LABORATORY GUIDE IN URINALYSIS MB TOXICOLOGY BY K A. WITTHAUS, A.M., M.D. Hi. ’ ’ PROFESSOR OF CHEMISTRY, PHYSICS, ANtT TOXICOLOGY IN THE MED. DEPT. CORNELL UNIVERSITY ; PROFESSOR OF CHEMISTRY AND TOXICOLOGY IN THE MED. DEPT. UNIVERSITY OF VERMONT ; MEMBER OF THE AMERICAN CHEMICAL SOCIETY, AND OF THE CHEMICAL SOCIETIES OF PARIS AND BERLIN, ETC. EDITION. NEWYORK WILLIAM WOOD & COMPANY 1898 Copyright WILLIAM WOOD & COMPANY 1898 STETTINER BROTHERS 22-26 READE ST PRESS OF NEWYORK. CONTENTS. PAGE. General Rules 1 Metric Weights and Measures 4 Manipulation and Analytical Reactions 5 Bunsen flame 5 Solution 6 Filtration . 6 Precipitation 8 Reaction 9 Reactions of Acid Residues 10 Chlorids 10 Hydrochloric acid 10 Bromids 11 lodids 11 Cyanids 12 Nitrates * 13 Nitric acid 13 Chlorates 14 Acetates 14 Oxids i 14 Sulfids 14 Sulfites 15 Sulfates 15 Sulfuric acid 15 Thiosulfates 16 Carbonates 16 Oxalates 17 Tartrates 17 Phosphates 18 Arsenates.... 18 Antimonates 19 Borates 19 Citrates 20 Summary 21 CONTENTS. IV PAGE. Acidic Elements Grouped for Analysis 23 Reactions of Bases 22 Manganese 34 Iron 24 Aluminium 25 Lead 25 Bismuth 26 Tin 27 Lithium. 27 Sodium 28 Potassium 28 Ammonium 29 Silver 29 Calcium 29 Barium 30 Magnesium 30 Zinc 31 Copper 31 Mercury 32 Summary . 34 Bases Grouped for Analysis 35 Examination of Mixtures of Salts 37 Qualitative Analysis of Urine 46 Physical Characters 46 Quantity 46 Color 46 Odor 46 Reaction 47 Specific gravity 47 Chemical Characters. Composition 49 Urea 49 Uric acid 50 Albumin 50 Paraglobulin 53 Mucin 53 Peptone 53 Glucose 54 Blood 58 Bile 59 CONTENTS. V Quantitative Analysis of Urine 68 Reaction 99 Chlorids 65 Phosphates 66 Sulfates 68 Urea 69 Uric acid Albumin Glucose IB Urinary Deposits Unorganized deposits Organized deposits I'S Qualitative Analysis of Urinary Calculi 83 Detection of Poisons 84 Volatile Poisons 84 Phosphorus 85 Hydrocyanic acid 87 Alcohol 87 Chloroform 88 Chloral 88 Phenol 89 Mineral Poisons Mineral Acids and Alkalies 90 Metallic Poisons 91 Arsenic 94 Antimony 99 Bismuth 160 Copper 401 Lead 101 Mercury 401 Barium 161 Zinc 401 Vegetable Poisons 162 General Reactions 464 Morphin 405 Meconic acid 406 Strychnin 166 PAGE. LABORATORY GUIDE. GENERAL RULES FOR WORKING. 1. The student’s table and shelves with the bottles and apparatus must be kept clean. 2. There is a place for everything, into which it must be put immediately after use. 3. The reagent bottles must be kept on their shelves with labels outward, and in the following order from the gas fixture— Middle Shelf, HCl—Hydrogen chlorid—Hydrochloric acid. H2S— “ sulfid. H2B04 “ sulfate—Sulfuric acid. HNOs— “ nitrate—Nitric acid. H(C2H3O2)—Hydrogen acetate—Acetic acid. Fe2Cl6—Ferric chlorid. HNa2P04—Disodic phosphate. KHO—Potassium hydroxid. FeS04—Ferrous sulfate. K4[Fe(ON)O]—Potassium ferro-cyanid. AgN03—Silver nitrate. NH4HO—AmmorMum hydroxid. Bottom Shelf. NH4Cl—Ammonium chlorid. NH4HS— “ hydrosulfid. (NH4)2COa— “ carbonate. CaCl2—Calcium chlorid. BaCl2—Barium chlorid. CuSo4—Cupric sulfate. Indigo solution. Fehling’s solution. Litmus papers. GENERAL RULES FOR WORKING. 2 Top Shelf {one bottle to four students). GaH202—Calcium hydroxid. NaClO—Sodium hypochlorite. Phenolphthalein solution. Guaiacum tincture. Ozonic ether. Bottles containing specimens. Mno2—Manganese dioxid (solid). NaCl—Sodium chlorid “ Na2Co3—Sodium carbonate “ HKSOj—Monopotassic sulfate “ Uric acid. 4. Other reagents will be found and used at the instructor’s table, but may not be removed. 5. Reagent bottles will be filled, and supplies ob- tained, at the assistant’s table. G. All apparatus issued to the students must be kept, when not in use, in the drawer or closet of the desk. 7. In replenishing reagent bottles from stock, fill them only half-full. 8. If the reagent in any bottle become cloudy, filter it. 9. Take up the reagent bottle by its body, thumb on one side of label, fingers on the opposite ; and while pouring or dropping from the bottle keep the label side up. Do not lay the stopper of the bottle upon the table. Remove it from the bottle by grasp- ing it between the little and ring fingers of the left hand, and hold it there, pointing outward from the back of the hand, until replaced in the bottle. 10. In liquid tests, use about two cent, of the liquid to be tested in a test-tube; not more unless so directed. ABBREVIATIONS. 3 11. Add the reagent in small quantity at first, and stop when the desired end is attained. 12. Prevent the last drop adhering to the lip of the bottle from flowing down its side, by catching it upon the stopper or upon the clean lip of the test- tube. 18. A separate portion of the original substance or liquid is to be used for each test, except when otherwise directed. 14. Before trying a reaction, read the description through, and then follow the directions literally. Should the result not he that described, ask for an explanation. 15. Wash apparatus as soon as possible after using, while still wet, then two or three rinsings with a small quantity of clean water will suffice. If not clean, use 2-3 drops HCI with 2-3 cent, water; or KHO, and even a probang or brush if necessary. Set aside in a clean place to drain. 16. Do not scratch the inside of any glass vessel with wire or a broken glass rod. 17. Let each piece of apparatus be clean before being put into its place, and let everything be in its place before you leave. Students are required to take notes, consult man- uals, and construct equations representing the simpler chemical reactions. ABBREVIATIONS. The following abbreviations are used in the text, and will be found convenient by the student in tak- ing notes: ppt. = precipitate pt.—pts. = part—parts pptn. = precipitation dil. = dilute METRIC WEIGHTS AND MEASURES. 4 sol. = soluble cent. = centimetres insol. = insoluble gtt. = drops soln. = solution sp. gr. = specific gravity cc. = cubic centimetre con. = concentrated L. = litre gm. = gram c. p. = chemically pure The formula of the reagent always applies to its solution, except where otherwise specified. Metric weights and measures, and the centigrade thermometric scale, are used throughout. One decimetre. 1 millimetre = 0.001 metre = 0.0394 inch. 1 centimetre =O.Ol “ = 0.3937 “ 1 decimetre =O.l “ = 3.9371 inches. 1 metre = 39.3708 “ 1 decametre = 10 metres = 32.8089 feet. 1 hectometre = 100 “ = 328.089 “ 1 kilometre = 1000 “ = 0.6214 mile. 1 millilitre = 1 cc. = 0.001 litre = 16.232 minims. 1 centilitre = 10 “ = 0.01 “ = 2.705 fluid drachms. 1 decilitre = 100 “ =O.l “ = 3.384 ounces. 1 litre =lOOO “ = 1.057 quarts. 1 decalitre = 10 litres = 2.642 gallons. 1 hectolitre = 100 “ = 26.418 “ 1 kilolitre ,= 1000 “ = 264.18 “ 1 milligram = 0.001 gram = 0 015 grain Troy, 1 centigram = 0.01 “ = 0.154 “ “ 1 decigram =O.l “ = 1.543 grains Troy. 1 gram = 15.432 “ “ 1 decagram = 10 grams = 154.324 “ “ 1 hectogram = 100 “ = 0.268 lb. Troy. 1 kilogram = 1000 “ = 2.679 lbs. “ “ “ “ = 2.205 “ Avdp. MANIPULATION AND ANALYTI- CAL REACTIONS. 18. Bunsen's burner is so constructed that street- gas is mixed with air to insure complete oxidation of the carbon without the intermediate or luminous stage. Bunsen Flame. To light the burner, close the air openings, a, Fig. 1, turn on the gas full, wait a second or two, then light at b, turn down the flame to about six cent, high, and open the air-holes gradually until the luminous part of the flame just disappears. If a smaller flame be desired, close the air- holes, reduce the flame, and then admit enough air to ren- der the flame colorless. A proper adjustment of air and gas will prevent the burner becoming lit below at the jet c. If this shopld happen it will be Fig. I.—Bunsen burner. and change in the shape and color of the flame. The gas must be turned off and the burner cooled before relighting. recognized by a peculiar odor 19. While heating a liquid in a test-tube, hold the tube inclined, point it away from the face, and keep the contents constantly agitated by shaking or turn- ing. In no case should the flame come in contact with a glass vessel above the level of the liquid within. SOLUTION—FILTRATION. 6 Solution. 20. Place 10 cc. water in a small beaker, add about one gram solid NaCl, agitate: the salt disappears, dissolving completely in the water. Now add some PbCr04, agitate: this compound does not dissolve, but remains suspended in the liquid. If allowed to stand several hours, the particles of chromate will fall to the bottom, and the clear liquid might be poured off or decanted. Complete separation may be obtained immediately by the use of a filter. Fig. 2. Filtration. Fig. 4. 21. The apparatus required for this purpose con- sists of a funnel and support for the same, a vessel to receive the filtrate {i.e., the liquid which passes through the filter), a wash bottle, stirring-rod, and filters. The funnel (Fig. 2) should be selected by testing with a piece of cardboard cut with an angle of 00° (A, Fig. 2), which should exactly fit it; and it should have the point of the stem ground off at an angle. The filters are discs of porous paper manufactured for the purpose (filter paper). The diameter of the FILTRATION. 7 disc selected should be somewhat less than twice the length of the sloping side of the funnel from rim to shoulder (B-C, Fig. 2). The filter must not pro- ject above the rim of the funnel. 