Appli > hi i . illiv sS^SssssSsSsS llillis \.j.i. xx c xyx.» jl^j • 111111 ■i i§iiiii .:-■:::•■■■ M® ■;.-. ■?.^ ; : ■■■.- Snail ■■M ■■■■ LIBRARY OF CONGRESS. - RS40 3 + m Shelf JD/O 5 o. UNITED STATES OF AMEEICA. APPLIED MEDICAL CHEMISTRY. WOLFF. Richters Chemistry. A Standard and Popular Text-Book. EACH VOLUME SOLD SEPARATELY. INORGANIC CHEMISTRY. Second American from the Fourth German Edition. Thoroughly Revised and Corrected. 89 Wood-cuts and Colored Lithograph of Spectra. i2mo. Cloth, S2.00. THE CHEMISTRY OF CARBON COMPOUNDS, or, Organic Chemistry. First American trom the Fourth German Edition. Illustrated. i2mo. Cloth, S3.00. AUTHORIZED TRANSLATION BY EDGAR F. SMITH, M.A., Ph.D., Prof, of Chemistry in Wittenberg College, Springfield; formerly in the Laboratories of the University of Pennsylvania ; Member of the Chemical Societies of Berlin and Paris, of the Academy of Natural Sciences of Philadelphia, tic. In most of the chemical text-books of the present day, one of the striking features and difficulties with which teachers have to contend is the separate pre- sentation of the theories and facts of the science. These are usually taught apart, as if entirely independent of each other. In this work, which has been received with such hearty welcome, theory and fact are brought close together, and their intimate relation clearly shown. From careful observation of experi- ments and their results, the student is led to a correct understanding of the interesting principles of chemistry. The matter is so arranged as to adapt the work to the use of the beginner, as well as for the more advanced of chemical science. From Prof. B. Silliman, Yale College, New Haven, Conn. " It is decidedly a good book, and in some respects the best manual we have." From F. A. Gexth, Prof, of Chemistry, and F. A. Genth, Jr., Ass't Prof, of Chemistry, University of Pennsylvania. " We have examined with much care the ' Inorganic Chemistry' of Prof. Victor von Richter, recently translated by Dr. E. F. Smith. Both theoretical and general Chemistry are treated in such a clear and comprehensive manner that it has become one of the leading text-books for a University course in Germany. We are indebted to Dr. Smith for his translation of this excel- lent work, which may help to facilitate the study of chemistry in this country." From the American Chemical Review. " These new features alone will recommend the work to teachers as well as students, while the eminent success of the former German edition amply proves that it also possesses more than ordinary merit in other directions." P. BLAKISTON, SON & CO., Publishers, Philadelphia. APPLIED Medical Chemistry. A MANUAL FOR Students and Practitioners of Medicine, BY, LAWRENCE WOLFF, M.D., DEMONSTRATOR OF CHEMISTRY JEFFERSON MEDICAL COLLEGE, MEMBER OF THE GERMAN CHEMICAL SOCIETY, THE PHILADELPHIA COUNTY MEDICAL SOCIETY, THE PHILADELPHIA COLLEGE OF PHARMACY, ETC. if n PHILADELPHIA: P. BLAKISTON, SON & CO., 1012 Walnut Street. 1885. Copyrighted, 1885, by P. Blakiston, Son & Co. PREFACE. As a rule, students at medical colleges are mainly acquainted with the principles of chemistry, but not their practical appli- cation. The result is, frequently, that their chemical knowledge is soon forgotten. Reference is freely made in medical text- books to chemical processes, but their execution is not satis- factorily dwelt upon. In the special works on chemistry they are exhaustively treated, but these works are intended for the chemist more than the physician. To collate and elaborate information from them to apply to special cases can hardly be expected of the busy practitioner. My object in writing this book is to present in as simple and concise a manner as accu- racy and easy execution will admit, such matter as will save much research and labor. The arrangement of this volume has been made in accord- ance with my system of demonstrations ; and the latest and more rational terms, forms, and processes, as well as their modi- fications, have been given wherever possible and advantageous. To afford exercises for the student, I have appended to each part a syllabus of the principal processes the physician may find useful in his practice. Though I have given my own version of the different manipulations from my personal experience, I have also drawn freely on the following works : Fresenius, " Anleitung zur Qualitativen und Quantitativen Analyse ;" Hoffmann and Power, " Examination of Medicinal Chemicals;" Wormley, " Micro-chemistry of Poisons ;" Sonnen- 6 PREFACE. schein, " Handbuch der Gerichtlichen Chemie ;" Witthaus, " General Medical Chemistry ;" Gorup Besanez, " Physiologische Chemie ;" Hoppe-Seyler, " Physiologische Chemie ;" Charles, "Physiological and Pathological Chemistry;" Loebisch, "An- leitung zur Harn-analyse ;" Marshall and Smith, " Chemical Analysis of the Urine ;" Tyson, " Practical Examination of Urine ;" Ludwig, " Medicinische Chemie," et al. I have written this volume as a manual for the medi- cal student in his college course, but I trust that it will also find a place in the library of the practitioner as a book of reference. L. W. 333 South Twelfth Street, Philadelphia, 1885. CONTENTS. PART I. Apparatus and Manipulations. TAGK Physical Apparatus, 9 Specific Gravity, 12 Manipulations and Technical Apparatus, 15 Analysis, 19 Reactions and Reagents, 23 Test Papers, 27 Volumetric Tests, 27 Alkalimetry, 27 Acidimetry, 28 Volumetric Analysis by Precipitation, 29 Stoichiometry, 30 Syllabus of Part I, 33 PART II. Chemistry of Poisons. Antimony, 35 Arsenic, 37 Copper, 42 Mercury, . . 44 Lead, 47 Phosphorus, 49 Alkalies and Acids as Poisons, 51 Potassic Hydrate, 52 Sodic Hydrate, 52 Ammonium Hydrate, 53 Sulphuric Acid, 53 Nitric Acid, 54 Hydrochloric Acid, 55 Carbolic Acid, 56 Oxalic Acid, 56 Hydrocyanic Acid, 57 Syllabus of Part II, 58 PART III. Physiological Chemistry. Albuminoids, or Protein Bodies, 61 Collagens, 68 Coloring Bodies, 69 Biliary Pigments, . 70 Urinary Pigments, : 71 Digestive Ferments, 72 Organic Amines and Amides, 73 Compound Ureas, 74 CONTENTS. PAGE Ureids from Uric Acid, 75 Amido Acids, 77 Biliary Acids, 77 Carbohydrates, 79 Amyloses, 79 Saccharoses, 81 Glucoses, 82 Alcohols, 83 Volatile Fatty Acids, 84 Glycollic Series, 85 Oxalic Series, 86 Acrylic Series, 86 Glycerides, 86 Syllabus of Part III, 87 PART IV. Excretions and Concretions. Urine, , 89 Analysis of Urine, 93 Inorganic Constituents, . . . 93 Organic Constituents, 97 Urinary Coloring Bodies, 104 Abnormal Constituents of Urine, 106 Adventitious Substances in Urine, 116 Urinary Sediments, ' 118 Cursory Examination of Urine, 120 Urinary Concretions, 121 Biliary Concretions, 124 Faeces and their Analysis, 126 Syllabus of Part IV, 129 PART V. Sanitary Chemistry. Atmospheric Air, 132 Water, 135 Milk, 141 Flour, 144 Bread, . I45 Preserved Fruits and Vegetables, 146 Confections and Candies, , 147 Wines, .147 Malt Liquors, 149 Whiskey, 150 Brandy, irj Vinegar, 152 Pharmaceutical Preparations and Their Active Principles, 152 Syllabus of Part V, 159 APPENDIX. Ptomaines, 1 61 Table of Elements, ....»..« 164 Weights and Measures, 165 Table of Equivalents of Centigrade and Fahrenheit Thermometric Scales, 166 Table of the Tension of Aqueous Vapor, 167 Index, 169 APPLIED MEDICAL CHEMISTRY. PART I. APPARATUS AND MANIPULATIONS. The execution of chemical manipulations depends on the employment of certain apparatus, which may be considered under the head of physical and technical. PHYSICAL APPARATUS. Physical apparatus comprises the instruments of precision needed to determine the influence of physical force upon matter. As this is relative in its nature, standards have been adopted by which to determine it. Gravity influences bodies by attraction in proportion to their amount. The attraction exerted upon bodies by the earth, manifested by the arrest of their progress towards its centre, has been termed their weight. This is ascertained by scales or balances, which in their execution involve different mechanical principles, to overcome friction, etc. The weights employed, almost universally, in chemical manipulations are those of the so-called metric sys- tem, depending for its unit on the metre, the ten-millionth part of the quadrant of the earth. The metre is equal to 10 decimetres, ioo centimetres, or iooo millimetres. The litre, the unit of fluid measure, is the cube of one decimetre, equal to IOOO cubic centimetres (c.c). The unit of weight is the gramme (grm.) the one one-thousandth part (1^0) of a litre of pure water at its maximum density. One gramme is equal to 10 decigrammes, or ioo centigrammes, or IOOO milligrammes. Thus one cubic centimetre (c.c.) of water at its maximum den- sity is equal to one gramme in weight. As the weights in or- 2 IO APPLIED MEDICAL CHEMISTRY. dinary use differ materially from those of the metric system, a table is annexed in this work for the ready conversion of the one into the other. The measurement of liquids and gases is accomplished by means of graduated vessels or tubes, termed respectively graduates, flasks, cylindrical jars, pipettes, burettes of various denominations, marked to express a certain quantity at 1 5° C. and suitably subdivided to admit of determining units and parts thereof. The influence of heat is determined by instruments known as thermometers which depend upon the equal expansion of cer- tain bodies at increased temperatures or vice versa. The usual instruments employed for this purpose are the Mercury Ther- mometers, consisting of a bulb of mercury with an elongated and graduated tube for measuring the expansion of the mercury in vacuo. Good thermometers should be of even calibre of tube, be absolute vacua, and be equally graduated into degrees and tenth or fifth parts thereof. The scales generally employed to indicate the temperature by the mercurial expansion are various ; the " Centigrade," almost universally employed by chemists and in chemical text-books, has a scale divided into one hundred equal parts between the freezing point and boiling point of pure water at normal barometric pressure. Thus 0° C. would indi- cate the freezing point of water while ioo° C. would be the point at which pure water boils, with the intermediate points to give relative measure for the approach thereto. The other principal scale commonly used in this country is termed " Fahrenheit," which fixes the freezing point at 32 F. and that of boiling at 2I2 C F. As the centigrade scale should be invariably used in chemical manipulations, a table for readily converting this into Fahrenheit and vice versa will be found in the last pages of this volume. The influence of atmospheric pressure is determined by means of a Barometer, consisting of a column of mercury, which is considered normally equipoised at a height of 760 millimetres at o° C. temperature. The measurement of gases will be largely influenced by this agency, and corrections should be applied to insure accuracy (compare Dietrich's tables, under Urea). The influence of galvanism upon matter takes an important PHYSICAL APPARATUS. II part in chemical relations, and is used variously to bring about reduction and decomposition, but as its scope embraces the consideration of other physical principles, the student is referred to the text-books on Physics for the details of the manipulations depending on it. LigJit and optical phenomena are utilized for chemical pro- cesses in a way that makes their influence of great import- ance. Spectroscopy. — Light in passing through a prism is dis- solved into various colors termed a spectrum. Spectra of dif- ferent substances produce variations in the positions of certain bands according to their locality. This phenomenon proves of importance to the medical chemist in the determination of blood, as oxyhemoglobin, reduced haemoglobin, alkaline hae- matin, etc. Polarimetry. — A ray of light in passing through certain media is divided into two, and thus doubly refracted it is termed polarized. The determination of the* influence of a body on polarized light, with a suitable instrument for this purpose, is of great importance, as many bodies have distinct analytical char- acters in this respect. This instrument consists of a polarizer, an analyzer, and a container. In the measure that optically active substances necessitate the rotation of the analyzer to the right or left, for extinction of different tints they are termed dextro-gyrous ( + ) or Icevo-gyrous ( — ). The specific rotary power of a body expressed in degrees and tenths thereof is ascertained by dissolving a certain quantity in a definite quantity of solvent and noting the degree of rotation for a certain column. If \_a\ is the specific rotary power looked for, w the weight of the sub- stance contained in I c.c. solvent, and / the length of column, the product of the latter two by division into the degree of rota- tion, a, observed would give specific rotary power, \_d] = j^t. With monochromatic light the specific rotary power is ex- pressed by [#] D . Knowing the specific rotary power of a body, the amount of substance contained in a certain column of solution can be demonstrated by the following; formula, W= r -, , This is of special value in determining the amount of sugar in 12 APPLIED MEDICAL CHEMISTRY. urine, as well as the quantity of alkaloids and other bodies present in solvents. Osmosis is of great utility in chemical manipulations for separating colloids and crystalloids, especially in the separa- tion of alkaloids and their salts, by dialysis, from the extracted mass of organic matter in toxicological analysis. Specific Gravity. — While the ordinary weighing with bal- ances and weights would show the apparent weight, the absolute weight of a body could only be ascertained by weighing them in vacuo, whereas the relative weight of equal volumes of matter is termed their specific weight ; the amount expressing how many times a body is heavier than the equal volume of some standard substance it can displace, its specific gravity. The method of determining the specific gravity of different sub- stances differs according to the state they are in. The specific gravity of gaseous substances is not easily determined and would come within the province of the chemist proper more so than the physician. It depends upon the weight of a certain volume of gas as compared with an equal volume of atmospheric air at equal temperatures and atmospheric pressure. The specific gravity of liquids is determined principally by two methods. The standard for this, as well as for solid bodies, is the weight of an equal volume of pure water at the same temperature. In speaking of a solution of sodic hydrate, specific gravity 1.8, we mean a solution which would weigh one and eight-tenth times as much as an equal volume of pure water at the same temperature. Thus the specific gravity of a saline solution affords means for the determination of the quantity dissolved therein. This, in the absence of other products, such as sugar or albumen, etc., is often employed for the approximate indica- tion of the amount of solids in urine. The most accurate and concise means of ascertaining the specific gravity of liquids is by the specific gravity or density flask, also called picnometer. This is a flask of known weight, usually of a capacity of 100 c.c. at 15 C. It is provided with a well-fitting glass stopper, with a capillary opening. The liquid to be examined should be reduced by surrounding it with cold or iced water to 15 C, or the difference in tem- perature should be well noted beforehand, and correction ap- PHYSICAL APPARATUS. I 3 plied for the expansion or contraction by temperature. The flask should be well dried, and then completely filled by im- mersion and adaptation of the stopper under the surface of the liquid, if this is possible on account of its character. After fill- ing, it is dried on the outside by blotting-paper, and weighed on the scales already containing the tare or counterpoise for the empty flask. The specific gravity is then obtained by mul- tiplying the weight of liquid in the bottle with iooo, and dividing the product by the weight of water which the bottle is marked to hold. Thus, if the liquid be urine, and the weight so arrived at 103.25, the product would be 103250; divided by 100, would give as specific gravity 1032.5 ; water as 1000. Where a 1000 c.c. flask is employed, the amount of weight of the liquid would give its specific gravity at once. The most common practice for determining the specific gravity of liquids is by means of hydrometers. These depend for their action on the fact that they displace a volume of water equal in weight to their own. While they are very serviceable and sufficiently accurate, if the liquid be of the temperature it is intended to be, they must be purposely constructed to answer for liquids lighter than water, or for those heavier, or for the purpose of examining liquids varying but little inside of 1000 and 1050, as is the case with urine, milk, etc. They should in- dicate on their scales only the specific gravity and not the amount of milk or water, etc., as is the case with some of them in the market. To have a thoroughly reliable hydrometer for urinary examination, it should be compared at various de- grees of immersion, with liquids, the specific gravity of which has been previously determined by the specific-gravity flask. The specific gravity of solids is obtained by various methods according to their character and condition. Solids heavier than water, and in a compact state, should first be weighed in air, and the weight thus obtained be noted. Then the respective solid is attached by a fine silk thread to the hook on one arm of a specific-gravity balance, and weighed while immersed in a beaker full of distilled water of the same temperature as the surrounding air. The weight obtained of the immersed substance will be found less than the former. By subtracting the weight in water from that in air, then the 14 APPLIED MEDICAL CHEMISTRY. weight in air divided by the difference will give the specific gravity. Thus a urinary calculus, well dried, was found to weigh in air, 28.50 grams. in water, 18.04 " difference, 10.46 " the quotient, 2 "5°= 2.71, is the specific gravity of the calculus. 10.46 If, however, instead of being insoluble in water, a substance is very soluble therein or if it is decomposed by it, as sodium or potassium, the determination would have to be obtained in a liquid of known specific gravity not affecting the substance, and determined as per following example : If a piece of fused potassic hydroxide (caustic potassa) were to weigh in air . . . . . . 10.25 a specific gravity vial of benzin (sp. gr. 0.730) were to weigh . . ... . . . . . 73.00 the combined amounts would be .... S3. 2 5 the weight of potassa in benzin . . . . .« 80.50 the loss would be .*.... 2.75 Weight of potassa, 10.2c; , , c , • x , , — = 3 7 2 X 0.730 (sp. gr. of benzin) =2.71 (sp. gr. IOSS, 2./5 , of potassa). That is, the loss of weight of the bottle containing the ben- zin and potassa from the combined weight of potassa and bottle filled up with benzin, divided into the weight in air of the po- tassa gives the quotient, which, multiplied with the specific gravity of the benzin, gives specific gravity of potassa. Solids in a pulverulent state (powders) require to be weighed in the air, and subsequently are introduced in a specific-gravity vial, and by shaking first with a little water, to thoroughly sat- urate them, in order to rid them of adhering air. The vial is then filled with water, and the loss so sustained divided into the weight in air will give its specific gravity, as, for instance : weight of iron by hydrogen, ..... 30.0 weight of water in vial, ...... 100.0 total weight, ........ 130.0 weight of iron and water in vial, .... 126.2 loss, .......... 3.8 Weight of iron in air, 30.0 c , , . r——= 7.89, sp. gr. of reduced iron, loss, 3*8 MANIPULATIONS AND TECHNICAL APPARATUS. 15 Solids lighter than water are examined for their specific gravity by attaching to them a substance sufficiently heavy to sink them in water. To ascertain, for instance, the specific gravity of a piece of cacao butter weighing ....... 33.00 attach to it a piece of iron weighing . joint weight, iron and cacao butter in water, . loss of both together, . loss of iron alone (previously ascertained), leaves loss of weight of cacao butter alone, 33: _ 0.96, specific gravity of cacao butter. 34.00 50.00 83.00 41.50 41.50 7-30 34.20 MANIPULATIONS AND TECHNICAL APPA- RATUS. As already stated, chemical processes depend on certain manipulations which in turn require the employment of suita- ble apparatus facilitating operations. These may be termed technical in contradistinction to the physical apparatus just described. The most important operations can be classed and subdivided as follows : Solutions. — These can be defined as simple and chemical. Under simple solutions are understood such in which the sol- vent does not change the chemical nature of the dissolved sub- stance, and from which they may be recovered chemically un- changed on evaporation of the former, or under conditions favoring their separation. Thus sodic chloride will be dissolved in water without change, and can be obtained from this simple solution by evaporation or by mixing it with alcohol without undergoing a chemical change. Solutions are best effected by powdering the substance to be dissolved, and, if necessary, agi- tating them in a mortar or by the aid of heat, in either test- tubes, capsules, flasks or beaker-glasses. Heat with most sub- stances facilitates and expedites solution. When a solvent has taken up as much as it can hold in solution at a relative tem- perature, it is termed saturated; but this can be spoken of only at the temperature referred to, which, when not otherwise ex- pressed, is taken at 15 C. For simple solutions distilled water 1 6 APPLIED MEDICAL CHEMISTRY. is the general solvent employed if not otherwise stated, or if alcohol be used its strength should be stated, and if acids or alkalies, their specific gravity must be given and their purity assured. Chemical solutions may be described as such in which the solvent exercises a chemical influence over the substance to be dissolved, changing either in their chemical character in such a manner that on evaporation or precipitation a substance of different chemical composition results. Chemical solutions can be promoted by heat, but they are not influenced by it in strength, as they reach only a stage of neutralization, but not of variable saturation as in simple solutions. Thus if mercuric oxide is dissolved in hydrogen nitrate (nitric acid), and the acid is neutralized to a certain point, no further action can be induced by application of heat, and a simple solution of mercu- ric nitrate has taken place which on evaporation will yield the latter mercuric salt. Crystallization. — This is understood as the molecular aggregation of matter in regular and mathematical form. It is usually obtained by the transition of a substance from the gaseous or liquid into a solid state. Thus to effect crystalliza- tion of a substance from a simple solution it is necessary to either reduce the volume of solvent as in NaCl or obtain satu- ration at a higher temperature, which is gradually reduced (as for instance in boric agd). The remaining liquids after crystal- lization are termed mother-liquors. The water, which forms an integral part of the crystal, to assume its form, is termed the water of crystallization. Bodies without crystalline formation are termed amorphous. Crystallization offers valuable aid in the recognition of certain bodies, especially in urinary analysis, such as urea nitrate, uric acid, triple-phosphates, etc. Precipitation may be termed the breaking up of solutions and can be either mechanical or chemical, according- to the manner in which the homogeneous nature of the solution is destroyed. Thus if the character of the solvent is altered by the admixture of other liquids, the substance held in solution would be precipitated without chemical change, as in the case of sodic chloride by the addition of alcohol to its solution ; this would be mechanical in its nature, but if the precipitant MANIPULATIONS AND TECHNICAL APPARATUS. 