by ammonia if produced it becomes much more powerfully tinctorial Brazil wood. None of the yellow dyes have been much examined Quercitron C. 222 Indigo. It is got from plants of the genus Indig ofera from is atus tinctoria or woad, found in the urine of cows & in that of men in some diseases. Sometimes occurs in milk to wh it gives the blue colour. Prep. The leaves of the indigo plant are macerated & CaO added & allowed to ferment; the indigo white is formed wh soon becomes insoluble indigo blue. Add a per salt of fe to indigo white & it becomes indigo blue. Indigo blue as it occurs in commerce has S.G 1.35. Crystallizes when quite pure in crystals wh have a coppery lustre. 223 HOSO3 dissolves it completely Pure indigo blue may be fused. You may suppose indigo blue to be the radical & indigo white the hydrate. Indigo blue C16 H5 NO2 - White C16 H5 NO2 H. There is one other method of dyeing. Topical dyeing. It is the means by wh you can get an insoluble powder on the surface of the cloth Albumen from blood & casein from cheese is sold for this. Casein is dissolved in NH3 mixed with the colouring matter & heated so as to allow the NH3 to evaporate. Very often these topical applications 224 applications are arsenic green. Or take albumen & colouring matter such as ultramarine expose to steam to coagulate the albumen. [Illustration] This method has enabled many styles of printing to be employed. Cu or As colours should not be employed as they occasion great injury to the health. Many colouring matters are glucosides. They seem to be weak bases. The best mordants are those oxides on the verge of being acids. Mordants are the metallic oxides Chemically they are called lakes. Colouring matter of lichens. They readily split themselves up into several acids, some of wh readily give colouring 225 matters with NH3. Erythric acid C46 H22 O20 Orsellenic C16 H8 O8 Orsellic C32 H14 O14 Evernic C34 H16 O14 Some when treated with stronger acids as HOSO3 or HONO5 break up into new compounds & produce colouring matters [Illustration.] adheres to albumen Albumen is printed on the cloth & coagulated by steam & dyed by the the archil colour. One or two animal colours are employed in the arts. Cochineal. It consists of the dried bodies of insects wh feed on a certain kind of fig. This dye contains carminic acid C28 H14 O14 226 This unites readily with bases. Another insect forms the lac dye used for dying cloth red. Volatile oils, resins & caoutchoue. Essential oils. They are occasionally found ready formed in plants as in the orange & lemon. In other cases it is made by the action of HO on seed as in bitter almond & mustard oil. In the animal kingdom These are rare, altho' they occur in ants. The general classification of essential oils is more pharmaceutical than chemical. They are either solid or liquid When solid they are easily fusible & are volatile Though the boiling points of some are high they generally 227 ally go over readily in steam. They produce a temporary stain on paper, fixed acids produce a permanent one. They have a peculiar penetrating odour generally agreeable. They are rarely pure in commerce They contain a solid substance wh is the oil oxidized or hydrated & wh are called stereoptenes. The oils are prepared in some cases as from the orange & lemon by pressure. More usually as from aromatic plants by hanging the plants in bags & passing steam thro' them & condensing it. They are prepared for perfumery by a peculiar process. A cake of tallow is taken & the flowering plants spread over it. It is then gently 228 heated not enough to melt the tallow. The tallow gradually extracts the oil. The tallow is then treated with alcohol wh dissolves out the oils. They may be divided into different classes. 1st Essential or volatile oils free from O. 2nd - containing O. 3d - S. 4th - wh suffer change by distillation. The central formula around wh they all turn is that of camphine C20 H16 for a 4 vol. formula. Some have only half that C10 H8. Some have these two formulas united C30 H24 229 Essences isomeric with camphine. Essence of bergamot - lemons - orange - birch - camomile - juniper - copaiba C30 H24 - carraway - cloves - ginger - cubebs - thyme - valerian Turpentine. By this is meant camphine C20 H16. Boils at 160°c S.G. 0.864. Got by wounding pines, when it flows out, this is distilled & gives essence of turpentine 230 In this state it is colourless transparent oil with a peculiar disagreeable odour & burning taste. Insoluble in HO, difficulty in common alcohol readily in absolute alcohol & ether concentrated acids dissolve it. It converts O into ozone. If you shake some up in a bottle with air you may detect the presence of the ozone formed applying the test. It contains so much H that if you moisten some cotton wool with it & having warmed it put it into some Cl, HCl fumes are formed & it takes fire. It combines with HO & forms solid stearoptines C20 H16 + 4 HO 231 C20 H16 + 3HO, C20 H16 + 2HO & C20 H16 + HO. These are called camphors of turpentine. Essences not isomeric with camphine. Oil of peppermint C20 H18 Contained as a solid hydrate in certain oils C20 H18 + 2HO. Essence of cedar wood C32 H26 C32 H20 + 2HO is a solid hydrate. Oxygenized essences. Camphors Common Camphor True laurel camphor C20 H16 O2 Obtained from camphor wood by chopping the wood in branches & distilling in HO. Fuses at 175°C boils at 205°C. Vap. density 5.32. Difficult to pound from its elasticity, but may be done 232 easily by putting a drop or two of alcohol on it & then pounding it. Borneo camphor C20 H18 O2. Got by puncturing the tree. Crystallizes in 6 sided prisms colourless & transparent Other camphors. Stearoptines of many plants are really camphors. In peppermint & cedar oil C20 H20 O2 C32 H26 O2 Resins These are exudations from They appear to be formed by the oxidation of the essential oils more oxidized than the camphors. Camphors C20 H16 O2 Resins C20 H16 O2 - n H + n O. 233 They are used for varnishes by mixing pounded glass with pounded resin & treating with alcohol or wood spirit Copal, Mastic, Sandarac Common varnish for maps 24 parts Mastic 3 - Venice turpentine 1 - Camphor 10 - pounded glass Mixed with 72 parts of oil of turpentine & filtered. Lac. Sold in 3 forms. Stick lac. An insect perforates certain trees & the lac It is sold in commerce on the twigs. This is pounded & heated with NaOCO2 wh dissolves out the colouring matter wh is used 234 for dye. The lac is melted in canvass bags & is squeezed on bamboos. & is then called shell lac. Got on ficus indigus or ficus religiosa. Used for sealing wax & for stiffening hats for wh purpose it is dissolved in wood spirit. Sealing wax 48 parts lac 12 venice turpentine 1 Balsam of Peru 36 Vermilion stirred up with it. For making lacquers of wh there are several kinds the usual one is, Lac is mixed with 1/2 its wt of sandarac & a little venice turpentine, dissolved in 10 to 12 parts alcohol. The brass is heated before it is applied. 235 Guayacum. Obtained from guayacum officinalis It is bluish green or brown The alcoholic solution is a good test for ozone wh makes it blue Jalaps. Contain glucosides Jalapin is a glucoside. Amber It is a fossil resin found in coal but chiefly thrown up on the shores of the Baltic between Memel Often contains insects of extinct species but related to present species. Seems to have been an exudation S.G 1.065. Insoluble in alcohol & ether, soluble in essential oils. After having been 236 once fused it is soluble in turpentine & then forms amber varnish By dry distillation it yields succinic acid & amber oil. With HONO5 it forms artificial camphor having a smell like musk. Caoutchouc. It is a resinous substance suspended in the milky juice of various plants. In its ordinary state in commerce it is impure. When separated from its impurities its formula shows it to be a hydrocarbon nC8 H7 Soluble in chloroform but is precipitated by alcohol, melts at 120°C & at 200°C it beings to decompose. Insoluble in HO & alcohol Soluble in turpentine, benzol 237 naphtha & chloroform. The solution in naphtha is used for water proofing cloths. Unites with S & forms vulcanized india rubber. Got by treating with sulphide of C or usually with chloride of S. S2 Cl . Gutta percha. Is like india rubber in its composition & many characters except its want of elasticity at common temps. Is the concrete juice of percha. Scarcely elastic at common temps. but becomes elastic at 212°f. Is worked at a high temp.; welds when soft is soluble in the same reagents as caoutchoue. Is not attacked by HFl. Vulcanized india rubber gradually 238 gradually loses its S & becomes brittle especially if kept in contact with metal wh takes the S. Asphalt & bitumen Occurs extensively in nature as springs some of wh contain the asphalt in solution The salt of the earth spoken of in the Bible probably means bitumen & when it is spoken of as having lost its savour it means that it had lost some of its volatile hydrocarbons. It was ordered to be used in burnt sacrifices & was probably smeared over the bodies & thus rendered them more combustible. Asphalt is the residue of mineral oils wh have lost their volatile hydrocarbons. 239 Occurs in Turkey Persia Egypt & even in our own country There was a spring near Edinburgh & there are in the Industrial Museum several black candles made from it. There is one near Alfreton in Derby from wh paraffine was first made. There are many mineral hydrocarbons like asphalt. Ozokerite C2 H2 n. Sheerit Found in brown coal in Germany Fichtilite C8 H7 Found in fossil pines. Hartit C6 H5. Idrialit C80 H28 O2 Found with cinnabar in Idria. 