22. Take a filter (a, Fig. 3) of suitable size and fold it across a diameter (b, Fig. 3), fold it again over a radius at right angles to the first diameter (c, Fig. 3), open the paper out into a conical bag by separating one thickness of the paper from the other three (d, Fig. 3). The filter is then adjusted in the funnel and pressed against its side with the dry finger until it fits closely. Now, holding the filter and funnel so that the nail of the forefinger is pressed against the upper end of one of the folds (Fig. 4), moisten the paper by directing upon it a jet of water from the orifice a of the wash-bottle (Fig. 5), produced by blowing gently into the tube b. Fig. 5. 23. Support the funnel containing the wetted filter over the vessel destined to receive the filtrate (if a flask or test-tube be used for this purpose, no other support is needed), and pour the liquid to be filtered into the filter, allowing it to flow along the stirring- PRECIPITATION. 8 rod, held as shown in Fig. 6, in successive portions until it has passed through; never, however, adding liquid in greater quantity than to within two to three millimetres of the edge of the filter. 24. Remove the sediment to the filter by directing a jet of water from the wash-bottle upward into the beaker. Detach adhering particles by rubbing with a small bit of rubber tubing slipped on the end of a stirring rod. 25. After all the solid matter has been transferred to the filter, it must be washed until free from the soluble salt. Fia 6. Direct a gentle stream from the wash-bottle on the sediment in the filter, avoiding any loss by spurting or overflowing. Repeat after each wash- ing has run completely through, and until the fil- trate has no taste or does not respond to a suitable reagent. 26. While the sediment is being washed, the fil- trate may be tested for NaCl. Take two cent, water in a test-tube, add a few drops of the filtrate and a Precipitation. REACTION. 9 drop or two of AgN03; a copious white precipitate results from the chemical union of the chlorin of NaCI and silver of AgN03; Nad + AgN03 = AgCl + NaN03. Agd is insoluble in water, hence the ppt.; NaNO, is soluble, therefore remains in solution.* Divide the contents of the test-tube, add to one part NH4HO and agitate: the ppt. dissolves. Add to the other HN03: the ppt. does not dissolve. Precipitation is complete when further additions of the reagent will not increase the precipitate. 27. Precipitates vary from a faintly visible cloud to a dense mass. They may be crystalline, amor- phous, or curdy (coagulum); may fall to the bottom of the vessel, float on the surface, or be disseminated throughout the liquid menstruum. Reaction. 28. Compounds are either acid, alkaline, or neu- tral, a property determined by their action on cer- tain coloring matters, as litmus, turmeric, or phe- nolphthalein, called Indicators. 29. Place 10 cc. water in a porcelain capsule, add a piece of blue and a piece of red litmus paper: there is no change, the water is neutral. Add to the water a few drops NH4HO, stir with stirring-rod: both papers are blue, the reaction is alkaline. Add HCI drop by drop until the papers turn red: the acid is then in excess, and the reaction is acid. 30. In dark-colored solutions the bits of paper * A Table of Solubilities will be found on pages 108, 109. By reference to this table the student will learn what substances may or cannot be present in solutions under examination. CHLOKIDS—HYDKOCHLORIC ACID. 10 should be removed from the solutions with a stir- ring-rod, or they may be drawn up the side of the capsule, for more careful examination, 81. In very weak solutions the change takes place slowly, and it is necessary to allow the test-papers to remain a minute or more before recording the reaction. 32. To neutralize an acid solution use NH4HO; or if alkaline, use HCI, except when otherwise directed. REACTIONS OF THE MORE COMMON ACID RESIDUES. 33. Add 5 gtt. HCI to 5 cc. H2O in a capsule, neu- tralize with KHO, divide the liquid in two test-tubes, and apply tests §§ 34 and 35, adding the reagent drop by drop. Chlorids. (M)'Cl. Use HCI. 31. AgNO, gives a white ppt. (AgCl) which dark- ens on exposure to sunlight. Divide ppt. in two test tubes, add to one NH4HO and agitate: the ppt. dissolves (sol. in ISTH4HO). To the other add HN03: the ppt. does not dissolve (insol. in IHSTOJ. KCN and ISra,2S208 will also dissolve the ppt. 35. Hg2(NOs)a gives a white ppt. (Hg2Cl2) which turns black on the addition of NH4HO. (See also § 44.) Hydrochloric Acid. HCI. 36. The free acid responds to the tests given above for chlorids, has a strong acid reaction, and when heated with powdered black oxid of manga- nese (MnOJ gives off chlorin; recognizable by its odor, its yellow color, and by its power of turning paper containing starch and potassium iodid blue. BROMIDS—lODIDS—DRY TEST FOR CL, BR, AND I. 11 Bromids. (M)'Br. Use KBr. 37. A gNO, gives a yellowish-white ppt. (Agßr), sparingly soluble in NH4HO and insoluble in HN03. 38. Chloriu water causes the solution to turn yel- low. This, shaken with 3-3 drops of carbon bisulfid, will give a brown-red color to the reagent, which sinks to the bottom of the tube. lodids. (MjT. Use KI. 39. AgNO, gives a yellowish ppt. (Agl), insoluble in NH4HO and in HNOs. 4-0. Chloriu water colors the liquid yellow, and gives a violet color to carbon bisulfid, with which it is agitated. If added to starch paste: turns black or purple. 41. CuS04. Add to an iodid a few drops of a mix- ture of one part CuS04 and two parts FeS04, warm; a white ppt. 42. HgCl2 gives a scarlet ppt. (Hgl2), sol in excess of either iodid or reagent. 43. Pb(C2H3O2)2 gives a yellow ppt. (PblJ. (Chlorids and bro- mids give a white ppt.) 44. Mix the solid substance (chlorid, bromid, or iodid) with a mixture of equal parts of HKS04 and Mn02, place in the bottom of a closed matrass, a, Fig. 7, using a narrow paper shovel; attach a piece of moistened blue litmus paper in the mouth of the matrass, b, and apply heat to the closed end. Note the color and odor of the gas Dry Test for Cl, Br, and I. Fie. 7. 12 CYANIDS. evolved, its action on the litmus, and condensation on the sides of the tube; Gas. Odor. Litmus. Condensation. Cl green characteristic bleaches none* Br red-brown pungent bleaches brown drops I violet peculiar reddens dark scales Cyanids. (M)'(CN). Use KCN. 45. H2S04 causes the evolution of HOIST gas, which is recognized by its odor of bitter almonds or peach blossoms. 4b. Moisten a piece of filter paper with a freshly prepared alcoholic soln. of guaiacum; dip the paper into a very dilute soln. CuS04, and hold it over a vessel from which vapor of HCN is given off: the paper turns bright blue. 47. AgN03 gives a white ppt, (AgCN) if the re- agent is in excess. The ppt. is sol. in NH4HO, insol. in HN03, and very so I. in excess of KdST. 48. Add NH4HjS to soln. and evaporate to dryness on water bath,* add neutral Fe2Cl6 to residue; a deep red color. 49. KHO, and then soln. of FeS04, shake until it turns dark; add HCI just to acid reaction; a blue ppt. either immediately or after standing. 50. Add dil. soln. of picric acid, heat, and allow to cool: a deep red color. * If the materials are not perfectly dry, colorless drops (of water) will condense. NITRATES—NITRIC ACID 13 51, Ferrocyanids, (M)ivFe(CN)„. Perricyanids, (M)vi[Fe(CN)6]2. Thiocyanates, (M)'CNS. Fe2Cl6 dark blue ppt., in- sol. HC1, sol. H2- C204,with KHO turns brown. green to brown color, no ppt. blood-red color,de- stroyed by HgCls. FeS04 light blue ppt., in- sol. HC1. dark blue ppt CuS04 AgNOs chocolate ppt. white ppt., insol. in NH4HO. yellow ppt. orange ppt.. sol. in NH4HO. Nitrates. (M)'NO3. Use dil. KNU)S 53. FeS04. Add an equal bulk of H,SO4 to the soln. in a test-tube, agitate and cool, then with a simple pipette, a, Fig, 8, float soln, FeS04 on the mixture: a dark-brown layer forms between the two solutions, immediately if in strong, or after standing if in weak solutions. 53. €u. Add some small pieces of On and H2S04 to a soln. of nitrate, and heat: brown fumes are given off. Nitric Acid. HNOs. Fig. 8. 54. The free acid responds to the FeS04 test for nitrates without the addition of H2S04. 55. Moisten a crystal of brucin with the liquid: a bright carmin-red color. Nitrates respond to this test after addition of H2S04. CHLORATES—ACETATES—OXIDS—SULFIDS. 14 56, Dissolve 252 pts. of mercuric cyanid and 266 pts. KI in H203 evaporate to crystallization; sepa- rate, and dry the crystals: a crystal introduced into nitric acid turns black 57. Acidulate the (colorless) liquid with HCI (c. p.), and add 1-2 gtt. indigo-carmin soln.; the blue color is discharged. Chlorates. (M)'CIO*. Use KCIO3. 58. Indigo soln. To a cold soln. of chlorate add soln. indigo to a distinct blue, then add a few drops HoS04: the blue color disappears. 59. H2S04 causes the escape of acetic acid, which is recognized by its odor. If to the soln. of acetate a few drops of alcohol be added, then H2S04, and heated: acetic ether will be given off, to be recog- nized also by its odor. Acetates. (M)/(C2H302). Use Na(CaH3O2). 60. Fe2CI6 gives a deep red coloration if neither solution contains free acid. Add HCI: the color changes to yellow. Oxids. [Hydroxids.] (M)'HO—(M)"H2O2. 61. The oxids of As, Na, K, Ca and Ba are solu- ble in water, being converted into hydroxids. Oxids are determined by negative results, i.e., by the ex- clusion of the acid residues. Sulfids. (M)"S. Use (NH4)HS. 62. H2S04 with heat causes the evolution of the gas HaS, with characteristic odor, and which will blacken paper moistened with Pb(C2H3OJ2. SULFITES—SULFATES—SULPUEIC ACID. 15 63. AgNO, gives a black ppt. (Ag2S), insol. in HN03. A drop of the original solution on a bright silver coin gives a dark spot. 61. F©2C16 gives a black ppt. (FeS). Sulfites. (M)"SOs. Use Na2SOs 65. H„S04 with heat disengages the gas S02—rec- ognized by its suffocating odor, and the change to a green color of a drop of K2Cr207 held on a stirring- rod within the tube; or by its action on paper moist- ened with starch paste and iodic acid, which turns blue. 66. AgN03 gives a white ppt. (Ag3S03) if the re- agent be in excess. The ppt. is very sol. in excess of sulfite, and sol. also in HN03. 