1 7 were to chemically alter the precipitate, that it would be unable to be longer held in solution, the effect would be chemical, as by the addition of ammonic hydrate to the above mentioned solution of mercuric nitrate. According to their character the precipitates are termed respectively crystalline, amorphous, flocculent, gelatinous and curdy, or if slight and held lightly in suspension and causing turbidity, or if sufficient only to impart a pearly light, as opalescent. Filtration and Decantation, Desiccation and Weigh- ing of Precipitates. — Decantation is ,most suitably em- ployed for heavy precipitates, which are not partly or wholly suspended in the liquid. It is accomplished by pouring off the liquid from the precipitate or by removing it by either syphon or pipette. By frequent addition of distilled water the precipi- tate is then washed out until the washings cease to show saline ingredients by chemical tests. Filtration is the separation of precipitates by means of an interposed septum. The septum for this purpose may either be pure sand as for strong acids, or asbestos, also muslin, or ab- sorbent cotton for non-corrosive liquids ; but best of all and most generally employed for watery, alcoholic, etc. solutions is white, chemically pure, filtering paper, such as is known as "Swedish." While plaited filters are employed in filtering solu- tions to clear them from suspended impurities, the plain filter only should be employed when the precipitate is to be used. For precipitates soluble in an excess of the solvent or partly or wholly suspended therein filtration alone is admissible, and the washing on the filter should be accomplished by means of a wash-bottle or spritz. The filter should be washed out on the funnel before adding the liquid holding the precipitate, and when this is to be done the pouring out should be guided by a glass rod. To remove precipitates from the filter the wash- ings should first be allowed to thoroughly strain off, and the filter should be placed on bibulous paper, with which gentle pressure is exerted until on examination the precipitate is found almost detached, and may be removed by a spatula to either a capsule, beaker, test-tube or watch-glass, as required. If the precipitate is to be dried, it may be placed with the filter in a dish or watch-glass, and this placed in a water bath or 1 8 APPLIED MEDICAL CHEMISTRY. warm place, or under a desiccator with concentrated sulphuric acid. To weigh a precipitate it is first well dried, placed in a watch-glass, which is covered by another, and both secured by a clamp. The precipitate is then weighed and again placed in a water bath or desiccator until on repeated weighings no further loss is experienced. Distillation depends upon volatilizing a liquid and condens- ing its vapors in apparatus for that purpose. Distillation of water is usually effected by copper apparatus suitably adapted to a worm or condenser. When water is distilled the first run contains always some gaseous admixtures, and should be thrown away, as well as after fresh additions thereof to the boiler. For chemical manipulations on a small scale distilla- tion is often carried on in retorts connected with a receiver cov- ered with felt or cotton, over which water is allowed to drop ; but more generally, where the amount warrants the same, a flask connected with a bent tube to a Liebig's condenser is used. It is well to remember here that tubes for distilling or gas generating purposes should have the end entering the flask broken off obliquely to admit the free dropping back of any condensed liquid at that point. The lower end of the condenser should be loosely fitted into a receiver. For distilling at a certain temperature, as required for separating liquids of different boiling points, as in fractional distillation, a thermometer is fixed into the retort or flask em- ployed. Evaporation. — Where the recovery of the solvent is of no consideration so as to involve distillation, or when the amounts are so small as not to admit it, it is effected by pouring the liquid into an evaporating dish, and if overheating cannot change or alter the products, placing it on a tripod, interposing a piece of wire gauze between it and the flame. When evaporation is to be carried on at a low heat, a water or sand bath and a well regulated flame should invariably be used, with a thermometer adjusted to indicate the degree of heat. Incineration is performed for the purpose of obtaining the fixed salts of compounds. It is conducted in either platinum or porcelain vessels made for that purpose, suspended on pipe- ANALYSIS. 1 9 clay or platinum triangles in an inclined position, over the flame of a Bunsen lamp. When the product is to be weighed it should be cooled over sulphuric acid in a bell-glass. If the salts are to be removed as such, the substance should be at first only carbonized in the covered crucible, then the salts ex- tracted by suitable solvents and the dried residue again further incinerated as described above. It is to be borne in mind that many substances affect platinum vessels, and the latter should for that reason not be employed under such circumstances. Analysis. As chemistry treats of the composition of matter, that por- tion of it intended to disclose, by the application of its princi- ples, the composition of certain bodies, either as a group or as an individual body, is termed analytical clicmistry, and the process employed for determining it, chemical analysis. This again may be subdivided under two heads, depending on the nature of the research, which, if only for the determination of the character of a body, is called qualitative, but if intended to convey information in regard to the amount of a body pres- ent, or the amount of other constituents in a chemical group or combination, it is known as quantitative analysis. The two require different methods of procedure, and while the former will be the one principally employed by physicians in applying chemistry for diagnostic purposes, a sufficient knowledge of the latter should be had to observe pathic conditions and their changes. Thus while it is of absolute importance for the physician to determine the character of a urinary calculus, to shape his therapy accordingly, the quantity thereof or of its components, would be of less value ; whereas to control the progress of a case of diabetes mellitus the knowledge of the amount of sugar excreted in a certain time would be of para- mount importance. A knowledge of the reactions and reagents, their relations to other bodies, and their products, are the prin- cipal requirements for analytical work, especially so for quan- titative analysis. Volumetric Analysis.— This is the application of certain solutions (volumetric tests, or standard, or normal solutions) of known strength, which, according to the law of fixed and defi- 20 APPLIED MEDICAL CHEMISTRY. nite proportions, form characteristic and readily recognizable compounds with the substance known in character, but un- known in regard to the amount present. The apparatus prin- cipally employed in volumetric analyses are pipettes for delivery of certain quantities, and burettes of different con- struction for measuring the quantity of tests employed ; also beakers and capsules for precipitation or neutralization as the process may require. Volumetric determinations may be arrived at either by neu- tralization, oxidation, reduction or precipitation. Neutralization is employed to ascertain the strength and quantitative presence of alkalies (alkalimetry), or of acids (acidimetry), the point of neutralization being determined by litmus solution, or, better still, for mineral acids, by using a solu- tion of phenolphtalein containing I gram in a mixture of 15 grams of alcohol and 75 grams of water; the reagent being for the former usually a standard solution of oxalic acid or sulphuric acid, and for the latter standard solutions of sodic or potassic hydroxide. Oxidation and reduction are employed to determine the amount of oxidizable bodies by means of oxidizing agents in standard solutions, such as potassic permanganate, potassic bichromate, etc., or by reduction, as in the case of the alkaline cupric tartrate, by sugar, etc. Volumetric determination by precipitation depends upon the known quantity of the standard solution requisiteto effect com- plete precipitation, or the beginning precipitation of a solution of unknown strength. While by means of chemical computa- tion the relation of the test to the substance to be tested can be determined, tables giving the proportionate amount of cer- tain bodies corresponding to a fixed measure of the test facili- tate this very much. (See volumetric tests.) The qualitative chemical analysis of solid substances in a dry way depends primarily on their behavior when exposed to heat, either alone or with reducing agents. A substance heated alone, in a narrow open tube without resulting change, shows the absence of organic matter, and of salts containing water of crystallization or volatile compounds. If it chars or blackens without volatilizing, emitting empyreumatic odors, compounds ANALYSIS. 2 1 of carbon are present; if it fuses, liberating aqueous vapors, which condense, salts with water of crystallization or decom- posable hydrates are indicated, and the reaction of the residue should be determined. Change of color to yellow, disappearing on cooling, would indicate zinc oxides ; transitory brown with sublimation of mercury, mercuric oxide ; sublimation with yellow color, mercuric iodide ; brown would indicate the oxides of lead and bismuth, also chromates ; liberation of gases or fumes, if violet, point to iodine and its compounds ; if brownish-red and bromine odor, to bromine and its com- pounds;, sulphates give rise to sulphur di-oxide; nitrates to nitric peroxide, easily recognizable by color and odor. Cyan- ogen by its odor indicates cyanides ; ammoniacal odors, am- monium and cyanogen compounds also nitrogenized organic bodies, the latter accompanied by charring and escape of cyanogen and empyreuma with ammonia. Sublimation takes place from volatile substances, such as sulphur or ammonium salts, compounds of mercury, arsenic, antimony, also from some organic acids (benzoic, succinic, salicylic, etc.). If on heating with soda lime ammonia vapors develop, ammonium salts or nitrogenous compounds are present. The behavior of substances with dry sodic carbonate on charcoal, in the heat of the blow-pipe flame, indicates by fusion and absorption, alkalies or their salts ; an infusible white residue, so formed, either directly or after fusion in water of crystalli- zation, shows the presence of compounds of calcium, barium, strontium, magnesium, aluminium, zinc or tin. Compounds of tin, silver and copper are reduced to the me- tallic state, and give malleable shining scales without formation of peripheral incrustation on the charcoal, as do also the com- pounds of iron, manganese, cobalt and nickel, but these yield, instead of scales, infusible gray powders, which can be recog- nized by being cut from the charcoal and levigated in the agate mortar. Incrustations are formed in the reduction of antimony com- pounds with a brittle metallic globule. Bismuth, brown-yellow with brittle metallic globule ; lead, yellow with malleable globule; zinc, white incrustation, non-volatile in oxidizing flame; cadmium, brown-red incrustation, no reduction; arsenic 22 APPLIED MEDICAL CHEMISTRY. compounds evolve smell of garlic ; borax and alum swell up, losing their water of crystallization ; sulphur compounds yield alkaline sulphides, which, if moistened on a clean silver surface, give a black stain, and with acids develop hydrogen sulphide.; nitrates, chlorates, iodates and bromates deflagrate. Flame Tests. — If a substance is heated on a looped wire of platinum, in the upper reducing portion of a non-luminous flame, a violet color indicates potassic salts, best observed through blue glass, and seen through the spectroscope as a violet and red bar ; a yellow color indicates sodic salts, seen through the spectroscope as a yellow bar. Moistened with HC1 a purplish-red flame indicates strontium ; carmine-red, lithium; yellowish-red, calcium; green, copper or barium, more distinct with Cu than Ba. When first dried by heat, and then moistened with H 2 S0 4 , a green color indicates phosphoric or boric acid, which is tran- sient if sodic compounds are present ; blue color is imparted by arsenic, antimony and lead. The glass beads formed, if a trace of the substance to be ex- amined is fused with borax on the looped end of a platinum wire, offer characteristic tests. In the outer blow-pipe flame a blue glass indicates cobalt ; amethyst-red manganese ; green, chromium or copper, the former on cooling is yellow, the latter blue ; brown, nickel or iron, the latter on cooling is often yellow ; yellow, uranium or lead ; colorless glasses are formed by mo- lybdic acid, tin, antimony, bismuth and the alkaline earths, the latter turning opaque on cooling. Some of the glasses pro- duced in the inner blow-pipe differ from these in color. REACTIONS AND REAGENTS. Phenomena accompanying and characteristic of the combi- nations and decomposition of bodies are termed reactions, and the known substance employed to develop such characteristic phenomena, in order to determine the nature or chemical com- position of unknown substances, are termed in accordance there- with, reagents. These latter can be subdivided into general and special reagents. The former of these may be described as such substances that will serve to indicate a class or group of other bodies affected in a similar manner by them, whereas special TESTS OR REAGENTS. 23 reagents would be those characteristic of one substance only. That some of the general reagents may be special, when sup- plemented by other general reagents, is often observed. A characteristic reagent is one that affects another body in such a manner as to leave no doubt as to the identity of the latter, while delicate reagents are those which act on the other if pres- ent in very minute quantities. While many reagents may be said to be characteristic they are delicate as well. That reagents should be chemically pure to avoid reactions due to contaminations is clearly obvious. The quantities of the re- agent to be employed is a matter that must be gauged from the understanding of the reaction taking place. Thus, if a test is to be made with potassic-iodide for mercuric-chloride the former must be added in very small quantities, to avoid a solution taking place of the mercuric iodide in an excess of the reagent. On describing the various reagents and test solu- tions commonly in use and coming within the sphere of this work they are given as to their strength, the composition of special tests, as well as the methods of preparing them, and under the volumetric tests their preparation and rules apply- ing thereto will be especially mentioned. TESTS OR REAGENTS. While a full list of the tests employed in the different manip- ulations enumerated in this work will be subjoined, alphabeti- cally arranged, a limited number of them will answer for ordinary office experimentation as well as class demonstration. Acid, acetic : specific gravity 1 .048. Acid, hydrochloric : specific gravity 1.16, containing 32.2 per cent, absolute acid. Acid, nitric : specific gravity 1. 42, containing 69.4 per cent, absolute acid. Acid, oxalic : 1 in 10. Acid, picric : saturated aqueous solution. Acid, sulphuric : specific gravity 1.84, containing 97 per cent, absolute acid. Acid, sidphar mis : specific gravity 1.046, saturated aqueous solution at 15 C. containing 36 volumes, or about 9.5 by weight of the gas. 24 APPLIED MEDICAL CHEMISTRY. Acid, tannic : I in a mixture of 18 water and 2 alcohol. Acid, tartaric : I in 5. Albumin: the white of one egg triturated with 100 c. c. water and filtered through cotton. Alcohol ' : specific gravity 0.820, containing by volume 94 per cent., by weight 91 per cent, absolute alcohol. Alcohol, absolute: specific gravity 0.795. Aluminium, metallic : in wire or ribbons. Ammonia water : specific gravity 0.959, containing 10 per cent, by weight of the gas. Amnionic carbonate : 1, in mixture of water 4, and ammonia water 1. Amnionic chloride : I in 10. Ammonic molybdate : I in 10 to which 10HNO3 are added. Amnionic oxalate : 1 in 20. Amnionic phosphate : 1 in 15. Amnionic sulphydrate : saturation of stronger ammonia water with H 2 S, and adding subsequently 2 ammonia water. Aniline sulphate : 5 drops aniline in 25 c. c. diluted H 2 S0 4 . Argentic nitrate : 1 in 20. Argentic nitrate ammoniated : prepared by adding in drops ammonia water to test solution of argentic nitrate until pre- cipitate is redissolved. Auric chloride : 1 in 20. Baric chloride : 1 in 10. Baric hydrate: saturated solution (containing about 5 per cent.). Baric nitrate : 1 in 20. Benzin (Petroleum ether): specific gravity O.670-O.67 5, boil- ing at 50-60 C. Borax: in powder. Bromine water : a saturated solution. Calcic chloride : 1 (cryst.) in 10. Calcic hydrate (lime water) : saturated solution. Carbon bisulphide : specific gravity 1.272. Chlorine ivater : saturated, containing about 0.4 per cent, by weight. To be freshly prepared. C hloroform : specific gravity 1 .480. Copper, metallic : in wire and foil. TESTS OR REAGENTS. 25 Cupric sulphate : I in 10. Cupric sulphate, ammoniated : prepared by adding drop by- drop to the test solution of cupric sulphate sufficient ammonia water to redissolve precipitate. Ether : specific gravity 0.750. Ferric chloride : 1 in 10. Ferrous sulphate : 1 part, obtained by precipitation with alco- hol, dissolved in 10 parts H 2 0. Ferrous sulphide : in granular form. Gelatin : 1 part isinglass, in 50 parts water ; dissolved and filtered through cotton. Glycerin: specific gravity 1.26. Gold: metallic, in leaf. Hydrogen, nascent : applicable in gas form as a test for ar- senic, by forming hydrogen arsenide which can be reduced either by heat, or by reducing with it argentic nitrate. See Marsh and Fleitmann's tests, under Arsenic. Hydrogen sulphide : Obtained by the action of H 2 S0 4 or HC1 on ferrous sulphide. For precipitation of sulphides from metals the ordinary glass bulb may be employed with its arm im- mersed in the liquid to be tested. Hydrogen sulphide water: a saturated solution of H 2 S in water at 15 C. to be freshly prepared. Indigo solution : 1 indigo to 6 fuming sulphuric acid; after subsiding, 20 times its volume of water is added and filtered. Iodine water : saturated solution in water. Iodine tincture : iodine 8, alcohol to make 100. Iodinized Potassic iodide : solution of I iodine, and 3 potassic iodide in 60 water. Magnesium : metallic, in wire or ribbon. Magnesium mixture: (Ammoniated Magnesium sulphate), II magnesic chloride or sulphate,- and 14 ammonic chloride in 70 stronger ammonia (sp. gr. 0.900) and 130 water. Magnesic sulphate : 1 in 10. Mercuric chloride : 1 in 20. Mercuroiis chloride : in substance. Milloiis reagent: 1 Hg. and 2 HN0 3 (sp. gr. 1.4) until former is completely dissolved, to be diluted with 2H 2 and decanted after 3-4 hours. 3 26 APPLIED MEDICAL CHEMISTRY. Phenolphtalein : I in ioo of a mixture of 25 alcohol and 75 water. Platinic chloride : 1 in 20. Plumbic acetate : I in 10. Plumbic acetate, basic: liquor plumbi subacetatis U. S. P. Plumbic nitrate : 1 in 10. Pot as sic acetate : 1 in 5. Potassic bichromate : 1 in 10. Potassic chromate, neutral: 1 in 10. Potassic cyanide : in substance. Potassic ferricyanide : 1 in 10, solution to be freshly made. Potassic ferrocyanide : 1 in 10. Potassic hydrate: 1 in 20, specific gravity 1.036. Potassic iodide: 1 in 20. Potassio-mercuric-iodide : 1.354 HgCl and 4.98 KI in 100 water. Pot as sio-mer curie iodide with potassic hydrate : (Nessler's test, see Water). Potassic nitrate : in substance. Potassic nitrite : fused. Potassic permanganate : 1 in 1 000. Potassic sidphocyanide : 1 in 20. Soda lime : Quicklime slacked with a solution of NaHO, so that about 2 of quicklime are mixed with 1 NaHO. The mix- ture is heated to redness, powdered and preserved. Soap test, Clarke's : see Water. So die acetate : 1 in 5. Sodic bicarbonate : saturated. Sodic bitartrate : saturated. Sodic hydrate: 1 in 20, specific gravity 1.059. Sodic hypochlorite : liquor sodae chloratse, U. S. P. Sodic hyposulphite : 1 in 10. Sodic molybdate : Frohdes test I in 100 H 2 S0 4 . Sodic phosphate : 1 in 10. Sodic sidphate : saturated. Starch mucilage : freshly prepared. 1 powdered starch mixed with 100 water and heated to boiling point and when subsided, decanted. Zinc : metallic, in sticks or fragments or slips. TEST PAPERS ALKALIMETRY. 2J TEST PAPERS. Blue litmus paper is prepared by drawing unsized white paper through the neutral litmus solution (litmus washed first with warm alcohol, and the residue treated with water). Red litmus paper, draw white unsized paper through the neu- tral litmus solution previously turned slightly red with a trace of H 2 S0 4 . Turmeric paper, white unsized paper drawn through a turmeric solution (turmeric I in a mixture of alcohol 4 and water 3, al- lowed to macerate for a few days and decanted). Plumbic acetate paper for the detection of HgS white unsized paper drawn through a solution of plumbic acetate. Starch paper, white unsized paper drawn through starch mu- cilage. VOLUMETRIC TESTS. The amount of the substances to be tested is generally ex- pressed by weight while the tests are always spoken of by measure. The normal solutions as a rule, contain for univalent sub- stances the weight in grams corresponding to their mole- cular weight in one litre. For bivalent substances, they contain one-half their molecular weights expressed in grams in each litre. For trivalent substances one-third, etc. Decinormal or centinormal solutions represent one-tenth or one hundredth of these values, and the amount of the solution can in this way indicate at once the percentage strength of the substance to be examined, but as such are limited in their ap- plication principally to special substances, other solutions are sometimes made empyrically according to their oxidizing power, etc. ALKALIMETRY. Standard solutions of oxalic acid 63 in 1000 at 15 C. ; 100 cubic centimetres thereof correspond exactly to 5.23 grams ammonic carbonate. 17.00 " ammonia water, sp. gr., 0.959. 6.07 " ammonia water,, stronger, sp, gr., 0.900. 28 APPLIED MEDICAL CHEMISTRY. 54.68 grams solution lead acetate basic, sp. gr., 1.228. 112.00 " solution potassic hydrate, sp. gr., 1.036. 80.00 " solution sodic hydrate, sp. gr., 1.059. 9.80 " potassic acetate. 10.01 " potassic bicarbonate. 18.80 " potassic bitartrate. 6.91 " potassic carbonate, pure. 10.80 " potassic citrate. 14.10 " potassic and sodic tartrate. 5.61 " potassic hydrate. 3.14 " potassic permanganate. 11.76 " potassic tartrate. 13.60 " sodic acetate. 8.40 " sodic bicarbonate. 19.10 " sodic borate. 14.30 " sodic carbonate. 4.00 " sodic hydrate. ACIDIMETRY. Standard solution of potassic hydrate containing 56 KHO in 1000. If properly prepared 100 cubic centimetres correspond to 16.66 grams acetic acid, sp. gr., 1.048. 100.00 " acetic acid, dilute, sp. gr., 1.0083. 6.00 " acetic acid glacial, sp. gr. 1.058. 7.00 " citric acid. 81.00 " hydrobromic acid dilute, sp. gr., 1.077. 11.41 hydrochloric acid, sp. gr., 1.16. 36.40 " hydrochloric acid dilute, sp. gr., 1. 049. 12.00 " lactic acid, sp. gr., 1.2 12. 9.08 " nitric acid, sp. gr. 1.42. 63.45 nitric acid dilute, sp. gr., 1.059. 6.30 " oxalic acid. 4.90 " sulphuric acid, sp. gr., 1.84. 49.OO " sulphuric acid, dilute, sp.gr., 1. 067. 7.50 " tartaric acid. Amongst the standard solutions for volumetric analysis by reduction, the most important for the physician is VOLUMETRIC ANALYSIS BY PRECIPITATION. 2 9 Fehling's standard solution of alkaline cupric tartrate. 17.32 grams pure crystallized cupric sulphate are dissolved in 100 c.c. water, and 85 grams pure crystallized potassic and sodic tartrate are dissolved in 300 c.c. of a 10 per cent so- lution sodic hydrate. Then the two are gradually mixed and brought with water to 500 c.c. Of this solution : 10 c.c. correspond to 0.05 grams grape sugar. 10 " " " O.067 " milk sugar. 10 " " " 0.0475 " cane sugar. For further information on this test see Urinary Analysis. VOLUMETRIC ANALYSIS BY PRECIPITATION. As before stated, this depends upon the power of a quantita- tively known precipitant to completely precipitate a fixed quan- tity of another substance, or to form an insoluble compound of the two in such a manner as to determine the unknown quan- tity of the substance to be tested, or as in the case of the cyan- ides until precipitation begins. The most important and generally employed volumetric solution for this purpose is the standard solution of argentic nitrate 16.97 in 1000 (decinormal) employed for the estimation of most chlorides, iodides, bro- mides, cyanides, also their acids. Each 1 c.c. corresponds to 0.00978 grams ammonic bromide. I ' " 0.00534 « ammonic chloride. I ' " 0.0155 u ammonic iodide. I ' ' " 0.01276 (( hydriodic acid. I ' 1 " 0.00808 « hydrobromic acid. I ' ' " 0.00364 u hydrochloric acid. I ' ' " 0.0054 a hydrocyanic acid. I ' 1 " 0. 01 198 << potassic bromide. I ' 1 " 0.00744 << potassic chloride. I ' 1 " 0.0130 « potassic cyanide. I ' ' " 0.01656 u potassic iodide. I ' 1 " 0.01028 (i sodic bromide. I ' ' " 0.00584 « sodic chloride. I ' 1 " 0.01028 << sodic iodide. For operating with the neutral chlorides, iodides, bromides, it is best to add a few drops of potassium 1 chromate to serve as indicator when tl le precipitation is complete, whereas in the es- 30 APPLIED MEDICAL CHEMISTRY. timation of hydrocyanic acid or cyanides, their solutions should be made slightly alkaline by adding a few drops of sodic or potassic hydrate and a few drops of sodic chloride. The com- pletion of the test in the latter case is indicated when a perma- nent cloudiness forms, as that would show the complete formation of the double cyanide of potassium and silver. Indicators are such reagents that will aid in observing, when the reaction by a volumetric test is completed. Thus litmus solutions will answer best for alkalimetry or acidimetry. The extinction of the blue color of Fehling's test will serve in Saccharimetry, but this can be more accurately determined if a few drops of the test when about extinguished be placed on a porcelain slab or dish, acidulated with a little HC1 and then tested with potassic ferrocyanide, which, if copper is pres- ent, will produce a brown color; this should be frequently re- peated towards the end of the process until complete reduction is insured. The indicators employed in precipitation have been mentioned under that head. STOICHIOMETRY. From aroixeiov (element). Analytical reactions and observations would be of little value in regard to quantitative composition of bodies without the abil- ity to compute their value with relative weights. It is for this purpose that the atomic weights have been ascertained (vide Table of Elements). A molecule being a group of atoms, the sum of the atomic weights would form a molecular weight. As symbols express atoms, and as molecules are expressed by the symbols of their component atoms, and chemical formulae and equations are the relative positions of the molecules in reactions, and, as the symbols of atoms and the sums thereof represent values by weights, formulae and equations can be expressed in figures representing weights ; the changes noted thus by equa- tions are quantitative as well as qualitative. Thus : H 2 S0 4 HNO3 Urea, CON. 2 H 4 C = 12 C = 12 H = I 2H= 2 H = 1 H= 1 = i6 0=i6 S = 32 S = 32 N=i4 N=i4 N = i4 2N = 28 = i6 40 = 64 = i6 30 = 48 H= 1 4H= 4 Mol. wt. H 2 S0 4 , 98 Mol. wt. HNO3, 63 Mol. wt. of urea, 60 Urea. Sodic hypochlorite. Carbon dioxide. CON 2 H 4 + 3NaC10 = co 2 STOICHIOMETRY. 