240 Animal Chemistry. We could make urea & grape sugar waste products of vital agency but chemistry has yet made but small progress in producing the The ruling agency in vegetable & animal life is vital agency. When we see plants growing on the same soil, nourished by the same substances, watered by the same rain & stimulated by the same manure & yet producing substances as different as starch & morphia we cannot tell what the hidden force wh produces these transformations is. Latterly we have got a more exact idea of force & know that, heat, electricity, chemical affinity &c 241 are all resolvable into motion. But although our ideas of force are extending & we can compare the animal body to a steam engine yet one force is left of wh we known nothing viz., vital force. We know the engine but not the engineer. Histogenetic substances. All those wh build up the frame- work of the animal body are termed histogenetic. They are the substances of wh the organs consist. Fat is not an organic, is not a histogenetic substance. Albumen Fibrin Casein Syntonin Fibrin in muscle Globulin found in the eye. 242 Hemato crystallin. Most of them, the first three at least are found indifferently in the animal & vegetable kingdoms. If you stir fresh blood with twigs fibrin coagulates on them. Whip fresh juice of cauliflower with twigs & you get fibrin Boil cabbage juice & you get albumen. You can get it from blood Add an acid such as HCl to casein & cheese is formed Add HCl to solution of peas & you get the same casein These substances exist both in plants & animals. General properties whence soever derived. Uncrystallizable translucent of a yellowish colour: tough 245 when dry, adhesive or jelly like when moist. Brittle gelatinous plates when dry. Exist in 2 forms In the soluble state as fibrin in the blood In the insoluble state as when the blood is out of the body. The exact cause of the transformation from the soluble to the insoluble state is not known They part with 2P.C of some proximate constituent* when they become insoluble. insoluble varieties They seem to dissolve unchanged in acetic & phosphoric acid. Mineral acids decompose them All are transformed by long boiling in HO When oxidized by HONO5 or *As soda or potash generally alkalies 244 other oxidizing acid they produce acids of the alcohol series beginning at formic & going up to caproic acid They also produce aldehydes. Some in oxidizing produce oil of bitter almonds & acids of benzyl series Digested with HOSO3 or strong HCl. they produce almost invariably Leucine & Tyrosine & commonly Glycine, besides NH3 salts under the influence of caustic alkalis When moistened they putrefy the elements dividing themselves according to their greatest affinities. Putrefaction thus differs from decay wh is a combustion. Among the products of their putrefaction are the carbonate butyrate & valerate of NH3 , NH4 S 245 Common test for these; for any of these nitrogenous bodies. Moisten with a salt of H8 having an excess of Hg & heat to [Illustration.] 212°. They become red on the surface. Do not heat too violently. This is a test for all histogenetic substances. Mulder argued that they all contained a substance called protein wh was the basis of them all. According to Mulder it has the formula C36 H25 N4 O10 + 2HO wh can be driven off by heat. Percentage composition of protein according to this formula. C = 54.7 N = 14.2 H = 6.8 O = 24.3 He supposed other bodies to be 246 protein combined with P & S. Though his views are no longer held by chemists the nomenclature is retained & they are called protein compounds. Probably they are all the same as regards organic composition & the ground work is the same in all & they differ merely in form. Albumen Is the chief type of the group. Exists in various states probably owing to the amount of alkali with wh it is united.* Occurs in vegetable juices in blood, chyle & lymph in all serous liquids, in the juice of flesh & cellular tissues, in white of egg. Prop. 1st. Soluble albumen As obtained from white of egg it is transparent, yellowish, *Thus its reactions are not always the same 247 soluble body of a glairy consistence. S.G 1.261. When put in HO it swells & dissolves, the solution reacts alkaline from the NaO it contains. Remove this by acetic acid & add HO & it becomes insoluble Metallic salts precipitate albumen Add HgCl to albumen & it forms an insoluble coagulum, on this account albumen is used in cases of poisoning by HgCl. When heated to 63°C it becomes opaline at 75°C it coagulates entirely. It is then insoluble in Tannic acid precipitates albumen. Albumen of blood. is not coagulated by dilute HOSO3 248 Insoluble albumen When albumen is acted on by heat it appears to be the first form from wh all the other nitrogenous substances are formed. It requires very little change to become muscle or the contents of nerve tubes Fibrin Occurs chiefly in blood, lymph & chyle in a state of solution Prop. Separates in an insoluble state in delicate filaments. We know nothing of pure soluble fibrin Coagulated fibrin is opaque yellowish fibrous mass hard & brittle when dry Swells in HO but is insoluble in it, dissolves in solution of KONO5 at 40°C but is coagulated by boiling & acetic acid 249 Digested at 150°C with HO under pressure, by sealing it up with HO in a tube. The fibrin is apparently converted into albumen. It becomes soluble & is coagulated by acids & behaves exactly like albumen. Vegetable fibrin is prepared by putting flour in a muslin bag & kneading it in a stream of HO. The starch is carried thro' the pores & the fibrin remains behind. Gluten of wheat is identical with fibrin Syntonine. Is fibrin of muscle Is the chief constituent of the striated muscles, is in smaller quantity in the smooth muscles & in the arterial coat & spleen When first taken from the body it is snow white. 250 Soluble in HO containing 1 PC of HCl, insoluble in KONO5. Is precipitated from its solutions in alkalis by KCl. or NaCl The solution in lime water is coagulated by heat. Casein. Occurs in the milk of mammals, in small quantity in blood under the name of serum casein. It exists in yolk of egg so intimately mixed with albumen that it used to be thought a separate substance & was called vitellin Exists in the juice of flesh in the juice of the thymous gland. In the vegetable kingdom in the seeds of leguminosæ Prop. Chiefly differs from the other allied substances in its mode of coagulating. Maybe got from milk by adding HCl or rennet 251 Acetic & Lactic acid precipitate it from solutions. Strong acetic acid however dissolves it. Rennet coagulates it. It is not precipitated by heat. The skin formed on the top of boiled milk is caused by the oxidation & not by the coagulation of casein. If boiled with CaCl or Mg OSO3 it is precipitated but the base goes down along with it. On account of this property it is used for cement for glass & earthenware. A poor cheese is made into a paste with lime. Vegetable casein of leguminosae or Legumin Occurs in leguminosae from 20 to 25 P.C. They are even too nutritive The casein is obtained by coagulating 252 coagulating their infusion by rennet or by adding acids. Casein of animals & vegetables is exactly the same Cheese is sold in China made from beans. Its solution when heated forms a skin on the top like milk heated. Globulin. Forms 36 P.C of the crystalline lens of the eye, & got its name from being supposed to be identical with the coagulable part of the corpuscles of the blood. Differs from albumen by coagulating at 93°C. The solution is not coagulable by acetic acid or NH3 . It becomes turbid when the acetic acid solution is heated. Is precipitated by CO2 253 Hemato crystalline It is albumen in a state in wh it can be crystallized Got from the blood of the guinea pig from wh it crystallizes in tetrahedra. Is in the blood of rats & mice. It is difficult to get from man's blood but from it & from the blood of carnivora it is in prisms From the hamster in rhombohedrous Differs from all other albuminous bodies by not being precipitated by metallic salts & Cl2 ONO5 It is obviously a glucoside* The characteristic of all histogenetic substances is that they all contain 15 P.C of N. B Derivatives from the albumenous group * the substance wh remains beside glucose has like same composition as albumen 254 They closely resemble albumenous bodies but contain rather less C. They differ in physical characters They do not form cells but form organic bases of certain tissues With strong HCl, HONO5, & prussiate of KO they are not precipitated Ossein. Prep. But a piece of bone in dilute HCl, & treat with alcohol & ether to take out the fat. Insoluble in HO, is converted into glutin by boiling *Glutin It is a transformed condition of ossein. Is called gelatin in commerce. It is colourless transparent & horny Brittle, heavier than HO, *Different form gluten wh is in wheat, Glutin is the general name for gelatine 255 tasteless insoluble in cold HO soluble in hot Water with 1 P.C of glutin is gelatinous. Long digestion in HO or destroys its gelatinous property Forms a precipitate with tannic acid. Dry distillation produces various bases from it as methytannin Glutin does not appear to be in the body except in the spleen. Chondrin Prep. Boil the permanent & articulate cartilages It much resembles glutin. It is precipitated by acetic acid, per salts of Fe, HCl alum Treated with Many albumenous bodies pass into glutin when boiled 256 Glutin & elasticin are known to us as common glue Glue is made from the parings of ox hides boiled in a coarse cloth cut into blocks & dried. Size is a less strong glue made from the parings of parchment & used in liquid state. Confectionery gelatine Made from the swimming bladders of fish & the parings of fine hides. Abroad it is made from the tendons of rats. In the abattoirs where horses are slaughtered, the carcases are put into rooms plastered so that the rats cannot make holes in them & two or three bricks are left wh can be removed & replaced at pleasure. The rats are allowed to enter at night to clean the bones of the 257 horses before the bones are sold to the P. makers. In the morning the bricks are replaced & a man having a mask & thick gloves & armed with a bludgeon enters & kills the rats, their skins are made into kid gloves & their thigh bones cleaned & made into toothpicks for the London clubs; the rest of the body is boiled down for gelatine. Leather is a tannate of gelatin There are various nitrogenous substances wh occur as derivatives in the animal body These substances are formed probably by the transformation of histogenetic substances arrested in their passage to complete oxidation. They are probably amides Amides contain their N as 258 amidogen NH2 . Kreatin C8 H9 N3 O4 + 2HO . Occurs in the striped & smooth muscles in urine in the brain in blood. It is best got from the flesh of fowls or skate fish in wh there are 3 parts of kreatin to 1000 parts of flesh. It is a clear, transparent colourless, brilliant body crystallizes in rhombic columns loses 2HO at 100°C. Insoluble in strong alcohol but soluble in dilute spirits of wine. Has a bitter taste, neutral in reactions. When heated with strong acids it becomes converted into kreatinin a substance wh also occurs in urine. C8 H9 N3 O4 = C8 H7 N3 O2 + 2HO. When heated with BaO it takes up 2HO, & becomes urea & sarkosine 259 C8 H9 N3 O4 + 2HO = Urea C2 H4 N4 O2 + sarkosine C6 H7 NO4 kreatinine Occurs in blood muscle & urine is is formed by the action of acids on kreatin Crystallizes in colourless rhombic prisms, soluble in HO + hot alcohol, the solution reacts alkaline & is a feeble base, when concentrated it tastes like dilute NH3 . By long keeping it becomes kreatin, especially in presence of lime water Kreatin & kreatinine are products of the oxidation of the tissues on their way to urea. Sarcosin. C6 H7 NO4 Although to be expected, yet it is not perfectly certain that it exists in the urine Prep. Act on kreatin by alkalis. BaOH5 It crystallizes in rhombic 260 prisms soluble in HO Seems to be ami When kreatin 2(C8 H9 N3 O4 ) + 10H8 O = 10Hg + 2HO + 4CO2 + (2C4 H7 N3, C4 H2 O8) Methyluramine C4 H7 N3. It is probably a triamine It is a strong base precipitates oxides, drives NH3 from salts, its constitution is unknown. Sarkin C10 H4 N4 O2 Occurs in the flesh of horses, oxen & men. Crystallizes in colourless transparent needles readily soluble