67. BaCI2 gives a white ppt. (BaSO3), sol. in HCI (c. p.). If chlorin water be now added, a white ppt., insol. in acids, is produced. 68. CaCI2 gives a white ppt. (CaSO3) in concen- trated solutions (5 per cent.), sol. in HCI. 69. F©„Cl6 gives a red-brown color if neutral. 70. Zn and HCI cause the production of H2S gas, which gives a brown or black stain on paper moist- ened with Pb(C.jH3O,J2 held at the mouth of the tube. Sulfates. (M/'SO*. Use dil. H2S04 + 3KHO. 71. BaCI2 or 8a(N03)2 gives a white ppt. (BaSOJ which is insol. in acids. 72. CaCl2, either immediately or on dilution with two volumes of alcohol, gives a white ppt, (CaSO4), insol. in dil. HCI or dil. HN03. Sulfuric Acid. H2S04. 73. The free acid answers to the above tests for sulfates. THIOSULFATES—CARBONATES. 16 74. Add very small fragment lead chromate, boil, filter; add KI (1 gtt.) and carbon bisulfid (2 to 3 gtt.), and agitate: the CS2 is colored violet. Agitate an- other portion of the liquid with CS2 after addition of KI: no violet color should be produced. 75. Dissolve 3 per cent, of cane-sugar in the liquid, moisten a piece of filter paper with it, and dry: the paper turns brown or black. 76. Moisten a little veratrin with the liquid, and evaporate over the water-bath to dryness: a crimson color. 77. H2S04 in cold solutions (not too dilute) deposits S, and becomes green on addition of K2Cr207. Thiosulfates. Use Na2S2O3. 78. AgN03 gives a white ppt. (Ag2S203), which be- comes black on standing or heating. The ppt. is sol. in excess of thiosulfate. 79. Fe2Cl6 gives a reddish-violet color. Carbonates. (M)"CO3. Use (NH4)2CO3. 80. H2S04 causes evolution of gas C02 with effer- vescence. A drop of 0aH202 on the end of a stir- ring-rod held in the gas in the test-tube, turns milky. Or hold tube upright until effervescence ceases, then pour the heavy gas into a test-tube con- taining about one cent, of CaH202, agitate: a white ppt. forms. 81- AgN03 gives a white ppt. (Ag2C03), sol. in dil. HN03. 82. BaCl2 gives a white ppt. (BaCO3), sol. in HCI (c. p.), insol. in NH4CI. 83. CdCI2 gives a white ppt. (CaCO3), sol. in acids, insol. in KH4CI. OXALATES—TARTRATES. 17 84. Fe2CL gives a reddish ppt. (Fe2[COs]3), sol. in HCI, insol. in NH4HO or KHO. Oxalates. (M/'CaOi. Use H3C204 or (NH^aCaOi. 85. H2B04 on a solid oxalate disengages the gases CO and C02; the first detected by burning with a blue flame when ignited, and the C02 by its action with CaH2G2. The solid does not blacken. 80. AgN03 gives a white ppt. (Ag„C204), sol. in dil. HN03 and in KH4HO. 87. BaCl2 in neutral solutions of oxalates (neu- tralize H2C204 with NH4HO) gives a white ppt. (8aC204), sol. in HCI (c. p.) or HNOs, insol. in NH4CI. 88. CaCl2 gives a white ppt. (CaC2O4), sol. in HCI or HN03, insol, in H(C2H3O2) or NH4HO. 89. H2S04 on solid tartrate blackens immediately on warming. Tartrates. Use KNatCiIUOo). 90. AglS08 gives a white ppt. (Ag2C4H406) in neu- tral solution, add dil. NH4HO until nearly dissolved, place in sunlight or in a vessel of water, which heat slowly up to about 60°: a silver mirror forms in the tube. The white ppt. is sol. in dil. HNOa. 91. BaCI2 gives a white ppt. (8aC4H406), sol. in HCI (c. p.), HN03, H(C2H3O2), or in NH4CI. 92. CaCI2 gives a white ppt. (CaC4H4O6), which collect, wash, dissolve in soln. KHO, and apply heat: a white ppt. 93. CaH202 gives a white ppt., sol. in excess of H2(C4H406). 94. To a neutral or alkaline soln. add a few drops K2Mn208, and heat slowly: the color is discharged and MnO precipitated. PHOSPHATES—ARSENATES. 18 Phosphates. Use HNa2PO4. 95. AgK03 gives a yellow ppt. (HAg2P04), sol. in HN03 (c. p.) and in NH4HO. 96. JBaCI2 gives a white ppt. (Ba3[POJ2), sol. in acids, insol. in NH4CI. 97. PaCI2 gives a white ppt. (Ca3[Po4]2), sol. in HCI or H(C2H3O2), insol. in KH4HO or NH4CI. 98. Fe2€I6 gives a yellowish-white ppt, (Fe2[Po4]2), sol. in HCI, insol. in H(C2H3O2), KH4HO, or KHO. 99. MgS04 with NH4CI and NH4HO gives a white ppt. (Mg[NH4]P04), sol. in acids, almost insol. in NH4HO. 100. H(NH4)WLoO4 in HN03 gives a yellow ppt,, which may be hastened by warming; sol. in alka- lies, insol. in HlSr03. Arsenates. Use HNa2As04. 101. AgN03 gives a brick-red ppt. (Ag3As04), sol. in HN03 or NH4HO, insol. in KHO. 102. BaCl2 gives a faint white ppt. (Ba3[AsG4]2), sol. in HCI or HK03, insol. in H(C2H3O2). 103. CaCl2 gives a white ppt. (Ca3[AsOJ3), sol. in HCI or HK03, insol. in NH4HO. 104. Fe2Cl6 gives a yellowish-white ppt. (Fe2- [AsOJ,), sol. in HCI, HNOa, or KH4HO, insol. in KHO. 105. MgS04 same as with phosphates (see § 99). 106. H(NH4)MoO4 gives a yellow ppt.; same as for phosphates, except that it appears only on boil- ing. 107. CuS04, in neutral soln., gives a bluish-green ppt. (Cu3[Aso4]J, sol. in HCI, HNOa, or NH4HO, in- sol. in KHO. ANTIMONATES—BORATES. 19 108. H2S. Add HCI and boil, then pass H2S through the hot soln.; a yellow ppt. (As2S3) forms slowly. 109, (For Arsenites, (M)"'AsOs, this last test may be applied to the filtrate obtained after separating the ppt. with MgSO.t: it gives a yellow ppt. (As2S3) immediately. AgNOs in solns, made slightly alka- line with JSTH4HO: a yellow ppt. [Ag3As03], sol. in NH4HO, insol. in HCI. With CuS04in similar solns. a yellowish-green ppt. [HCuAsOJ.) Reinsch and Marsh tests. See §§ 398, 399. Antimonates. (M)///Sbo4. 110. AgK03. Add KHO to distinct alkaline reac- tion, then AgK03, which gives a brown ppt., sol. in NH4HO. (Antimonites give a dark ppt., insol. in NH4H0.) 111. Kl. Acidify with HCI, warm, and add soln. KI; a brown color results, which on addition of starch soln. turns blue. (Antimonites fail to give this reaction.) 112. H2S. Acidify with HCI and add soln, H2S: an orange-red ppt. (SbS3), sol. in warm KHO or in KH4HS. 113. Reinsch and Marsh tests. See §§ 398, 399, 406, and 407. Borates. (M)"'B03. Use NaaB407. 114. AgN03 gives a white ppt., sol. in HN03 or NH4HO. 115. BaCl2 in concentrated solns. gives a white ppt., sol. in HCI (c. p.) and in alkaline salts. CITRATES. 20 116. CaCI2 in concentrated solns. gives a white ppt., sol. in HCI or NH4CI, insol. in NH4HO. 117. Fe2Cl6 gives a yellow ppt., sol. in excess of reagent or in HCI, insol. in NH4HO. 118. Turmeric paper moistened with a borate and dried turns brown. 119. Flume test. Concentrate on a watch-glass, add a drop of HCI, and examine with a clean plati- num or iron wire: gives a green coloration. Citrates. (M),//C6H607. Use HgCeHsOr. 120. H2S04 on solid citrate and heated, blackens after a time. 121. A%m3 gives a white ppt., sol. in HN03 (c. p.) or in NH4HO. This ppt. will blacken on prolonged boiling. 122. BaCI2 in concentrated solns. gives a white ppt,, sol. in HCI (c. p.), insol. in NH4CI. 123. CaCl2 in neutral soln. gives a white ppt. on heating, sol. in HCI or H(C2H3O2), insol. in KHO, 124. C,iH202 gives a white ppt. on heating, which redissolves on cooling. Primary tests. Secondary tests. Refer to §§ 11 h2so„. Heat. AgN03. DU. HN03, NH4HO. BaCl2 or CaCl2. HC1, H(C2H302),NH4HO, nh4ci. Fe2CJ6. Chlorids 33 white ppt-1 “ “ I £) AA Bromids 37 lodids 39 yellow “ Cya.m'ds TTflT'J p-as. odor.. Nitrates 52 (Add equal bulk Ha SO*."cool, float stroi ig cold FeSO<; dark-brown layer.) Chlorates 58 (Add cold soln. indigo to distinct blue, add HsS04; blue color discharged.) Acetates 59 H(C2H302)vapor..(white ppt Oxids 61 (Determined by negative results). Sulfids 62 black ppt. Sulfites 65 white ppt .... red-brown color. Sulfates 71 “ “ insol. acids.. Carbonates.. 80 “ “ insol. NH4CI.. red-brown ppt. Oxalates 85 00 and CO-> gas... i ( t 6 it a it n Tartrates 89 solid blackens.. .. u a “ “ sol. “ Phosphates.... 95 “ “ insol, “ yellow ppt. Arsenates.. . . 1 pi <( ft it ti Antimonates 111 t i H Borates. ... 115 “ “ sol. NH4CI yellow ppt. 121 solid blackens.. . . < a 125. SUMMARY OF REACTIONS OP ACID RESIDUES (in neutral solutions, see § 32). REACTIONS OF THE MORE COMMON BASES. 22 ACIDIC ELEMENTS GROUPED FOR ANALYTICAL PURPOSES. 126. Acid Residues grouped according to reac- tions. Add strong H2S04; if no gas evolved, apply heat. Oyanids, gas, odor. Acetates, “ “ . Sulfids, “ “ . Sulfites, “ “ . Carbonates, effer- vescence Add AgNOs to original; if ppt., filter; test ppt. witbdil. HlSTOs; test filtrate as below. Chlorids white! Bromids “ I ppt. in- i' sol. lodids yellow J Phosphates yellow ) . Arsenates red r « i Borates white ) Antixnonates brown Add BaCl2 to original or to filtrate from AgN03 ppt.; then HCI (c. p.). Oxalates, efferves- cence, if con *Tartrates, blacken. “ * Solids. Sulfate, white ppt, insol. If not, test for ni- trates, chlorates. If not, is an oxid or hydroxid. REACTIONS OF THE MORE COMMON BASES. 127. The elements, which form bases, are grouped, for purposes of analysis, according to their characteristic precipitations with H2S, in acid solu- tions; NH4HS, in neutral solutions; (NH4)2CO3, in alkaline solutions; and flame colorations, as follows: GROUP I. K. Na. NH4. [Li. Cs. Rb.] GROUP 11. Ba. Sr. Ca. Mg. GROUP 111. Al. Cr. [Be. Tb. Zr. Yt. Ce. La. D. Ti. Ta. Cb.] GROUP IV. Zn. Mn. Ni. Co. Fe. [U. Tl. In. Ga. V.] GROUP V. Ag. Hg. Pb. Cu. Bi. Cd. [Pd. Rh. Os. Ru.] GROUP VI. Au. Pt. Sn. Sb. As. [Gr. Ir. Mo. W. Te. Se.] REACTIONS OF THE MORE COMMON BASES. 23 H2S Test. Use Pb(C2H3O,)2. 