3 1 If we take the equation for the decomposition of urea by sodic hypochlorite, we will find : Water. Nitrogen. Sodic chloride. + 2H 2 -4- 2N + 3NaCl ( I2+i 6-l 2 8+4)+(35-5+ 16+23)3= (i2+ 3 2) + (2+i6) 2 +(i4) 2 +(35-5+23)3 60 223.5 44 3 6 28 175.5 283.5 = 283.5 This shows that, if an equation is to be correct, the sum of the molecular weights on both sides must be equal ; while the above equation can also be read as following: 60 parts of urea with 223.5 parts sodic hypochlorite yield 44 parts of carbon dioxide, 36 parts water, 28 parts nitrogen, and 175.5 parts sodic chloride; all parts represented by the same weight-unit. The computation of the percentage weight contained in any substance is readily effected. As the molecular weight of a body relates to 100, the molecular weight of the desired group relates to the percentage thereof. Thus : 46.6 Again, it will be seen that 100 grams urea contain 46,666 grams of nitrogen. Or, if on the contrary we have 100 grams of nitrogen from the decomposition of a quantity of urea, the equation would be N Urea N 28 : 60 = 100 : x= — = 214.28s grams urea. 28 * ° s t. e. t if a specimen of urine on decomposition yielded too grams of nitrogen, the amount of urea contained therein would be 214.285 grams. To determine how much sodic hypochlorite is about con- tained in 100 c.c. of a certain Labarraque's solution, the equation would be as follows : Jrea : 100 = Nitrogen : x 60 : 100 = 28 IOO.28 60 Urea. Sodic hypochlorite. Urea. Sodic hypochlorite, 60 : : 233.5 233-5 — I 3-89 : x 90 i. e., one gram urea decomposes 3.89 grams sodic hypochlorite. 32 APPLIED MEDICAL CHEMISTRY. If the sodic hypochlorite in 100 c.c. Labarraque's solution is decomposed by 2.5 grams urea, the amount of sodic hypo- chlorite in that solution would be (irrespective of errors 3.89 X 2.5 = 9.725 grams. Therefore, to determine how much of such a solution to employ, to decompose the urea in 10 c.c. urine containing about 1.25 per cent, of urea, the equation would be (urea in 10. ex.): 1 : 3.89 = 0.125 : x = 3-89X0.125 = 0.4.86 grams, thus: c 48.6 9.7 : 100 = 0.4 6 : x = - — — 5 c.c. 97 of the solution necessary to decompose urea in the 10 c.c. of urine containing 1.25 per cent. urea. (The amounts here are taken arbitrarily). To compute volume from weight it is necessary to know the weight of a certain measure of the body to be so computed. Say that if one litre of nitrogen weighs 1.2565 grams, then 1 c.c. would weigh 0.0012565. If, therefore, 60 urea yield 28 nitro- 28 gen, 1 urea will yield — == 0.466 grams nitrogen. If N N 0.0012565 : 1 c.c. = 0.466 : x 0.466 5^^565 = 368 - 9 C ' C - i. e. t the nitrogen developed from one gram urea would measure 368.9 c.c. If, therefore, 368.9 c.c. nitrogen will correspond to I gram urea, each cubic centimetre nitrogen developed will represent ' = 0.027 grams urea. i. e.. each cubic centimetre nitro- 368.9 / *> gen developed from urea represents 2.7 milligrams of urea. Correction for Barometric Pressure. — As gaseous vol- umes are inversely and their density in direct ratio with the pressure they are subjected to, it will be seen that gases cannot be accurately measured unless correction is made for the baro- metric pressure. As stated elsewhere, normal pressure is accepted as 760 millimetres of mercury at O C, a gaseous volume is increased if the barometer is below, and diminished if above, the normal. Thus, a volume of nitrogen measuring 50 c.c, at 725 m.m. : SYLLABUS FOR PART I. 33 Normal pressure. Diminished pressure. Measured gas. 760 : 725 = 50 : x 725 X 50 = -^ — 5_ = 47.9 c.c. volume of X under normal pressure. 760 Measurement of Gases. — Correction for Temperature. — The volumes of gases are not alone influenced by barometric pressure, but also by expansion or contraction due to temper- ature, contracting or expanding to the same amount for the same increase or decrease of temperature. This amount, called its coefficient, is 273 of the volume of gas at 0° for every degree centigrade. Expressed in decimal fractions, it is equal to 0.003665, and at i° C. it would, therefore, be 1.003665, at 2° C. 1 + (0.003665 X 2) = 1.00733. With this coefficient duly adjusted for degrees, the volume *s divided if measured above 0° C, or multiplied if measured below. Thus, if 50 c.c. of nitrogen were measured at 10° C, then the coefficient would be (1 -f(ioX 0.003665) = I =03665. 50 1-03365 = 48.37 c.c., corrected volume for 0° c. SYLLABUS FOR PART I. (1.) Weigh solids, and measure liquids and gaseous bodies. (2.) Compare the temperature of different bodies with ther- mometers of different scales. (3.) Note barometric pressure. (4.) Make observations with spectroscope of sunlight, sodium flame, potassium flame, blood-spectra. (5.) Make observations with polariscope of neutral and active bodies, determine them analytically by this instrument. (6.) Determine specific gravity of liquids by specific-gravity bottle and hydrometer; also, of a solid heavier than water; and one lighter than water ; also, of a body soluble or incompatible with water, and of a body in powder form. (7.) Make a simple and a chemical solution, also a precipi- tate from either. Crystallize a salt from a solution. Make a plain and plaited filter. Separate precipitates by decantation and filtration. (8.) Distil a liquid, and sublime a solid. Also, evaporate a solution, and incinerate the residue. 34 APPLIED MEDICAL CHEMISTRY. (9.) Make qualitative analysis of a solution of KI, and a quan- titative analysis of simple bodies by volumetric process (NaCl by AgN0 8 ). (10.) Make hydrogen by the zinc and aluminium process. Oxygen from HgO ; also make hydrogen sulphide and chlor- ine by the respective processes. (11.) Determine amount of oxygen obtainable from a certain amount of HgO. Convert the weight thereof into volume. Compute the correction of this amount for expansion at 18 C. temperature. Compute correction for this amount for baro- metric pressure at 720 m.m. PART II. CHEMISTRY OF POISONS. One of the provinces of chemical science in its application to medicine is the detection of poisonous substances, either wil- fully or accidentally introduced into the human system with deleterious or fatal effect. A poisonous substance or poison is one of indefinite meaning, unless it applies to any substance which in small quantities works injury to organized beings. Poisons in small doses may, however, not alone exert no dele- terious or injurious effect, but in medicinal doses may exercise a remedial influence on the body. If this influence, however, be much increased beyond that limit, the poisonous effect makes itself manifest, or, if it be applied to an organism particularly sensitive, as in a child or very weak person, a medicinal dose may become a poisonous one. A poison could, therefore, be declared only such a substance that is known in established quantities and form to affect injuriously or fatally the normal functions of the organism. Thus, pieces of glass will operate to the destruction of the organism by destroying the continuity of the organs it comes in contact with, although in fine powder it may pass through the body without doing harm. Acids or alkalies in their concentrated form, may destroy the organs of digestion, though, in their diluted form, they may safely be ANTIMONY. 35 consumed ; certain salts and their solutions act directly in the same manner, and secondarily by intoxicating the nerve-centres after absorption, as is done by neurotics, amongst which alka- loids and some volatile principles must be classed. The part of the medical chemist is to determine the pres- ence and nature of a poisonous substance, its effect, if mechanical, the condition in which present, or the chemical change that it may have undergone in the body, also the quan- tity obtainable from the remains of the body, if it has worked fatally, or from the secretions, excretions, dejecta or ejecta, to establish crime, accident, or to confirm diagnosis in chronic intoxication from such agents. The technical manner and le- gal requisites necessary in such cases are subjects not within the scope of this work, but can be found in all handbooks on toxicology and forensic medicine; suffice it, to describe here the chemical procedure and principles involved. That this is principally based upon a thorough understanding of analytical chemistry and the chemical relations of the toxic agents under certain conditions, need scarcely be mentioned. Chemically, poisons are divided into inorganic and organic, according to their origin. A further subdivision might lead us to consider them as metallic, mineral, acids, alkalies, vegetable and animal products and derivatives. Their separation from the body, organs, suspending liquids, or solvents, is often a matter of diffi- culty, but can be satisfactorily accomplished by various chemi- cal as well as physical means, especially by well devised and properly operated dialyzers; while there will be comparatively little trouble in establishing their identity, their quantity, which alone characterizes them as toxic agents in a legal sense, can be established only by tedious processes, and by means of va- rious and often ingenious methods. The poisonous agents considered hereafter form a limited part of the many known, but are the principal ones met with ordi- narily. ANTIMONY. Stibium, Sb Hi = 122, specific gravity 6.715. A bluish-gray solid substance of metallic lustre, crystalliz- able, with fracture of crystalline appearance, brittle and pulver- $6 APPLIED MEDICAL CHEMISTRY. izable, tasteless, odorless ; melts at 450 C, and volatilizes at red heat. It is often used as alloy with other metals to impart hardness to them. It resembles in its chemical character arsenic very much, without oxidizing as readily as the former, though if sufficiently heated with access of oxygen it forms a crystalline trioxide Sb 2 3 . Like arsenic it unites with H to form hydrogen-anti- monide or stibamine SbH 3 . The formation of SbH 3 under the conditions usually employed for detecting arsenic in Marsh's test, makes it of importance in comparison to AsH 3 . Like this it decomposes a solution of argentic nitrate ; but the precipi- tate is silver antimonide and not metallic silver, as in the case of arsine. If the hydrogen in Marsh's test is developed from zinc or aluminium, with a solution of potassic hydrate in- stead of acids, hydrogen antimonide is not formed. If by the acid process, however, an antimonial stain is produced from the Marsh test, this is insoluble in sodium hypochlorite, in which the arsenic stain is soluble. Besides, the stain, if dissolved in HN0 3 , and allowed to dry or evaporate, turns brick-red on the addition of argentic nitrate solution, if arsenical, but is not col- ored if antimonial. Although three oxides of antimony are known, only the trioxide is used in medicine, antimony oxide (Sb 2 3 ). The so- called James powder, pulvis antimonialis (Br.), is a mixture of antimony trioxide and tricalcic phosphate. If 3 parts antimony trioxide are boiled with 4 parts of hydro-potassic tartrate for one hour, filtered and allowed to crystallize, Potassio-antimony tartrate 2(K(SbO)C 4 H 4 6 )H 2 = m.w. 664, Tartar emetic is produced. The crystals of this are right rhombic octahedra. Its solutions are acid in reaction, have a metallic, nauseating taste, are dextrogyrous = -f- 156,2° and precipitable by alco- hol. Antimony, like arsenic, forms acids, which, however, are of little practical interest. With chlorine antimony forms two chlorides and several oxychlorides ; of the former the antimony trichloride SbCl 3 is known in medicine as butter of antimony, Liquor Antimonii chloridi, specific gravity 1.47, from which by addition of water, Algaroth is precipitated and used in the manufacture of Tartar ARSENIC. 37 emetic. Antimony pentachloride SbCl 5 is comparatively of little interest to medicine. Of the combinations with sulphur the antimony trisulphide SbS 3 and the antimony pentasulphide SbS g are best known. The former occurs in nature as black antimony, and is precipitated from tartar emetic by an excess of hydrogen sulphide as an orange red precipitate turning brown. If this be boiled with potassic or sodic hydrate and allowed to cool, a complex body separates known in medicine as Kermes mineral, which, if treated with H 2 S0 4 , yields a mixture of tri- sulphide and pentasulphide known as golden sulphuret of anti- mony. Toxicology of Antimony. — The principal preparation to be considered under this head is Tartar emetic, which is poisonous in doses of 3 grains and upwards, though larger doses seem to be comparatively less serious than smaller ones, as they are> as a rule, speedily ejected. If given in small doses for some time it produces chronic poisoning, the subject thereof dying of exhaustion. As it is eliminated by the kidneys, the exami- nation of urine in such cases should furnish a clue to diagnosis. Chemical antidotes are warm water to produce emesis, followed by tannin or substances containing it, to render insoluble com- pounds. Analytical Characters. — Hydrogen antimonide by Marsh's test from acids ; orange red precipitate from an acid solution by hydrogen sulphide, soluble in hot HC1. Deposit of bluish metallic film on bright copper foil from solutions acidulated with HC1; if the copper strips so treated are heated to redness with access of air, a white sublimate results. To determine quantitatively SbS 3 should be converted into Sb 2 4 , antimony orthoantimonate, of which 100 parts correspond to 1 10.52 Sb 2 S 3 . ARSENIC. As. iiiandv__y^ specific gravity, 5.75. A brittle, steel-gray solid substance of metallic lustre. It volatilizes without fusion. Its vapor has a garlicky odor. It readily oxidizes if heated in the air, accompanied by its char- acteristic odor. It forms compounds with oxygen, hydrogen, chlorine, bromine, iodine and most of the metals. It is used 38 APPLIED MEDICAL CHEMISTRY. in the arts, pyrotechnics, in making shot, fly poison, and occurs as a contaminant of various medicinal substances, especially bismuth. Arsenic forms compounds with hydrogen, the prin- cipal one of which is known as hydrogen arsenide, or arsine AsH 3 , a poisonous gas which is formed directly by the action of nascent hydrogen on an arsenical compound. Upon this depends one of the principal and most delicate tests for arsenic. It burns with a green flame, giving rise to vapors of arsenic trioxide ; but if the flame is cooled by the introduction of a cold substance, elementary arsenic is deposited thereon. If in- troduced into solution of argentic nitrate it decomposes it into metallic silver and leaves arsenic trioxide As 2 3 and the pentox- ide As 2 5 . The former is most generally known as white arsenic, or commonly arsenic. It may be either crystalline or vitreous, but when sublimed it forms characteristic brilliant octahedral crystals. It is of slightly sweetish, afterwards acrid metallic taste ; it is odorless and, in solution with water, of slight acid reaction. Its degree of solubility in water has been given variously according as to whether crystalline or vitreous. It is oxidized by HN0 3 , arsenic pentoxide being formed. It is reduced by sodic carbonate with potassic cyanide by heat. Its solution with HO is reduced by metallic copper, upon which a gray film is deposited ; upon this reaction depends the test known as Reinsch's. There are four acids of arsenic, of which the following only are of interest : Arsenious acid, H 3 As0 3 ; arsenic acid, H 3 As0 4 . Of the three sulphides, arsenic disulphide, As 2 S 2 , arsenic tri- sulphide, As 2 S 3 , and arsenic pentasulphide, As 2 S 5 , the trisul- phide is the one of principal importance as obtained by pre- cipitation from arsenical solutions by H 2 S. As such it is of a bright yellow color, insoluble in HC1, but soluble in alkaline hydroxides, especially NH 4 HO; also in solutions of alkaline carbonates and sulphides. It is of importance, as in cases of poisoning by arsenic the trioxide may be changed into a tri- sulphide by the H 2 S, liberated by the decomposition of the tis- sues. Arsenic trichloride, AsCl 3 ; arsenic tribromide, AsBr 3 ; arsenic triiodide, Asl 3 . The latter two are medicinal agents, the iodide with Hgl 2 in solution forming Donovan's solution (each i in 100 H 2 0). ARSENIC. 39 Of the salts of arsenious acid are to be mentioned, the so- called Scheele's green, a mixture of cupric arsenite and hy- drate, and the Schweinfurt or Paris green, a mixture of cupric arsenite and acetate, very poisonous substances, which, through their common use as insecticides, are apt to be frequently the cause of serious poisoning cases. The potassium arsenite as an ingredient of Fowler's solution, and sodium arsenate as the base of liquor sodii arsenatis (iNa 2 HAs0 4 - iooH 2 0), are also frequently giving rise to poisonous uses or accidents. Toxicology. — The preparations of arsenic are amongst the most common used with homi- or suicidal effect, and give often rise also to accidental intoxication. Thus the trioxide seems to be the favorite poison with both poisoners and suicides, and the Paris green, the cupric arsenite pigments in confections and otherwise, are those which give most often rise to acci- dental poisoning, while overdoses of medicinal arsenical prepa- rations both by internal use or by absorption from the cutaneous surfaces are frequently heard from, and poisoning by arsenical wall-paper and clothing are by no means rare. When directly taken into the stomach as arsenic trioxide, it will produce a certain amount of inflammation, proportionate with the condi- tion of the stomach and the time it has been in contact there- with. The principal antidote after the employment of emetics, such as zinc- or cupric-sulphate, mustard and hot water, or the use of the stomach pump, is the Ferric hydrate freely admin- istered as a magma. To make it, as should always be done, fresh at the time, the ferric sulphate is precipitated with ammo- nium hvdrate. As the ferric chloride under such circum- stances is probably nearer at hand, it may readily be prepared therefrom as per following reaction : Fe 2 Cl 6 + 6NH.HO = Fe 2 H 6 6 + 6NH.C1, which, after being strained and deprived of an excess of am- monia as well as ammonic chloride, is given in tablespoon doses at freqent intervals, changing the arsenic trioxide into an insoluble ferrous arsenate. 2Fe 2 H 6 6 + 2As0 3 H 3 =Fe 3 2AsO, + FeO + 9H 2 Tests and Analysis. — The tests for the presence of arsenic differ according to the state in which arsenic is found. If 40 APPLIED MEDICAL CHEMISTRY. arsenic trioxide is found in substance dispersed amongst the food, it should carefully be recovered by draining off the liquids and then picking the small particles carefully from the sur- rounding material with the aid of forceps and a magnifying glass. If sufficient of it is obtained in this way it may, after dry- ing, be weighed and a part of it ignited on charcoal with the blow-pipe flame, when the alliaceous odor of the oxidized metal will be observed. This may be confirmed by heating a small quantity in the point of a reduction tube, when it will be vola- tilized without melting, and will sublime at a further and cooler point of the tube. If the sublimate be inspected under the mi- croscope, it will then be seen to consist of beautiful minute octo- hedral crystals. If in a similar tube a small particle be placed at the end and a small splinter of charcoal above it in the small end also, and it be heated to volatilize the arsenic and heat the charcoal to redness, the arsenic trioxide vapor will be reduced and a ring of grayish blue elementary arsenic will sublime a little distance above. The same may be effected by heating a mixture of arsenic with sodic carbonate and powdered char- coal in a plain reduction tube or bulbed for that purpose. The identity of the arsenic may be shown by adding a small quan- tity of a solution of sodic hypochlorite, in which it will dis- solve ; or if the tube be cut off below the arsenic sublimate and this heated with access of air, a ring of white crystals of arsen- ious trioxide will be formed above, which can by means of heat be readily chased along the tube. A mixture of about equal parts of sodic carbonate and potassic cyanide placed over the arsenic either as trioxide or trisulphide in the reduction tube in several times its volume, will be found a very delicate re- ducing agent. When the arsenic is obtained only in solution it will give a yellow precipitate with a solution of ammonio- argentic nitrate. With the ammonio-cupric sulphate solution it will give a beautiful green precipitate of amorphous cupric arsenite. The most useful and ready method of precipitating arsenic from its solutions is by means of a stream of hydrogen sulphide developed from a gas bulb containing ferrous sulphide and sulphuric acid, FeS + S0 4 H 2 = S0 4 Fe + H 2 S ; this, with the As 2 O s , gives As 2 3 -f- 3H 2 S = As 2 S 3 + 3H 2 0. The arsen- ical solution should be slightly acidulated with HC1, when a ARSENTC. 41 precipitate of beautiful yellow color, As 2 S 3 , will result. If this is filtered and washed, then dried and placed in a reduction tube with equal parts of each, sodic carbonate and potassic cyanide, the reduction will give an arsenical ring, as above described, which can be confirmed as before. This can be made still more delicate if the reduction is made, according to Fresenius and Babo, in a current of dry carbon dioxide. The Reinsch's test consists in boiling a strip of pure copper foil in an arsenic solution acidulated with HC1 for about five minutes, when it will be covered with a bluish-gray film of elementary arsenic. If the copper is then removed, carefully wiped and dried, rolled up and placed in a reduction tube, a white ring of arsenic trioxide will sublime in the tube, which can be readily recognized under the microscope. By far the most delicate and largely used test for the detection of arsenic is the so-called Marsh's test, which depends on the formation of hydrogen arsenide in the presence of nascent hydrogen, if arsenic in solu- tion be present. The hydrogen in Marsh's test is generated from pure zinc, by means of pure H 2 S0 4 and water. Zn -f H 2 S0 4 + H 2 = ZriSO, + H, + H 2 0. The apparatus in this process should first be tested to insure its freedom from arsenic by burning the hydrogen from the point of exit and showing absence of arsenic stain on a cool porcelain surface. Then arsenic solution is added, when the flame will turn green, light vapors of arsenic tri-oxide will arise, and if cooled against a porcelain slab, an arsenic stain will be produced. This can be proven as such by dissolving it in sodic hypochlorite solution, or if on moistening with HN0 3 and evaporating, it gives a brick-red stain with argentic nitrate. If the tube along its course be heated to redness a ring of arsenic will be deposited, which, if cut off and sublimed with access of air, can be proven crystals of arsenic trioxide. As this test may give rise to confusion with antimony, a better plan is to employ instead of the zinc and H 2 S0 4 aluminium and a solution of potassic hydroxide, as follows : 2A1 + 2KHO + 2H 2 = Al AK 2 + 6H. The advantage of this is the absence of arsenic in the mate- rial employed, greater and more rapid generation of gas, and 4 42 APPLIED MEDICAL CHEMISTRY. the absence of hydrogen antimonide, which does not develop from the alkaline solution. As a modification of this, a very- ingenious test has been proposed by Fleitmann, by adding to a few pieces of aluminium in a test tube a little solution potassic hydroxide, not exceeding f^th volume of tube, adding thereto the solution to be tested, and capping the test tube with white filtering paper on which a drop or two of argentic nitrate solu- tion has been placed. If arsenic is present a dark stain will show the reduced metallic silver on the paper, which with antimony does not take place. To detect the presence of arsenic in the tissues they should be cut up fine, and treated with HC1 and additions of KC10 3 thereto until a clear yellow liquid supervenes, which is again treated with sulphur dioxide until all odor of chlorine has disappeared, after which the liquid is treated by one of the above tests. To test quantitatively for arsenic by Marsh's test the AsH 3 is led into a properly diluted solution of AgN0 3 , which must be kept slightly in excess ; the AgN0 3 is decomposed into Ag, and As 2 3 is obtained in solution. When precipitation ceases the solution is treated with HC1 to precipitate excess of N0 3 Ag as AgCl, after which the arsenic is precipitated by H 2 S, and determined as As 2 S 3 . COPPER. Q u i and u __ 63.5, specific gravity 8.9. A brownish metallic substance of great ductility, malleable, and a good conductor of heat and electricity. It is largely used for making culinary vessels, and enters into various alloys of importance. It combines with oxygen to form two oxides, the Cuprous, Cu 2 and the Cupric oxide, CuO. A yellowish- red hydrate of cuprous oxide is precipitated if cupric salts are boiled with glucose in presence of an excess of alkali. There are two chlorides, the cuprous, Cu 2 Cl 2 and the cupric, both of little interest in medicine. Only one nitrate is known, the cupric Cu(N0 3 ) 2 , also only one cupric sulpliate, the common Milestone or blue vitriol, CuS0 4 -f- 5H 2 0. This is one of its most important salts. It comes in beautiful blue oblique prisms, soluble in about 2.5 parts of water at 15 C. It is efflorescent, and at about 225 ° loses its water and forms a white amor- copper. 