in HO difficultly in alcohol Fuming NO5 converts it into Guanin Guanin C10 H5 N5 O2 . Occurs in guano & spider's 261 excrements in the liver & cavities of pancreas White or yellowish isomorphous mass without taste or smell Insoluble in HO alcohol & ether, soluble in alkalis. Unites with salts as ZnCl. By NO5 or HOSO3 & MnO2 it becomes xanthin. Guanin C10 H5 N5 O2 Xanthin C10 H4 N4 O4 Xanthin occurs in urine occasionally, forms calculi has been found in flesh & salivary ducts An amorphous white mass Soluble in acids & alkalis, little soluble in HO. Resembles sarkosin & in less decidedly basic then they. Cystin C6 H6 NS2 O4 Is a rare constituent of urinary 262 calculi. Has been lately found in nerves & liver Crystallizes in colourless transparent- 6 sided [crossed out] tables. Neutral, insoluble in HO & alcohol soluble in acids & alkalis. Allantoin C8 H6 N4 O6 Occurs in cows, [illegible] & in the urine of calves & dogs Is got by the oxidation of uric acid Is most easily got from calf's urine. Crystallizes in colourless brilliant prisms, tasteless having no smell neutral, soluble in hot HO & alcohol insoluble in ether soluble in alkalis but is decomposed when boiled with them taking up 10HO. C8 H6 N4 O6 + 10HO + 2(C4 H2 O8) + 4NH3 Tyrosin C18 H11 NO6 Occurs in the liver, pancreas in cochineal in root of 263 & is a general product of the decomposition of albuminous bodies by acids & alkalis. Prop. Occurs in white silky crystals. Soluble in hot HO insoluble in alcohol & ether Dissolves without change in alkalis & acids forms conjugate bodies with HOSO3. Aloxan C8 H2 N2 O8 + {2HO or 8HO} Made from guano. By the oxidation of uric acid by NO5. Occurs in octahedral crystals Soluble in HO, the solution colours the skin red. It reddens litmus paper. At 100°C it loses HO. Forms like alkalis HONO5 oxidizes it & forms parabanic acid. 264 Reducing agents as HS convert it into aloxantin. Aloxantin is readily changed Thyanuric acid is C8 H5 N3 O2 S2 Formed when aloxane is treated with SO2 & saturated with NH3. Aloxantin C8 H5 N2 O10 Got by acting on aloxan by reducing agents Crystallizes in colourless prisms dissolves in NH3 with a purple colour. The solution is acid. it gives a violet precipitate with BaO. Its products of oxidation are similar to those of alloxan. Cerebrin C34 H33 NO5 Occurs in the brain. It is a white porous powder, tasteless 265 tasteless, having no smell, insoluble in HO, soluble in alcohol & ether neutral. Decomposed by boiling acids at 80°C Amide acids. Taurin C4 H7 NO5 S2. Occurs in the muscles of all mollusca, in the lungs, sometimes in the kidneys & often in the liver of higher animals. Produced by the action of acids on Taurocholic acid a constituent of bile. Prep. Heat or bile with HCl. Evaporate & exhaust with alcohol. It has been got artificially by heating isotinate of ammonia C4 H9 O8 NS2 it loses 2HO H2 O2 C4 H7 O6 NS2 Taurin It is thus the amide of isatinic 266 acid. It forms colourless transparent 6 sided prisms dissolves easily in HO, insoluble in alcohol & ether. dissolves in acids, is neutral. Leucin C12 H13 NO4 Exists in blood vascular glands spleen, in thymous gland In liver & bile, the pancreas & salivary glands & thin secretions. In the contents of small intestines in the lungs & kidneys* It is always produced by the action of strong acids & alkalis on albumenous bodies Prepared synthetically by heating valeric anhydride with HCy. Valeric anhydride C10 H10 O2 + HC2 N + 2HO = C12 H13 NO4 Leucin is the amide of caproic acid. Caproic acid C12 H11 O3, HO Leucin C12 H10 (NH2 )O3 , HO * has been found in diseased brain 267 Prop. When quite pure it crystallizes in colourless brilliant plates, Freely soluble in HO less so in alcohol & insoluble in ether. The solutions are neutral. With HONO5 it gives various products among others Leucic & Lactic acid. Uric acid. C10 H4 N4 O6 It is biatomic = 2HO C10 H2 N4 O4 . Occurs in small quantity in the urine of man & carnivora, scarcely at all in that of herbivora. The urine of birds & serpents chiefly consists of this & also that of tortoises. Largely in the excrements of butterflies & beetles Traces of it in healthy blood Increases in gout & Brights disease Is in excess in cholera, bronchitis & pneumonia Is a frequent substance in calculi. 268 Prep. Urates in serpents excrements are urate of amonia principally. Treat with alkalis (KO) & add HCl & the sparinly soluble uric acid is precipitated. It is a white crystalline powder difficultly soluble in HO insoluble in alcohol & ether. When heated it is converted into urea, cyamuric acid, NH4 oeo2 HCy. Peroxide of Pb makes it into alantoin, urea, oxalic acid & CO2. This is important. It is only a feeble acid but is bibasic & forms acid & neutral salts. Urates. General formula MO} HO} = Uric Urate of NaO. NaO HO /U 1 eq of HO in uric acid is replaced by 1 of NaO. 269 Difficulty soluble in cold HO, more so in hot. This is the reason that urine sometimes though clear when ejected becomes turbid on cooling. Acid urate of ammonia NHO HO /U Crystallizes in fine needles or an amorphour precipitate scarcely soluble in cold HO Urate of lime CaO HO /U Occurs in calculi & sometimes as a urinary sediment Forms chalk stones in the joints of gouty persons. White amorphous & difficultly soluble in cold HO. Derivatives of Uric acid. When HONO5 acts on uric acid, it is dissolved with a yellow colour & various products are formed. By careful evaporation to dryness & treating with NH3, it becomes purple. 270 Bestway. Take 4 grs. aloxantin & 7 of hydrated alloxan, dissolves in 1/2 an oz. of HO by boiling. Add to 1/6 oz. by measure of saturated solution of NH4 OCO2, & murexide is formed. It must be boiling before adding to NH4 OCO2 . Murexide C16 H8 N6 O12 Has the synonym of precipitate of ammonia. Is used in dyeing. Its owing to the formation of murexide that the guano colours are formed. Guano consists of the excrements of sea fowl It is treated with KO to dissolve the uric acid. The uric acid when treated with NH3 forms murexide. It is then treated with salts of PbO & Hg. Properties of murexide 271 Crystallizes in 4 sided prisms, of a golden green beautiful metallic lustre. Difficultly soluble in HO readily in KO with a purple colour. Test for uric acid. Dissolve uric acid in HONO5 & alloxan is formed It is supposed that murexide contains a compound called purpuric acid & that it is a NH3 compound of this. NH4O} HO} purpuric acid C16 H3 N5 O10 No substance has yielded so many compounds to organic chemistry as uric acid. Some of the chief are, Uric acid & nitric acid form alloxan C10 H4 N4 O6 + 2HO +20 = alloxan C8 H2 N2 O8 + Urea C2 H4 N2 O2 Act on alloxan by a feebly oxidizing agent as KO. 272 C8 H2 N2 O8 + 4HO = mesoxalic acid C6 H2 O10 + Urea C2 H4 N2 O2 Cynuric acid Seems to take the place of uric acid in the urine of the dog. Crystallizes in 4 sided prisms Melts when heated & exhales the odour of hemp nitrile Dissolves in acids & alkalis & has all the charactes of a feeble acid. Inosic acid. HO, C10 H6 N2 O10 . Found in the juice of flesh in small quantity. Forms a solid white uncrystalline mass, soluble in HO, insoluble in alcohol & ether. Reddens litmus, tastes like flesh forms salts. Acids of bile. Bile besides less essential constituents contains NaO salts of 2 nitrogenous acids. 273 These acids are like glucosides They do not contain grape sugar but bodies corresponding to it. The one contains glycin the other taurin instead of glucose. Both contain the same acid. viz, cholic acid. Cholic acid with taurin & glycin forms conjugate acids. Glycocholic acid HOC52 H42 NO11 Occurs as glycocholate of NaO in bile. Is the main constituent of ox gall & is in small quantity in that of other animals except the pig. Glycocholic acid crystallizes in very delicate needles, soluble in hot HO & alcohol, difficulty in ether. The solution tastes sweet & then intensely bitter, reddens litmus With HOSO3 & sugar it gives 274 an intense purple red. Soluble in concentrated acids, without colour at first but absorbs O & becomes coloured. When long boiled with BaO it is decomposed C52 H43 NO12 + 2HO = cholic acid C48 H40 O10 + glycin C4 H5 NO4 glycin is the amide of acetic acid & is a product of the action of acids on gelatin Hence glycocholic acid is a conjugate acid. Taurocholic acid C52 H45 NO14 S2 So called because it contains taurin instead of glycin. It is the second chief acid in bile Occurs as the NaO salt in the bile of man, ox, dog, goat frog boar, anaconda &c. In certain fresh water fishes. Has been detected in the blood in transudations *In the boar is is apparently alone not accompanied by other acid 275 & in urine in cases of suppressed excretion of bile. White amorphous bitter powder soluble in HO Easily decomposed by heating Is decomposed by boiling with BaO taking 2HO. cholic acid taurin C52 H45 NO14 S2 + 2HO = C48 H40 O10 + C4 H7 NO6 S2 Taurin is the amide of isithionic acid. With HOSO3 & sugar it gives the same reaction as glycocholic acid. With ferments the taurs & glycocholic acids are broken up as with [ferment] alkalis. Cholic acid C48 H40 O10 . Crystallizes in transparent colourless tetrahedral crystals Has a bitter but sweet taste, readily soluble in alcohol & ether, difficulty in HO. Its alcoholic solution reddens litmus & dries CO2 from its salts. 276 With alkalis it forms crystalline salts. With HOSO3 & sugar it gives the purple reaction of bile. Hyoglycholic acid C54 H43 NO10 . Substitutes these other acids in the bile of the pig. Not found in that of any other animal. A white resinous substance melts in boiling HO. Insoluble in HO & ether It is a conjugate acid & contains glycin & Hyocholic acid Hyocholic acid C50 H40 O8 . There is another corresponding to it in the bile of the pig. Hyotaurocholic acid C54 H45 NO12 S2 . Lithofellinic acid C40 H36 O8. Exists in oriental. in the biliary concretions of antelopes & goats, of wh it forms the chief part. 277 It belongs to the same class as these others When cholic acid is acted on by acids it forms several substances one of wh is called choloidic acid. Cholic C48 H40 O10 - 2HO = choloidic C48 H33 O8 Amorphous mass melts on boiling readily soluble in alcohol. Cholosterin C52 H44 O2. It is a crystalline fatty substance found in bile but generally in biliary concretions. It is like a monoatomic alcohol Found in the brain blood, lungs It is neutral melts at 145°C sublimes at 360° Gives an aromatic oil by distilling having a smell like the geranium Insoluble in cold alcohol, soluble in boiling alcohol & ether. * Found abundantly in biliary concretions 278 Solutions of bile dissolve it readily It unites with one equivalent of acetic acid with displacement of one eq. of HO. Compound ethers may begot from it as from cedernal C52 H44 O2 C4 H3 O3. All bile of animals is coloured by a substance wh forms a bile pigment. Originally brown in man but, becomes green by oxidation Solid constituents of animals Bones. Those of vertebrate animals are tolerably constant in composition When dried at 212° they have 1/3d. of their weight of organic matter & 2/3ds of mineral matter. Large bones & those wh have much work have more mineral matter General average of the composition of bones taken from various analyses. 