128. Take 2 cent, water in a test-tube, add about 10 drops of soln. of substance, add few drops HCI. (If HCI gives a ppt., then repeat, using HN03 in- stead of HCI.) Add to the acidified soln. one-half its bulk of H2S soln., agitate and warm. Or, in place of H2S soln,, the gas H2S may be bubbled through the mixture until pptn. is complete. Col- lect the ppt. on a filter and wash with hot water. Transfer small portions of ppt. with stirring-rod to watch-glasses, and apply secondary tests, as NH4HS or HN03. Is insol. in former and sol. in latter. § US. The H2S solution decomposes on standing, and must be fresh and strong to give its reactions. NH4HS Test. Use FeSO4. 129. Take 2 cent, water, add about 10 drops of substance, add -10-15 drops NH4CI and 2-3 drops NH4HO, or more if necessary to neutralize or render slightly alkaline; then add NH4HS as long as a ppt, forms. Collect, wash, and test as in the H2S test. (NH4)2CO3 Test. Use CaC)2. 130. Take 2 cent, water and about 10 drops of substance, add 10-15 drops NH4CI and 4-5 drops NH4HO, or to distinct alkaline reaction; add (NH4)2CO3, and test solubility of ppts. directly in test-tubes. Flame Test. Use KHO. 131 Concentrate about 10 drops of substance in a watch-glass, held in fingers and passed back and forth through a very small flame. Add when cool MANGANESE—IKON. 24 one drop HCI, moisten a piece of clean platinum or iron wire in the substance and bring to the side of the flame near the mouth of the burner. Examine with blue glass or indigo prism. Flame colored violet. Manganese. Mn" iv 54. Use MnCh (fresh soln. Oxidize with HNO3 for manganic.) 132. NH HS gives a pink or tawny ppt. (MnS), sol. in acids, insol. in NH4CI. (Perform test as in § 129.) 133. (NH4)2CO3 gives a white ppt. (MnCOJ, sol. in HCI or NH4CI, insol. in NH4HO or KHO. 134. KHO gives a white ppt. (MnH2O2) changing to brown, insol. in excess of reagent or NH4HO. Manganous. Manganic. 135. KCN gives a rose ppt (Mn[CN]2), with brown solution if in ex- cess. 136. K4Fe(CN)c, faint reddish-white ppt. (Mn2- Fe[CN]„), sol. in HCI. 137. KBFe„(ON)12, brown ppt. (Mn3Fe2 [CN]I2), in- sol. in HCL light-brown ppt. (Mn„- [CN]6). greenish ppt. ([Mn2]2- 3Fe[CN]J. brown ppt. ([MnJFe2- [CK]J. Iron. Fe"-iv 55.9. Use FeSO4 and Fe2Cl6. 138. NH4HS gives a black ppt. (FeS), insol. in ex- cess, sol. in HCI, insol. in NH4CI or F1(C2H302). Ferrous. 139. (NH4)2CO3 or KHO greenish white ppt., in- sol. in excess, changes to green, then to rust, sol. in HCI, insol. in NH4HO. Ferric. rust-colored ppt. (Fe2- [CO3]3 or Fe2H606), with same solubilities. ALUMINIUM—LEAD. 25 Ferrous. Ferric. 140. NH4HO in absence of NH4 salts, greenish ppt. (PeH2O2), sol. in NH4CI. 141. K4Fe(CN)6 white ppt., changing to blue in air, insol, in HCI. 142. K6Fe2(CN)12 blue ppt., sol. in KHO, insol. in HCI. rust ppt. (Fe2H6O6), sol. in NH4CI. blue (Prussian blue) ppt., sol. in NHJHOor KHO, insol. in HCI. green soln., add SnCl2: a blue ppt. 143. KCNB gives a dark-red color, prevent- ed by C 4H606 or C 6H807, 144. Tannin gives a blue-black color. Aluminium. 27.02. Use (NHASChAI^SOA. 145. NH4HS gives a white ppt. (AI2S3), sol. in HCI or KHO, insol. in NH4CI. 146. (NH4)2CO3 or NH4HO gives a white ppt. (Al2Heo6), insol. in excess, sol. in HCI or KHO, insol. in NH4CI. 147. JKHO gives a white ppt. (A12H606), sol. in ex- cess. To a part add HCI gradually until neutral : ppt. reappears. Add more acid : ppt. disappears. Lead. Pb"iv 206.92. Use Pb(C2H3O2)2. 148. H2S gives a black ppt. (PbS), insol. in NH4HS or cold dil. acids, sol. in hot HN03. 149. NHJHS gives a black ppt. (PbS), insol. in ex- cess or HCI, sol. in hot HN03. 150. (NH4)2CO3 or NH4HO gives a white ppt. (PbCO3 or PbH202), insol. in excess, sol. in HNO„ insol. in H2S04. BISMUTH. 26 151. KUO gives a white ppt. (PbH2O2), sol. in ex- cess or HN03) insol. in HCI or H2S04. 152, HCI gives a white ppt. (PbCl2), if not too dilute, sol. in boiling water. 152 a. HS04 gives a white ppt. (PbSOJ, sol. in (NH4)2C4H406. 153. KI gives a yellow ppt. (Pbl2), sol. in a large excess of boiling water. Decant mixture after pptn, into small flask, add H.,0 to about one-half full, make a paper holder of folded writing-paper, bend around the neck of flask; boil for a minute or two, then filter into beaker and set aside to cool: flaky yellow crystals of Pbl2 should appear. 151. K„CrO4 gives a yellow ppt. (PbCrOJ, sol. in KHO. 155. H,2S and NH4HS give reactions very similar to those of lead (Bi2S3), Bismuth, Bi'" 206.5. Use 8i(N03)3 + HNO3. 156. (NH4)2CO3, NH4HO, or KHO gives a white ppt. (Bi2[Co3]3 or BiH3Os), insol. in excess, and which turns yellow on boiling. The pjit. is sol. in HCI, HN03, or H2S04. 157. K4Fe(CN)fi gives a yellowish ppt. (Bi4[Fe- (ON.)].), sol. in HCI, insol. in H„S04. 158. KOFe,(CN)12, a yellowish ppt. (Bi2Fe2[CN]J, sol. in HCI, HN03; insol. in NH4HO, KHO, HC2H302, h2so4. 159. KI gives a brown ppt. (BilJ, sol. in excess. 160. Infusion Galls gives an orange ppt. 161. Reinsch test gives reduction without subli- mation. See § 398. 162. H„0 gives a white ppt. Add KH4HO to strong solution, collect the white ppt. on a filter, TIN—LITHIUM. 27 wash, dissolve with hot HNOs, dil. with equal vol. H2O, and allow the drops from the funnel to fall into clear water : a white ppt. Tin. 117.7. Use SnCl2(+ HN03 for stannic). Stannous. Stannic. 163. H2B a brown ppt. (SnS), sol. in HH4HS, KHO, and hot HCI, insol. in HN03, but turns white on boiling (H2Sn6Oll). yellow ppt. (SnS2), with same solubilities. 164. NH4HS a brown ppt. (SnS), sol. in excess. yellow ppt. (SnS2), sol. in excess. 165. (NH4)2CO3 a white ppt. (Sn[OH]2), insol. in excess, sol, in strong acids or KHO. white ppt. (Sn[Co3]2), with same solubilities. 166. NH(HO a white ppt. (Sn[OH2]), insol. in excess. white ppt. (Sn[OH]4), sparingly sol. in excess. 167. KHO a white ppt. (Sn[OH]2), sol. in excess; on boiling deposits tin. white ppt. (Sn[OH]4), sol. in excess. 168. K4Fe(CN)„ a white gelatinous ppt, (SnJFe- [CN]e). same. 169. HgCl„ in excess a white ppt. (Hg2Cl2). 170. Zn in soln. acidi- fied with HCI causes a deposit of Sn. 171. Na2S203 gives a yellow ppt. (Sn[S2OJ2) on heating. Lithium. Li' 7. Use LiCl. 172, (NH4)2CO3 gives in concentrated soln. and in absence of NH4 salts a white ppt. (Li2CO3). SODIUM—POTASSIUM. 28 173. HNa2P04 gives a white ppt. (HLi2PO4) in neutral or alkaline solutions, sol. in acids and in NH4CI. 174. Flame test gives red, best seen through the thin part of an indigo prism. Sodium. Na' 22.998. Use NaCi. 175. H2BiF6 gives a gelatinous ppt. (JSTa2SiF6), if soln. not too dilute, sol in strong acids. 176. H2K2Sb207 gives a white, flocculent ppt. (H2Na2Sb2O7) in neutral solns. and in absence of metals other than K and Li; the ppt. becomes crys- talline on standing. The solution of H2K2Sb2G7 must be freshly pre- pared, Dissolve a little of the solid in i-3 cent, of boiling water, filter, and use filtrate. 177. 11104 in excess gives a white ppt. (Nalo4) in not too dilute solns. 178. Flame is enlarged and colored yellow. Potassium. K'39.131?. Use KCK 179. PtCl4 with a drop or two of HCI gives a yel- low ppt. (K2PtCIJ, sparingly sol. in H2O. 180. C 4Hf.Oc gives a white ppt. (HKC4H4G6) in con- centrated solns., sol. in strong acids and alkalies. 181. H2SiF6 gives a translucent, gelatinous ppt. (K2SiF6), which forms slowly and is sol. in strong alkalies. 182. H104 gives a white ppt. (KIOJ, sparingly sol. in H2O, insol. in alcohol. 183. Phosphomolybdic add gives a white ppt., which forms slowly. 184. Flame is colored violet, seen through blue glass or indigo prism. WITTHAUS LABORATORY GUIDE. COLORS OF URINE. AMMONIUM—SILVEE—CALCIUM. 29 Ammonium. (NH4)' 18.044. Use NH4CI. 185. Salts of ammonium are volatile at high tem- peratures. 186. PtCl4 gives a yellow, crystalline ppt. ([NH4]2PtCI6) in concentrated solns. 187. HNaC4H406 gives a white, crystalline ppt. (H[HHJC4H4O6) if not too dilute. •188. KUO and heat cause the evolution of ammo- nia gas, which is recognized by its odor, action on litmus, union with vapor of HCI in form of a white cloud. 189. H2B or NHJHS gives a black ppt. (Ag2S), insol. in NH4HS or HCI, sol. in hot HH03. Silver. Ag' 107.675. Use AgN03. 190. (NH4)2CO3 gives a white ppt. (Ag2C03), sol. in excess, in HISr03, H2S04, or NH4HO. 191. KHO gives a brown ppt. (AgHO), insol. in excess or HCI, sol. in HN03, H2S04, or HH4HO. 192. NH4HO gives a brown ppt. (AgHO) in neutral solns., sol. in slight excess,.insol. in HCI or KHO. 193. Htl gives a white, curdy ppt. (AgCl), sol. in NH4HO, insol. in HK03. 191. KBr gives a yellowish-white ppt (Agßr), changing to black, insol. in acids, sol. in NH4HO. 196. KI same as with KBr, except less soluble in NH4HO (Agl). 196. NH4HS gives a white ppt. if the Ca salt is a phosphate, oxalate, or fluorid. Calcium. Ca" 40. Use CaCl2. 197. (NH4)2CO3 in neutral soln. gives a white ppt. (CaCO3), insol. in excess or H2S04, sol. in HCI. 198. (NH4)2C204 gives a white ppt. (CaC2O4), insol. in C 2H402 or NH4HO, sol. in HCI. BARIUM—MAGNESIUM. 30 199. H2S04 gives a white ppt. (CaSC4), either im- mediately or on dilution with three volumes of alco- hol; very sparingly sol. in H2O, sol. in Na2S203, soon turning yellowish-white (S). 200. Na2W04 gives a dense white ppt. (CaWOJ, even in dil. soln. 201. Flame is colored a reddish yellow. Barium. Ba" 136.8. Use BaCla. 202. (NH4)2CO3 in neutral solns. gives a white ppt. (BaCO3), insol. in excess or H2S04, sol. in HCI or c 2h4o2. 203. HNa2P04 gives a white ppt. (Ca3[POJ2), insol. in excess, NH4HO, or KHO, sol. in HCI or C 2H4Oa. 204. H2S04 gives a white ppt. (BaSOJ, insol. in strong acids. 205. Flame is colored a greenish yellow. Magnesium. Mg" 24. Use MgSO*. 206. (NH4)2CO3 gives a slight ppt. (3[MgC03]- MgH202) from hot cone, solns. in absence of NH4 salts. 207. Na2C03 or K2C03 gives a white ppt. (3[MgC03]- MgH202), best from hot solns.; prevented by pres- ence of NH4 salts. 