43 phous powder, which is again soluble with blue color; it is of acid reaction, and styptic, nauseant, metallic taste. With am- monium hydroxide it yields a dense blue precipitate, which is redissolved in excess of ammonia, but may be crystallized by addition of alcohol ; it is called ammonio-cupric sulphate. The preparations known as Scheele's or Schweinfurt, also Paris green, have been treated under arsenic on account of the greater importance of their arsenical components. Cuprous sulpiride, Cu 2 S, and cupric sulpiride, CuS, are of but little interest to the physician, as are the cupric carbonate, CuCo 3 , the di-cupric carbonate, CuC0 3 CuH 2 2 , and the tri- cupric or cupric sesqui-carbonate. Next to the sulphate as toxic agents rank the cupric diace- tate, Cu(C 2 H 3 2 ) 2 + H 2 0, and principally the basic cupric ace- tate, well known as verdigris. This is a complex of various lower acetates of a bluish-green or green color, and of a dis- tinct acetous odor. Toxicology. — Copper is no longer considered as poisonous or dangerous as once thought ; in its metallic state it is even considered without serious effect on the organism, and many of the poisoning cases attributed to it from food prepared in a copper vessel, are attributable rather to contamination of the copper itself with arsenic or the solder employed. Its com- pounds, however, especially the acetates, are markedly and actively poisonous, and are often taken with suicidal intent. Food containing vinegar or acids should not be cooked in copper vessels, nor should food of any kind be allowed to stand in them. A source of danger from the poisonous effects of copper are soda water apparatus of copper, which are not, or improperly, protected. While pure water will not act on copper, the carbonic acid water acts on it very readily, and vomiting after the consumption of such waters should throw suspicion on their purity and lead to analysis thereof. The cupric sulphate acts as an irritant, which should be taken into con- sideration in the treatment. Establishing but small amounts of copper in a body after death is of no significance, as it is generally present in traces. Copper salts are said to be occasionally employed to color canned vegetables or pickles, but this can be readily detected 44 APPLIED MEDICAL CHEMISTRY. by inserting a clean iron or steel surface, which will soon be coated by metallic copper. Poisoning by copper salts should be treated by encouraging the emesis probably taking place, or producing it by warm drinks, or even by the stomach pump. Albumen is serviceable as an antidote if administered in large quantities, as well as milk, but emetics should always follow the antidotes. Tests and Analysis. — H 2 S black precipitate soluble in po- tassic cyanide and hot HNO s . KHO, pale-green precipitate, rendered black on boiling. Ammonium hydrate gives a blue precipitate, soluble in excess with beautiful dark-blue color. Potassic ferrocyanide produces a chestnut-brown precipitate of cupric ferrocyanide, decolorized by KHO. A bright iron or steel instrument inserted in an acidulated solution of copper salt is coated with metallic copper in a short time. MERCURY. Hg ' and m = 200, specific gravity 13.596. A bright metallic liquid, congeals at — 40 , slightly vola- tilizes at all temperatures, boils at 350 C. Hot H 2 S0 4 dissolves it, forming mercuric sulphate and sulphur dioxide ; with cold HNO3 it forms nitrate. It is used in its metallic state for filling thermometers and barometers, also as alloys called amalgams for covering looking- glasses. In medicine metallic mercury enters hydrargyrum cum creta, massa hydrargyri and unguentum hydrargyri. It forms two oxides, of which the merciirons, Hg 2 0, is formed by the action of calcic hydrate (lime water) on mercurous chloride (calomel), the mixture being known in medicine as black wash, lotio nigra. The mercuric oxide, also called red oxide of mercury, HgO, is prepared in two ways, and accordingly, if sublimed in a crys- talline state, it is called red precipitate, whereas, if precipitated from a mercuric solution with sodic or potassic hydrate, it forms an amorphous yellow powder called yellow oxide of mercury, hydrargyri oxidum flavum. Exposed to red heat in a test tube or retort it is decomposed, and metallic mercury is distilled over and oxygen liberated. MERCURY. 45 The sulphides have little importance, the mercurous Hg 2 S being unstable, and the native mercuric sulphide HgS, the cinnabar or vermilion of commerce, is claimed not to be poi- sonous, and is largely used in the arts and as a paint. The mercuric salts are best determined quantitatively as sulphides, , hence their mention here. The chlorides of mercury offer the greatest interest of all the mercury compounds for the physician. They are not alone important medicinal agents, but the mercuric also ranges with arsenic as the most frequently used poison, leading in its use to the most serious consequences. The mercurous chloride, Hg 2 Cl 2 > (calomel) comes generally as a white amorphous powder, though crystallizable. It is sublimed by heat without fusing, and is insoluble both in cold water and alcohol. Its most frequent contaminant is mercuric chloride, which can be detected by immersing a bright iron instrument into a mixture of Hg 2 Cl 2 and alcohol. If a dark stain forms HgCl 2 is present. Hg 2 Cl 2 in the presence of HCl r or HC1 -f HN0 3 , also CI and alkaline chlorides, is converted into HgCl 2 , a fact that should be borne in mind when so dispensed. By the action of alkaline hydrates or carbonates it is reduced to Hg 2 0. Mercuric chloride HgCl 2 , corrosive sublimate, is of crystal- line form, which, if sublimed, consists of rectangular octahedra ; and, if crystallized by evaporation, ortho-rhombic prisms. It is white, semi-transparent, specific gravity 5.43, melts at 265 ° C. and boils at 295 °. It dissolves in water, alcohol and ether, and has an acrid, metallic, nauseant taste, and reacts acid. With H 2 S it forms HgS, which first is white, then yellow, and finally black. Potassic, sodic, calcic and magnesic hydrates precipitate it from its solutions as HgO. With KI it forms a bright scarlet precipitate Hgl 2 , soluble in excess. It is precipitated by albu- men as albuminate, which is soluble in an excess. By NH^HO it is decomposed into Amido-mercuric chloride, ClHgNH 2 , called white precipitate, which finds use in medicine as an external application. The mercurous iodide, Hg 2 I 2 , or green iodide, can be best prepared by precipitating a mercurous nitrate with KI, or by 46 APPLIED MEDICAL CHEMISTRY. triturating metallic mercury with iodine and alcohol. It is largely employed in syphilis. Mercuric iodide, Hgl 2 , or red iodide of mercury, is prepared from HgCl 2 and KI, avoiding excess of the latter, in which it rapidly forms potassic iodo-hydrargyrate, which and also Hgl 2 are largely employed internally. Mercuric cyanide, Hg(CN) 2 , is occasionally used medicinally. Of the three merciirons nitrates, one is of special interest, Hg 2 (N0 3 ) 2 + 2H 2 0, prepared by treating mercury in excess with nitric acid and H 2 0, equal parts, and evaporating until prismatic crystals separate. Of the three mercuric nitrates, Hg(N0 3 ) 2 , made by treat- ing Hg with an excess of HN0 3 is important. It is contained in the liquor hydrargyri nitratis, and also enters into the unguent, hydrarg. nitratis. The two sulphates, Hg 2 S0 4 and HgSO^, are of no interest in medicine. Toxicology. — Although metallic mercury has no poisonous action as long as it remains in its metallic state, and is known to have been taken in immense quantities with impunity, its vapors at all degrees of temperature exert a poisonous effect, noticeable with those handling it in the arts. Its compounds are less dangerous the more insoluble they are, but may, under favorable circumstances for their conversion into soluble com- pounds, readily prove of serious consequence. The most powerful of all its compounds are undoubtedly the mercuric chloride, iodide and cyanide. The former on account of its general use, both as a medicinal agent and insecticide, is the most frequently encountered as a toxic. That its primary effect, as a corrosive, is almost as much to be feared as its constitu- tional effect, is well known, as it can be injected hypodermically in doses that are inadmissible when taken by the mouth. That it is capable, however, of being rapidly absorbed, even after forming albuminates, would appear from the reported toxic effect after its free use as an antiseptic. It is excreted by the saliva and urine, and can be detected in both. If taken in poisonous doses albumen or milk should be freely administered, but promptly removed by the stomach pump to prevent its being redissolved, again to be followed by LEAD. 47 more albumen or milk and emesis, and finally with demulcents. For chronic mercurialism give KI. Tests and Analysis. — The chemical tests for mercurous salts are, hydrogen sulphide, black precipitate ; sublimation in tube without fusion ; Hg 2 Cl 2 turns black on addition of calcic hydrate; metallic mercury can be recognized by volatilizing and condensing on gold foil as a white stain. Paper saturated with ammonio-argentic nitrate is stained black by vapors of Hg. A solution of mercuric salt, if dropped on a copper surface with a drop of solution of KI added, produces a mercury stain. H 2 S gives with mercuric solutions, if gradually added, first white, then yellow, lastly black precipitate ; potassic or sodic hydrates, yellow ; ammonium hydrate, white ; potassic iodide, scarlet precipitate, the latter redissolved in excess of precipi- tants. To determine corrosive sublimate, test similar as with Reinsch's test without heat. The copper coated with mercury, if placed in reduction tube, will sublime minute globules of mercury, to be recognized by the microscope ; if in sufficient quantity and touched with a little iodine it turns red (Hgl 2 ). If in urine it should be acidulated with HC1. It can be detected also by immersing a zinc staff covered with gold leaf into the acidulated urine or fluid, and then subliming it therefrom, as in the copper test. To determine HgCl 2 quantitatively its solution should be acidulated with HC1 and precipitated with H 2 S, and the precipitate well washed and dried. 100 parts of sulphide so derived represent 1 16.8 parts HgCl 2 or 82.6 Hg. LEAD. Pb UandiT =207, specific gravity 1 1.3. A heavy metallic element which fuses at 325 ° C. It is largely employed, both pure and in alloys, for making water pipes, also to make pewter vessels, and as solder. Its principal oxides are litharge, lead monoxide, PbO. The plumbic ortho-phnnbate, PbgPbO^, sometimes written as Pb 3 + is known as minium, and as such largely employed as pigment. The native sulpiride, PbS, a grayish crystalline substance of metallic lustre, is known as galena. The chlorides, PbCl 2 and PbCl^ are principally of analytical interest. 48 APPLIED MEDICAL CHEMISTRY. The lead 'iodide , Pbl 2 is used externally in medicine. The lead nitrate of the Pharmacopoeia, Pb(NO s ) 2 is occasion- ally employed as a disinfectant. The neutral lead sulphate, PbS0 4 is an insoluble white powder. As toxic agents the lead carbonate, chromate and acetates are most common. Lead carbonate, PbC0 3 is very largely used as a white pig- ment in paints. Lead chromate, PbCr0 4 , of beautiful yellow color, is also used as pigment, and* while insoluble in water, is soluble in alkalies. It is not infrequently used as coloring for confections, and as such very deleterious. Neutral lead acetate, sugar of lead, Pb(C 2 H 3 2 ) 2 -f- 3H 2 0, crystallizes in oblique rhombic prisms, has sweet metallic taste, is efflorescent, fuses at 75 ° C, loses acetic acid at ioo°, and at 280 it fuses, and if further heated on charcoal with blowpipe flame leaves a soft malleable globule of metallic lead. The basic acetates are of interest as medicinal agents, by forming the principal ingredient of liquor plumbi subacetatis. Toxicology. — The soluble lead salts and many of the in- soluble ones are active poisons, and on account of their slow elimination are very dangerous as such. While probably little is to be feared from poisoning by lead with homicidal intent, as a contaminant of food and beverages it is frequently met with and provokes most distressing and dangerous symptoms. Though metallic lead does not exert poisonous action as such, water pipes containing it, by the alternate action of air and water, are soon affected and converted into soluble and poisonous compounds. The chronic poisoning known as painters' colic depends often for its recognition on chemical tests, and is often provoked by the handling of lead pigments, leaden vessels, and has been known to be induced by hair-dyes containing it. Though slow of elimination, its presence may be often con- firmed in the urine, sweat and dejecta. The principal antidote after the ingestion of soluble lead salts is sulphuric acid, and better still, magnesic sulphate to form insoluble lead sulphate, which should be removed by prompt emetics or stomach pump. For chronic lead poisoning potassic iodide is the most service- able remedy, as favoring its elimination in a soluble condition. PHOSPHORUS. 49 Tests and Analysis. — H 2 S gives a heavy black precipitate from acid solutions, insoluble in acids ; ammonium sulphydrate black precipitate, insoluble in excess. NH 4 HO, white precipi- tate, insoluble in excess. KHO, white precipitate, soluble in excess. HgSO^, white precipitate. KI, yellow precipitate. KCrO, yellow precipitate of PbCr0 4 , soluble in KHO. For the detection of lead in potable water, Blyth recommends a I per cent, alcoholic tincture of cochineal, which gives a precipitate. In testing for lead in the stomach, intestines, etc., the contents should be treated with HN0 3 and precipitated by H 2 S, which is also to be done in testing urine for lead, by evaporating and treating residue in such a manner. Quantitatively lead may be determined as sulphide, of which ioo parts represent 86.19 metallic lead. PHOSPHORUS. pal ana ir — ^j 5 specific gravity 1.83, red 2.2. This exists in two allotropic conditions known respectively as white and red. The white is a yellowish waxy substance which melts at 40°C. In air it gives rise to white vapors and the smell of ozone ; it is luminous in the dark (phosphorescent). It is preserved under water, as it readily ignites in the air. It is soluble in ether, carbon disulphide, and in the fats and oils. Its most common application, in the manufacture of matches and rat poisons, gives often rise to toxic effect from it. The red variety is without taste and odor, of dark red color, does not melt nor ignite at ordinary temperature, and is non- luminous. Phosphorus forms three direct compounds with H, of which the gaseous hydroge7i phosphide, H 3 P, phosphine, is of prin- cipal interest. It is spontaneously inflammable, poisonous, of garlic odor, specific gravity 1.24, prepared by heating P. with solution of KHO or by the action of H 2 on calcic phosphide. The phosphorus trioxide, P 2 3 , and pentoxide, P 2 5 , require no mention here. Hypophosphorous acid, H 3 P0 2 , and its salts are of impor- tance as remedial agents. The three principal acids of phosphorus are mono-hydric 50 APPLIED MEDICAL CHEMISTRY. phosphate, glacial or metaphosphoric acid, HP0 3 , coagulates albumen, white precipitate with baric and calcic chlorides, gelatinous precipitate, with AgN0 3 . Dihydric phosphate, pyro-phosplioric acid, H 4 P 2 7 , does not affect albumen, calcic or baric chloride; white precipitate with AgN0 3 + a little NH 4 HO. TriJiydric phosphate, ortho-phosphoric acid, H 3 P0 4 (officinal), does not affect albumen, calcic and baric chlorides; with AgN0 3 + a little NH 4 HO, it gives a yellow precipitate ; with ammonium molybdate solution and HN0 3 , yellow precipitate. Toxicology. — Phosphoric acid can be said to be non-poison- ous in ordinary doses, though the meta- and pyrophosphoric acids seem to act on the heart in a manner that may produce serious effects. Hydrogen phosphide is poisonous, but so rarely met with as to be of no importance as a toxic. Red phos- phorus, owing to its insolubility, is considered non-poisonous, while the white variety is one of the most dangerous poisons there is. The recoveries from its effects are very few, and, though some time may elapse after its ingestion, the patient is apt to develop alarming symptoms and die suddenly. The me- chanical effect is often inconsiderable, and the toxic effect mani- fests itself notwithstanding. Constitutional symptoms may result even from external burns by phosphorus, and these should be treated at once by chlorinated lime or soda solutions or chlorine water. The treatment of poisoning by phosphorus calls for speedy emesis, preferably with cupric sulphate. Calcined mag- nesia is the most reliable antidote, and though fits are con- traindicated, old oil of turpentine has been much recommended in such cases, but no positive chemical antidote for it is known. Chronic poisoning by phosphorus is often reported in persons employed in match factories, where white phosphorus is used, and often results in necrosis of the maxillary bones. Many preventives against this have been proposed, but the use of red phosphorus alone can be said to answer to that end. Tests and Analysis. — The tests for phosphoric acid have been given under that head, and as phosphorus is used as a toxic agent principally in substance, the examination for un- oxidized phosphorus in human remains, etc., is of importance. It may frequently be recognized by its odor and phosphor- ALKALIES AND ACIDS AS POISONS. 5 I escence on mere inspection, but this should in all cases be con- firmed by chemical tests. Thus if the suspected' fluid is acid- ulated with a little tartaric acid or H 2 S0 4 in a flask, and attached to the cork is a strip of argentic nitrate paper, this on heating will turn black, owing to the formation of silver phosphide. As H 2 S may be present, however, and this have the same effect, it is well to prove its absence, by a strip of plumbic acetate paper introduced in the same manner. After such preliminary ex- amination the flask is attached to a glass Liebig's condenser placed vertically, and the vapors driven over with a current of dry C0 2 , when the presence of phosphorus is revealed by the luminosity of the unoxidized phosphorus in the cool por- tion of the condenser. As this is interfered with by certain essential oils, alcohol and ether, and especially oil of tur- pentine, frequently employed as antidote, and thus negative results obtained, the vapors are to be passed through a neutral solution of AgN0 3 , which, if phosphorus is present, will yield a black precipitate of silver phosphide. To confirm this, the deposit is put in a Marsh apparatus, when the gas therefrom will show in the inner flame a bright green. To test quanti- tatively, the distillate obtained above together with fragments of phosphorus found, should be treated with chlorine water for twelve hours, evaporated, saturated with NH^HO, precipitated by magnesium mixture, as ammonio-magnesic-phosphate, this collected and by ignition converted into magnesic pyrophos- phate and weighed: ioo parts of this represent 27.92 phos- phorus. ALKALIES AND ACIDS AS POISONS. These would comprise certain caustic alkalies or alkaline hydrates and acids which act as corrosive poisons, and as a rule give rise to toxic effects more from accident than intent, also certain organic acids and their derivatives, which prove consti- tutional poisons, and are frequently used with homi- and sui- cidal intention. 12 APPLIED MEDICAL CHEMISTRY. POTASSIC HYDRATE OR HYDROXIDE. KHO. This in substance is frequently met with in cylindrical form and commonly known in solution as potash lye. It acts very destructiveiy on animal tissues, gives rise to a soapy touch be- tween the fingers and has a soapy taste ; forms many soluble compounds in the body and acts destructively on the coats of the stomach and intestines, so much as to give rise to perfora- tion in many instances. The treatment in cases of poisoning should be with a view to its neutralization with dilute acids, lemon juice, etc., or also with a view to saponification by oils, milk, or, best of all, oleic acid, if on hand. Many of the neutral salts of potassium are also poisonous if taken in suffi- cient quantities especially the chlorate, nitrate and sulphate. Tests and Analysis. — Potassic hydrate and potassic salts may be recognized by imparting to the outer flame of a Bunsen burner a violet tint recognized through the spectroscope as red and blue lines. The alkaline reaction and neutralization by acids without effervescence besides the flame test would indicate potassic hydrate. If neutralized it will cause, like all pot- salts, a yellow precipitate of platino-potassic chloride with platinic chloride, insoluble in alcohol, but soluble in e: water. With tartaric acid potassic hydrate solutions precipi- tate crystalline hydro-potassic tartrate (cream of tartar). Picric acid forms, when in excess, yellow precipitate of potassic picrate. The quantitative determination of KHO must be conducted by the process mentioned under Alkalimetry, or if and how far neutralized, may be determined as chloride, or bromide by the volumetric solution of AgX0 3 . SODIC HYDRATE OR HYDROXIDE. XaHO. Like the foregoing, this is generally met with in s and solution, the latter also termed soda lye. Its action on the economy is the same as that of pota- hydrate, and the treatment for cases of poisoning by it should be the same. Tests and Analysis. — It imparts, like all sodium salts, a yellow tint to the cuter flame of a Bunsen burner, which is SULPHURIC ACID. 53 readily recognizable through the spectroscope as a yellow band. The alkaline reaction and neutralization without effervescence or precipitation would characterize it, together with the flame test, as sodic hydrate. The quantitative analysis would also be conducted by alka- limetry, ascertaining by subsequent volumetric determination the amount of neutral salts admixed thereto. AMMONIUM HYDRATE OR HYDROXIDE, XH 4 HO. A solution of ammoniacal gas in water, of various strength. Water is capable of taking it up in large quantities, and as it occurs in commerce it is of sufficient strength to act as a corro- sive poison. It has all the physical characters of alkaline hy- drates, but by heat it is, as well as its salts, entirely volatilized. Its neutral salts, if warmed with KHO or XaHO, give off ammoniacal odor, which, with HC1, forms dense white vapors of XH.C1. Its action upon the tissues is similar to that of the aforementioned KHO and XaHO, and the measures to be adopted for poisoning by it are also alike. Tests and Analysis. — The odor of ammonia is so charac- teristic that it can readily be recognized, if not neutralized, or if present in sufficient amount. The white vapor created with HC1 is readily observed. Mercuric chloride gives a white pre- cipitate with ammonia. As much of the ammonia taken in- ternally is neutralized in the stomach, the test for its salts will be necessary. They yield with platinic chloride a yellow pre- cipitate ; strong solutions give a white precipitate of amnionic tartrate with tartaric acid ; with picric acid a yellow precipi- tate of ammonic picrate ; Xessler's test q.v. . orange yellow precipitate. Its quantitative estimation is accomplished by the normal solution of oxalic acid and that of its salts as chloride by AgNO, SULPHURIC ACID, Hydrogen Sulphate, H 2 SO.. This acid gives rise to poisoning more often from accidental ingestion than from any attempt of homicide or suicide, al- though instances of this kind have been reported. It acts upon 54 APPLIED MEDICAL CHEMISTRY. the tissues as a purely corrosive agent, as sufficiently diluted in ordinary doses it has no toxic action. As result of extreme corrosion, perforation of the alimentary tract seems its most usual effect. Besides its internal abuse, the habit of vitriol- throwing with the intent of disfigurement of features and apparel has become quite frequent, and with it the necessity of proving its identity in such cases. Its effect on dark textiles is to produce red stains, which, when fresh, can be removed by ammonic hydrate, but if left alone they will soon turn brown and cause the destruction of the material. The treatment of cases, where H 2 S0 4 has been swallowed, consists in neutralizing it as speedily as possible by calcic car- bonate (chalk), magnesic carbonate and alkaline carbonates in milk. Solution of soap is perhaps one of the best, if not the best antidote, as the oleo-palmitic acid so formed is not alone a demulcent, but keeps the sodic sulphate in an emulsi- fied state, in which it is readily ejected by emesis. Tests and Analysis. — Baric chloride or nitrate give a white precipitate with H 2 S0 4 , or its salts, insoluble in HC1 or HN0 3 ; strontium nitrate, a white precipitate, somewhat soluble in HC1 and HN0 3 ; lead acetate, white precipitate, sparingly soluble in acids and alkalies ; CaCl 2 , white precipitate, soluble in warm water. Metallic copper, with H 2 S0 4 , gives rise to sulphur dioxide and blue solution of cupric sulphate. Cane sugar, if treated with H^SO^, is charred. The quantitative estimation of H 2 S0 4 is best effected by the volumetric method, with a standard solution of KHO, of which 100 c.c. correspond to 4.9 grams of H 2 S0 4 , specific gravity 1.84; also by converting it into baric sulphate, 100 parts of which correspond to 42.06 H 2 S0 4 , or 34.33 sulphuric anhy- dride (S0 3 ). NITRIC ACID, Hydrogen Nitrate, HN0 3 . Like the preceding, this acid cannot be said to be a true poison, but only destructive to life by its corrosive local action. It has the property of producing light yellow stains, which gradually turn brown. Its yellow stain on dark textiles can- HYDROCHLORIC ACID. 55 not be extinguished by the application of NH 4 HO. The treat- ment for cases of poisoning by this acid is the same as laid down for H 2 S0 4 . Tests and Analysis. — Metallic copper yields when heated with HN0 3 a greenish-blue solution of cupric nitrate, with es- cape of brown fumes of nitrogen tetroxide. HNO a , mixed with equal volumes of H-jSC^, and a piece of ferrous sulphate added to the mixture, turns first black, then brown and reddish- brown. Sulphindigotic acid boiled, with sufficient HC1 to color it blue, has its color discharged by boiling the mixture with HN0 3 . A few drops of H 2 S0 4 and a little aqueous solu- tion of brucine is an addition of HN0 3 , colored blood-red, or pink if dilute. The quantitative estimation of HNO s cannot be readily accomplished directly, but if the acid is converted into baric nitrate it can be estimated as a sulphate by precipitation with H 2 S0 4 , 100 parts of baric nitrate corresponding to 77.2 HNO s , specific gravity 1.424. HYDROCHLORIC ACID, Hydrogen Chloride, HC1. Like the foregoing, this acid acts as a corrosive ; on dark textile material it produces bright red stains, but does not destroy the texture as rapidly as H 2 S0 4 . On addition of NH^HO the stains, if recent, will disappear. The treatment for over- doses should also consist of neutralizing agents and demulcents. Tests and Analysis. — With argentic nitrate it gives a curdy white precipitate, insoluble in HN0 3 , soluble in NH^HO, potassic cyanide, sodic hyposulphite, and turning purplish- brown on exposure to sunlight. With manganese dioxide it yields chlorine ; with mercurous nitrate a white precipitate of Hg.Cl, Quantitatively it is determined by volumetric analysis with the standard solution of argentic nitrate. I c.c. decinormal argentic nitrate solution corresponds to 0.00365 HC1. Gravi- metrically 100 parts argentic chloride formed, correspond to 25 43 absolute HC1. 