279 3CaO, PO5 57 parts. CaO CO2 8 Ca Fl 1 3MgO, PO5 1- mineral matter 67 Cartilage 33 The mineral matter in bones increases with age. The teeth resemble the bones in composition. Dentin is like dense bone. Organic matter in it 28 P.C. The enamel contains no cartilage. Mineral matter in teeth 3CaO PO5 81-88 P.C CaO CO2 7-8 Ca Fl 3-4 3MgO, PO5 1-1 1/2 Muscular tissues. They are extremely complicated & contain many substances but may be on an average. HO 74-80 P.C Solid ingredients 26-20 PC. Among the solid ingredients 280 There are in the 26 parts. Syntonin 15.4-17.7 Gelatinous substances 0.6-1.9 Albumen 2.2 -3.0 Kreatin } Kreatinine } Inosite } Inosic acid } Hypoxanthin } Traces Fat 1.50-2.30 Lactic acid 0.60-0.68 PO5 0.66-.70 NaO 0.07-0.09 KO 0.50-0.54 Mgo } ZnO 0.02-0.03 } Traces. NaO is chiefly confined to the blood & KO is in the flesh. Many of these are dissolved in the fluid surrounding the fibres of the muscles. Healthy muscles have an alkaline reaction but after the rigour of death an acid reaction. Contraction of muscle is always accompanied by oxidation CO2 being evolved 281 In this the sapid constituents of the meat reside & the bodies wh. are so important for nutrition as the phosphates. If you take the flesh of the fox & venison & express the juice & dip the flesh of the fox in the juice of the venison & cook it, you cannot distinguish it from venison. If you take away these juices Supposing you wish to make soup you wish to get out the sapid constituents, in boiling meat you want to keep in these. To make the strongest soup. Mince the meat, put it in cold HO & gradually raise the temperature. You must go beyond 150°F before you coagulate the blood & till this is done the soup 282 has a red colour. To boil meat plunge it at once into boiling HO on about 1/4 hour & then reduce the temp. to 160° by adding cold HO. x The boiling HO at once coagulates the albumen on the surface & the sort of crust thus formed keeps in the sapid & nourishing constituents. To make the strongest possible soup for invalids Take one lb of lean beef mince it & mix with 1lb of HO, heat it very slowly till it boils & all the soluble & gelatinous matters are extracted. You then strain it thro' a cloth The effect on the patient is very different if you leave it with its straw colour or colour it with burnt sugar or burnt onion. If you colour it they think it is much stronger. * Keep simmering & about the end of the operation you may raise to [illegible] again 283 Evaporate this to dryness & you get the true extract of flesh. That sold in shops is only glue. In boiling beef the albumen coagulates at 140°F but the blood globules do not coagulate before 158°F. On this account in roast meat although it is perfectly cooked, the inside sometimes appears raw, the heat there having never been up to 158°. Relative values of meat In 1 lb of each. Veal Beef Mutton Pork HO 10oz-0grs. 8oz-0grs 7oz 16.6.69 3 grs Gelatine 1-2 1-62 1-52 0.385 Fibrin & albumen 1-199 1-122 0-385 0-315 Fat 2-281 4-340 6.176 8-0 Mineral matter 0-312 0-350 0-245 0-105. Salting of meat. When meat is placed in salt a curious action goes on. 284 From its affinity for HO the salt takes the HO from the outside of the meat & dries it. The juice from the inside of the meat is then diffused into this & thence into the brine. But the brine does not easily penetrate into the meat. The sapid constituents & the mineral salts come out. A great part of its nutriment is thus removed from salted meat. When it is long used scurvy & other diseases arising from defective nourishment make their appearance. Components of the brain. They are not satisfactorily made out. Among them are oleine, oleic acid, leucin, margaric acid Cholesterine, stearic & palmitic acid 285 The two characteristic ingredients are cerebric acid & oleophosphoric acid. Cerebric acid. It is a phosphorized fatty acid. & is found partly free & partly in combination with NaO. Insoluble in HO but swells like starch when the HO is heated. Oleophosphoric acid. It is a greasy oily liquid partly found free & partly in combination. Found also in the yolk of egg. When long boiled it is decomposed into oleine & phosphoric acid. Mineral ingredients are of very small amount. They amount in the human brain to 0.027 PC of these 3KO, PO5 55 P.C 286 3NaOPO5 23 PC 3MgOPO5 3FeOPO5 3CaOPO5 There is also PO5 either as stronly acid phosphates of free also SiO2 Glands & their juices Leucin is in the pancreas & spleen, in thymous gland in thyroid body & in living ox. Lyrosin Hypoxanthin in the spleen thymous gland Uric acid in spleen. Formic, acetic, succinic & lactic acid are found in these glands. Inosite in the spleen, liver, kidney Thymous gland pancreas & lungs. Cystin. Taurin Guanin in the pancreas of ox. The mineral ingredients in glands vary much In the liver the KO salts predominate 287 predominate over those of NaO. The reverse is the case in the spleen. Cl forms 2 1/2 P.C. of the ash of the spleen & 3/10 PC of the spleen PO5 forms 33.5 PC of ash of liver & 18.5 P.C of ash of spleen. CaOMgO in small quantity In spleen Fe is abundant, forming 7 to 16 PC of the ash. Mn, Cu & Pb are commonly but not always found both in the liver & spleen. In occasionally Digestive fluids Saliva S.g 1.004 to 1.006 It is always alkaline but more so during meals than when fasting. The saliva of the pyrotid gland contains ptyalin as a marked ingredient It has the same power as diastase of converting starch first into [illegible] & then into sugar It is an albuminous matter in a state of change 288 Ptyalin It is an albumenate of NaO. Forms 1/3 of the whole sold residue of saliva. It is very prone to decomposition or putrefaction. It is a strong ferment. The conversion is almost instantaneous. Composition of saliva of pyrotid gland. In 1000 parts from the dog. HO 995.3 Solid residue 4.7 Of the residue Organic matter 1.7 Alkaline chlorides & sulphocyanides 2.1 CaOCo2 1.2 In certain animals the sulphocyanides exist more than in others. Add a per salt of Fe to saliva & a red color is produced showing the presence of sulphocyanogen. The composition of human saliva is like that of the dog's. 289 HO 994.10 solid residue 5.90 The presence of sulphocyanide of NaO is characteristic. The daily secretion of saliva by an adult man is about 48oz. but differs according to his food. Mineral matter in it consists of KO, NaO & CaO salts. The last when acted on by the air & converted into CaOCo2 forms the solid encrustration froth on horses mouths. CaOCo2, 3CaOPO5 & mucus form tartar. The sulphocyanide of K on the teeth is a medicine The function of saliva is partly chemical & partly mechanical. Healthy saliva is frothy & carries down 0 into the stomach * The KSCy exists chiefly in saliva of man & sheep 290 stomach wh aids the digestion Its chief function is to convert the starch of food into sugar. The [crossed out] saliva from the pyrotid gland alone has not this power. Various nations have found out this power of saliva. The formation of diastase is the use of malting. In South America there is a fermented drink made from maize. Old women chew it & spit it into jars, it is then fermented. The pancreatic fluid is like saliva. It is alkaline like it & converts starch into sugar It is a colourless clear, frothy, tenacious substance S.G 1.008. Coagulates only slightly when gives 1.36 P.C of solid matter Contains a solid substance, like albumenate of NaO but not identical 291 identical with it is prone to decomposition Ptyalin An adult man secrets 10lbs of pancreatic juice daily. Pancreatic juice of dogs. HO 980.45 solid residue 19.55 pancreatic ferment 12.71 Mineral bodies 6.84 Its chief juice is to convert into sugar the starchy matters wh have escaped the action of the saliva. Bernard of Paris asserts that it acts as amulcin & breaks up fats* Pancreatic juice does this out of the body It is possible that the pancreatic juice may reform the NaCl broken up in the process of digestion. Gastric juice It is the fluid poured out from Into glycerin & fatty acids 292 the lining membrane of the stomach. It is neutral in the empty stomach. acid when food has been recently taken in. S.G 1.0023. The acid is generally lactic acid. Shmidt's analysis HO 994.4 solid ingredients 5.596 peculiar ferment pepsin 3.195 free HCl 0.2 CCl 0.06 NaCl 1.46 Lactic acid is with it in varying quantity. The saliva is mixed with it in analysis. Marked ingredients. Pepsin & free acid. Pepsin. It is an albumenous body soluble in HO insoluble in alcohol. The HO solution is precipitated by [illegible] H8, Pb. 293 Converts coagulated albumen into the soluble form only does so in presence of free acid, The fresh gastric juice of the dog dissolve 1/20th of its wt of coagulated albumen. Its function is to render the nitrogenous parts of the food soluble but to accomplish this it must have free acid. Bile immediately suspends the action of pepsin. * The quantity of gastric juice secreted by animals is almost incredible about 1/4 of their wt daily. In the case of Katharine Cutt a person who had a fistula thro' wh the stomach could be observed it was about 30 lbs daily. Yet it is not sufficient to dissolve all the albumenous bodies introduced as food. *Thus the gastric juices has no effect on food after it has passed into the intestine 294 The stomach is protected from the action of the gastric juice by the epithelium & not by its vitality for the hand legs of a frog introduced into the stomach thro' a fistula were digested, the vitality of the frog not preventing it. The intestinal juice seems to combine the effects of the pancreatic & gastric juice. About 10oz one secreted daily Bile is the liquid produced from venous blood by the liver. It is a viscid tenacious fluid of a brown or green colour & musty odour & bitter taste S.G 1.02. It putrefies readily but if freed from mucus it does not change. Sometimes alkaline often neutral. Composition. HO [crossed out] 90.44 Biliary bodies 8. 