208. NH4HO gives a voluminous white ppt. (MgH202) from neutral solns., insol. in excess, very sol. in NH4CI. 209. KHO or NaHO gives a white ppt. (MgH202) from warm solns.; prevented by HH4 salts and cer- tain organic substances. 210. HNa2P04 gives a white ppt. (Mg3[POJ2) from hot and not too dilute solns. 211. H2Cr04 with JSTH4HO gives a white ppt. [MgCrOJ, not formed in presence of NH4 salts. ZINC—COPPER. 31 212. There is no pptn. with (NH4)2CO3 in presence of NH4CI, which is added to the (NH4)2CO3 tests for Ca and Ba, §§ 197, 202, to prevent a ppt. (MgH202) when Ca and Ba are tested for in presence of Mg. Zinc. Zn// 64.9. Use ZnS04. 213. H2S in neutral solus, gives a white ppt. (ZnS). In presence of an excess of a mineral acid this ppt. is prevented, unless Na(C2H3OJ be also present. 214. NH4HS gives a white ppt. (ZnS), insol. in excess, KHO, KH4HO, or C 2H402, sol. in dil. mineral acids. 215. (NH4)2CO3 gives a white, gelatinous ppt. (ZnCO3), sol. in excess, HCI, NH4HO, KHO, or NH4CI. 216. K2C03 or Na2C03 gives a white ppt. (ZnCO3) in absence of an NH4 salt. 217. NHHO, KHO, or NaHO gives a white ppt. (ZnH2O2), sol. in excess. 218. HNa2P04 gives, in absence of KH4 salts, a white ppt. (Zn3[POJ2), so 1. in acids or alkalies. 219. K4Fe(CN)6 gives a white ppt. (ZnaFe[CK]6), sol. in NH4HO or KHO, insol. in HCI. 220. H2S or NH4HS gives a black ppt. (CuS), spar- ingly sol. in NH4HS, sol. in hot concentrated HISTO, and in KCK. Copper. Cu" 63.2. Use CuSO*. 221. (NH4)2COs or NH4HO gives a pale blue ppt. (CuH2O2), sol. with deep blue color in excess. 222. KHO, NaHO, K2C03, or NasGO, gives a pale blue ppt. (CuH2O2 or CuC03 + CuHaOa), insol. in ex- cess. On boiling with KHO the ppt. turns black (3CuO, HaO). MERCURY, 32 223. KCN gives a greenish-yellow ppt. (Cu[CH]3), sol in slight excess, HCI, HNOs, or NH4HO, insol. in KHO. 224, K4Fe(CN)# gives a chestnut-brown ppt. (CusFe[CN]#), insol. in excess or weak acids, decol- orized by KHO. 225. Fe. A clean knife-blade or needle held in an acidulated soln. of Cu becomes coated with metallic Cu. 226. Flame is colored green Mercury. Hg" 199.7. Use Hg.2(NOa)ii and HgCl2. Mercurous. Mercuric. 227. HCI a white ppt, (Hg3Cl3), insol. in H3O or in acids, turns black with KH4HO. 228. H3S a black ppt. (HgS + Hg), insol. in NHJHS, HCI, or HN03, partly sol. in boiling HHOg, sol. in aqua regia. ppt. at first white, then orange, then black (HgS + HgCh). 239. NH4HS a black ppt. (HgS + Hg), insol. in excess. ppt. white to black, insol. in excess, except in presence of organic matter. 230. (NH4)2CO3 a dark gray ppt., sol. in hot HN03, insol. in H2S04. white ppt., sol. in great excess of reagent, in H3S04, or in NH4HO (K3CO3 gives a red ppt.). 231, KHO a dark gray ppt. (Hg00), insol. in ex- cess, HCI, or KH4HO, sol. in hot HN03. yellowish-red ppt. (HgO), sol. in HCI, HH03, or nh4ho. MERCURY 33 332. NH4HO same as KHO. Mercurous. white ppt. (KH2HgCI), slightly sol. in excess, strong acids, or NH4CI. Mercuric. 233. K4Fe(CN)6 a white* gelatinous ppt. white ppt. changing to blue. 234. KI a greenish ppt. (Hg2I2), converted by ex- cess into Hg, which is de- posited, and Hgl, which dissolves. yellow to salmon to red ppt. (Hgla), easily sol. in excess of KI or in great excess of the mercuric salt. 235. Reinsch test, see §§ 398 and 413 Preparatory. Primary tests. Secondary. Refer to §§ HC1 or HNO, H2S §128. NH4HS or KHO. nh4ci+nh4ho NH4H8 § 129. add excess. nh4ci+nh4ho (NH4)2C03 §130. add excess. KHO add excess. nh4ho add excess. K4Pe(CN)g add HC1. Manganese... 132 flesh color, in- white, insol... whiteto brown, whiteto brown, red-white, sol. sol. insol. insol. Iron (ous) 138 black, insol.,.. white green to sameas(JNH.4)2- sameas(NH4)2- white to blue, rust, in sol,.. COs. co3. insol. “ (ic) 6 i i{ rust, insol sameas(JNH4)2- same as fflff,).- .... C03. ' C03. sol. Aluminium.. 145 white, “ white, insol... white, sol. .. white, insol... white. Lead 148 black, insol.... black, “ it “ <• <4 “ insol. Bismuth.... 155 a a 4 4 4 4 “ insol... <4 44 yellowish, insol Tin (ous) 163 brown, sol brown, sol n << “ sol white to olive, white, insol. insol. “ (ic) yellow, “ — yellow, “ 44 “ (( it white, sp. sol.. 4 4 4 4 Lithium 172 (Concentrate, add HC1, heat on Pt wire m name: a crimson-red color.) Sodium 175 ( < “ <4 4. n (6 6( U an enlarged yellow flame.) Potassium ... 179 ( ( 44 44 <{ (4 44 44 44 a violet color.) (Ammonium). 185 (Heated with KHO gives off NHS; odor and action on litmus.) Silver 189 black, insoh... black,insol white, sol. .. brown, insol . pale brown,sol. white, insol. Calcium 196 “ insol... Barium 202 (i < < Magnesium .. 206 white, insol... white, insol.... Zinc 213 white insnl “ sol .... white, sp. sol. Copper 220 black,insol— black, si. sol.. green-blue, sol. pale blue to pale blue soln. mahogany, in- to blue soln. brown on boilg. sol. Mercury (ous) 227 “ insol dark gray, insol dark gray,’insol black, insol white, insol. “ (ic).. white to black, white to black, white, sp. sol.. yellow, insol.. white, sp. sol.. white to blue, insol. in sol. sol. 286. SUMMARY OF THE REACTIONS OF THE BASES. Precipitated by HC1: (Consult §§ 128-131). Pb If not, add H2S in excess, precipitated: * Ag Hg(ous) § 288 Bi -) brown Sn(ous) ! or Cu j black, Hg(ic) J § 289. As ) yellow, Sn(ic) [ § 240. Sb, orange. If not, apply NEUHS test to original solution, precipitated: Mn, pink. Pe, black. If not, try (NH4)2COs test with original solution. A1 ) white, Zn (§ 241. Ca \ white, Ba J § 242. If not, try the flame test with original substance. If not, add HNa2P04. A yellowish-white ppt. with H2S is sulfur. Li, crimson. Mg, white. Na, yellow. K, violet. If not, test for NH4, § 188. 237. Bases grouped according to behavior with grouping reagents. BASES GROUPED, ETC. 36 238. Collect ppt. by HCI on a filter, wash, trans- fer a portion to a watch-glass, add a drop or two NH4HO: the ppt. does not change Pb. the ppt. dissolves Ag. the ppt, turns black Bg (ous). 239. Collect the black ppt. by H2S, wash with hot water, transfer to watch-glasses, and test with NH4HS and heat: the ppt. dissolves Sn (ous). Test another portion with hot HNC^: The ppt. does not dissolve Hg (ic). Test the original solution with NH4HO: a blue ppt., sol. in excess, dark-blue soln (Ju. with NH4HO a white ppt. (verify by §163) Bi. 240. Collect the yellow ppt., wash, transfer to watch-glass or test-tnbe, and warm with (NH4)2COs: the ppt. dissolves As. the ppt. does not dissolve Sn (ic). 241. Collect and test the white ppt. by NH4HS with NH4HO: the ppt. is soluble. The original soln. gives white ppt. with NH4HO, sol. in excess, Zn. the ppt. is insoluble. The original soln. gives white ppt. with NH4HO, insol. in excess Al. 242. Collect the white ppt. by (JSTH4)2CO3, dissolve with C.2H402, and add K2Cr04: a ppt. forms Ba. a ppt. does not form Ca. DETERMINATION OF THE BASES. 37 EXAMINATION OF MIXTURES OF SALTS SOLUBLE IN WATER* Determination of the Bases.l 243. Dissolve in water, note the reaction of the solution, and add HCI (if alkaline, to distinct acid reaction): a. No ppt. = absence of Ag, Hg (ous), or notable quantity of Pb. Pass on to § 244. 5. A white ppt. (the original solm was neu- tral or acid); add HCI, drop by drop, until precipitation is' complete, then 8-10 gtt, more, agitate, filter and wash ppt. twice, examine filtrate and washings according to § 244. Treat ppt. on filter with boiling H2O; add H2S to filtrate: a black ppt.. Lead. Treat ppt. on filter (if any remain) with NHJHO: aa. It turns black Mercury (ous). bb. It dissolves, or diminishes, add HNOs to filtrate to distinct acidity, a white ppt Silver. 244. To the soln. in which HCI has failed to ppt., or to the filtrate from 2485, add H2S until it smells strongly of the reagent, and warm slightly: a. No ppt. = absence of Pb, Bi, Cd, Cu, Hg, Au, Pt, As, Sn, and Sb. Pass to § 248, 5. A ppt. is formed ; * This is not intended as a complete analytical scheme, but simply as one for the training of the student in the simpler methods of qualitative separations. In preparing the mixtures to be submitted to students the instructor should avoid combinations not provided for in this scheme. f The acids are determined according to § 126. DETERMINATION OF THE BASES. 38 bl. It is yellowish white, and does not disappear on addition of HCI: the ppt. is sulfur and a ferric compound is prob- ably present. Pass to §248. b2. It is colored. Saturate the soln. thoroughly with H2S, with moderate warming and occasional agitation, fil- ter, wash ppt., examine filtrate and washings according to § 248, and ppt. according to § 245. 245. Treat a small portion of the ppt. with (NH4)2S, with moderate warming, in a test-tube: a. It dissolves completely=absence of Cd, Pb, Bi, Cu, and Hg. Examine the remain- der of the ppt. according to § 246. b. A part or all remains undissolved: filter, add HCI to a part of the filtrate, and agitate with benzene or petroleum ether; aa. Only a white ppt. produced by HCI, dissolved by benzene or petroleum ether—absence of As, Sb, Sn, Au, and Pt; examine remainder of ppt. accord- ing to § 247. bh. A colored ppt. remains: warm the en- tire ppt. produced by H2S, § 344, with (NH4)2S in a flask; filter, after sub- sidence, wash with H2O containing a small quantity of (JSTH4)2S; examine the insoluble part for Cd, Pb, Bi, Cu, Hg according to § 247, and the solution for As, Sb, Sn, Au, and Pt according to § 246. 