56 APPLIED MEDICAL CHEMISTRY. CARBOLIC ACID, Phenyl hydrate, C 6 H 5 HO. This hydrate of the monad radical C 6 H 5 cannot be classed with acids, and would better be called phenic alcohol, but as it is commonly called an acid it will be taken up here under this heading. It forms colorless or pinkish crystals, soluble in ether and alcohol and in 20 parts of water 15 , melts at 35 , and boils at 187 . It has a characteristic odor which is less un- pleasant the purer it is. It rapidly coagulates albuminoids and produces white stains on fingers and hands, accompanied by a feeling of numbness. On account of its free use as an antiseptic in medicine and its popularity as a disinfectant, cases of accidental poisoning with this substance have become very frequent of late. Al- though its poisonous action is to be attributed principally to corrosion of the alimentary organs, it also exerts some consti- tutional toxic effect, which is shown by the fatal cases of absorption from wounds and abraded surfaces. It whitens the mouth and tongue when swallowed, and is excreted by the kidneys, rendering the urine often of various colors, from green to black, but as a rule without decomposition. Treatment. — Oils, fats, absorbents, demulcents, followed by emetics. Tests and analysis. — HNO s in excess produces yellow pris- matic crystals of trinitro-phenol, picric acid. A very delicate test is to add to its aqueous solution a small quantity of NH 4 HO, and if then brought in contact with vapor of bromine, a bright blue color is obtained. An aqueous solution of car- bolic acid with mercurous nitrate and traces of HN0 3 , if heated, gives intense red color with separation of Hg. From urine and tissues it should be recovered by distillation after acidulat- ing the liquids with tartaric acid, extraction of distillate with ether, evaporation and solution in water and applying one of the above tests. OXALIC ACID, C 2 H 2 4 +2H 2 = i26. A dibasic acid existing in many plants and occasionally in urine, now artificially prepared, crystallizing in transparent HYDROCYANIC ACID. 57 prisms, fusing at 98 ; heated to 177 it volatilizes and does not char. Heated with H 2 S0 4 it decomposes without charring into Co or Co 2 . It dissolves in 14 parts of water, also in 6 parts 95 per cent, alcohol and 7 parts glycerin. It forms salts with potassium, sodium, etc. It is largely employed for clean- ing copper and iron, and to remove iron stains, etc. Toxicology. — On account of its popular use it is frequently met with as a poison, often occasioned by being mistaken for Epsom salts. It gives rise to local irritation, but its toxic effect is more that of a narcotic than a corrosive. Death may result either at once or after the lapse of some time. The hydro- potassic oxalate acts similar, and is also encountered in this way. Poisoning by oxalic acid or oxalates should be treated promptly and energetically by the use of slaked lime or mag- nesia, demulcent drinks and emetics where no corrosive action is apparent; diluents are contraindicated. Tests and analysis. — With AgN0 3 it gives white amor- phous precipitate, exploding when heated on platinum foil. Calcic hydrate, chloride or sulphate solutions give a white granular precipitate, soluble in HC1 and HN0 3 . Baric chloride, a white crystalline precipitate soluble in HC1 and HN0 3 . Lead acetate, a white precipitate soluble in HC1 and HN0 3 , insoluble in acetic acid. Urine should be examined microscopically for crystals of calcic oxalate. Quantitative determination by the standard solution of potassic hydrate, 100 c.c. of which corre- spond to 6.30 oxalic acid. HYDROCYANIC ACID, Hydrogen cyanide, Prussic acid, HCN or HCy — 27. A colorless liquid of a specific powerful odor, very poisonous and volatile. It mixes with alcohol, water and ether in all pro- portions. It is used medicinally, and when properly and freshly prepared, the officinal solution should contain 2 per cent. Litmus paper is reddened by it, which, however, is transient. Many of the other cyanides are also very poi- sonous, and amongst them potassic cyanide is foremost. This is frequently used for chemical purposes and is often employed with homicidal or suicidal intent, and accidents with it are not of rare occurrence. 5 58 APPLIED MEDICAL CHEMISTRY. Hydrocyanic acid is one of the most powerful and rapidly acting poisons known, rarely admitting of treatment to coun- teract its effects ; treatment should nevertheless be instituted if life is not entirely extinct. Treatment. — Ammonia vapor, chlorine either in vapor or water, stimulants, and cold affusions, artificial respiration, and galvanism. Chemical antidote, mixture of ferrous and ferric salts with alkaline hydrates or carbonates. If patient lives for one hour, prognosis more favorable. Tests and analysis. — Characteristic odor of the poison. AgNo 3 white precipitate, insoluble in cold HN0 3 , soluble in alkaline cyanides and hyposulphites ; ammonic sulphhydrate and ferric chloride, red color. Potassic hydrate and mixture of ferrous and ferric salts, green precipitate, which with HC1 turns blue. Neutralized with KHO and picric acid it gives blood-red color. Mercurous nitrate gray precipitate of Hg. Guaiac paper moistened with cupric sulphate is turned blue by vapor of HCy. For forensic investigation the suspected liquid after dilution and acidulation with tartaric acid is distilled and tested as above. If to be determined quantitatively the distillate must be rectified with borax or calcic carbonate, to avoid HC1, if present therein, and then distilled into a solution of AgN0 3 to be recovered as argentic cyanide, ioo parts thereof correspond- ing to 20.15 parts absolute hydrocyanic acid. If potassic fer- rocyanide is present, the suspected liquid should be slightly acidulated with H 2 S0 4 , and the ferrocyanide precipitated as Prussian blue with ferric chloride, and after neutralizing the HoS0 4 with neutral potassic tartrate, the liquid is then distilled as before. SYLLABUS OF PART II. (1.) Precipitate solution of tartar emetic with hydrogen sul- phide; dissolve precipitate with hot HC1. Treat acidulated solution of an antimonial compound by Reinsch's test, roll up copper slip and volatilize antimony with access of air, note crystals under microscope. Test antimonial solution by Marsh's test, also by Fleitmann's test. In the latter case no silver stain is produced by antimony. (2.) Test arsenious acid by ignition an charcoal, note gar- SYLLABUS OF PART II. 59 licky odor. Precipitate solution of arsenious acid with H 2 S. Note bright yellow color and solubility in NH 4 HO, insolubility in HC1. Separate precipitate of As 2 S 3 , dry and reduce with mixture of potassic cyanide and sodic carbonate; arsenic ring convertible in As 2 3 . Prepare antidote by precipitating Fe 2 Cl 3 by NH^HO. Apply Reinsch's test and volatilize arsenic from copper by heat and examine sublimate under microscope. Test by Marsh's test ; arsenic film on porcelain slab dissolves in sodic hypochlorite; treat with HN0 3 , dry and apply AgN0 3 , brick-red color; heat tube in its course, cut off and heat with access of air, arsenious trioxide will be formed, recognized by microscope. Treat by Fleitmann's test, dark stain on argentic nitrate paper. (3.) Precipitate cupric sulphate solution with H 2 S. Add to solution of CuS0 4 a solution of KHO green precipitate turns black on boiling; add to former NH 4 HO, blue precipi- tate soluble in excess ; add potassic ferrocyanide brown precipi- tate, decolorized by KHO. Insert a bright iron instrument into an acidulated copper solution, it will be covered with metallic copper. (4.) Add to Hg 2 Cl 2 calcic hydrate and observe black precipi- tate. Heat metallic mercury in test tube and note sublimate under microscope as globular mercury which on gold foil pro- duces white stain. Add potassic or calcic hydrate to HgCI 2 and note yellow precipitate. Add to HgCl 2 a little KI, note red precipitate soluble in excess. Apply Reinsch's test and volatilize mercury from copper, which examine under micro- scope for globular mercury. (5.) Treat solution of lead nitrate, with H 2 S, black precipitate ; with KI, yellow precipitate ; with H 2 S0 4 , white precipitate. Re- duce lead acetate with blowpipe on charcoal ; a globule of me- tallic lead is formed surrounded by yellow margin on charcoal. (6.) Note luminous appearance of phosphorus and its char- acteristic odor. Add to a flask containing phosphorous water a little tartaric acid and heat having closed mouth with cork to which a strip of argentic nitrate paper is attached, which will turn black. Place silver phosphide into test tube contain- ing zinc and H 2 S0 4 and burn the hydrogen phosphide ; note green flame. 60 APPLIED MEDICAL CHEMISTRY. (7.) Note brown color of turmeric paper on touching with KHO. Observe violet color of flame test. Neutralize KHO and note yellow precipitate with platinic chloride. Add KHO to tartaric acid and note white granular deposit. Test with volumetric solution of oxalic acid in presence of litmus solution to determine strength. Examine flame through spectroscope. (8.) Introduce sodium salt on platinum wire into flame of Bunsen burner, and note yellow tint, also yellow bar through spectroscope. Observe alkaline reaction of sodic hydrate on test paper and note absence of effervescence when neutralized with acids. Determine strength volumetrically with standard solution of oxalic acid in presence of litmus solution. (9.) Hold bottle of HC1 to bottle of NH 4 HO and note white fumes. Note white precipitate of NH 4 HO with HgCl 2 . Pre- cipitate with platinic chloride, yellow ; with Nessler's test, orange ; volatilize salts of ammonia in tube. Determine strength of NH 4 HO volumetrically with standard solution of oxalic acid, or its salts with that of AgN0 3 . (10.) Add to H 2 S0 4 or a solution of sulphate a little baric chloride, note white precipitate. Add in test tube copper cut- tings to H 2 S0 4 and note odor of sulphur dioxide and bluish color of solution. Add to H 2 S0 4 a piece of cane sugar and evaporate, note charring. Make volumetric test of H 2 S0 4 with standard solution of KHO. (11.) Add to HNO3 in test tube cuttings of copper and note brown vapors. Add to sulphindigotic acid a little HC1 to render it blue, add HN0 3 to this and it will extinguish the color. Add to a few drops H 2 S0 4 some aqueous solution of brucine which on addition of HNO s turns red. Determine HNO3 by neutralizing with baric hydrate, precipitating with H 2 S0 4 , and compute amount of HN0 3 employed. (12.) Add argentic nitrate to HC1, white precipitate soluble in NH 4 HO and potassic cyanide. Add HC1 to manganese dioxide and observe chlorine liberated. Determine HC1 volu- metrically with standard solution of AgN0 3 . (13.) Add to carbolic acid HN0 3 in excess and note yellow crystalline deposit. Add to carbolic acid a little NH^HO, this with bromine vapor turns blue. To carbolic acid add a little mercurous nitrate, red color will result. ALBUMINOIDS OR PROTEIN BODIES. 6 1 (14.) Add to oxalic acid a little AgN0 3 ; white precipitate if heated on platinum foil will explode. Add calcic hydrate to oxalic acid and note white granular precipitate soluble in HC1 or HXO3. Add lead acetate to oxalic acid, and note white precipitate soluble in HC1 or HX0 3 . Determine volumetrically by standard solution of potassic hydrate. (15.) Note characteristic odor of HCy. White precipitate on addition to AgN0 3 soluble in alkaline cyanides and hypo- sulphites. Ammonium sulphhydrate and ferric chloride red color. Add KHO and a mixture of ferric and ferrous salts to HCy and observe precipitate which, on addition of HC1, turns blue. PART III. PHYSIOLOGICAL CHEMISTRY. The investigation of the substances composing animal struc- ture and of those capable of being elaborated into it constitutes this Part. ALBUMINOIDS OR PROTEIN BODIES. These are bodies of great complexity in composition, derived from organic life, and differing in their solubility in water ; they are mostly insoluble in alcohol and ether, and generally col- loidal in character. They all yield an identical derivate, syn- tonin, and by the action of the gastric ferments are rendered soluble and diffusible as peptones, and are laevogyrous. On boiling with sulphuric acid, they yield amides known as leu- cine and tyrosine. With alkaline cupric sulphate solution, they produce a blue or violet color, deepening on boiling. With boiling HN0 3 , they are colored yellow, changing to orange and reddish-brown on addition of NH 4 HO when cold (xanthoproteic reaction). A red coloration is produced by them with Millon's test (q. v.). Al- though they differ in special features, their general characters are as follows : They coagulate on boiling ; nitric, metaphos- phoric and phosphotungstic acids precipitate them completely, as do also carbolic, picric and tannic acids. With a mixture of 62 APPLIED MEDICAL CHEMISTRY. sulphuric and molybdic acids, they give a blue color. With an excess of glacial acetic acid, they give a violet color. When treated with alkaline hydrates, they form alkali albumin, and with very dilute acids are changed into acid albumin. They are very prone to putrescence, and, on account of their complex chemical composition, are subdivided according to their physi- cal characters and behavior to solvents. I. Soluble in Pure Water. (i.) Coagulable by heat: Serum albumin, Egg albumen. (2.) Non-coagulable by heat : Peptones. II. Insoluble in Water, but Soluble in Dilute (i per cent.) Sodic Chloride Solution. Globulins, coagulable by heat, carbonic acid, and readily forming albuminates. (1.) Precipitable with strong NaCl solution: Fibrinogen, Fi- brinoplastin, Myosin. (2.) Non-precipitable with strong NaCl solution : Vitellin y Crystallin. III. Insoluble in Water, or Dilute NaCl Solution; Sol- uble in Acids or Gastric Juice. (1.) Soluble in dilute HC1 or dilute alkalies : Acid albumin ; Alkali albumin ; Casein ; Fibrin. (2.) Insoluble in dilute acids and alkalies, but soluble by aid of digestive ferments : Coagulated Albumin. (3.) Insoluble in water, NaCl, dilute acids or gastric juice, soluble in stronger alkalies and strong HC1 : Lardacein (amy- loid substance). Serum albumin (Seralbumin, Serine), existing in blood, chyle, milk, lymph, serous fluids, liquids of cysts, muscles, and in urine pathologically. Its solutions are precipitated by HN0 3 ,HC1 (in an excess of which it is soluble and reprecipi- tated by dilution with water), tannic acid, metaphosphoric acid, metallic salts. It turns opaque when heated to 6o°. Coagu- lates at from 70 to 75 °. Preparation, from blood-serum or hydrocele fluid, by dropping in acetic acid, filtering and neu- ALBUMINOIDS OR PROTEIN BODIES. 63 tralizing with sodic carbonate, and evaporating below 35 °. Remove paraglobulin by magnesic sulphate, filter, dialyse, and evaporate the dialysate in vacuo or sulphuric acid dessicator. Egg albumen (ov-albumen), from the white of eggs. It ap- pears to be a mixture of two bodies coagulating respectively at about 6o° and at 74 . It is coagulated when shaken with ether or when treated with mineral acids and prolonged con- tact with alcohol, the precipitate thus resulting being insoluble in water. Peptones. — The result of the action of gastric and pancreatic secretions on albuminoids in the course of digestion. They are also produced by contact with animal and vegetable tissues (vegetable digestive ferments). They are considered as albumin hydrates, and their dehydration reproduces albumin coag- ulable by heat. They are soluble in water, insoluble in alco- hol, which precipitates them from their solutions. They are precipitated by mercuric chloride and nitrate, argentic ni- trate, lead acetate, tannic, picric and biliary acids, and by phospho-molybdic and phospho-tungstic acids. They are diffusible through animal membranes, and are pre- pared by digesting freshly precipitated fibrin with an acidulated (with HC1) solution of pepsin. When dissolved, the acid solu- tion is neutralized with sodic carbonate filtered, boiled and the filtrate again acidulated and then precipitated with alcohol, after which the result is dried below 30 . Globulins, as stated, are coagulable by heat, precipitated by alcohol, carbonic acid, and soluble in dilute solutions ( 1 per cent.) NaCl. Fibrinogen [Metaglobulin) occurs in the blood, chyle, lymph, and serous fluids, particularly in hydrocele and pericardial li- quids. It generates fibrin with fibrin ferment and coagulates at 52°-55°. It is insoluble in water or saturated solutions of NaCl or magnesic sulphate, but dissolves in dilute solutions of neutral salts and the dilute alkaline hydrates and their car- bonates. Prepared best from hydrocele-fluid, by mixing with about 10 parts of water, and passing carbonic anhydride through the mix- ture for half an hour, or by neutralizing with dilute acetic acid, or by precipitating with a mixture of alcohol and ether (3 to 1). 64 APPLIED MEDICAL CHEMISTRY. Fibrinoplastin, Paraglobulin is contained in the serum of blood after coagulation, in the pale corpuscles, in lymph, chyle, pus, serous fluids, connective tissue, and in the cornea. With fibrinogen, in the presence of fibrin-ferment, it forms fibrin, but it is not altered by fibrin-ferment alone, though fibrinogen is converted by fibrin-ferment into fibrin. Fibrinoplastin can be best prepared by diluting serum with 15 times its bulk of distilled water, adding a few drops of di- lute acetic acid (1-4), or the diluted serum may be precipitated by an excess of sodic chloride ; also, by passing a stream of carbonic anhydride through dilute serum for a half hour. After subsiding for 10-12 hours, the fine granular precipitate is washed with carbonic-acid water. Myosin, muscle-fibrin. Muscle juice is a yellowish, opales- cent, distinctly alkaline liquid, which coagulates at ordinary temperature, forming a jelly separating into myosin and acid- serum. The separation can be readily effected by addition of very dilute acids or solutions of NaCl stronger than 10 per cent. Vitellin, a white, granular substance, from the yolk of egg, very soluble in solutions of NaCl, and not precipitated by ex- cess, coagulates between 70 and 8o° ; soluble in dilute HC1 (1 in 1 odd) and weak alkalies; is precipitated by alcohol. Pre- pared by treating yolk of egg with water and ether as long as they are rendered yellow. The residue is treated with a 10 per cent, solution of NaCl, which dissolves vitellin, and on dilution with water slightly acidulated with acetic acid it is precipitated. Crystallin, or Globulin, from the crystalline lens. It is not precipitated by NaCl, is readily precipitated by alcohol, differs from fibrinoplastin by causing no coagulation with fibrin fer- ment; prepared by triturating the crystalline lens with washed sand, and dissolving the albuminoids from this with water. To separate paraglobulin pass a current of carbonic anhydride through the filtered liquid. Acid albumin (Syntonin, Albumose, Parapeptone). — It is a white gelatinous substance insoluble in water and sodic chlo- ride solutions, readily soluble in very dilute HC1 and dilute alkaline hydrates. It is precipitated when neutralized in the ALBUMINOIDS OR PROTEIN BODIES. 6$ presence of sodic or potassic phosphates, but not affected by boiling. It yields a precipitate with HN0 3 dissolving with an intense yellow color on heating. A purple violet color appears when a few drops of sodic hydrate solution are added to acid albumin, followed by a little dilute cupric sulphate solution. With Millon's reagent, in the absence of sodic chloride, it gives a red color. To make an acid albumin, treat serum or egg albu- men with HO, leave stand until blue color appears, then dilute with twice its volume of water. The precipitate is dissolved in water, neutralized with sodic carbonate, and the resulting precipitate washed with water. Syntonin is made by treating muscles with \ per cent, solution of HO. The filtered solution is saturated with sodic carbonate, and the precipitate washed with water. Alkali albumin is present in blood corpuscles, blood serum, chyle, muscle, pancreas, nerve tissue, lens and cornea. Alkali albumin contains no sulphur. It is not coagulable by boiling. On being neutralized, albumen is precipitated. Alkali albumin is made by treating egg albumen with potassic hydrate, having first pressed the egg albumen through a muslin strainer. Enough of the alkaline hydrate should be added to cause the formation of a fine jelly, which is cut up, tied up in gauze, and well washed with water. Casein, an albuminoid, found in milk, is considered by some as alkali albumin, but it contains sulphur and is coagulated by rennet. It is not coagulated by boiling but precipitated by many acids, in the excess of which it is soluble. Calcic chlo- ride, or magnesic sulphate, on boiling with casein, separates it from its solutions. On standing for some time, casein is con- verted into fat. To separate casein from milk, the latter should be diluted with ten volumes of water, and precipitated with acetic or hydrochloric acid, after which a current of carbonic anhydride is to be passed through it, filtered, and the coagulum washed first with alcohol, then with ether. Casein from human milk is best precipitated with magnesic sulphate to saturation at 30 C.j then treated with alcohol and ether, and the magne- sic sulphate finally separated by dialysis. Fibrin, a white elastic substance, insoluble in water, and di- lute solutions of Nad. It swells up in dilute acids, more so 66 APPLIED MEDICAL CHEMISTRY. than in alkaline solutions, and dissolves slowly in them. Thus obtained, it is coagulable by heat, and the coagulum can be dissolved in pepsin solutions. At 35 ° to 40 it is somewhat soluble in solutions of potassic nitrate and in 10 percent. NaCl and NaS0 4 solutions, the solutions being coagulable by heat, acids, and alcohol. With strong HC1 it forms a violet-colored solution. With KHO, it forms ammonia and potassic sulphide. Guaiacum paper is turned blue by being immersed in a solution of hydrogen peroxide containing fibrin. It is obtained by stirring fresh blood thoroughly, and washing the coagulum well with water, then with alcohol and finally with ether. It can also be obtained by treating hydrocele fluid with blood ferment. Blood ferment is readily made by digesting a washed blood clot in an 8 per cent, solution of sodic chloride and fil- tering. Coagulated albumins are the products of egg or serum albumen, which have been exposed to heat, or of the globulins or fibrin when suspended in water, and dissolved by saline solu- tions and then coagulated under the same circumstances, or by the action of alcohol on these bodies. Two forms are recog- nized, Metalbumin and Paralbumin, of which the latter is of pathological interest, as occurring in ovarian cysts. Amyloid Substance. Lardacein. A white amorphous sub- stance of pathological origin found in the brain, prostate, liver, spleen, kidneys and walls of bloodvessels. It is insoluble in water, alcohol, ether, dilute acids and alkaline carbonates. It is not dissolved by gastric juice at ordinary temperature. Soluble in strong HC1, from which it is precipitated as syntonin on addition of water. Boiled with dilute H 2 S0 4 it dissolves with a red color, and is decomposed by strong H 2 S0 4 into leucin and tyrosin. It dissolves in alkaline hydrates. Iodine stains it reddish-brown; iodized zinc chloride, red coloration; stained with iodine, and H 2 S0 4 added, it gives a blue or violet color. Aniline violet stains it reddish-pink. With Mil- Ion's reagent it gives a red color and the characteristic xanthoproteic reaction. To extract lardacein from an affected organ the vessels are removed as much as possible, the organ diminuted and washed in water and boiled, the residue is treated with alcohol and ALBUMINOIDS OR PROTEIN BODIES. 6j then with ether, after that it is boiled in alcohol acidulated with HO. Treat then with gastric juice at 40 until no more peptone or albuminoid comes off. The residue is then again boiled with alcohol acidulated with HO and washed with water when pure lardacein remains. As Protein derivatives leucin and tyrosin deserve mention here. • Leucin or amido-caproic acid C 6 H 13 N0 2 belongs to the amido-acids of the fatty series; it is found in the pancreas, spleen, thymus, salivary glands, lungs and brain. It is formed by decomposition of albumen and nitrogenized animal substances, on heating them with strong acids or alkalies, or by trypsic digestion or decomposition ; it is also synthetically obtained. Cheese on decomposition yields leucin. It is frequently accompanied by tyrosin in urine. It occurs in shining lamellae, is fatty to the touch, insoluble in ether and chloro- form, soluble in acids and alkalies, and combines with the salts of lead and silver. It sublimes unchanged, with the odor of amylamine, and condenses in woolly masses of thin rhombic plates, grouped in rosettes. It forms easily soluble salts with HO and H 2 So 4 and crystallizes from alcohol in crystals resem- bling cholesterin or in groups of needles radiating from a centre. It is sparingly soluble in cold, readily so in hot water. It can be detected in the urine by treating the residue after evaporation with boiling alcohol from which it crystallizes on cooling, when it can be recognized with the microscope. Another way is to treat urine with basic lead acetate, filter, and treat filtrate with H 2 S in excess; the lead sulphide is sepa- rated by filtration, and the filtrate evaporated over the water bath, when leucin and tyrosin will crystallize out. To separate the two treat with boiling alcohol, in which leucin is soluble but tyrosin not. Tyrosin C 9 H n N0 3 properly belongs to the amido acids of the aromatic series. It generally accompanies leucin in animal tissues, and is derived as decomposition product from proteids by oxidation; it has also been obtained synthetically. It occurs in long, fine, white, silky needles, grouped in rosettes or stellate bundles if obtained from water or ammoniacal solu- tions. It is sparingly soluble in cold, more so in hot water and 68 APPLIED MEDICAL CHEMISTRY. is almost insoluble in alcohol. When heated it turns brown and is decomposed, giving off an odor of phenol, but does not sublime. A watery solution boiled with Millon's reagent gives a red color and if concentrated a dark red precipitate. COLLAGENS. Though allied to albuminoids, these do not yield syntonin when treated with acids or dilute bases. When dissolved in hot water they solidify in jellies on cooling. The principal members of this group are ossein, gelatin and chondrin, while mucin and elastin are allied thereto. Ossein is the collagen of the bones and is probably identical with that of the other tissues. When dried bone is treated with 10 per cent. HC1, the calcic salts are dissolved and the ossein remains. By boiling with water it is changed into gelatin. It is dissolved by alkalies. Gelatin is the collagen of white connective tissues converted by the action of boiling water. It is amorphous, translucent, yellowish, almost colorless and tasteless, swells up in cold water and dissolves in hot water, cooling into a jelly. It is insoluble in alcohol and ether, but soluble in warm glycerin. It is decomposed by putrefaction, yielding leucin, glycosin, ammonia and fatty acids, but no tyrosin. By the action of HC1 or pepsin it is rendered diffusible. It yields leucin if boiled with KHO neutralized with H 2 S0 4 evaporated and extracted with boiling alcohol. Mercuric and platinic chlo- rides, tannic acid, alcohol and chlorine water precipitate gelatin, but it is not precipitated by alum. Chondrin is obtained from the cartilages by boiling, also from Cliondrogen by boiling this with water. The cornea also yields chondrin. It is a hard transparent yellowish sub- stance, insoluble in alcohol and ether, swelling up in cold and dissolving in hot water and alkaline solutions. It forms jelly on cooling from its watery solution. Decomposed by H 2 S0 4 it yields leucin, but almost no tryosin or glycosin. On being boiled for some time with HC1 or H 2 S0 4 , or when digested with gastric juice, it yields a substance resembling acid albumin and a nitrogenous body, chondroglacose, reducing the alkaline cupric solution. By oxidizing agents it is changed into COLORING BODIES. 