295 Aqueous extract, alkaline salts. phosphates chlorides & lactates 0.85 Mucus 0.30 NaO & KO 0.41 Characteristic bodies Resinous matter. Cholic acid. Tauro & Glyco-cholic. It unites with alkalis like resins Cholosterine is always in healthy bile in small quantity 1 part in 10000 parts of bile. Retention of bile concentrates it. A man of 10 stone secrets 5 lbs daily. Its main use is to promote the digestion of fatty matters. Lehman considers the bile as the waste matter of formation of blood corpuscles If you moisten one capillary tube with HO & the other with bile & put them in a fatty substance the fat rises higher in the tube wetted with bile than in that wetted with HO. 296 It probably neutralizes the acid chyme from the stomach. Excrement It consists of undigested particles of food of epithelium & mucus decomposed biliary constituents. Its smell is due to decomposed biliary constituents or the imperfect combustion of albumen. If you distil albumen with KOHO you get essence of excrements. When the diet is mixed the colour is yellow brown on a flesh diet it is darker & on a milk diet it is yellow. Its action is generally alkaline In an adult man there are about 5oz daily. It contains 73 PC HO 27 PC solid constituents. The N in the fœces & in the urine 297 correspond closely to the N introduced in the food. There are few soluble salts in the foeces these having passed out in the urine. There is more MgO than CaO in proportion to the food, showing that some CaO has been taken into the system. The foecal ash gives 31 P.C. of tribasic PO5 . Taurin is always found & a peculiar crystalline body very unpleasant to prepare called excretin C78 H78 O2 S. Intestinal gases They owe their origin partly to air conveyed to the stomach & partly to the decomposition of the intestinal contents The O has disappeared in the large & middle of the small intestine The chief gases are CO2 & N. 298 H sometimes appears & when it does so in large quantity to extent of 25 PC Carbonetted H sometimes appears. HS rarely exceeds 1-2 P.C. Blood. General properties. It is a thick viscid fluid S.G 1.055 in human blood, usually of a bright cherry red, arterial blood is lighter coloured than venous when removed from the body it changes & separates into the clot or cross amentum & serum. When warm it has a peculiar odour stronger in the blood of man than women. If you add HOSO3 to blood it gives a stronger smell If you add HOSO3 to the blood of the horse & heat the smell of the stable becomes perceptible, or if to cows blood, the smell of the cow 299 house. The S.G of women's blood especially during pregnancy is less than that of men's. Blood is not only a solution but an emulsion holding solid particles suspended in it. It contains blood corpuscles, lymph corpuscles fat globules Blood corpuscles. They are thick circular slightly biconcave discs. In human blood they about 1/3200 th of an inch in diameter. In most mammals except the elephant they are smaller than in man. In amphibia they are very large. Lymph corpuscles. They are lighter than blood. The fluid in wh they float is called the liquor sanguinis 300 & contains fibrin in addition to the solid constituents of the serum The clot is coagulated fibrin & contains the blood corpuscles & some serum. The composition of living & dead blood is different Living blood Blood corpuscles Liquor sanguinis Dead blood 2 minutes after being taken from body. clot = fibrin & corpuscles Serum. Average of 22 analysis of healthy human blood. HO 781.60 } solid constituents 218.40 } in 1000 parts. Of the solid constituents Blood corpuscles 135.0 Albumen in serum 70.0 Fibrin 2.50 Fats 1.55 Soluble salts 6.0 Earthy phosphates 0.35 301 Fe 0.55 Extracted matter 2.45 Various analyses have been given of blood corpuscles & liquor sanguinis. The blood corpuscles contain 16.75 hæmatin } 241.07 hematocrystalline } in 1000 parts Liquor sanguinis contains neither of these but contains 4.05 fibrin 78.84 Albumen. The two characteristic constituents are hematin & hematocrystalline. Hematocrystallin is a glucoside Prep. of Hemat Mix defibrinated blood with a saturated solution of NaOSO3 & wash with alcohol & ether. C44 H22 N3 O6 Fe. Hæmatin Occurs in blood in the soluble form. 302 It is got also as a brownish black substance without smell or taste On ignition it leaves a considerable quantity of Fe2 O3 Dissolves in alkalis but is precipitated by acids. If you add KONO5 to blood the fibrin does not coagulate. HCl, NaCl, KOSO3, acid phosphate of KO & of NaO, bibasic phosphate of CaO & MgO are the mineral constituents of blood. In the liquor sanguinis NaCl, phosphate of NaO & HCl in small quantity are found. Gases in blood. CO2, N & O. They are found almost entirely in the blood corpuscles & hardly in the serum. If you shake up serum with gases it does not absorb them, but the blood corpuscles 303 corpuscles do to a considerable extent. In arterial blood there is relatively but not positively more O than in venous blood. Ratio of O to CO2 in arterial blood is as 6 to 16 & as 4 to 16 in venous blood. Coagulum. The clot is produced by the coagulation of fibrin. The cause of this is due to a considerable extent to the escape of NH3. 1 part NH3 keeps 3000 parts of blood fluid in a close vessel at 98°F. Agitation hastens coagulation & free access of air also Dilute solution of salts retard coagulation. In inflammatory diseases there is a constant increase of fibrin in the blood. In inflammatory blood it is covered with free corpuscles. In dysentery the fibrin also increases & albumen diminishes 304 Serum After the separation of the blood corpuscles & fibrin the serum is sometimes turbid owing to fat globules in drunkards & pregnant women's blood It is usually a straw coloured liquid The serum of womens blood contains 1 P.C. more of HO than men's. In mans blood 90.71 PC -women's- 91.71 The serum of arterial contains more HO than that of venous blood. Albumen in serum 7.9-9.8 - in collective blood 6.3-7.1 Albumen decreases in most diseases especially scurvy Bright's disease In intermittent fever & cholera it increases & after drastic purgatives Dropsy begins when the albumen in the serum is below 6 PC. 305 Various salts in small quantity are found in the serum. Analysis of ash serum. KCl 4.054 P.C NaCl 61.087 NaOCO2 28.78 acid phosp. NaO. 3.195 KOSO3 2.784 NaOCO2 & KOSO3 probably exist in the blood as lactates of NaO & KO. Chyle It is the liquid into wh the nutritious portion of the blood is converted. Its composition varies according to the food. It is an opalescent fluid, has a feebly alkaline reaction. & maukish taste When boiled it deposits a small quantity of floculent albumen. That from the lacteals does not coagulate. The fibrin in chyle seems to be less elaborated than in blood 306 Casein, fat, lactic acid & sugar are said to occur in chyle. There have been few opportunities of examining healthy human chyle. That of animals seems to be a dilute kind of blood. When exposed to air it becomes red. There is 12 P.C. of mineral residue in the solid residue. NaCl is abundant & alkalis combined with albumen. Lymph. It is a colourless or yellowish fluid got from the lymphatic. The ingredients seem to be the same as those of blood It coagulates in from 5 to 20 minutes after being taken out. Analysis of lymph. HO 957.6} Solid ingredients 42.4} in 1000 parts. Fibrin & lymph corpuscles 0.37 307 Albumen & extractive matter 34.72 Mineral matter 7.31 It is supposed that 22 lbs of lymph are formed in the body of an adult man in 24 hours. Fluids of generation & development The seminal fluid has been mixed with secretions of prostate & other glands before analyzed. It is commonly heavier than HO slightly alkaline, is coagulated by alcohol but not by heating. Characteristic ingredient Seminal filaments The motions of these are arrested by various solutions, as of kreosote.* Fluids of the egg. Generally consist of 2 parts the yolk & the white. The yolk contains fat globules & corpucles surrounded by fluid The corpuscles are phosphorized *And neutral salts &c. 308 fat probably glycerophosphoric acid The molecular granules are casein They form 14 P.C. of yolk. Albumen 3 . Collective fats 30. Glucose is always in the yolk. There are two pigments yellow & red. Mineral of constituents 15 P.C. White of egg contains 12 1/2 PC of albumenous ingredients, & ale Margarine oleine & glucose. The mineral ingredients are soluble & consist in a great measure of NaCl. The shell contains 97 PC. of CaOCO2 . & a little phosphate of CaO, MgO & organic matter Milk. It is an opaque fluid, of a white, bluish white or yellow colour. It is generally alkaline, sometimes acid.* s.g of women's milk 1.032. *as in carnivores 309 Under the microscope it is a clear liquid with fat globules wh have a fibrous covering. When this cover is broken in churning it allows the butter to gather These globules floating to the top produce cream. It does not coagulate but on heating it forms a scum from oxidation. Average of 89 analyses of human milk. HO 889.08} solid ingredients 110.92} in 1000 Milk sugar 43.64 P.C. Casein 39.24 P.C. Butter 26.66 Salts. 1.38 The quantity of casein increases with animal food During suckling the milk becomes changed. The butter remains tolerably constant 310 The casein increases as the child becomes developed Milk of dark haired women is better than of blondes & is richer in fats. The composition of asses milk is nearer that of women than any other animal. Composition of Cows Milk. HO 86.2 P.C Casein 4.2 Butter 5. Milk sugar 4.1 Mineral matter Urine. The urine is a liquid secreted by the kidneys from the blood. It removes the nitrogenous parts of decomposed tissues. Human urine is a clear fluid of a bitter saltish taste & bright amber colour 311 S.G 1.015 to 1.025. In a state of health it never exceeds 1.03. It has an acid reaction. In clean vessels it has no great tendency to putrefy but if there is any decaying organic matter present it does so readily. As it cools it often deposits a cloudy sediment, especially morning urine. On standing crystals of uric acid appear The composition of urine varies according to the food & exercise. In an experiment a man of 11 stone passed 52 oz of urine in the 24 hours. In this Urea 520 grs Uric acid 8 Hippuric acid 15 Kreatin 7 Kreatinine 4.5 Xanthin & Hypoxanthin Traces *Found after eating green [illegible] & fruits containing benzoic acid 21 312 Mineral matter 376 grs. Of wh NaCl forms 266 grs. The chief characteristic ingredient is urea. It is a product of the oxidation of the tissues. It is said that when albumen is oxidized by MnO2 urea is produced but this is doubtful. It is however certainly produced in the system from the oxidation of the tissues It is also got by the oxidation of uric acid & by the action of alkalis on kreatin & [crossed out] alloxan. NH4 O CyO when heated becomes urea Urea has the same empirical formula as NH4 OCyO though it is arranged in a different way N2} } H2 } H2 } H2 Na} } C2 O2 } H2 } H2 313 Crystallizes in 4 sided prisms like KONO5 soluble in alcohol & HO forms salts. It forms 77 to 82 P.C of urine evaporated There are about 25 parts of urea in 1000 parts of common urine. A man of 10 stones wt excretes daily 442 grs urea. - " - 520 grs. From 58 observations on young men the average is 549 grs per day. The average of 58 observations on young women is 425 grs. If the same weight of children from 6 to 3 years old & of old men. The children secrete 3 times as much as the old men. The average of urea is 244 Adult man on mixed diet 518 grs - vegetable - 389 - 314 Adult woman on mixed diet 412 grs - vegetable - 309 Professor Fry of Trinity College Dublin made various experiments on the students. Well fed flesh eating wine drinking students yeilded 576 grs daily Well fed water drinking vegetarians 394 grs Certain diseases influence the quantity of urea. it is increased in typhoid fever, in pneumonia pleurisy & rheumatic fever. Uric acid in urine. In urine it is generally combined with NaO. It is rarely more than 1/10 P.C in urine. From 7-8 grs in an adult man. In perfect health there ought to be no uric acid. In Professor experiments on students he found 315. Beef eating wine drinking students 4 1/2 grs daily HO drinking vegetarians 1 1/2 grs - Hippuric acid. Occurs chiefly in the urine of herbivora. If you become a vegetarian, hippuric acid takes the place of uric acid in the urine. A large amount of HO taken into the system lessens the uric acid as also sulphate of quinine taken as a medicine. Xanthin & Hypoxanthin Kreatin 5-7 grs in 24 hours Kreatinine is a product of the metamorphosis of kreatine. Extractive matters are less abundant in the urine of the child than of adults. Extractive matters are uncrystallizable bodies wh we do not 316 know. In starvation the exceed the ureaic in quantity. Among them are damaluric, carbolic & other acids & some volatile acids. Urine pigments. Indican the glucoside of indigo blue. Mineral ingredients. Of these NaCl is far the largest in amount Daily average in 8 students. .269 grams in 24 hours The average is generally taken as 200 grs for an adult male & less for women & children In acute diseases of the febrile sort the chlorides rapidly diminish, but when convalescence begins the chlorides increase rapidly. 