246. Add HCI to the solution 245hb to acid reac- tion, agitate with benzene, collect the ppt. on a fll- DETERMINATION OF THE BASES, 39 ter, and wash. If this ppt. is brown or black, Sn, Au, or Pt is present; if yellow, As; if orange, Sb. A black or brown ppt. may contain As or Sb, and a yellow or orange traces of Sn, Au, or Pt. Boil ppt. with strong HCI as long as H2S is given off, dilute slightly, filter; a. Filtrate may contain SbCl3 or SnCl3. Place liquid in Pt capsule, immerse rod of Zn in fluid so that it touches Pt outside of the liquid: al. A black stain adherent to Pt, insol- uble (after washing) on boiling with HCI Antimony. a 2. Loose metallic granules, soluble (after washing) on boiling Avith HCI. Soln. gives ppt. with HgCl Tin. h. Ppt. may contain As2S3 (yellow), Au2S3, or PtS2 (black). Shake with (NH4)2CO3 soln. (cold), filter. hi. Filtrate. Add HCI in excess, a yel- low ppt Arsenic. b2. Black ppt. Dissolve in aqua regia, dilute; divide into two parts: 1. With SnCl2, a purple ppt.. .Gold. 2. With KOI and alcohol, a yellow, crystalline ppt Platinum. 247. The ppt. by H2S, insoluble in (NH4)2S from 245aa or 245bb, which may contain Pb, Bi, Cu, Cd, Hg, is boiled with dilute HN03: a. A black residue remains, filter, wash, examine filtrate according to 2476, Mercury. h. Ppt. dissolves completely (except small quantity S), filter, expel most of HN03 by DETERMINATION OF THE BASES. 40 concentration. To a part of filtrate add excess dil. H2SG4, warm, and let stand: bl. Awhiteppt., add excess dil. H2S04to entire filtrate, evaporate to near dry- ness, dissolve residue in H2O + trace H2S04, filter, and examine filtrate ac- cording to b2 Lead. b2. No ppt. (or filtrate from bl). Add NH4HO in excess to remainder of liquid: bb. A white ppt., filter and examine filtrate according to bbl, Bismuth. bbl. No ppt. (or filtrate from bb). Evaporate nearly to dryness, add H2O and HOI to faintly acid reac- tion; hbb. A part with K4Fe(CN)6 gives a brown-red color orppt., bbhl. Remainder, with more HCI and H2S, a yellow ppt., Copper. 248. Boil a part of the solution in which neither HCI nor H2S has caused ppt., or of filtrates from §244 bl and b2, add a few gtt. dil. HN03, boil, and note color (yellow indicates probable presence of Fe), add NH4HO just to alkaline reaction, and then (NH4)2S: Cadmium. a. Neither NH4HO nor (NH4)2S causes a ppt. = absence of Fe, Ni, Co, Zn, Mn, Cr, Al. Pass to § 249. b. NH4HO causes a ppt., presence of Fe, Cr, or Al, or one is produced by (NH4)2S. DETERMINATION OF THE BASES. 41 Add to entire soln. of which a portion was tested with NH4HO and (NH4)2S, first NH4CI, then NH4HO just to alka- linity, then excess (NH4)2S, agitate, warm, let stand, filter and wash. Examine fil- trate according to § 249. aa. The ppt. is pure white =? absence of Fe, Co, Ni. Dissolve ppt. with small quantity dil. HCI by warming in cap- sule, boil to expel H2S, filter if neces- sary, concentrate to small bulk, add cone. NaHO soln. in excess, and boil: aal. The ppt. caused by NaHO dis- solves completely on boiling with excess = absence of Mn and Cr. Presence of A 1 or Zn. Divide soln. into two parts; aaa. Alkaline soln. with H2S gives a white ppt Zinc. bbb. Add HCI to alkaline liquid to acid reaction, then NH4HO in slight excess: a white, floc- culent ppt Aluminium. aa2. The ppt. does not dissolve completely on boiling with excess NaHO; dilute, filter; test filtrate for A 1 and Zn as directed in aaa, bbb above. Wash and dry the ppt.: The ppt. is brown or brownish, Manganese. The soln. in dil. HCI, 248aa, was bb. The ppt. is not white=it contains blue violet Chromium. DETERMINATION OE THE BASES. 42 Cr, Mn, Fe, Co, or Ni. Treat the ppt. immediately with dil. HCI: bbl. It dissolves completely (except a little S) = absence of Co and Ni. Boil the soln., add HN03, boil again, filter if necessary, concen- trate to small bulk, add excess KHO, boil during constant stir- ring, dilute, filter, wash ppt., ex- amine filtrate, then ppt.: Filtrate.—Apart with H2S gives a white ppt Zinc. A part with HCI to acidity, then NH4HO just to alkalinity. gives a white ppt. .Aluminium. Ppt,—Dissolve a part in HCI, add K4Fe(CN)B, a blue ppt., Iron. Dry a part of ppt., fuse with Na2C03 + KCI03, extract with H2O: The soln, is yellow, The soln. is red or green, Chromium. Manganese. Dissolve a part of ppt. in HCI, evaporate to small bulk, add NaC,,H302, treat with H2S, a bb2. It leaves a black residue: filter, wash; examine filtrate as in bbl. Dry and ignite the filter and resi- due, warm with HCI and a little HN03, add H2O, then NH4HO in white ppt Zinc. DETERMINATION OF THE BASES. 43 slight excess, filter, evaporate the filtrate, and ignite the residue. Heat a part of the residue with borax in the inner and outer blowpipe flame: The bead in the oxidizing flame is violet when hot, red-brown when cold, and is gray and opaque in the reduction flame, Nickel. The bead is blue in either flame, hot or cold Cobalt. 249. Add to a portion of the liquid in which neither HCI, H2S, ISTH4HO nor (NH4)2S has caused a ppt., or of the filtrate from § 2486, first NH4CI, then NH4HO and (NH4)2CO3, and warm sometime gently: a. No ppt. is produced = absence of Ca, Ba, or Sr; examine the remainder of the liquid according to § 250. 6. A ppt. is produced: treat the remainder of the liquid with NH4CI, NH4HO, and (NH4)2CO3, warm gently, filter, examine the filtrate according to § 250. Wash the ppt. with H2O containing NH4HO, dissolve in C 2H402, and add K2Cr04 in excess: 61. A yellow ppt., filter and examine fil- trate according to 62 Barium. 62. To a small portion of the filtrate add CaS04 and warm gently: 661. A ppt. is formed, filter, ex- amine filtrate according to 662, the dried ppt. + HCI on Pt wire colors Bunsen flame crimson, Strontium. DETEEMINATION OF THE BASES. 44 663. Add to filtrate from 661, or to a portion of liquid from 6 if CaS04 caused no ppt. in 6£, NH4HO and (NH4)2C204: a white ppt., Calcium. 350. To a portion of the liquid from § 249 a, or of the filtrate from § 2496, add NH4CI (if not already added), then NH4HO and HNa2P04, rub inside of test-tube gently with glass rod, and let stand: a. A white ppt., crystalline, and formed if in small quantity where test-tube has been rubbed Magnesium. 6, No ppt. is produced, pass to § 251. 251. A. Magnesium was absent in § 250, evapo- rate another portion of the liquid § 249 a or § 2496 to dryness and ignite gently: a. No residue remains=absence of K or Na, proceed to § 253. 6. A residue remains=presence of K or Na, examine residue according to § 252. B. Magnesium was present in § 250; evaporate another portion of the liquid § 249 a or § 2496 to dry- ness, ignite until NH4 salts are expelled, warm resi- due with H2O, add BaCl2 so long as it produces a ppt., then BaH2G2 during heating to distinct alkalin- ity; boil, filter, add (NH4)2CO3 + NH4HO in slight excess to filtrate, warm gently some time, filter, evaporate, and ignite residue gently until NH4 salts are expelled: a. No residue remains = absence of K or Na; pass to § 253. 6. A residue remains = presence of K or Na; examine residue according to § 252. 252. Dissolve residue from 251M6 or 251.86 in DETERMINATION OF THE BASES. 45 a little H2O, add a little NH4HO, then (NH4)2CO,, warm some time, filter if necessary, evaporate clear liquid or filtrate to dryness, ignite gently to expel NH4 salts, dissolve residue in small quantity H2O; divide clear liquid into two parts: a. Add to half the liquid in a porcelain cap- sule PtCl4; a yellow, crystalline ppt., b. To other half of liquid (neutralized, if acid, with Na2C03) in a watch-glass add a freshly prepared and filtered soln. of K2H2- Sb207; a white, crystalline ppt Sodium. Potassium. 253. To a portion of the original soln. or solid add excess of CaH202, and H2O if necessary, and boil: steam smells of NH3, blues red litmus, and gives white cloud from glass rod moistened with HCI, Ammonium. QUALITATIVE ANALYSIS OF UETEE. PHYSICAL CHARACTERS. 254, Collect all urine passed by the patient dur- ing twenty-four hours, and measure in a cylindrical graduate (Fig. 9) divided v ) into cubic centimetres. Quantity. Normal = 1,000 to 1,500 cc. All examinations of urine should he made with samples of the mixed urine of twenty-four hours, unless otherwise directed. Color. 255. Put 100 cc, urine (filtered if cloudy) into a beaker of 6 to 7 centime- tres diameter ; look through it at the light from a window, and compare the color observed with the color plate. (See plate.) Record this, by using the numbers of the colored squares, as free color. Add 5 cc. HCI to the urine; stir, let stand four hours, compare color as before, and record as total color. 256. Note whether the odor is natural or ‘‘urinous,” or “ammoniacal,” “like violets,” or otherwise peculiar. Odor. Fig. 9 REACTION—SPECIFIC GRAVITY. 47 Reaction. 257. If the reaction be found to be alkaline, it remains to determine whether the alkalinity is due to fixed or volatile alkali, to carbonates or phos- phates. These determinations must be made with the urine so soon as possible after it has been voided, and, preferably, with the morning urine. 258. Moisten one-half of a piece of red litmus paper with the urine, and hang it up to dry. If, after drying, the paper retain its blue color, the alkalinity is due to fixed alkali; but if the paper re- turn to its original red, to volatile alkali (ammonia). To obtain reliable results, the paper must be dried in a position where it is not exposed to the fumes coming from bottles containing NH,HO, HCI, or HN03, or to other acid or aramoniacal vapors. 259. To a portion of the urine in a test-tube add a slight excess of HCI, and warm, if necessary. If effervescence ensue, the alkalinity is due to carbon- ates; if not, to phosphates. If volatile alkali be found in 258, and carbonate in 259, the urine contains ammonium carbonate. Specific Gravity. 