69 gelatin. Chondrin is precipitated by dilute mineral acids, the precipitate being soluble in excess. Tannic acid produces opalescence but no precipitate. Alum yields a precipitate with chondrin soluble in excess. Mucin, classed with the albuminoids, contains no sulphur and exists in mucus, saliva, bile also in the swelling of mixcedema, etc. It is a yellowish viscid substance, swells up in water without dissolving, soluble in dilute HC1 (5 per cent.), in pancreatic juice, alkaline solutions; and insoluble in alcohol, ether, dilute acetic acid and gastric juice, and is not coagulated by heat. It gives a red color with Millon's reagent, and gives the xanthoproteic reaction, Elastin is a brittle yellowish substance obtained from yel- low elastic tissue. Soaked in dilute acetic acid it is elastic and fibrous. It contains no sulphur and is soluble with brown color in KHO solution which when neutralized with H^SOi yields a precipitate with tannic acid; with HN0 3 or H 2 S0 4 it dis- solves if warmed, and yields leucin but no tyrosin. With Mil- lon's reagent it gives a red color. Keratin the basis for epidermal growths such as hair, nails, horns, etc. It belongs to this class, though probably a com- plex of different other chemically defined bodies. It contains sulphur to a large extent, and loosely combined. It is insol- uble in alcohol and ether, soluble in alkalies, swells up in boiling water. With boiling dilute H 2 S0 4 or alkaline hydrates it yields aspartic and other volatile fatty acids and both leucin and tyrosin. COLORING BODIES. These are bodies to which organs, tissues, or liquids owe their characteristic color. Haemoglobin (Haemato-globulin, Hsemato-crystallin, Cru- orin, Erythrocruorin). A crystalline substance of complex com- position, containing iron, and forms the greatest part of the solids of the red blood corpuscle. It exists as oxy-haemo- globin and haemoglobin (reduced haemoglobin). These differ in color, the former being scarlet red and the latter purplish. They are distinguished by their absorption spectra, which in the former are two bands in D and E, while the latter shows only one broad band between D and E. It is insoluble in yO APPLIED MEDICAL CHEMISTRY. alcohol and ether, soluble in water and in alkaline solutions, and crystallizes in prisms or rhombic plates. It is not diffus- ible ; in its solutions it is decomposed on boiling, and reacts feebly acid. It gives the protein reactions ; alcohol and acids precipitate and decompose it. Nitric and nitrous oxides unite with haemoglobin, also H 2 S. Treated with dilute acid it splits into globulin and a ferruginous pigment hcematin (q.v.). Blood tests. — If to old oil of turpentine a little tincture of guaiacum is added, and to this a few drops of blood, a blue color will result. On the dry stain, it can be detected by wash- ing it with water, adding a few drops of ammonia which will not affect the color ; on boiling the washings will turn turbid, which disappears on the addition of a drop or two of KHO, the solution appearing green with transmitted and red with reflected light. Haematin, a derivative from haemoglobin, is a bluish-black amorphous substance insoluble in water and alcohol, but sol- uble in alkalies and their carbonates. It exists both in an oxi- dized and reduced condition. Its alkaline solution gives an absorption band at D of the spectrum which increases in with concentration towards C and E. The reduction of oxyhemo- globin furnishes an intermediate product, the hcemochromogen of Hoppe-Seyler, which is probably nothing more than reduced haematin, also giving a distinct absorption band in the spec- trum. In acid solutions haematin soon decomposes into hcema- toporphyrin. Haemin, a crystalline bluish-black or dark -brown body of metallic appearance, considered a haematin chloride, soluble in HC1 and H 2 S0 4 also in alkalies, and alkaline carbonates. BILIARY PIGMENTS. In the fresh normal human bile bilirubin is undoubtedly the only pigment present, while the others must be consided as de- composition products present in bile or biliary calculi. Bilirubin, C 16 H 18 N 2 O a (Bilpliaein Bilifulvin CholepyrrJiiri), is an orange-yellow amorphous body or reddish-brown crystalline substance considered as probably identical with hcematoidin, the blood-crystals from old extravasations. In its free state it is found in the bile, and in combination with alkaline earths, in hepatic calculi. It is, in its free state, soluble in chloroform, URINARY PIGMENTS. 7 1 benzole and carbon disulphide, but in its alkaline combinations it is not. It combines with soda, lime, baryta, etc. Treated with a mixture of HN0 3 and H 2 S0 4 it turns first green, then blue, violet, red and yellow. An alcoholic, ethereal, or chloro- form solution of bilirubin to which is added an alcoholic bromine solution (5 per cent.) or 20 per cent, solutions of chloric or iodic acids is turned, first green, then blue, violet, reddish-yellow, and is finally decolorized. Biliverdin, C 16 H 18 N 2 4 , a green amorphous powder, derived from an alkaline solution of bilirubin on standing or by the action of light. It is insoluble in water, ether, or chloroform, but soluble in alcohol, acetic acid, and alkaline solutions. It gives the same play of colors with HN0 3 as bilirubin. Hydrobilirubin [Urobilin, Stercobilin) C 32 H i0 N 4 O 7 found in bile and urine, but principally in faeces. An amorphous dark- brown substance, soluble in alkalies, acetic and sulphuric acids, alcohol, ether, and chloroform. Its solutions, which are reddish, do not show play of colors with HN0 3 . Bilifusin (C 16 H 20 N 2 OJ, a black substance obtained from old hepatic calculi in small quantity. It is sparingly soluble in water, ether, and chloroform, soluble in alcohol and alkaline solutions. Biliprasin (QgH^N^), from human gallstones and icteric urine. A black shining substance, insoluble in water and ether, soluble in alcohol and alkaline solutions. URINARY PIGMENTS. Urobilin [Hydrobilirubin), is already described above under the latter name. Urochrome, claimed byThudicum and Charles as a distinct amorphous dark -yellow body, soluble in water but less so in alcohol, ether, dilute acids, and alkalies. It is decomposed by boiling with dilute acids into Uromelanin, Uropittin and Omicholin. Indican. Uroxanthin [indigogen) a substance occurring in normal urine in smaller, but in larger quantities in pathological urine, especially in cancer of the liver, cholera, Addison's dis- ease, etc., etc. It gives urine an intense yellow color. If pres- ent in larger quantities it gives a white pulverulent precipitate ,~ 2 APPLIED MEDICAL CHEMISTRY. when boiled with HO, and on addition of a few drops sat- urated solution of chloride of lime it turns red, violet, green and blue. Normal amounts of indican will give on addition of 30-40 drops of urine to strong HC1, a red, violet or blue color, which will be intensified by addition of a few drops of HXO^ For its quantitative estimation see Urinary Analysis. Melanin, a black pigment occurring in the choroid, in the skin of the colored races, in the hair, the lungs and tumors. It is normally in granular form in the cells, but pathologically in flat rhombic plates with sharp angles. It contains iron, and in this respect is not unlike haematin, from which it is probably derived. DIGESTIVE FERMENTS. These are bodies influencing albuminoids or carbohydrates in a manner to change their chemical character, and render them diffusible instead of colloids. While there have been various ferments described as present in the animal organism, the principal ones are ptyalin, pepsin and pancreatin. Ptyalin is a substance contained in the saliva, possessing the property of converting starch into sugar. Though not an albuminoid, it bears close analogy to them. It resembles diastase in its property and characters, and the latter is usually substituted for it. When extracted from the salivary glands by glycerin and precipitated by alcohol it forms a white amor- phous powder, precipitable by the lead acetates, but not by nitric or tannic acid, nor the mercuric or platinic chloric Its pow^r of converting starch into sugar is greatest at 35 °— 40 ; if heated above 60 c it becomes inactive. Diastase ex- tracted with water and ether from bre east and precipi- tated by alcohol, or even in a watery infusion from malted barley, can, like ptyalin, convert boiled starch rapidly into sugar, but does so most actively at 6o°— 70 . Pepsin, the well-known digestive principle of the gastric juice. It is a nitrogenous body and gives no albumin reaction, a yellow or grayish amorphous powder, soluble in water, glycerin and acids, but insoluble in alcohol. From its watery solution it is precipitable by the lead acetates. It is devoid of peptogenic action unless in acid solutions. It changes under such conditions at from 37° to 38° albuminoids, collagens, e: ORGANIC AMINES AND AMIDES. 73 into diffusible peptones, which by L. Herman were considered as hydrated products thereof, but it does not act on keratin and carbohydrates. While small portions of sodic chloride favor its peptogenic action, it is precipitated by larger quantities thereof from its solutions. For its preparation its solubility in glycerin is taken advantage of, and from these solutions it is pre- cipitated by the addition of absolute alcohol. Pancreatin : The active substances in the pancreatic secre- tion are claimed to be three or four, according to the distinctive characters they exhibit. On extracting a pancreas which has been treated with alcohol by glycerin and precipitating the glycerin solution with alcohol, a substance is obtained which has been given the name of pancreatin, and is claimed to pos- sess all the functions exhibited by the pancreatic juice. Its principal component, capable of changing proteids into peptones in neutral and alkaline media is trypsin. Another is said to be the ferment curdling the casein of milk. A third, similar to ptyalin, and by Roberts termed pancreatic diastase, converts starch and glycogen into sugar and dextrin, while the emulsive ferment is capable of emulsifying fats and partially saponifying them. The pancreatic peptones obtained from trypsin are pre- cipitated by acids. ORGANIC AMINES AND AMIDES. Neurine or Choline, Bilineurine, C 5 H 15 NOo, a decomposition product of lecithin, obtained from the decomposition of prota- gon and lecithin in the brain, yolk of eggs and bile. It is a thick, syrupy liquid, soluble in water and alcohol. It prevents coagu- lation of albumen, redissolving this and fibrin when coagulated. It is alkaline and forms crystallizable salts with HC1. Urea, Carbamide , CON 2 H.t, generally considered as an amide of carbonic anhydride. CCk tjq Carbonic acid. CO \ y^y\ Carbamide. It is isomeric with ammonium cyanate, CN (CO)) I = H 2 VN 2 , ONH 4 Hj 6 74 APPLIED MEDICAL CHEMISTRY. which is readily converted into it. It is found in, the animal fluids and organs and is present in the blood normally in about ^-^ per cent., but in Bright's disease is found as high as ten times that amount. It forms the principal excretive substance of the urine, being present therein as high as from 2 to 4 per cent. It occurs in long flattened prisms, from alcohol in four- sided prisms, transparent with oblique ends. It is soluble in water and alcohol and melts at 130 , decomposing at higher temperatures. It forms compounds with acids, bases and salts. When a cold concentrated solution is treated with HN0 3 crys- tals of urea nitrate, CON 2 H 4 HN0 3 , are formed. If treated with oxalic acid a urea oxalate (CON 2 H 4 ) 2 C 2 H 2 4 , results. Mercuric nitrate forms compounds with urea, as also mercuric chloride. To prepare it treat urine evaporated to a syrupy consistency with HNO3, allow this to cool, then mix with baric carbonate and hydrate to saturation, precipitate these with carbonic anhy- dride, filter and crystallize from alcohol. When treated with alkaline hypochlorites or hypobromites urea is decomposed, CON 2 H 4 + 3C10Na = CO, + 2H 2 + 2N + 3ClNa, carbonic anhydride and nitrogen being liberated. With min- eral acids and alkaline hydrates urea is also decomposed, car- bonic anhydride and ammonia being liberated. For quantita- tive estimation of urea see Urinary Analysis. COMPOUND UREAS. Uric Acid,C 5 H 4 N 4 3 m.w. 1^8, found in small quantities in the urine, blood, spleen and other organs. It is a white crys- talline powder devoid of taste and smell. The crystals are of various forms ; as crystallized from urine they form rectangular or rhombic plates. They also appear as rhombic prisms, loz- enge and dumb-bell shaped or stellate ; as deposited from urine they are always colored. It is almost insoluble in water, alcohol and ether ; readily soluble in cold H 2 S0 4 , from which it is precipitated unchanged on dilution. It is also soluble in HNO3, also in NaHO and KHO; also in the alkaline solu- tions of lactates, acetates, carbonates, phosphates and borates to form neutral urates. It is decomposed by heat. By the UREIDS FROM URIC ACID. 75 action upon it of cold HN0 3 alloxan, alloxantin and urea are formed. On heating the mixture the former are changed into parabanic acid. When treated with HN0 3 to solution and NH 4 HO added to this and slightly heated, a fine purple color oi murexid or ammonium purpurate is developed (murexid test). In very small quantities the vapor of ammonia will answer. If treated with NaHO or KHO, instead of NH.HO in the forego- ing reaction, violet or blue will appear. If a solution of sodic hypochlorite is added cautiously to a solution of uric acid, a rose-red color is produced, which is extinguished by an excess of the hypochlorite. To detect uric acid in serum of blood or serous liquids, they are evaporated after acidulation with acetic acid, and a thread or fibre is immersed in the concentrated liquid and allowed to cool, when crystals of uric acid will adhere to the thread or fibre, and can be detected microscopically. As already stated, the alkalies dissolve uric acid and form salts with it. These are usually found in urinary sediments and calculi. As uric acid is bibasic it forms both acid and neutral' salts, of which the principal ones are : Amnionic urate, acid, C 5 H 3 N 4 3 (NH 4 ), sparingly soluble in water, soluble in warm HC1, from which the acid crystallizes on cooling. Sodic urate, acid, C 5 H 3 N 4 3 Na, occurs in urinary sediments and calculi of gouty persons. Calcic urate, acid (C^HgN^O^Ca, is found in urinary sedi- ments and calculi as chalkstones. UREIDS FROM URIC ACID. Alloxantin (mesoxalyl-tartronyldiurea), C & H 4 N 4 7 , forming rhombic tables, giving a transient blue coloration with ammo- nia and ferric chlorides. It forms a violet precipitate with baryta water and is prepared by treating uric acid with dilute HNO s . Alloxan (mesoxalylurea), CJrT 2 N 2 4 , a derivative of the former, obtained by treating uric acid with cold HN0 3 . It forms color- less crystals soluble in water and turns red on exposure. Murexid (ammonic purpurate), C 8 H 8 N 6 6 , shining green y6 APPLIED MEDICAL CHEMISTRY. four-sided tables, giving a red solution with water, turned blue by KHO. Parabanic acid (oxalylurea), C 3 H 2 N 2 3 , derived by oxida- tion of uric acid or alloxan by hot nitric acid. It comes in six- sided prisms, of acid taste, soluble in water and alcohol. Allantoin (glyoxyldiurea), C 4 H 6 N 4 2f found in the allantoid fluid, in small amounts in urine of the foetus and infant and after the use of tannic acid. It comes in colorless prisms slightly soluble in cold, more so in warm water. Boiling HN0 3 decomposes it into urea and allantoic acid, and alkaline hydrates into oxalic acid and ammonia. Related to uric acid are the following : Xanthin, C 5 H 4 N 4 2 , an ingredient of certain rare forms of urinary calculi, also found in small quantities in urine and in cer- tain glands and the brain; artificially prepared from hypoxan- thin, also from guanin. It is a white amorphous substance, soluble in boiling water, alcohol and ether. It is precipitated by acids forming crystalline salts. If dissolved in HN0 3 and evaporated it gives a yellow residue, turning reddish-yellow with KHO and violet on heating. Hypoxanthin, Sarkiii, C 5 H 4 N 4 0, found in the muscles, the spleen, pancreas, thymus, in the liver of yellow atrophy and in the blood and urine of leucocythaemia. It is closely related to uric acid and xanthin, and can be formed from either by reduction. Guanin, C 5 H 5 N 5 0. Originally found in guano and also pres- ent in the pancreas and liver. It is a white or yellowish amor- phous substance, odorless and tasteless, soluble in acids and alkalies, with which it forms compounds insoluble in water, alcohol and ether. Evaporated with HN0 3 it gives a yellow residue, turning dark yellow with KHO and NH 4 HO. Carnin, C 7 H S N 4 3 , a chalky-looking body, in microscopic crystals; sparingly soluble in cold, soluble in hot water, insol- uble in alcohol and ether. It is obtained from extracts of meat, but not from fresh meat. It forms a hydrochlorate with HC1, crystallizing in needles. AMIDO-ACIDS — BILIARY ACIDS. J*J AMIDO-ACIDS. Glycocin {glycin, glycocol, amido-acetic acid), C 2 H.N0 2 , a sweet substance derived from gelatin when treated with dilute H 2 S04. It is synthetically prepared by the action of mono- chloracetic acid on ammonia. It is found as compound with amine bases in the liver. It is also found in the urine with ben- zoic acid as Hippuric acid, benzoylglycocin, benzoylamido-acetic acid, C 9 H 9 N0 3 , a glycocin in which one atom, H, is displaced by benzoyl (C 6 H 5 CO). Principally found in the urine of herbi- vora, but also present in the urine of omnivora. It forms white needles or colorless prisms, is odorless, bitter, sparingly soluble in cold water, and less so when acidulated with HC1 ; boiling water and alcohol dissolve it. It reduces an alkaline solution of cupric sulphate. When heated it gives an odor of bitter almonds ; also when boiled with nitric acid ; it is distinguishable from benzoic acid by its non-solubility in ether. With ferric chloride it gives a brown precipitate, and heated with lime, benzene and ammonia. From urine it can be recovered by evaporation, acidulation with HC1, then crystallizing and purify- ing crystals with cold water and alcohol. BILIARY ACIDS. The salts of two acids are found in the bile; respectively, glycocholic and taurocholic acids, which form the principal hepatic secretions ; they are found as alkaline, principally sodic compounds, and as the products of fatty acids may be viewed as soaps, soluble with water and emulsifying fats and oils. They are both dextrogyrous. Glycocholic acid, QgH^NOg, is found in human bile and in small quantities in the blood and urine of jaundice. It crystal- lizes in transparent needles, is sparingly soluble in water, soluble in warm water and alcohol, almost insoluble in ether. Its re- action is acid and of sweetish bitter taste. With baric hydrate it splits into cholic acid and glycocin. It is soluble in H 2 SO it from which it is precipitated on dilution. It is monobasic, forming compounds with alkalies, alkaline earths, silver and lead. Its alcoholic solution is dextrogyrous = 29 . • yS APPLIED MEDICAL CHEMISTRY. Glycocholic acid, C 26 H 43 N0 6 , can be decomposed into cholic acid, C 24 H 40 O 5 , and glycocin, C 2 H 5 N0 2 , and taurocholic acid, C 26 H 45 NS0 7 , into cholic acid, C 24 H 40 O 5 , and taurin, C 2 H 7 NS0 3 . Sodic glycocholate, C 26 H 42 N0 6 Na, is found in bile, crys- tallizes in stellate needles, is soluble in water, but less so in alcohol, insoluble in ether, and is dextrogyrous = 25. J°. Taurocholic acid, C 26 H 45 N0 7 S, is also found as sodic tauro- cholate in the bile. In crystalline form it comes in silky needles, rapidly deliquescing, gradually changing into an amorphous mass. It is soluble in water and alcohol, insoluble in ether, is very bitter, and dextrogyrous in alcohol == 24.5 , in water 21.05 . It is very unstable, decomposing into cholic acid and taurin. It is not found in the urine of jaundice. Taurocholates are neutral, soluble in water and alcohol and crystallize with ether. Like glycocholates, they dissolve choles- terin and emulsify fats and oils. Cholic acid, C 24 H 40 O 5 , is a product of decomposition of the above two acids. Is said to occur in the intestines and faeces and in the urine of jaundice. It crystallizes in different forms from different solvents. Is slightly soluble in water, but readily so in alcohol and ether. Tests for Biliary Acids. — When treated with H 2 S0 4 they form a yellow solution, increasing in intensity and having a green fluorescence. Their solutions in water on addition of a small quantity of cane sugar and H 2 S0 4 at a temperature not exceeding 6o° gives a distinct cherry-red color, gradually changing to dark purple (Pettenkofer reaction). Drechsel proposes substitution of syrupy phosphoric acid for H 2 S0 4 to avoid the charring of the sugar. It is to be borne in mind that many other products of the animal organism give the same reaction, but the spec- troscopic examination of biliary acid solutions shows an ab- sorption band between D and E and a second on the red side of F. Taurin, C 2 H 7 NS0 3 , the decomposition product of tauro-cholic acid, is rich in sulphur, which by heating is apparent as sulphur dioxide. It crystallizes in transparent six-sided prisms, is not decomposed by boiling with dilute acids and alkalies, but de- composed by nitrous acid. CARBOHYDRATE- Other amido acids are : Kreatin. C t H 9 N 3 2 , a normal constituent of the liquid of muscles, brain, blood and amniotic fluid, crystallizes in trans- parent, colorless, oblique rhombic prisms, and when anhydrous hite and opaque. It is sparingly soluble in cold, more so in hot water, moderately soluble in alcohol, and insol- uble in ether. Upon heating for some time, or by the action of strong acids, it is converted into kreatinin. Barium hydrate decomposes it into sarkosin and urea. Kreatinin. C 4 H T N 3 0. — As already stated this is a product of dehydration of Kreatin, and normally found in urine, amniotic fluid, blood, and muscles. It is increased in fevers, and de- creased in anaemia, diabetes, and Bright's disease. Its crvstals are oblique rhombic prisms, soluble in water and hot alcohol, alkaline of reaction displacing ammonia from its salts, and forms double salts with platinum, zinc, etc. It can be precipi- tated from the urine by zinc chlori : Cystin C ri-XSCX. found in the kidneys and urine of children and young people. It is sometimes found in urinary calculi. It forms transparent, hexagonal, sometimes rhombohedral. plates. It is soluble in mineral acids, oxalic acid and alkaline hydrates, precipitable from the former by ammonic carbonate, and from the latter by acetic acid. It is insoluble in alcohol, water and ether. Burns with green flame and fetid odor. If heated with sodic hydrate on silver it gives a sulphur stain. Its diluted alkaline solution gives a rich violet color with potassic nitro- prusside. CARBOHYDRATES. Compounds of carbon, hydrogen and oxygen, containing six carbon atoms or multiples thereof, and the hydrogen and : xy gen atoms in the same proportion as in water. They cor. sist of three groups, the members of which are isomeric, respectively amyloses.^QH^Og); saccharoses, C^H^On; glucoses, QH Starch, amy lose ^ n QH 10 O 5 ), not found normally in the human organism, but one of its most important foods, is a der, consisting of the fecules of various plants, tubers and seeds. They differ in appearance according to the plants or parts thereof from which they are derived ; all, however, have 80 APPLIED MEDICAL CHEMISTRY. a central spot termed hilum with concentric lines according to the layers surrounding it. It is insoluble in water, alcohol, ether, and cold acids. If boiled with water the granules burst and form a gelatinous mass, soluble in water and termed hy- drated, which can also be effected by cold dilute alkaline solu- tions. As such it is dextrogyrous = 216 . It is a colloid, and to be absorbed must be converted into sugar, which is partly effected byptyalin and pancreatic diastase. This is also accom- plished by malt diastase and an infusion of malt containing it, as well as by warm solutions of HC1 and oxalic acid, which change it into dextrin and glucose. A solution of hydrated starch is precipitated by tannic acid as a yellow precipitate soluble by heat. Free iodine in solution produces a deep blue color with all forms of starch disappearing on heating and reappearing on cooling. Dextrin, a gum derivative of starch and intermediate between it and glucose, exists in the blood and organs of carnivora and herbivora. It is produced by heating starch to 175 , or boiling it with dilute H 2 S0 4 at 90 , or by partial action of diastase upon starch. It is a whitish-yellow powder, readily soluble in water, insoluble in alcohol, and is dextrogyrous = 138. 