317 The chlorides are carried off in the watery stools & in perspiration Sulphates. They occur in varying quantity The HOSO3 excreted daily as sulphates is 32 grs. The proportion rises in the afternoon & during digestion Animal food & active exercise increases the amount of the sulphates Phosphates PO5 is found in the urine partly as NaO PO5 & partly as phosphates of MgO & CaO In an adult man 50 to 60 grs of PO5 are excreted daily as phosphates. The maximum & minimum is the same as with the sulphates. Animals food increases the phosphates. Earthy phosphates excreted daily 318 are 15 grs. Fe in minute quantity is in urine. SiO2 & Fl in very minute traces. Secreted daily by an adult man. NaCl 266 grs HOSO3 (as sulphates) 32 PO5 (as phosphates) 55 Alkalis, CaO MgO & other salts. Undetermined. Abnormal ingredients. The presence of albumen in the urine often indicates Bright's disease, but it may be due to accidental causes. The urine may sometimes coagulate in health. Taking cantharides or a stimulant diuretic & pressure of blood in the kidney as in heart disease produces albumen in the urine. In boiling urine always add a 319 drop of NO5 after the operation When albumen remains persistently in the urine it is dangerous symptom. Fibrin sometimes occurs in urine Sugar does not exist in healthy urine but in diabetes & gout When the flow of 4th ventricle of the brain is punctured sugar appears in the urine & remains for some hours Sugar appears to be in the foetal urine. Fat does not occur in healthy urine but does in Bright's disease & chronic insanity. fatty degeneration of kidneys in in rapid emaciation but generally from Biliary compounds are found in jaundice. NH3 never occurs in healthy urine unless it has been accidentally 320 changed in the kidneys as by too long retention. In scarlatina it appears even though the urine be acid. When urine is alkaline NH3 generally is present, urea being very readily decomposed. Urine of animals The composition of that of the carnivora most nearly approaches to the human. It is light yellow & nasty odour bitter taste Has an acid reaction It contains much urea, little or no uric acid & much pigment. Dogs urine contains cyanuric acid That of the herbivora is yellow turbid. Contains hippuric but no uric acid. oxalate of lime & only a small amount 321 amount of phosphates relatively to man When they are fed on animals diet as the calf while suckling they give urine like that of the carnivora. The urine of birds forms a white coating to the solid excrement consists chiefly of urates of NH3 & CaO The urine of frogs is liquid & contains urea NaCl & phosphates. That of serpents is at first pulpy but soon dries & consists mainly of urates of alkalis, with a little urea Urinary sediments The occurrence of sediment in fresh urine as soon as cooled may sometimes show disease. It consists either of organized or unorganized substances. Inorganic sediment Uric acid Urates Organized Mucus & epithelial scales. 322 Inorg. Hippuric acid Oxalate of lime Earthy phosphates Cystin Org. Blood corpuscles Pus corpuscles Cancerous & tubercular matter Fibunous coats of the tubes of the kidneys Spermatozoa fungous bodies and infusoria Uric acid. Only occurs in strongly acid urine in any quantity; may be deposited after fermentation from decomposition of urates When free lactic acid is voided it decomposes urates & deposits uric acid. Uric acid sediment is always coloured, generally yellow or brown. Test. With HONO5 & NH3 it forms murexide. The urates are the most common of the sediments all occur in acid urine except that of NH3 Their colour varies from greyish white 323 to brownish red or purple. Urate of NaO. The cause of the sediments is partly their greater solubility in hot than cold HO. Sometimes from the HO in the bladder having exuded & left too little to dissolve them. Hippuric acid rarely occurs as a sediment. If a fruit like greengages containing benzoic acid be taken freely or if benzoic acid be taken as medicine or otherwise, hippuric acid appears in the urine Oxalate of lime It is sometimes produced by changes in old urine so it is not to be confounded with that deposited from fresh urine Earthy phosphates always appear when the urine is alkaline. 324 Urinary Calculi. They are formed in the kidneys or bladder by deposition or retention of urinary sediment. Around a nucleus more matter gradually accumulates. Sometimes the matter is not all of one kind The composition of the calculi is generally the same as that of the sediment. Uric acid or urates Kanthin Cystin Oxalate of lime CaOCO2 . Phosphate of lime Phosphates of MgO & NH3 . Fibrin & mucous compound Phosphate of MgO may be formed by throwing MgOSO3 into urine & allowing it to stand. The substances valuable as manure 325 manure may thus be removed, Fibrin & mucous compounds Respiration. The act of respiration consists essentially in the interchange of gases existing in the blood with those in the air. In animals low in the scale it takes place on the surface of the body but most animals have definite respiratory organs. The gases given out from the body are in the venous blood, but this does not come in the direct contact with the air. The lung tubes branch out into small ramifications & thus present an immense surface in small space. The air & blood are separated by a thin moist membrane thro wh the gases interchange by exismosis. The O is changed for CO2. 326 The change of colour in the venous blood from dark to light red is due not so much to the absorption of O as to the expulsion of CO2. If the CO2 be expelled & H substituted the same change takes place. The O taken in is in greater volume than the CO2 given out. The reason of this is that the O has to oxidize the tissues & convert them into urea & to make H into HO. When O is converted into CO2 it occupies the same volume so the interchange would be volume for volume if the O had not more work to perform in the body. For each volume of O absorbed in the lungs, there is only 0.8516 vol. of CO2 evolved. Hence there is 1/7th more O taken into the body than what is required for conversion into CO2 327 When we examine the volume of air expired after it has cooled & dried it is less than that inspired. The aqueous vapour expired in 24 hours is from 11 to 14 oz. Some of this is due to the HO taken as drink as well as to that formed in the system. The N in the air is little affected by respiration. A very slight increase of N in the air expired may be due to that dissolved in the HO we drink. The air expired is 0.402 ricer in O than that inspired. There is a very small quantity of NH3 to be detected in the air expired. The most important gas is CO2. The expired air of a healthy man contains 4.334 P.C of CO2. 328 Only a small part of the O of the air is taken up. Weight of gases expired by an adult man taking a general average during 24 hours. CO2 27.8 oz N in excess that inhaled .5 Aqueous vapour 14. Inhaled. O. 23.3 So that about 3 oz of O are retained in the system or go out in other excretions. The amount of CO2 in expired air depends on the frequency of respiration In Gerhardts' experiments Acts of respiration per minute 6 12 24 CO2 in 100 vols of air expired 5.528 4.262 3.355 329 48 2.984 96 2.662 When the breathing is undisturbed 30.5 cub. in. are expired in one respiration. But the rhythm of the respiration is Not all the CO2 in the pulmonary vessels is removed as it passes thro' the lungs. The respiration of air richer in O than common air produces no marked difference in the CO2. An animal breathes undisturbed though the O be increased to 3 times its normal amount. When decreased by one third they show no change but when decreased by two thirds they show great distress & if reduced to 3 P.C they rapidly 330 die. CO2 if added gradually to air does not impede respiration up to 12 P.C. When the animal has absorbed about 1/3 of their bodily volume of CO2 they show symptoms of poisoning tho' the O supplied along with the CO2 [illegible] The CO2 cannot escape by diffusion The largest portion of inhaled air goes back unchanged, only 1/5 th of the air in the lungs is changed in one respiration. Gases have no tendency to diffuse into themselves & when the air is charged with CO2 that in the system does not diffuse out. It is this wh renders CO2 a poison. A rabbit may breathe in an atmosphere of 20 P.C. CO2 for 20 hours if there be a constant supply. 331 CO in minute quantity will produce death if there be no ready method of diffusion. An atmosphere of 1 P.C. CO2 has been known to produce death especially if mixed with CO. According to Dr. Edward Smith's experiments the expiration of CO2 is less in hot parts of the season than in the cold. In the middle of August the CO2 is 30 P.C less than in the cold season. The maximum is in April & May & begins to fall at the end of May or in the beginning of June. It ascends in October & is high in December. Moisture in the air increases When there is change of barometric pressure in either direction there is an increased amount of CO2. 332 The effect of fasting is to diminish the amount of CO2. Some cats experimented on at first converted 80 P.C.O into CO2. 77 P.C the 2nd day & when they died of starvation 73 P.C. Dr E. Smith fasted for 27 hours & expired 0.25 P.C less CO2. There was a remarkable uniformity in the composition of the expired air but the number of respirations was less. Influence of sex & age. The male expires more CO2 than the female. Boys of like age expire more than girls. Charling's experiments age weight in kilograms CO2 per hour in grams CO2 per hour for every 1000 grams of wh Man 35 65.5 33.53 0.5119 youth 16 57.75 34.28 0.5887 soldier 28 82. 