260. Test the urinometer (which should not be smaller than 12 centimetres in length, and divided into single degrees) with the solutions of known specific gravity furnished in the laboratory for that purpose, making the readings as directed in § 261, and note the error in different parts of the scale. The differences from the true readings are to be noted on the box. and added or subtracted, as the error is minus or plus, in all subsequent readings. 261. To use the urinometer: The cylinder should SPECIFIC GRAVITY. 48 be of the shape shown in Fig. 10, without pouring- lip, of such depth that the urin- ometer may be completely im- mersed, and of a diameter double that of the wide part of the urin- ometer. Hold the cylinder in an inclined position, and pour into it urine to within 2 centimetres of the top. Set it upright, float the urinom- eter in the urine, and add more urine until the level “ heaps ” above the rim of the cylinder. Now bring the eye to about the level of the top of the cylinder, and, seeing that the urinometer does not touch the wall of the cylinder, read off the specific gravity at the highest point where the liquid, drawn up by capillary attraction, cuts the graduation of the urinometer (A, Fig. 10). 262. The temperature at which the gravity should be determined is 60° F ( 15°.4 Cent.). If the urine be of a different temperature, cool it by im- mersing the vessel in cold water, or warm it until 60° is reached. Fig. 10. Corrections for variations of temperature cannot be accurately made in the case of a liquid of such complex and varying composition as the urine. NORMAL URINE —UREA. 49 CHEMICAL CHARACTERS—COMPOSITION. Normal Constituents. N. B.—Obviously a qualitative examination of the urine for its normal constituents is never practised by the physician. The student is required to test for the more important of these substances, to afford practice in the methods of manipulation and obser- vation. Normal Urine Contains: Water, Chlorids, Sulfates, Phosphates, Sodium, Potassium, Calcium, Magnesium, Urea, Uric acid, Urates, Hippnric acid, Creatinin, Coloring matters, etc., etc. Urea. 263. To a moderately concentrated cold soln. of urea in a watch-glass add colorless H]Sr03 in equal volume immediately, or after a few moments, crys- tals of nitrate of urea (Fig. 11) separate. 264. To a few drops of a soln. of urea upon a watch- glass add a few gtt. of Mil- lon’s reagent,* and heat—a yellow color, changing to FIQ- n- * Made by dissolving 1 pt. Hg in 2 pts. strong HNO3 over the water-bath, diluting with 2 pts. H2O, and decanting after four hours. URIC ACID—ALBUMIN. 50 red, is produced. A somewhat similar appearance is produced with albumins. 2(15, Heat a fragment of urea in a dry test-tube until, after having fused, it is converted into an opaque, white solid; let cool; add about 1 cent. KHO and 2 gtt. of a very dilute soln. CuS04—a pale rose-red color. This test, known as the “biuret reaction” produces a similar appearance with pep- tones. See § 281. Uric Acid. 260. Moisten the solid in a porcelain capsule with a few gtt. HNO,,; heat on the water-bath until dry; cool; add jSIH4HO—a brilliant red color appears, which fades after a few moments. This is known as the “murexid test” Abnormal Constituents. PROTEIDS - ALBUMINOIDS. Before testing for albuminoids, the urine must be separated from all solid particles, must be rendered perfectly clear and transparent; this is accomplished by filtration. 267. It frequently happens that urine does not yield a clear filtrate by simple filtration. When this is the case, add to the turbid filtrate enough KHO to communicate a distinctly alkaline reaction, and a few gtt. of magnesia mixture, warm slightly, and filter again through a fresh filter. Albumin. 268. Heller’s test.— Put about 2 cent, HJST03 into a test-tube. Fill a pipette with the filtered urine. Hold the test-tube at a small angle to the horizontal, and allow the urine to flow slowly from the pipette (whose upper end has been roughened by the file) ALBUMIN. 51 upon the surface of the nitric acid (Fig. 12). Re- move the pipette, turn the test-tube cautiously into Fig. IS. the vertical position, and examine the point of junc- tion of the two liquids. In the presence of albumin a milky zone, whose upper and lower borders are both sharply defined, is seen at the point of junction of the acid and urine (Fig 13, a). If no reaction be observed, set the tube aside and examine it again in half an hour. 269. Repeat the testing’, as in § 268, with a non-albuminous urine. A band of deeper color- ation is observed at the point of junction of the two liquids: this is not to be confounded with the milky zone observed with albu- minous urine. 270. Repeat the testing, as in § 268, using a urine containing an excess of urates, but no albu- min. A white zone is observed above the point of junction of the liquids, whose lower border may be sharply defined, but whose upper border fades off gradually into the Fig. 13. ALBUMIN. 52 layer of urine, the whole of which may become turbid (Fig 13, h). 271. Heat and Nitric Acid test.—Determine the reaction of the urine. If it be alkaline, add acetic acid cautiously until it shows a faintly acid reaction with blue litmus paper. Fill a test-tube to within 2-3 cent, of the top with the acidulated urine, and, holding- the test-tube by the bottom, heat the upper portion of the liquid nearly to boiling. An opal- escence, cloudiness, or coagulum is formed, accord- ing to the amount of albumin present. Now add slowly sto 10 gtt. of concentrated HNOa; the ppt. does not diminish (it may increase) in amount. 272. Apply heat, as in § 271, to a sample of the alkaline albuminous urine, without acidulating. No reaction is observed. 273. Apply heat, as in § 271, to another sample of the urine, to which an excess of acetic acid has been added. No reaction is observed. 274. Apply the test, as directed in § 271 (but do not acidify), to a sample of urine containing no albumin, but containing an excess of earthy phos- phates. An appearance similar to that observed in the case of the albuminous urine is obtained; but on addition of HN()3 the ppt. redissolves and the liquid becomes transparent. 275. If the urine, when heated, becomes cloudy, and again clears on addition of HNOa in the amount mentioned in § 27J, it contains an amount of earthy phosphates in excess of the normal. 276. Picric Acid test.—Float some of the clear urine on acetic acid as in Heller’s test. If any cloudiness be observed at the junction of the two liquids, treat a larger quantity of the urine with PARAGLOBULIN—MUCIN—PEPTONE. 53 acetic acid to acid reaction, and filter. Pour about 7 cent, of the clear filtrate, or of the clear urine, which gives no cloudiness when floated on acetic acid, into a test-tube; float upon its surface about 2 cent, of a saturated solution of picric acid, and warm the point where the two liquids come together. A cloudiness at this point, which does not disappear when heat is applied, is evidence of the presence of albumin. A cloudiness which does disappear on the applica- tion of heat may be produced by alkaloids, urates, etc. Paraglobulin. 277. Dilute the filtered urine with water to sp. gr. 1.002. Float on the surface dilute acetic acid (1 to 10); a cloudy zone is formed in the presence of para- globulin in large amount. If no cloudiness be observed after half an hour, pass through the liquid a slow current of carbon dioxid, A cloudiness indi- cates the presence of paraglobulin. Mucin. 278. Pour about 2 cent, of acetic acid into a test- tube, and float the clear urine upon its surface. A cloud, which usually appears only after standing for a time, just above the line of contact of the liquids, shows the presence of mucin, provided it does not disappear on the application of heat. Peptone. 279. Add soln. of neutral lead acetate to 500 cc. urine until the ppt. no longer increases; filter. To the filtrate add acetic acid and a few gtt. of potas- sium ferrocyanid soln.; if any cloudiness be pro- GLUCOSE. duced, continue the addition of ferrocyanid soln. until the precipitate no longer increases, and filter. 280. To a portion of the last filtrate obtained as in § 279, add one-fifth its bulk of acetic acid and then an acid soln. of sodium phosphotungstate.* A cloud- iness immediately, or after a few moments, indi- cates the presence of peptone. 281- To the remainder of the filtrate, § 279, add half its volume of strong HCI, and then phospho- tungstate soln. to complete precipitation. Collect the ppt. on a filter as rapidly as possible, wash with bf the liquid under examination and one of the reagent near each other on a slip of black glass and bringing the two to- gether with a pointed glass rod. 419 Add to an acidulated soln. of an alkaloid a soln. of phosphomolybdic acid; a white or yellow ppt. 420. Add to an acidulated soln. of an alkaloid a soln. of phosphotungstic acid; a white, flocculent ppt. 421 The following reagents also produce ppts in faintly acidulated solns. of alkaloids: iodin in potassium iodid, brown; tannin, white or yellow; platinic chlorid, yellowish, usually becoming crys- talline; auric chlorid, yellowish; phosphoantimonic MORPHIN. 105 acid, white; potassium iodid and cadmium iodid, white or yellow; picric acid, yellow. Morphin. 4:22. Moisten a crystal with H]Sr03: an orange color, changing to yellow. 423. Moisten with H2S04 : the alkaloid dissolves, forming a colorless soln. Warm until white fumes are given off, cool, introduce a trace of HN03: a red- violet color. 