88°. With HNO3 it yields oxalic acid on boiling. With iodine it gives a red color, and when boiled with dilute HC1 it gives the glucose tests. Glycogen a yellowish-white body discovered by Claude Ber- nard in the liver. It has been met with in the blood and almost all organs. It is inodorous and tasteless, amorphous, and in- soluble in alcohol and ether. With water it swells up and forms an opalescent solution on heating, which is dextrogyrous to about three times the extent of grape sugar. In its character it much resembles dextrin, and, like it, forms glucose with dilute acids, ptyalin diastase, pancreatic diastase, and besides, with the glycogen ferment of the liver and tissues, and soluble albumi- noids. With potassic-iodide-iodine solution it gives a wine-red solution, which disappears on heating and reappears on cooling. With dextrin the latter does not take place. It does not reduce the alkaline cupric solution, but after boiling with a little HC1, ©r the action of the above ferments or soluble albuminoids, the glucose reaction is readily obtained. SACCHAROSES. 8 1 To prepare glycogen the liver of a freshly killed animal is promptly removed, minced and treated repeatedly with boiling water. The pulp is then expressed, and the infusion filtered through animal charcoal and evaporated to a syrupy consistency, and then precipitated with stronger alcohol. The precipitate may be purified by repeated precipitations, and finally dried. The liver ferment is made by depriving a fresh liver well minced first of its water by alcohol, and after removing this by extrac- tion with glycerin for several days. The ferment is destroyed by boiling. SACCHAROSES. Saccharose, Cane Sugar, C 12 H 22 O n . — A crystallizable saccha- rine substance found in many plants, but most generally derived from sugar cane and from sugar beets. As generally found it is white and crystalline, forming monoclinic prisms, which are larger or smaller according to the time consumed in crystallization. Its specific gravity is 1.606, and it dissolves in about one-third of its weight of cold water. Its solutions are dextrogyrous =73.8°. It forms compounds with alkaline earths ; does not reduce alkaline cupric solutions. By the action of warm dilute acids it is converted into dextrose and laevulose, while sulphuric acid chars it, sulphur dioxide being liberated ; glucose is not affected in this manner. Saccharose is not a nor- mal, constituent of the animal organism, and after ingestion is converted into glucose. It is fermentable only after being con- verted. Lactose, Milk Sugar, Lactine. — This is only found in the lacteal animal secretions, and is a saccharine body, specific gravity I.53, crystallizing in transparent prisms. It does not impart as sweet a taste as the other sugars, and is soluble only in six parts of cold water, the solutions being dextrogyrous = 59. 3 . It is more stable than saccharose, but by boiling with acids is converted into galactose. It reduces the alkaline cupric solutions and ferments after conversion into galactose. In its decomposition with casein it yields lactic acid and butyric acid, and by the pancreatic secretions it is changed into galactose. Maltose, a saccharine body derived from malt, and also by the action of diastase and dilute HC1 upon starch. Its dextro- 82 APPLIED MEDICAL CHEMISTRY. gyratory power is three times that of glucose. It is ferment- able and reduces alkaline cupric solutions. GLUCOSES. Glucose, Dextrose, Grape sugar, C 6 H 12 6 , a saccharine sub- stance largely distributed through the vegetable and animal organisms. It is found in the chyle, blood, liver, bile, lungs, and elsewhere, and pathologically in the urine, saliva, faeces, and sweat. It crystallizes only under very favorable conditions, and appears then as warty masses consisting of fine needles, or in different forms according to solvent. It dissolves in all propor- tions with hot water and in about one-third of cold water, and is soluble in alcohol. In taste it is less sweet than cane sugar, and is dextrogyrous = 57-6°. It dissolves in H 2 S0 4 without change of color, and with alkaline hydrates it turns brown. It reduces the alkaline cupric solutions on boiling. A solution of indigo slightly alkaline with sodic carbonate, when heated to boiling point with a solution of glucose, loses its blue color and turns violet and finally yellow, but recovers its blue color on cooling and agitation. Bismuth subnitrate, if boiled with a solution of glucose slightly alkaline w r ith a little sodic carbon- ate, is turned black. Picric acid and an alkaline solution of grape sugar will give a deep reddish-brown color. (For quan- titative determination of glucose see urinary analysis.) Inosit, muscle sugar, is found in the muscle of the heart, also in the blood, brain, liver, lungs, kidneys, etc. ; pathologically it has been found in hydatid cysts, in the urine of albuminuria and diabetes. It crystallizes in monoclinic tables and prisms, and from alcohol in lamellae resembling those of cholesterin. It is efflorescent, of sweetish taste, is readily soluble in water and very little soluble in cold alcohol, and is optically inac- tive. It is not changed by dilute acids or alkalies, is not fer- mentable, and does not reduce the alkaline cupric solutions. A solution acidulated with HN0 3 , and evaporated, if treated with ammonia and calcic chloride, produces a rose-pink color. Mer- curic nitrate gives a yellow precipitate with it, which turns red on heating, red color disappearing on cooling. ALCOHOLS. 83 ALCOHOLS. Ethylic alcohol, spirits of wine, C 2 H 5 HO, ethylic hydrate, a product of distillation from fermented grain, fruits, and other sources, containing glucose subjected to fermentation. It is a colorless, volatile liquid of characteristic odor, hot taste, of various specific gravities according to the amount of absolute alcohol, and has a specific gravity 0.7938. It burns readily, and boils at 78.5 °. It is miscible in all proportions with water without causing turbidity, and coagulates albuminous substances. When heated either with potassic hydrate or H 2 S0 4 it should not darken. With H 2 S0 4 and a dilute solution (one-third per cent) of potassic bichromate a green color is produced. Alcohol does not occur in nature as such, nor is it a product or part of the animal organism, though as a beverage it is of im- portance, and also on account of its physiological effects, and its poisonous effects when consumed in large quantities. While in dilutions with water it can be determined by its specific gravity, when mixed with food or solid ingredients these have to be subjected to distillation until exhausted, and the distillate after condensation must be determined as before mentioned. Glycerin, Propenyl alcohol, C 3 H 5 (HO) 3 , a triatomic alcohol, forming a colorless, viscid liquid, of acrid, sweetish taste, spe- cific gravity 1.26 at 15 , soluble in all proportions with water and alcohol, but insoluble in ether and chloroform. It is very hygroscopic, and a good solvent for many substances. Not met with in its free state as part of the economy, it is found in the intestines as a result of the splitting up of fatty bodies by pancreatic action. It is derived from fats and oils, with which it forms ethers termed glycerides. Cholesterin, Cholesteric-alcohol, C 26 H 43 HO. The only free alcohol which is part of the animal organism is a fatty body found in the brain, bile, blood, nerves, spleen, and forms the principal ingredient of biliary calculi. It is also found in the vegetable kingdom as well as in the yolk of egg and pathological growths. It exists in its crystalline state either with or without water and according to the solvents employed, crystallizes in silky needles from benzol, absolute ether or chloroform, or in rhombic plates from alcohol. It is soluble in hot alcohol, ether, 84 APPLIED MEDICAL CHEMISTRY. benzol, acetic acid and glycerin, slightly soluble in cold alcohol, and boiling water, and insoluble in cold water, alkalies, and dilute acids. Its specific gravity is 1.046; it is laevogyrous = 3 1.6°. It combines with the volatile fatty acids, and with hot HNO3 ^ forms cholesteric acid (C 8 H 10 O 5 ). Treated with a little HNO3 an d evaporated a yellow residue is formed, which turns brick-red on addition of NH 4 HO, which is not changed by KHO. Heated with a mixture of two parts HC1 and one of ferric chloride solution it turns violet Heated with a little H 2 S0 4 and a little iodine, colors are produced rang- ing from violet, blue, green, and yellow to brown. With H 2 S0 4 it is turned red, turning green on addition of water or chloro- form. VOLATILE FATTY ACIDS. Formic acid, CH 2 2 = C.HO.HO, is found in various organs and fluids of the body as well as in the secretions of red ants and other insects, also in various plants. It is obtained by the oxidation of organic substances, such as sugar, starch, fibrin, albumen, etc. It is a colorless liquid, of pungent taste and sharp odor, which vesicates the skin, and mixes with water in all proportions. Acetic acid, Acetyl hydrate, C 2 H 3 O.HO = CH 3 CO.HO, a col- orless liquid, solidifying in its strongest form below iy° into an ice-like body, glacial acetic acid. It is found in the juice of muscles, the spleen, bile and sweat, and the intestinal canal as result of fermentation. When the strong acid is brought in con- tact with the epiderm it destroys it and vesicates. When heated with H 2 SO • it can be recognized by its specific odor. With ferric chloride it gives a dark-red color, which is extinguished by excess of HC1. Propionic acid, C 3 H 6 2 = C 3 H 5 O.HO, a colorless liquid re- sembling acetic acid, found sometimes in the perspiration, in diabetic urine and intestinal tract, and said to occur in leukaemia and the dejections of cholera. Butyric acid, C 4 H 7 O.HO, a colorless liquid, of a penetrating odor of rancid butter, and acid taste, is found in the sweat, faeces, and urine, muscle juice, and in decomposing animal and vege- table substances. It occurs pathologically in the stomach, GLYCOLLIC SERIES. 85 urine, blood, fluid of ovarian cysts, and sputa of gangrene of the lung, often together with lactic acid. Caproic acid, C 6 H n HO. — An oily liquid contained in butter, and found in the faeces and perspiration. Valerianic acid, C 5 H 9 HO, occurs in several isomeric forms; it is an oily, colorless liquid, of penetrating odor, and sharp, acrid taste, soluble in alcohol and ether in all proportions, and slightly in water. It is often present in the faeces and the perspiration. Palmitic acid, Ethalic acid, C 16 H 31 O.HO, a solid, fatty body, crystallizing in white needles or scales, without odor or taste, insoluble in water, soluble in alcohol and ether, fuses at 62 °. It is sometimes met with in cheesy tubercles, and in sputa from gangrene of lung. Stearic acid, C^H^HO. — The most abundant of all fatty acids, forming the principal constituent of all animal fats. It is a white, odorless, and tasteless body, of scaly, crystalline structure, fatty to the touch, soluble in alcohol and ether. It is generally found, together with palmitic acid, in oleo-stearates but occurs free in the intestinal canal, being separated by pan- creatic action. GLYCOLLIC SERIES. There is only one of these that is of interest for the medical chemist, i. e. : Lactic acid C 3 H 6 3 , occurs in two, if not three isomeric con- ditions. Ethyline or isolactic acid, obtained from lactic acid fermentation, as met with in the intestinal canal, some glands, and nerve cells ; ethidene or para- also sarco-lactic acid, which is still doubtful, claimed to be present in the muscles ; and ordinary lactic acid, optically inactive lactic acid, the result of lactic fermentation from various sources. A syrupy, colorless liquid, of acid taste, specific gravity 1.2 1 2, miscible in all pro- portions with water, alcohol, ether, and glycerin. It cannot be distilled without decomposition. It is found pathologically in the blood of leukaemia and pyaemia, purulent discharges, in the urine after phosphorus poisoning, in the saliva of diabetes, and in yellow hepatic atrophy. 86 APPLIED MEDICAL CHEMISTRY. OXALIC SERIES. Oxalic acid (for properties, see " Chemistry of Poisons ") exists in the blood only as calcic oxalate, CaC 2 4 , and as such in urinary deposits and concreta. It is occasionally found in the mucous membrane of the uterus and gall-bladder, in the urine of chronic vesical catarrh, and in other catarrhal conditions. Succinic acid. QH 6 4 , crystallizing in colorless oblique rhombic prisms or plates, melts at 180 , and can be sublimed ; slightly soluble in water, more soluble in alcohol, little so in ether. It occurs in urine after ingestion of asparagus and malic acid fruits, in the spleen, thyroid and thymus, and in the fluid of hydroceles, hydatid cysts, and hydrocephalus. It forms as result of oxidation of the fatty acids. Neutralized with am- monia and treated with ferric chloride, it gives a reddish-brown flocculent precipitate, soluble in HC1. ACRYLIC SERIES. Of this, only one is of interest here. Oleic acid, C^H^C^HO, a monobasic acid, found in all the fats of the body. It is a light yellowish, oily substance, specific gravity 0.808, crystallizing at -4 , and melting at 14 . It has a characteristic odor and acrid taste, is soluble in alco- hol, ether, and benzin, insoluble in water. It absorbs oxygen rapidly, and turns yellow with a rancid odor and acid reaction in contact with the air, and is decomposed on exposure to heat, but can be distilled unchanged with superheated steam. With nitrous acid it forms an isomeric elaidic acid. GLYCERIDES, Palmitin, QH 5 (C 16 H 31 C0 3 , a tripalmitin, crystallizing in needles and plates, soluble in ether, fusing at 50 , and solidify- ing at 46 . It is one of the principal components of animal fats and formed largely in those of vegetable origin. Stearin, C 3 H 5 (C^H^CX^, a tristearin. The hardest, fatty substance of the body, obtained from animal fats of which it forms the principal constituent. It can be crystallized from SYLLABUS TO PART III. 8? its hot alcoholic solutions in brilliant quadrangular plates. It fuses at 68°, and solidifies at 6i°. Olein, C 3 H 5 (QgH^O^, a triolein. A colorless, odorless, tasteless, oily substance, found in all vegetable and animal fats from which it can be separated by first treating the fats with boiling alcohol, and freezing and filtering subsequently. It is soluble in alcohol and ether, insoluble in water; specific gravity, O.92. Amongst the glycerides must also be classed : Lecithin, a yellowish, white, somewhat crystalline powder, hygroscopic and fusible ; soluble in warm ether and alcohol, chloroform and benzole ; insoluble in water in which it swells up like starch, forming an emulsion precipitable with NaCL Dissolved in alcohol and acidulated with HO, it gives a yellow, flocculent precipitate with platinic chloride, and a white one with cadmic chloride. It is derived from nerve-tissue, brain, yolk of egg t semen, blood-corpuscles, serum, milk, bile, etc. It can be considered as a glyceride, in which a fatty acid radi- cal is displaced by phosphoric acid and neurin added to it. The lecithins are very prone to decomposition, yielding neu- rine, stearic, palmitic or oleic acids, and glycerophosphoric acid (C 3 H 9 P0 6 ). Protagon appears to be a glucoside of lecithin. It is found in the brain, the white substance of Schwann, in the blood, and elsewhere. In its decomposition, it yields glucose and the decomposition products of lecithin. It is insoluble in water, swelling up in it like lecithin, soluble in warm alcohol and ether, and is crystallizable in small fine needles. SYLLABUS TO PART III. (1.) Test a protein body by the alkaline cupric and xantho- proteic test. (2.) Prepare serum albumin and egg albumin, and show their respective reactions. (3.) Make a peptone, and precipitate by alcohol, mercuric chloride, tannic or picric acid. (4.) Prepare fibrinogen from hydrocele-fluid, also fibrinoplas- tin, and produce fibrin by mixing them with blood ferment. 88 APPLIED MEDICAL CHEMISTRY. (5.) Prepare acid albumin from albumen and from muscle as syntonin, and observe its reactions. (6.) Make alkali albumin, and show its properties. (7.) Make fibrin from blood and with blood ferment from hydrocele fluid ; test with guaiac paper and hydrogen peroxide. (8.) Show the stain of amyloid substance with iodine and anilin violet, also its reaction with Millon's test. (9.) Produce leucin, and observe its properties and tests, and its differential test from tyrosin. (10.) Make a solution of gelatin, and show its precipitation by tannin and absence of precipitate with alum. (11.) Show haemoglobin test with spectroscope, also test for reduced haemoglobin, also that of haematin. Show guaiac test for blood. (12.) Show test for bilirubin and biliverdin. (13.) Exhibit presence of indican in a specimen of urine. (14.) Show action of ptyalin by mixing saliva with starch solution, and heat to 35°-40°, and test for sugar. (15.) Test pepsin in acid solution for its digestive power on coagulated albumin and fibrin. (16.) Take an alkaline pancreatic solution, and test it for its power of converting starch into sugar, its peptogenic action on coagulated albumin or fibrin in alkaline solutions, its curdling action upon milk, and its emulsive power on fats. (17.) Crystallize urea from urine as urea nitrate, and observe its crystals. (18.) Treat uric acid with HN0 3 and NH 4 HO, and observe the forming of murexid. Test a solution of uric acid with a solution of sodic hypochlorite, and observe the rose-red color. (19.) Show the Pettenkoffer reactions for biliary acids on a specimen of bile. (20.) Make a starch solution, and show its precipitation by tannin, its reaction with iodine, and its conversion into sugar by a malt infusion. (21.) Test a specimen of glycogen with potassic-iodide-iodine solution, and observe red color. Prepare glycogen from liver. (22.) Dissolve a specimen of glucose in H 2 S0 4 , and note absence of coloration ; and also its change to brown on treat- ment with alkalies. Boil it with a dilute solution of indigo, URINE AND ITS ANALYSIS. 89 rendered alkaline by sodic carbonate ; on boiling, the color turns first red, then yellow, but returns after cooling and agita- tion. Boil with alkaline water containing bismuth subnitrate which will turn black. Test with alkaline solution of Picric acid, and note brown color. (23.) Acidulate a solution of inosit with HNO s , evaporate and treat with NH 4 HO, and note pink color. (24.) Treat cholesterin with HN0 3 , evaporate, and add to yellow evaporate NH 4 HO ; it will turn brick-red, and will not be changed by KHO. Heat with a mixture of 2HCI and 1 ferric chloride solution, and note violet color. Add to a little cholesterin a few drops of H,S0 4 , and note red color, which turns green on addition of chloroform. PART IV. EXCRETIONS AND CONCRETIONS. Urine and Its Analysis. Urine is, for diagnostic purposes, undoubtedly the most important of the human excreta. As the product of renal elimination, it contains normally the most of the waste-mate- rial separated from the blood in the process of regressive meta- morphosis, and abnormally a number of substances showing impaired physical action of the kidneys, or in other cases, superinduced by the latter condition, a retention of some of the excretory bodies which by their presence in the circulation produce pathic action. The physical process which constitutes the kidneys emunctories of the circulating fluids, is not to be considered here, but it is well to- bear in mind that the cellular membrane can only separate true solutions, and that others than those are products of a secondary process. Many of the com- ponents of urinary excretion have already been mentioned in 7 90 APPLIED MEDICAL CHEMISTRY. the previous part of this work, and others will appear in the further consideration of this subject For diagnostic purposes, it is necessary first to possess a knowledge of the normal com- ponents of urine ; secondly, to recognize the components result- ing from pathic conditions of the secernating organs ; and, thirdly, the adventitious components of the circulating fluids, whence components foreign to normal urine are derived. The normal urine exhibits properties which to a great extent are influenced by the general conditions of the system, the nutritive changes, and the condition of the circulating fluids. Thus, the quantity excreted depends upon renal activity and the condi- tions influencing the same. While an excretion of about 1200- 1600 c.c. is claimed to be the average amount voided in twenty- four hours by a healthy male adult, the quantity excreted by the female is held to be somewhat less. In both cases this is much influenced by cutaneous excretion, which by great activity may depress the amount to 400-500 c.c. in twenty-four hours, while through an increase in blood pressure, as in augmented dilution of the circulating fluid, the amount is proportionately increased. Again, the presence of sugar, salts, etc., favoring the osmotic process as well as psychical conditions, may vastly in- fluence the excreting power of the kidneys, as also the presence in the blood of substances foreign to the organism, such as med- icinal agents, which either by their influence upon the nervous system, or their effects upon the conducting vessels, may bring about changes in the volume of the excreted fluid. Whatever the variations of the quantity of urine under normal conditions, the amount of the excreta contained therein in solution should be about the same in twenty-four hours. It is of primary im- portance, therefore, in all examinations of urine, to determine the total quantities voided in certain periods under observation, or to establish the ratio of the solids contained in a certain amount of urine. This is easily accomplished by ascertaining the specific gravity of a specimen of all the quantities voided in twenty-four hours, after being duly corrected for the conditions influencing it. The manner of obtaining the specific gravity has been explained under another head, and is ordinarily ac- complished in connection with urinary analysis by either the specific-gravity vial or more readily by hydrometers and urino- URINE AND ITS ANALYSIS. 9 1 meters intended for this purpose, and ranging from 1000, the specific gravity of distilled water at a stated temperature, to 1040, the degree corresponding to the specific gravity for a liquid of that density obtained by other methods. By evaporating a number of specimens of urine, and weighing their solid ingre- dients in comparison to their specific gravity, an empyrical co- efficient was obtained, by the application of which the solids of a certain specimen of a known specific gravity can be readily determined. This coefficient is set down at 2.33 (but usually only 2 is employed), and a multiplication of this with the two numbers expressing the specific gravity from the right to the left, gives, accurately enough for practical purposes, the number in grams of the solid ingredients contained in 1000 c.c. of the specimen under examination, or better still, one-tenth of this will give the percentage of solids in a specimen of urine so examined. Thus, if the specific gravity of a sample of urine were found to be 1013 the amount of solids therein would be 13 X 2.33 = 29.69 grams in 1000 c.c, or 2.97 per cent., and if the amount voided in twenty-four hours were 1500 ex., the total solids thus excreted would be 44.53 grams. This, of course, is approxi- mate only, and apt at times to be fallacious, and, therefore, if accuracy is attempted, a certain volume of urine should be evaporated over the water bath to dryness, until no further loss is experienced at repeated weighings, and the residue left to cool under a dessicator and then determined. Abnormally, large amounts of urine, voided with a high specific gravity, invariably point to sugar contained therein, small amounts, with a low specific gravity would indicate renal disease, while con- centrated urine with diminished amount of solids for the twenty- four hours are observed after copious perspiration, diarrhoeas, and emesis. A small volume of urine, voided with low specific gravity, is also found in chronic affections, and towards the fatal end of many diseases, where vital metamorphosis is de- pressed. The average distribution of the solids, according to their chemical characters in normal urine, has been ascertained by J. Vogel, from a large number of examinations, of which he gives the following as average : 92 APPLIED MEDICAL CHEMISTRY. In Twenty-four Hours. Volume, 1500 Specific gravity, ......... 1020 Water, H'O Solids, 60 Urea, 35 Uric acid, .......... 0.75 Sodic chloride, ......... 16.5 Phosphoric acid, . 3.5 Total of earthy phosphates, ...... 1.2 Ammonia, .......... 0.65 Sulphuric acid, ......... 2.0 Free acids, .......... 3. The color of the urine is variable and depends on the dilution thereof by the volume of water as well as on certain abnormal, or the excess of normal, products it contains, as also on the presence of adventitious matter, such as medicinal agents therein. It may appear in all shades from pale yellow, red- brown to brownish-black, and these shades may often serve as an indication for diagnostic purposes. Thus pale yellow would point to affections where the volume of water is largely in- creased, as in diabetes as well as in hysteria and after epileptic attacks, and would certainly exclude the existence of an acute febrile process, while the dark urine appears after heavy meals and exercise, copious perspiration and also in acute fever processes. Red and reddish-brown urine would point to the presence of coloring matter from the blood, yellowish-green to j» biliary pigments, brownish-black to Melanosis, while occa- sionally a blue coloration may appear due to indigo. The influence of certain medicinal agents on the urine is quite char- acteristic, senna and rhubarb produce a yellow color turning red with alkalies and yellow with acids, while gallic acid and car- bolic acid render it dark-brown to black. In its normal condition urine is always clear and any turbidity must occur subsequent to secernation. Turbidity may be occasioned by oversatura- tion and crystallization at a lower temperature, as with uric acid or urates, or from a change from the acid to the alkaline condi- tion, also from admixture of mucus, epithelium, blood, pus, etc. When shaken, its froth should rapidly disappear, unless it contains albumen. Its odor is specific and is changed by de- •composition to ammoniacal, and by various foods or by medi- ANALYSIS OF URINE INORGANIC CONSTITUENTS. 