36.62 0.446 girl 17 55.75 25.34 0.454 333 Boy 10 22. 20.338 0.924 Girl 10 23. 19.162 0.883 Effect of exercise Exercise increases the CO2. Influence of food. The food influences the CO2 evolved. More O is absorbed to form CO2 when starch is used than when animal food is used. Less N is evolved on a vegetable than on an animal diet. In dogs fed on suet 6g P.C of the absorbed O was evolved as CO2. Fats contain a good deal of H as well as as C & O is required to oxidize this. In starch the H is combined with O.* Respiratory equivalents or amounts of food required to produce the animal heat in the body itself. 100 parts fat require 292.14 Oxygen *Animal food requires much O to oxidize albuminates & form urea 334 100 Starch 118.52 100 Sugar 106.67 Malic acid 82.78 Albumenous bodies 153.31 Dr E. Smith has drawn some conclusions wh however require farther confirmation. He says that food may be divided into 2 classes, those wh excite respiration & those wh do not. Exciters. Nitrogenous foods, milk sugar rum, beer, stout, the cereals Nonexciters. Starch, fat, certain alcoholic compounds, volatile elements of urine & spirits & coffee leaves. Pure alcohol, rum, ale & porter generally increased the respiration. Sherry lessened the air inspired but increased the CO2. Tea, coffee, chicory, & cocoa are respiratory exciters. Tea is the most *Brandy lessened it 335 powerful*, next coffee, next cocoa & lastly chicory. The addition of sugar & milk increases the respiratory effect. Its influence is immediate, its maximum is in about 20 minutes its duration is from 1 to 2 hours. Cause of sleep When trying to sleep the first thing we do is to take away the pressure, of the column of blood on the heart, wh we do by getting into a horizontal position. We lessen the respiration by lying in a fixed posture. The amount of O dissolved in the blood in the system is lessened. At every vital act there is change of matter. They are only destroyed in the act of oxygenation. *Therefore recommends tea to be given in suspended animation as a respiratory waiter 336 In every thought a portion of the brain is destroyed & as we get the O diminished in the blood the brain finds more difficulty in manifesting itself to the external world. In the case of the drunkard the O unites with the alcohol & the brain refuses to manifest itself & he becomes dead drunk. Sleep of hybernating animals During summer they accumulate fat round the heart & gradually push up the diaphragm against the lungs, this prevents the O being inspired readily & it falls asleep. Some wh do not accumulate so much fat as the tortoise take a roll of grass to push up the diaphragm. They are like a lamp slowly 337 burning the fat being the fuel. When this is consumed the diaphragm falls down the lungs begin to play the brain becomes active & the animal awakes. The conditions in wh we are most prone to sleep are when we have taken a large dinner wh pushes up the diaphragm. As there will be less combustion during sleep & so less animal heat we draw near the fire to compensate for this. Respiration of the lower animals. Carnivora living on ordinary food exhale more N & CO2 in proportion to their wt than herbivora Active birds consume 10 times more O than sluggish birds. Frogs & lizards convert 75 P.C & the salamander 82 P.C of O into 338 CO2. The wakeful ones consume 9 times & the half torpid ones 3 times as much as those wh are entirely rigid in winter. Origin of the CO2 It was once supposed that the CO2 was produced in the lungs. There seems to be no combustion at all in the lungs, for if there were the blood should be warmer there. This is not the case, as the blood is cooled in the lungs the blood of the left side of the heart is 2° colder than that on the right side: It seems to be produced in the tissues Every vital tissue of animals yields CO2 to the air pump. Gustave Liebig says that the muscles of the frog possess irritability * so long as the exhale *So long as they absorb O. If placed in H their irritability stops. 339 CO2. The changes are produced in the muscles . General conclusions That 8 1/2 oz of C are converted into CO2. in 24 hours, for wh. 22.66 of O would be necessary, but as only 85 P.C of O is used for CO2, 26.7 oz of O or 1 1/2 lb are daily consumed by an adult man. He destroys daily 117 oz of air wh. is equal to 164900 cub. in. In the course of the year he destroys 7 hundred weight of O. 1/5 is made into the body. It is an old tradition that the body of an animal changes once in 7 years, but this is not true as all the C would be burned in 3 days*. A man of 11 stones has 4 lbs albumenous bodies in blood. 27.5 in tissues *If there were no supply of Co you may calculate the rate of concrete from the N in the urine & excrement. 340 5lbs in bones The whole body would be changed in 18 weeks supposing that they were all changed at the same rate. Animal Nutrition Plants live on mineral food, wh they find in the atmosphere, CO2 HO & NH3. They assimilate the C from the CO2 into their system & give out the O. They get their N from NH3 & sometimes though rarely from NO5 but not from the N of the air. They get their H from HO. They have nothing to do with volition & on this account they have the property of moulding inorganic substances into organic forms. Animals have the function of volition to preform & so have not this property. 341 All animals are essentially herbivorous, even carnivora being so although indirectly. All food may be divided into 2 classes characterized by one essential difference. Those wh contain N. Those wh are destitute of it. Nothing destitute of N can build up the muscle of an animal. Those wh contain N are the histogenetic substances, casein, albumen &c, whether got from plants or animals We may call the one sort wh contain N flesh formers & the other heat givers. There is necessity for a mixture of food of both classes* It was long supposed that gelatine was an extremely nourshing substance but a commision both *If only one kind be given the animal dies just as if it received no food as only one part of its nut is supplied 342 of France & Holland appointed to examine into this found that when animals were fed entirely on it they died. In milk there is an admirable admixture of both kinds of food. Casein flesh formers Butter, sugar heat givers There is also mineral matter in it In all cookery we try to obtain this mixture. We eat beef with potatoes mutton with rice & pork with peas or beans Nitrogenous food or flesh formers. All the tissues wh form any part of an organ of an animal contain 15 P.C of N. Animals are certainly unable to take N from the atmosphere. There is one apparent exception: when an animal takes benzoic acid containing, no N it voids hippuric acid wh does. This is however in question of excretion; not of nutrition. There is no ground to suppose *and also the blood 343 that flesh can be formed from nonnitrogenous substances by assimilating N from any other source. The nutrition of a carnivorous animal is very simple. It takes the flesh & blood wh it finds ready formed & appropriates them to its own system. That of a sucking animal is equally simple. It is like a carnivorous animal eating its mother. It finds casein in the milk & appropriates it. The nutrition of every animal is equally simple. We find the histogenetic substances in plants. Thus the juice of the cauliflower contains fibrin assitedd of blood. Animals do not form the components of their flesh & blood out of unlike matters but they find 344 them ready formed in vegetables The process of nutrition consist in extracting them & giving them a place & form in the organism. This is the great law of animal nutrition Plastic elements { {Flesh animal Fibrin {Blood Albumen {Casein This excludes gelatine Gelatine may indirectly act as food by supplying food for the cellular tissue & thus saving the other food. Gelatine may thus in the case of a very weak person be of use when administered along with some other food, not alone, by supplying material for the cellular tissue wh has been much wasted by illness. & thus allowing the other food to be applied to the purpose of building up the organs. 348 Non nitrogenous substances. Fat, starch, gum, cane sugar, grape sugar, milk sugar, pectin bassarin, wine beer & spirits Since they are wholly free from N they cannot build up the frame work of the body yet they fulfil a very important function viz. supporting the animal heat. The temp. of fishes and amphibia is only a few degrees above the medium in wh they live. That of quadrupeds is 99-100° F birds 105 man 98-99 child 102 In lower animals even in health the temp. is to a certain degree regulated by the medium in 103 they been In the higher animals there is always a fixed temp. in health. Depression of this temp is attended 346 attended with a depression of the functions of an animal. There must be some means of regulating this temp. since the temp. of a man at sunny Palermo or of a traveller in the polar regions is the same. The appetite of the man is the regulator. Non-nitrogenous substances are usually the fuel. though the tissues of the body are sometimes as in the carnivora. The hyena moves about in order to burn his tissues to keep up the animal heat. From the known composition of food it is easy to calculate how much food is required to keep up the same temp. on different kinds of food. The heat giving equivalents 347 or the quantity of food required to keep the animal heat the same. Weights of different bodies requires to produce the same amount of heat. Fat 40.2 Cane sugar 100 Alcohol 53.8 Grape - 106 Starch 97.2 Flesh 309.7 Flesh has 8 times less respiratory value than fat. After deducting the heat necessary to evaporate HO as vapour in the breath we find that the rest taken in diet is sufficient to raise 143 lbs of HO from 32° to 99° & the specific heat of the substances wh compose the body is less than that of HO. Varying quantity of respiratory food. The body of a man may be represented as a chamber to be kept at the same temp in 348 summer & winter & in different climates. If you transport a man from India to the poles the temp. of his body remains the same but you must put in more food to sustain it. In extreme cold man takes enormous quantities of food. Sir John Franklin says that during the whole of the march they found that no clothing could keep them warm as long as they were fasting but when they could go to bed with full stomachs they could sleep comfortably. Parry took an Esquimaux lad not full grown & set him down to a weighed repast. the quantities he devoured are the following., 349 lbs oz Sea horse flesh hard frozen 4 - 4 -boiled 4 - 4 Bread & bread dust 1 - 12 Rich gravy soup 1 1/4 pints Spirit 3 glasses Strong grog 1 tumbler Water 1 gallon 1 pint Ross says that an Esquimaux eats daily on an average 20 lbs of flesh & oil Admiral Sarcheff says that a yacot took in 24 hours the hindquarter of an ox & 20 lbs of fats. [illegible] proportionate quantity of melted butter