424. Dissolve a crystal of iodic acid in H2O, and shake a part of the soln. with CHC13 : the latter should not be colored. Add to a soln. of a morphin salt a few gtt. of the iodic acid soln., and agitate : the liquid assumes a yellow color. Add a gtt. of CHC13, and agitate: the CHC13 which separates at the bottom is colored violet. Float some dil. NH4HO on the surface of the liquid: the test-tube will contain different colored layers; violet below, then yellow, dark yellow or brown, and faintly yellowish. 425. Moisten a crystal of morphin with, or add to a neutral soln. of one of its salts, a soln. of neutral Fe2Cl6: a blue color. 426. To a crystal of morphin add a soln. of mo- lybdic acid in H2S04 (Frohde’s reagent) : a violet color, changing to blue, dirty green, and faint pink. Water discharges the color. 427. Add NH4HO to AghT03 soln. until the ppt. is nearly dissolved, filter, add soln. of a morphin salt, and warm ; a gray ppt. Filter off the liquid and add to it HN03 : a red or pink color. 428. Heat morphin with cone. H2SG4 to 200° C. t392° F.) until green-black; add a drop of the liquid MECONIC ACID—STRYCHNIN. 106 cautiously to H2O: the solution turns blue. Shake a portion with ether: the ether turns purple. Shake a portion with chloroform: the chloroform turns blue. 429. Warm the solid alkaloid with cone. H2S04; add cautiously a few drops of a 30$ alcoholic soln. of KHO: a yellow color is produced, changing to dirty red, then steel blue and sky-blue, and. with a further quantity of KHO soln., cherry-red. 430. Add soln. Fe2Cl6 ('l-16) to soln. potassium fer- ricyanid (1-50): the mixture remains yellow (a blue color is due to impurity of reagents). Add morphin soln.; a deep blue color. 431. Antidotes.—Stomach-pump; wash out stom- ach with H2O holding powdered charcoal in sus- pension, or with infusion of tea. ZnS04. Keep patient awake. Atropin? Meconic Acid. 432. To portions of the acid in three watch-glasses add Fe2Cl6 soln.: a red color is produced. To one watch-glass adddil. HCI: the color is not discharged. To the second watch-glass add HgCl2 soln.: the color is not discharged. To the third watch-glass add so- dium hypochlorite soln.: the color is discharged. 433. Add Fe2CI„ soln. to a thiocyanate in a watch- glass: a red color, similar to that with meconic acid, is produced Add HgCl2 soln : the color is dis- charged. Strychnin. 434. Place a minute drop of a soln. of a strychnin salt on the tongue: a persistent, intensely bitter taste. 435. Add H2S04: the alkaloid (or its salts) dis- STRYCHNIN. 107 solves, forming a colorless soln. Draw through the soln, a fragment of a crystal of potassium dichro- mate; it is followed by a streak of color; at first blue (very transitory and frequently not observed), then a brilliant violet which slowly changes to rose pink and finally to yellow. 436. Evaporate a drop of soln. of a strychnin salt on a slip of Ft foil, moisten the residue with con- centrated H2S04, connect the foil with the + pole of a Grove cell, and bring a Ft wire, connected with the pole, in contact with the surface of the acid: a violet color on the surface of the foil. 437. Moisten a fragment of strychnin with a soln. of iodic acid in H2S04: a yellow color, changing to brick-red and then to violet-red. 438. Let an assistant hold a small frog by the hind legs. Raise the skin of the back at the root of the legs with a forceps, make a small incision with a scissors, and allow a few gtt. of a very dilute soln, of a salt of strychnin to flow into the lymph pouch. Place the frog under a glass shade: within ten min- utes the animal has violent tetanic spasms, with opisthotonos or emprosthotonos, increasing in fre- quency, and provoked on the slightest touch, or by blowing upon the surface. 439. Add a few gtt. of a dil. soln. of potassium dichromate to a soln. of a strychnin salt: a yellow, crystalline ppt. Collect the ppt. and moisten it with cone. H2S04: a play of colors as in § 435. 440. Antidotes,—Stomach-pump; wash out stom- ach with infusion of tea. Chloroform, chloral. TABLE OF SOLUBILITIES. Wor w = soluble in H2O. Aor a = insoluble in H2O ; soluble in HCI, HNO3, or aqua regia. lor i = insoluble in H2O and acids. W-A = sparingly soluble in H2O, but soluble in acids. W-I = sparingly soluble in H2O and acids. A-l = insoluble in H2O, sparingly soluble in acids. Capitals indicate common substances. Fresenius, Aluminium. Ammonium. Antimony. Barium. Bismuth. Cadmium. Calcium. Chromium. Cobalt. Copper. Ferrous. Ferric. Acetate W W W w w a w w W w W Arsenate a w a a a a a a a a a a Arsenite w a a a a A a a Benzoate w w w w w a w a Borate a w a a w-a a a a a a a Bromid w w w-a w w-a w w w-i w w w w Carbonate a w A A a A a A A A a Chlorate w w W w w w w w w w w Chlorid w W2 W-A8 W W-A10 w w W-I w w w w Chromate w a a a a w-a a a w W Citrate w w a a w-a w w w w w Cyanid . — w w-a a w a a-i a a-i Fen icyanid w w i i W Ferrocyanid .... w w-a w i i i i Fluorid w \v w a-i w w-a A w w a a w-a w Formate w W w w w w w w w w w Hydrate A w A w a a WA A A a a A lodid w w w-a W a vv w w w w w w Malate ... w vv w-a w-a w Nitrate. . w w vv W“ W w w w vv w w Oxalate a \v a a a a A w-a A a a a Oxid A-J a7 vv a a W-A A-I A A a A Phosphate a W3 w-a w-a a a W-A a a a a a Silicate A-I a a a a a a a a Succinate w-a W w-a w w-a w-a w-a w Sulfate W‘ w* a A w w W-I W-A12 vv vv w w Sulfld a w A* W a A W-A a-i a13 A A A Tartrate w W5 a9 a a w-a a w w w w-a VV14 1 (A12)(NH4)2(504)4 = W ; (A12)K2(504)4 = W. 2 As(NH4)CI4 = W; Pt(NH4)2CI. = W-I. 3 HNa(NH4)PO4 = W; Mg(NH4)P04 = A. 4 Fe(NH4)2(SO4)2 = W ; Cu(NH4)2(SO4)2 = W. 5 C 4H406K(NH4) =W. 6 SbOCl =A. 1 Sb203 = soluble in HCI, not in HN03. 8Sb2S3 = sol. in hot HCI, slightly in HNO,. 9 C4H4O.K(SbOj = W. 10 BiOCl = A. 11 (BiO)N03 = A. 12 (Cr2)K2(SO4)4 =W. 14 CoS - easily sol. in HNO,, very slowly in HCI. 14 (C4H4G6)4(Fe2)K2 = W. TABLE OF SOLUBILITIES—Continued. Frbsenixjs, Wor w = soluble in H2O. A or a = insoluble in H2O; soluble in HCI, HNO3, or aqua regia. lor i = insoluble in H2O and acids. W-A = sparingly soluble in H2O, but soluble in acids. W-I = sparingly soluble in H2O and acids. A-I = insoluble in H2O, sparingly soluble in acids. Capitals indicate common substances. Lead. Magnesium. Manganese. [ Mercurous. Mercuric. Nickel. Potassium. Silver. Sodium. Strontium. Stannous. Stannic. Zinc, Acetate W w w w-a w w W w W w w w W Arsenate ... a a a a a a W a W a a a Arsenite a a a a a a w a w a a Benzoate.... a w w a w-a w w-a w Borate a w-a a a w a w a a a Bromid w-i w w a-i w w w a w w w Carbonate... A A A a a A w a w A A Chlorate w w w w w w w w W w w w Chlorid W-I w w A-I W16 w W20 1 w w w w w Chromate— A-l w w a w-a a w a W w-a a w Citrate a w a a w-a w W a w a w-a Cyanid a w a w a-i w i W w a Ferricyanid.. w-a w i i Wr i w a Ferrocyanid a w a i w i w w a-i Fluorid a a-i a w-a w-a W w w a-i w W w-a Formate w-a w w w w w W w w w w w Hydrate. a A a a w w w a a a lodid .... W-A w w A A w w i w w w w w Malate w-a w w a w-a W w-a w w w w w Nitrate w w w w w w w w w w w Oxalate a a w-a a a a w a w a a w a Oxid A A A10 A A A w a w vv a AH A Phosphate... a a3 a a a a W a w a a a a Silicate a a a a w w a a Succinate— a w w a w-a w W a W w-a a w-a Sulfate A-l w w w-a W 17 w W12 W-A w 1 w w Sulfld A a a a A'« A19 w a2*l w w a22 A 22 A23 Tartrate. ... a w-a w-a w-a a a 1 w a W a a a 15 Mno2 = sol. in HCI; insol. in HNO3. 16 Mercurammonium chlorid A. 17 Basic sulfate =A. 18 HgS = insol. in HCI and in HNOS) sol in aq. regia. 19 See 13. 20 PtK6Cl0 = W-A. 21 Only soluble in HNOs. 92 Sn sulfids = sol. in hot HCI; oxidized, not dissolved, by HNO3. Sublimed SnCl4 only sol. in aq. regia. 23 Easily sol. in HNO3, difficultly in HCI. AuaS = insol. in HCI and in HNO3p sol. in aq. regia. Außr3, AuCls, and Au(CN)3 =w; Aul3 =a. PtS2 = insol. in HCI, slightly sol. in hot HN03; sol. in aq. regia. Ptßr4, PtCl4, Pt(CN)4, Pt(NOs)4, (C2O4)2Pt, Pt(So4)a =w; Pto2 =a; Ptl4 =i. INDEX. Calcium, 29 oxalate, 76 Calculi, 82 Carbonates, 16 Casts, 80 Chloral, 88 Chlorates, 14 Chlorids, 10, 65 Chloroform, 88 Citrates, 20 Copper, 31, 101 Cyanids, 12 Cystin, 78. Abbreviations, 3 Acetates, 14 Acid, carbolic, 89 hydrochloric, 10 hydrocyanic, 87 meconic, 106 nitric, 13 prussic, 87 residues, 10, 21, 22 sulfuric, 15 uric, 50, 71, 75 Acidimetry, 62 Acids, 10, 21, 22, 90 Albumin, 50, 73 Alcohol, 87 Alkalies, 91 Alkalimetry, 63 Alkaloids, 104 Aluminium, 25 Ammonium, 29 Antimonates, 19 Antimonites, 19 Antimony. 99 Arsenates, 18 Arsenic, 94 Arseni tes, 18 Decantation, 6 Epithelium, 79 Ferric, 24 Ferrous, 24 Filtration, 6 Glucose, 54, 73 Hydroxids, 14 Barium, 30, 101 Bases, 23, 84, 35, 37 Bile, 59 Bismuth, 26, 100 8100d,58 corpuscles, 79 Borates, 19 Bromids, 11 Bunsen burner, 5 lodids, 11 Iron, 24 Lead, 25, 101 Leucin, 77 Lithium, 27 Magnesium, 30 Manganese, 24 INDEX. Manganic, 24 Manganous, 24 Measures, 4 Mercury, 32, 101 Morphia, 105 Mucin, 53 Mucous corpuscles, 78 Sulfates, 68 Sulfids, 14 Sulfites, 15 Tartrates, 17 Test, Boettger's, 55 biuret, 50, 54 Fehling’s, 58, 73 fermentation, 57 Gmelin’s, 61 Heller's, 51 Marsh's, 97, 100 Moore’s, 55 Mulder-Neubauer, 56 murexid, 50 Oliver's, 60 Pettenkofer’s, 59 Reinsch’s, 96, 99 Trommer s, 55 Thiosulfates, 16 Tin. 27 Tyrosin, 77 Nitrates, 18 Oxalates, 17 Oxids. 14 Paraglobulin, 53 Peptone, 53 Phenol, 89 Phosphates, 18, 66, 77 Phosphorus, 85 Poisons, 84 metallic, 91 mineral, 90 vegetable, 102 volatile, 84 Potassium 28 Precipitation, 8 Pus. 78 Urates, 76 Urea, 49, 69 Urinary deposits 75 Urine, color, 46 composition, 49 physical characters, 46 odor, 46 qualitative analysis, 46 quantitative analysis, 62 quantity, 46 reaction, 47, 62 specific gravity, 47 Reaction, 9, 47, 62 Reactions of acids, 10, 21, 22 of bases, 22, 84, 30, 37 Rules, 1 Silver, 29 Sodium, 28 Solubility, table of, 108, 109 Solution, 6 Spermatozoa, 81 Stannic, 27 Stannous, 27 Strychnin, 106 Sugar, 54 Weights, 4 Zinc, 31, 101