for drink. These accounts are not more astonishing than the difference between the coal we burn in summer & winter. The character of the food is made to suit the climate. Fruits & rice contain 20-30 PC of C. Blubber 80-90 In India beer & butter are freely 350 taken but apparently less as food than to unctuate the body & prevent excessive perspiration. Ordinary food contains fat In Cocoa 50 PC In coffee 12 PC A man inhales daily to consume these about 3000 gallons of air, much of the O of wh is burned by the food. The starchy matters & fat in the food produce fat in the body. In a grate where there is a free access of air the fuel is converted into CO2 , but in a gas retort where there is only a very limited supply of air various tarry matters distil over. Thus in the muscular arm of an Arab who is almost constantly in the open air & taking exercise 351 exercise there is no fat, but in a man leading a sedentary life & taking little exercise the fat accumulates. If there is a free introduction of air the starch is converted into CO2. In hybernating animals the fat is formed by imperfect combustion of the food in summer & in winter they live on it. There was a very fat pig weighed to be sent to an agricultural show, but just before being sent a slip of land from a neighbouring hill overwhelmed it. It was thought to be dead & no farther trouble was taken about it. About 120 days after the slip was removed for the purpose of building & the pig was found alive but it had decreased 352 140 lbs in weight. Proportion between flesh formers & heat givers. Plastic Cow's milk 10 30 Woman's - 10 40 Lentiles 10 21 Beans 10 22 Peas 10 23 Fat mutton 10 27 - pork 10 30 Beef 10 17 Hare 10 2 Veal 10 1 Wheat flour 10 46 Oatmeal 10 50 Rye - 10 57 Barley 10 57 White potatoes 10 86 Blue - 10 115 Rice 10 123 353 Buck wheat meal 10 130 Mineral matter in food The body of a man weighing 150 lbs contains Phosphate of lime 5lbs 13oz 0 grs Carbonate - 1 - 0 - 0 CaFe 0 - 3 - 0 NaCl 0 - 3 - 376 NaOCO2 acid phosphate of soda 0 - 0 - 400 KoSO3 0-0-400 Feo 0-0-150 KCl 0-0-12 Phosphate of potash 0-0-100 3MgOPO5 0-0-75 SiO2 0 - 0 - 3 The different organs exercise a selection, thus, P is taken to the brain,* Ca Fl to the teeth, SiO2 to the hair & nails, S is generally distributed but is taken especially *3CaOPO5 354 especially to the hair, phosphates of MgO & KO to the flesh, phosphate of NaO to the blood & cartilages. NaCl may act by facilitating absorption of HO by diffusion or by aiding the solubility of albumen or by affording HCl to the gastric juice & NaO to bile & pancreatic fluid. Fe is an essential ingredient of blood, gastric juice, hair & the black colouring matter of the eyes. To find the proportion of flesh formers in the food estimate the N in it & multiply by 6 3/10ths. Amount of the several kinds of food required The circumstances of age variation of climate &.c. influence this. There are two ways of finding how much food is required. We might find how much C was expired as CO2 & how much C & N 355 are in the foeces & urine, An adult man Expires as CO2 8.8oz C daily in urine & foeces 2.2oz C N in urine foeces & mucus 334 grams The C excreted daily is thus about 11 oz & the N is equal to 4 8/10 oz of flesh formers. Average diet 4 oz flesh formers 3 oz fat. 10 1/2 oz amylceous food 1 oz injested salts. 84 oz HO. 33 oz O. Another mode is take the experience of public dietaries We find by these on an average that for an adult man, daily 5 oz flesh formers 10 oz C *The amount of N in excrements in health indicates the amount of urine wasted in the day, By multiplying it by 6.25 you get the amount of tissues 356 are required When we contrast the diet of the aged with this we find that with them the flesh formers have sunk to 40oz but that the C is the same The proportion of C in the heat givers to that in the flesh formers is now as one to five. In children form 10 to 12 years of age flesh formers 2 1/2 oz C 8 oz In the young the process of supply is greater than that of waste. In the adult it is equal & in the aged less. It is during sleep that the body is built up. An adult spends 17 waking hours & in mechanical labour & 7 in sleep. An infant spends 4 waking 357 hours & 20 in sleep during wh its growth takes place. An old man spends 20 waking hours & 4 in sleep. In an adult the waste is to the supply as 100 to 100 In an infant as 25 to 250 In the aged as 125 to 50 In an infant there would not be ptyalin enough to convert its [illegible] food into sugar & so it finds the sugar ready formed in the milk. The casein is also in a soluble state. in the milk so the gastric juice has not to convert it into a soluble state. In cooking we try to get the same proportion of the different kinds of food as in milk. Pauper & prison diets. Prison diets were & still are by no means well regulated. 358 It was thought that a man on long confinement required much more food than one on short confinement. The question however is what is the waste if the tissues. Work-house diet is about 3 1/2 oz of flesh formers daily. The hard labour diet is no more than this & is quite insufficient for hard labour. Besides they are on the system of alteration according to the time of excrement. 1st Cerials yield nutritious meals of varying composition. The finest flour is not the most nutritious on an average they contain 14.6 PC flesh formers 69. heat givers Mineal matter 1.6 P.C 359 Oats contain 5 PC. of fat 17 flesh formers 66.4 heat givers 3.0 mineral matters Probably half the human race partake of tea Tea leaves contain 5 P.C. HO 3 Theine 15 Casein 6.7 aromatic oil The casein does not come out unless you put in soda. 360 The peculiar aroma of coffee is due to an essential oil wh it contains Action of alcoholic beverages. Their action is to reduce the waste of the tissues When the amount of food is sufficient this is injurious acting like too much food The cheapest way of taking alcohol is in beer The cost of one oz of alcohol taken in different beverages is as follows in beer 2D. spirits 4D wines 18 6 D. 361 For the support of strength you can get an equal amount of nourishment from vegetables or animals. The character of men depends much on the food they take. It required 5oz. of flesh formers daily to do good day's work. To get this from potatoes, it is necessary to take 25 lbs, but even an Irishman's stomach can only take in half that quantity, so that an Irishman living on potatoes alone could only do half a day's work. The Irish famine caused new material for food to be introduced* wh being more nourishing than potatoes *And spread his work over the whole year instead of only 2ce a year 362 enough for a good days work could be taken without inconvenience. Who gave us trouble in the Indian mutiny? Not the rice eaters of Bengal but the pulse eaters We may sum up the general conclusions in the words of Prior. Was ever Tartar fierce or cruel Upon the strength of water gruel. Balance between animal & vegetable life The functions of animals & vegetables are precisely opposite in a chemical sense. A vegetable is a reducing apparatus, reducing CO2 An animal is an apparatus for oxidation. 363 Vegetables are fixed Animals have the power of locomotion A vegetable evolves O absorbs heat & electricity Decomposes CO2 - HO - NH3 Produces organic substances Transforms inorganic matter into organic Derives its elements from earth & air An animal absorbs o evolves heat & electricity Produces CO2 - HO - NH3 Consumes organic substances. Transforms organic matter into inorganic Restores its elements to earth & air Functions of vegetables. Animals find their substance in vegetables. The vegetable kingdom is 364 the great laboratory of organic life. They are powerful reducing agents. For every cubic foot of CO2 they reduce 1 cubic foot of O is restored to the atmosphere. The vital force of a plant growing in the dark is unable to reduce CO2, light is required for this. Nitrate of ammonia is formed by lightning flashes. 365 Functions of animals. In animals we certainly find organic matter in its highest forms but for a limited time only Then function is not to create organic matter but to transform it into inorganic matter. They use the organic matter of vegetables & make it into organs wh have high functions to perform. Broken down from the complex molecule, into wh it was formed by vegetables it becomes less & less complex at every change. Every change of them is a degradation. they being finally converted into CO2 & NH3 The process of decay produces CO2 & NH3. 366 [illustration] The substances of dead animals passes thro' the same change as the non-nitrogenous substances in their bodies The animal stands midway between the vegetable & mineral kingdoms. It has nothing to do with forming organic bodies 367 Mutual relation of plants & animals. Animals derive nutrition from plants. Plants truly feed animals but animals as truly feed plants. It is certain that the atoms of wh. we are composed have passed thro' a succession of animals & men. Perhaps the brain with wh. I (Professor Playfair) am now thinking once formed part of the liver of the Emperor of China. There is the mineral kingdom as represented by air & soil. The vegetable elaborating organic matter from the mineral. The animal living on plants but breaking them 368 down to mineral matter. Index Absorption in animals Acetates 76 Acetic acid artificial production of 73 Acetification process of 74 Acetone 68 & 75 Acetyl 67 Aconitin 100 Acrolene 100 Acid acetic 72 - anhydrous 70 - glacial 75 aconitic 134 acrylic 100 amido - acetic (glycocoll) angelic 101 benzoic 117 butyric 79 capric caproic Caprylic Carbazolic 113 Carbolic 111 Carminic Cerebric 285 Choleic [tairiochalic] 274 cholic 275 citraconic citric 132 cyanuric 159 dextroracemic 129 erythric 218 excretolic formic fulminic 158 fumaric 128 gallic 134 gallobaunic 136 glucic 198 glycocholic 273 glycolic 92 hippuric 315 humic hydrocyanic 142 hydroferrocyanic 149 hyocholic 276 hyoglycholic 276 hyofaurocholic 276 indigotic kinic (quinic) lactic 92 lauric licanoric leucic lithofellic malic 127 margaric meconic melanuric mesoxalic Mucic 199 Nitrobenzoic Nitrocinnanic Nitrococcussic Nitrophenic Oenanthic Oenanthylic Oleic oleophosphoric orsellesic oxaluric oxamic palmitic 82 parabanic 263 parellagic pectic pelargonic phenic picric 113 pinic propionic pyrogallic 135 pyroligneous quinic 132 quercitannic racemic 129 ruberythric 218 rutic 82 saccharic salicylic sebacic sorbic stearic 83 suberic succinic sulphobenzoic tannic 135 tartaric 128 taurocholic thionuric toluic ulmic uric 267 usnic vaccinic valeric xanthic Acids acetic group of - series of amidated 265 fatty oleic oxalic stearic dyective colours Albumen Albumenoid group pro- perties of. Albuminous urine Alcoates Alcohol, absolute - action of acids on allylic amylic - bases, mode of preparing butylic benzoin caproic cerotic caprylic cuminic ethylic hexylic (camoic) caurylic melissylic methylic oetylic price of propylic radicles synthesis of alkoliolic fermentation