93 cinal agents which may give it characteristic odor, as in the case of turpentine, etc. In reaction, normal urine is acid or neutral, occasionally' answering both acid and alkaline tests The acidity is due to sodic and potassic acid — phosphates and also probably to acid urates as well as free uric, carbonic and hippuric acids. Its reaction is also influenced by certain con- ditions such as fasting or by vegetable diet which render it slightly alkaline. It undergoes a so-called fermentation in- creasing for some days in acidity and subsequently turning alkaline. The alkalinity of urine is due either to ammonic or sodic carbonate or disodic phosphate. To determine the de- gree of acidity of urine, the rules laid down under the head of acidimetry should be applied (q.v.). The normal constituents of urine may be divided into inor- ganic and organic. The former are chlorides, sulphates and phosphates of sodium, potassium, ammonium, calcium and magnesium, also iron in combination, silicic, nitric and nitrous acid in combination with the above and hydrogen peroxide. The organic constituents of normal urine are urea, uric and hip- puric acids, xanthin, hypoxanthin, kreatin and kreatinin, oxalic, oxaluric, lactic, glycerophosphoric, benzoic, succinic, phenol- sulphonic, indoxylsulphuric and skatolsulphuric acids, also urinary pigments and sugar. The free gases present according to Planer amount at an average to about 5 c.c. in 100 c.c. of urine, of which carbonic acid forms 87.53, nitrogen 11.22, and oxygen 0.62 per cents. ANALYSIS OF URINE. After duly noting the quantity and color of urine voided in 24 hours and obtaining its reaction by means of either litmus or turmeric paper, the specific gravity is ascertained and the amount of solids computed therefrom ; any sediment present is then separated by decantation and the urine itself filtered. INORGANIC CONSTITUENTS. Sodic chloride — To determine this qualitatively add, with pipette, argentic nitrate solution which will give a heavy curded precipitate of argentic chloride and phosphate ; on addition of HNO3 the argentic phosphate is redissolved and the chloride 94 APPLIED MEDICAL CHEMISTRY. can be separated and confirmed by its solubility in NH 4 HO and by gradually assuming a darker color when exposed to sunlight. The amount of NaCl excreted in the urine in 24 hours should be about 10 to 15 grams in adult persons. It is normally increased after meals and by exercise and copious draughts of water, also proportionately with its ingestion. In inflammatory exudative affections the chlorides are diminished in the ratio of the progressive inflammation, reaching often at its height -fe of the normal quantity or disappearing even almost entirely. In renal affections accompanied by albuminuria the amount of NaCl is always diminished as well as in dropsy and ascites, also in chyluria, typhus and recurrent fevers, and it is totally absent in cholera. For the approximation of the quantities of chlorides present in urine, a small quantity of it is acidulated with HN0 3 , to pre- vent the precipitation of silver phosphate and then, drop by drop, the argentic nitrate solution is introduced until no further precipitation takes place, and the amount of silver chloride so formed is then estimated according to the density of the pre- cipitate. Quantitative determination of NaCl in urine. Several methods are in vogue for this purpose but the simplest and perhaps also the most correct is that of Mohr as modified by Neubauer. The former depends upon the use of mercuric nitrate and the latter of argentic nitrate solution, which precipitates the sodic chloride first and the phosphates afterwards, a solution of neu- tral potassic chromate being used to indicate when the chlorides have been precipitated. The argentic silver solution is made by dissolving 29.075 grams of pure fused argentic nitrate in 1000 c.c. distilled water, so that I c.c. of this solution corresponds to 0.01 NaCl. The solution of neutral potassic chromate is simply saturated. Urine that is not too highly colored, can be titrated by the above solution directly by diluting 10 c.c. urine with water to 100 c.c, a few drops of the chromate solution being added. The argentic nitrate solution is then dropped into it from a burette until a be- ginning orange tint indicates the completion of the chloride pre- cipitation. As the beginning of the orange tint already indicates an excess of argentic nitrate, 1 c.c. should be deducted when reading off the latter. INORGANIC CONSTITUENTS. 95 In highly colored urine containing many organic compounds these should be removed as follows : I to 2 grams potassic nitrate are added to io c.c. urine in a platinum or porcelain dish, and the contents evaporated to dryness. The dry residue is incinerated and allowed to cool and is then dissolved in 20 to 30 c.c. water and filtered. It is then slightly acidulated with di- lute acetic acid ; a few drops of the chromate solution is then added and the solution titrated with the argentic nitrate solution as above. Phosphates — Phosphoric acid is contained in the urine, partly combined with alkalies, partly with alkaline earths and also -in the organic ingredients as glycerophosphoric acid and lecithin. The normal amount of phosphates excreted in 24 hours is about 2 to 5 grams, of which about 2 /^ are of the alkalies and 1/3 of alkaline earths (calcium and magnesium). While the phosphates are diminished by starvation they are never totally absent like the chlorides. In febrile conditions they are diminished and increase with convalescence; while in meningitis the earthy phosphates are increased, also in osteomalacia, rachitis, and chronic rheumatism ; in renal affections they are diminished, and said to be totally absent in acute atrophy and cirrhosis of the liver. The phosphates of the alkalies are not precipitable from their solutions by alkalies, but by magnesium sulphate or calcic chloride. The phosphates of the alkaline earths are kept in solution in the urine by the weak acids, carbonic, etc., and pre- cipitated therefrom by NH 4 HO or KHO. The triple phosphate, ammonio-magnesic phosphate (NH 4 MgP0 4 -j- 6H 2 0), of characteristic microscopic crystalline struc- ture, occurs in urine as a consequence of decomposition and liberation of ammonia. Qualitatively the phosphates in the urine can be shown by precipitation with baric chloride or nitrate after neutralization of the acid phosphates. By precipi- tation of the chlorides first in presence of neutral potassic chro- mate with argentic nitrate, and separation of the argentic chloride and chromate the phosphates can be precipitated from the filtrate by further addition of the argentic nitrate. Am- nionic molybdate precipitates phosphates as a yellow fine pre- cipitate, if slightly warmed. By treating urine with a mixture g6 APPLIED MEDICAL CHEMISTRY. of magnesic sulphate I part, water 8 parts, ammonic chloride I part, and ammonia 44 parts, all the phosphates can be sepa- rated as triple phosphates. . The quantitative determination of the phosphates in urine is accomplished by means of a standardized solution of uranic acetate in the presence of an acidulated solution of sodic acetate with potassic ferrocyanide as indicator; this shows any uncom- bined uranic acetate as a chocolate colored precipitate. The solutions necessary are, the standardized solution of uranic ace- tate, 20 c. c. of which should correspond to 50 c. c. of the sodic phosphate solution (10.085 in 1000 c. c. water) equal to 0.1 grams P 2 5 , the litre of the uranic acetate solution to contain 20.3 grams uranic oxide; a solution of 100 grams sodic acetate and 100 c.c. acetic acid in iooo c.c. water, and a saturated solution of potassic ferrocyanide. To determine the P 2 5 in the urine add 5 c. c. of the sodic acetate solution to 50 c. c. of urine ; heat to boiling point and add from a burette the standardized solution of uranic acetate, stirring after each addition, and test- ing a drop on a porcelain slab with the indicating potassic ferro- cyanide solution, continuing as long as a precipitate results and until a chocolate-colored test with the potassic ferrocyanide is obtained. As 20 c. c. of the uranic acetate solution correspond to 0.1 grams P 2 5 , 100 c. c. will be equal to 0.5 grams, and each c. c. of the uranic solution will indicate 0.005 P 2 5 . Thus if 13.5 c. c. of the uranic solution have been consumed to saturation, the amount of P 2 5 contained in the 50 c. c. of urine is 13.5X0.005 = 0.067 grams or 0.135 P er cent. To obtain the amount of P 2 5 in the earthy phosphates of a specimen of urine, a certain volume is rendered alkaline with NH 4 HO, the deposit, after twenty-four hours dissolved in acetic acid and titrated as above; the amount so formed and deducted from the total amount of P 2 5 formed gives the quantity of P 2 5 combined with alkalies. The sulphuric acid excreted in the urine is found in two differ- ent forms, as sulphates of the alkalies and of the aromatic organic bases. The former comprise about 90 parts of the total amount so excreted and the latter 10 parts, the total amounting to about 2.5 to 4 grams in 24 hours. As the sulphates are derived princi- pally from the albumins, the amounts excreted would be in- ORGANIC CONSTITUENTS. 97 creased in febrile processes and will diminish with convalescence or the falling off of albuminous food. Abnormally it is in- creased in urine by ingestion of sulphur compounds, phenol, thymol, liquor potassse, and in delirium tremens ; it is dimin- ished in leukaemia, diabetes mellitus, eczema, and chlorosis. If carbolic acid is taken in large quantities the sulphuric acid of the alkalies is present as potassic phenylsulphonate, and as such is not precipitated by baric chloride. The presence of sulphuric acid compounds in urine can be ascertained by treating urine acidulated with acetic acid with baric chloride, which gives a precipitate of baric sulphate. It can be made to show in two successive stages the organic and inorganic sulphates. Quantitatively sulphuric acid as sulphates of inorganic and organic bases may be determined together and again the latter singly, giving the difference between the two by the gravimetric method, by first precipitating the neutral and subsequently the acidulated urine, separating the first precipitate and then pre- cipitating and weighing the precipitate from the filtered liquid. By acidulating and precipitating at once with the baric solution the total sulphates are obtained. Volumetrically it is determined by a standard baric chloride solution containing 30.5 grams in 1000 c. c. One c. c. of this is equal to 0.0 1 grams S0 3 . 100 c. c. urine are acidulated with a little HC1 and boiled, and the baric solution is allowed to flow in gradually, time being allowed for the precipitate to subside after each addition. Excess of baric chloride must be carefully avoided. As 1 c. c. of the baric solu- tion is equal to 1.01 grams S0 3 , 20 c. c. of the standard solu- tion necessary for complete precipitation would indicate 0.2 grams in 100 c. c. urine or 0.2 per cents. ORGANIC CONSTITUENTS. Urea — The' final product of the eliminative process of most of the nitrogenous material of the body, of which about 30-40 grams are excreted in 24 hours by a healthy male adult. Women eliminate less and children relatively more. As al- ready stated elsewhere, it is found in the blood, chyle, liver, glands, but not distinctly shown to occur in the muscles. It has been also detected in the ejecta, saliva, pus and milk during 98 APPLIED MEDICAL CHEMISTRY. renal inaction, as well as in the dejecta of cholera. Its deter- mination is one of the most important diagnostic aids to ascertain the albumin decomposition in various affections, as in inanition, fevers, etc. It is increased in typhus, pneumonia, diabetes, also in acute febrile affections and phthisis, while it is decreased in profuse perspiration, diarrhoea, cholera, the last stage of Bright's disease, cachectic states, gout and chronic rheumatism, in neuroses, melancholia, hysteria, and in hepatic affections, especially yellow atrophy. Crystallized from water it appears in silky needles ; if HN0 3 is added, rhombic and hexagonal plates of urea nitrate are formed. It produces a white curdy precipitate with mercuric nitrate, which in the presence of sodic bicarbonate is turned yellow as soon as all the free urea is precipitated and mercuric nitrate is in excess. The solutions of sodic hypobromate or hypochlorite decompose it, without heating, the former more rapidly than the latter, nitrogen being liberated and the carbonic anhydride is ab- sorbed. Nitrous acid will have the same effect. Oxalic acid forms urea oxalate similar to the nitrate. To demon- strate urea in urine condense the latter by evaporation, treat with alcohol, evaporate alcoholic solution, and into the aqueous solution of the residue introduce a thread with one end protruding. Touch the end of the thread with HN0 3 or oxalic acid and observe the crystals forming on both sides of the thread. Albuminous urine should be first freed from albu- men by boiling. If to concentrated urine an equal volume of HNO3 * s a ^ded, the nitrate of urea will soon be found to crys- tallize. To separate urea from blood, difibrinate with several volumes of alcohol, evaporate the alcoholic solution and dis- solve residue with water. Precipitate the phosphates with baric hydrate, filter and remove excess of baric hydrate with carbonic acid. Test the filtered liquid with HN0 3 , or oxalic acid, or mercuric nitrate, as above. The volumetric determination of urea can be accomplished by several methods, depending on some of the above reactions; the precipitation with mercuric nitrate, being known as the Liebig's process, is, however, open to errors and now generally abandoned for the hypobromite or hypochlorite process above indicated. ORGANIC CONSTITUENTS. 99 The hypobromite solution used in this process should be pre- pared as needed in the following manner : ioo grams sodic hydrate are dissolved in 250 c.c. of water, and when cooled 25 c.c. bromine are mixed with it. This allows for an excess of sodic hydrate to absorb the carbonic anhydride liberated along with the nitrogen. The apparatus necessary consists in a flask of about 75 c.c. capacity, with a sufficiently wide neck to admit a test tube of about 15 c.c. The flask is well closed by a gum stopper, per- forated and containing an india-rubber tube connected with a burette of 50 c.c. capacity, suitably subdivided. The burette ends on top in a drawn out, open point, to which the said tube is con- nected, and is open at the bottom, floating in a cylindrical glass, with water, long enough to contain the entire burette. To con- duct the operation the test tube is filled with about 5 c.c. of urine to be examined, while surrounding it in the containing flask are 25 c.c. of the hypobromite solution, or 50 c.c. of sodic hypochlorite solution, the solution of chlorinated soda of the U. S. Pharmacopoeia. The india-rubber tube attached to the burette is then temporarily removed to allow the burette to fill with water to o.c.c, and this to be on a level with the water in the cylinder, when the india-rubber tube is again attached. By canting over the flask containing the hypobromite solution the urine is allowed to gradually flow into the former, and amidst effervescence the nitrogen is now liberated and displaces the water of the burette. After all the urine has thus been mixed with the hypobromite solution and the test tube well rinsed out and the solution well shaken, the apparatus is left to assume the surrounding temperature, when, by bringing the level of the water in the burette to the level of the water in the cylinder, the amount of nitrogen liberated can be read off and noted. Each c.c. of nitrogen so obtained represents 0.0027 grams of urea, if the temperature were o°C. and the barometric pressure 760 mill. For ordinary purposes the product of the multipli- cation of the number of c.c.'s of nitrogen developed with O.0027 would give the amount of urea contained in the 5 c.c. of urine, but when accuracy is attempted due correction should be made for temperature and barometric pressure, else a vitiation of about 10 per cent, of the result obtained will be occasioned. 100 APPLIED MEDICAL CHEMISTRY. How to compute the corrections for these factors has been shown under the head of Stoichiometry, but a much easier plan is to correct it from the table of Dietrich, found below, giving the weight of I c.c. nitrogen at the respective temperature en- tered from the right and barometric pressure entered from the top. As it has been shown that the weight of nitrogen repre- sents 2.14 times the weight of urea, it is only necessary to com- pute the amount of nitrogen measured into its weight, corrected for temperature and barometric pressure, and multiply this with 2.14 to obtain the correct result. Weight of one C. C. Nitrogen in Milligrams. u 3 « u V Barometric Pressure. s 720 722 724 726 728 730 732 734 736 738 74o 742 744 IO° 1. 1338 1. 1370 1. 1402 1 -1434 1 .1466 1 .1498 1. 1529 1.1561 IJ 593 1. 1625 1. 1657 1. 1689 1.1721 u u 1. 1288 1 .1320 I-I352 1.1384:1.1415 1.1447 1. 1479 1.1511 1. 1542 1. 1 574 1. 1606 1. 1638 1 .1670 I2 U 1. 1237 1 .1269 1.1301 1.1333I1.1364 1. 1396 1.1428 1.1459 1.1491 1. 1573 1. 1554 1.1586 1.1618 I3 U 1.1187 1.1219 1.1251 1 .1282 1 . 1314 1.1345 1. 1377 1. 1409 1. 1440 1. 1472 1. 1503 1. 1535 1.1566 14- 1.1136 1.1168 1. 1200 1.1231 1.1263 1. 1294 1.1326 1. 1357 1.1389 1 .1420 1 .1452 1. 1483 I-I515 i5 u I .1085 T . I II7 I . I I49 I.Il8o T .1211 1.1243 1. 1274 1. 1305 1. 1337 1. 1368 1. 1399 1.1431 1. 1462 ib u I . IO34 I. I066 I. IO97 I.II28 I.Il6o 1.1191 1. 1222 1. 1253 1. 1285 1.1316 1. 1347 1. 1378 1. 1409 1 7 I.0983 I.IOI4 I. IO45 I .IO76 I.IIO7 1.1138 1. 1170 1.1201 1. 1232 1. 1263 1 .1294 1-1325 I-I356 1 8° I.O93O I. 0961 I.0992 I . 1023' I .IO54 1. 1085 1.1117 1. 11 48 1. 11 79 1 . 1209 1 . 1241 1. 1272 1. i3°3 19° 1.0877 1.0908 1.0939 1.0970 I.IOOI 1. 1032 1. 1063 1.1094 1.1125 1.1156 1.1187 1.1218 1. 1248 20° I.0825 I.0855 1.0886 1. 0917 1.0948 1.0979 1. 1009 1. 1040 1.1071 1.1102 1. 1133 1.1164 1.1194 2I U I .O77I I.0802 1.0832 1.0863 1.0894 1.0924 1.0955 1.0986 1.1017 1. 1047 1. 1078 1. 1 109 1.1139 22 U I. O7I7 I.O747 I.O778 I.0808 I.0839 1.0870 1.0900 1.0931 1. 0961 1.0992 1. 1023 1. 1053 1 .1084 23 U I.0662 1.0692 1.0723 1.0753 1.0784 1. 0814 1.0845 1-0875 1.0906 1.0936 1.0967 1 .0997 1. 1028 2 4 U I.0606 I.0636 I.0667 L0697 I.O728 1.0758 1.0789 1. 0819 1 .0849 1 .0880 1 .0910 1 .0940 1 .0971 25° I.O55O 1 .0580 1. 0610 1. 0641 1. 0671 1. 0701 1.0732 1.0762 1.0792 1.0823 1.0853 1 1 1 1 ! 1.0883 1. 0913 ■u 3 rt u 1) Barometric Pressure. s 1) H IO° 746 748 750 752 754 756 758 760 762 764 766 768 770 1. 1753 1. 1785 1.1817 I. 1848 1. 1880 1 .1912 1-1944 1.1976 1 .2008 1 . 2040 1 .2072 1. 2 104 1. 2136 II U 1.1701 I-I733 1. 1765 I.I7I7 I .1829 1. i860 1. 1892 1. 1924 1. 1956 1 . 1988 1. 2019 1. 2051 1 .2083 I2 U 1.1649 1.1681 1-1713 1.1744 I. I776 1. 1808 1. 1839 1.1871 1 . 1903 1 . 1934 1 . 1966 1 . 1998 1 .2029 13" 1 . 1598 1 . 1630 1.1661 I. 1693 I. I724 1. 1756 1.1787 1.1819 1.1851 1. 1882 1.1914 1. 1945 1. 1977 i4 u 1. 1546J1. 1577 1 . 1609 1. 1640 I. 1672 1. 1703 I-I735 1. 1 766 1.1798,1.1829 1.1861 1. 1892 1. 1923 15° 1. 1493 1.1525 1. 1556 I. I587 I.1619 I.165O 1.1681 i.X7 J 3 1. 1744 1. 1775 1. 1807 1,1838 1. 1869 16° 1.1441,1.1472 1-1503 1. 1534 I. I566 I. I597 1 . 1628 1. 1659 1.1691 1.1722,1.1753 1. 1784 1.1816 17° 1. 1397 1.1419 1-145° i. 1481 1.15x2 x. 1543 1.1*74 1. 1605 1. 1636 1. 1667 1. 1699 1. 1730 1.1761 1 8° 1. 1334. 1. 1365 1. 1396 I. I427 1.1458,1.1489 1.1520 I-I55I 1. 1582 i.i6h 1. 1644 1. 1675 1. 1706 x 9 o 1 .1279 1.1310 1.1341 I. I372 I. 1403' I. I434 1. 1465 1. 1496 1. 1527 1. 1558 1. 1589 1. 1620 1. 1650 20° 1. 1225 1. 1256 1. 1287 I.I318 I. 1348 1.1379 1. 1410 1.1441 1. 1472 1. 1502 1. 1533 1. 1564 1 -1595 2I U 1 . 1170 1 . 1201 1 .1231 I. I262 I. 1293 I . 1324 I-I354 1. 1385 1.1416 1.1446 1. 1477 1. 1508 L^ 220 1.11x5 i-"45 1.1176 1.1206 i.i237 | i.i268 1.1298 1. 1329 1.1359 1.1390 1.1421 1.1451 1.1482 23° 1. 1058 1. 1089 1 .1119 1.1150 1.1180 1.1211 1. 1241 1. 1272 1.1302,1.1333 1. 1363 1. 1394 1. 1424 24 u 1.1001,1.1032 1 . 1062 1 .1092 1. 1 123 1. "53 1.1184 I . 1214 1.1244^.1275 1. 1305 1. 1336 1. 1366 25 u 1.0944 1.0974 1 .1004 1. 1035 1. 1065 1 • 1095 1.1126 I.II56 1.1186 1.1216 1. 1247 1. 1277 1 1 . 1307 ORGANIC CONSTITUENTS. IOI Thus if 5 c.c. of urine yielded at 25°C. temperature and 750 mill, barometric pressure, 16 c.c. nitrogen, one c.c. would weigh, under these circumstances, 1.1004 milligrams. This multi- plied by 16 would give 17.6 milligrams nitrogen obtained, and would correspond to 2.14 times that weight of urea = 37.664 milligrams urea in 5 c.c. urine, or 20 times that amount would give the percentage 0.75 of urea found in the urine; or in an average yield of urine of 1200 c.c. in 24 hours, the amount of urea excreted in that period would be 12 X 0.75 = 9.00 grams. As the hypobromite solution is at best an unstable preparation, the sodic hypochlorite solution (solution of chlorinated soda), on account of its greater stability and equal efficacy in double the quantity, can readily be employed, and as it is found of good quality in the market, the latter would recommend itself for physicians' use in ureometry. Uric acid is found normally in the urine in quantities vary- ing from 0.5 to 2 grams in 24 hours, and next to urea it is that excretive substance which eliminates most nitrogen from the blood. Normally it is found in the urine with urea in a pretty constant proportion of 1 to 45, in solution with disodic phosphate, with which it combines to acid — sodic urate and monosodic phosphate. As it is soluble only in 18,000 parts of cold and 15,000 parts hot water, uric acid is at times found in the bladder in concrete form. Abnormally uric acid excre- tion is increased in febrile conditions, with impairment of the respiratory functions, chronic emphysema, leukaemia, indiges- tion, eczema. It is diminished by the free use of sodic chlo- ride and water, large doses of quinine, potassic iodide, sodic sulphate and carbonate, and lithic carbonate, etc., also in gouty and chronic diseases as a rule. Qualitatively uric acid can be determined by taking a quan- tity of urine (deprived of albumen if any were present), evapo- rating to dryness over water bath and depriving it of the urea and extractives by alcohol. The residue, containing uric acid, mucin and fixed salts, is treated with a few drops of HNO ;i , so that it will dissolve, then is evaporated until a reddish-yellow residue remains ; if touched with a drop of ammonia, it gives a splendid purple-red color, or if KHO or NaHO is used in its place, a purple-blue is obtained (murexid test). If the uric acid 102 APPLIED MEDICAL CHEMISTRY. residue as above obtained is dissolved in KHO and then a few drops of HC1 or acetic acid are added, the uric acid will, on standing, crystallize out in transparent rhombic tables. A solution of the residue in sodic carbonate, if added to a drop or two of argentic nitrate solution on test paper, will reduce the latter, a dark spot of reduced silver appearing. A solution of the residue in a little caustic soda, if added to a sodic hypo- chlorite solution, produces pink coloration. The quantitative determination of uric acid depends on its presence in the urine in soluble salts, which, upon acidulation, are decomposed, the liberated acid, on account of its small solu- bility, crystallizes out and is weighed as such. To accomplish this 300 c.c. urine are mixed with about 5-10 c.c. HC1 and set aside at a low temperature for 24 hours or longer. Almost the entire uric acid has by this time separated in crystals and is now collected on a washed, dried and weighed filter. After washing the crystals on the filter with a little water, added little at the time, the filter with the crystals dried is then weighed, and the latter weight, less the first weight of filter, gives the amount of uric acid corresponding to 300 c.c. urine. As owing to the slight solubility of the free acid in the urine and water employed for washing, the result will always be too low; 0.0038 grams. Uric acid should be added to the result for every 100 c.c. of fluid (i.e., 300 c.c. -j- the water employed for washing the crystals). Hippuric Acid. — Found normally in human urine in quan- tities varying from 0.3 to I grams in 24 hours. On boiling with acids or alkalies hippuric acid is decomposed into benzoic acid and glycocin, and in an inverse manner if benzoic acid is ingested it combines with the glycocin of the body to hippuric acid. It is stated to be increased in fevers and decreased in icterus. In parenchymatous nephritis benzoic acid is excreted without change. Hippuric acid is deposited in the acid urine, if present in suf- ficient quantity in transparent four-sided prisms or needles, and can be demonstrated by a similar reaction as that of ben- zoic acid, by boiling it with HN0 3 , evaporating and heating the residue, when a distinct odor of oil of bitter almonds is devel- oped. To approximate it in urine 300-500 c.c. of urine are ORGANIC CONSTITUENTS. IO3 rendered slightly alkaline with sodic carbonate, evaporated to syrupy consistence and extracted with absolute alcohol. The alcohol solution is then evaporated, the residue dissolved in water and the solution acidulated and well shaken with acetic ether. To avoid presence of benzoic acid the residue of the ether evaporation is treated with petroleumbenzin, when hip- puric acid alone will remain. Kreatinin. — A derivate of the kreatin of muscle normally found in the urine in quantities varying from 0.5 to 1.3 grams in 24 hours. It is abnormally increased in febrile processes and lessened in anaemia, chlorosis, diabetes, Bright's disease and tetanus. To demonstrate its presence in urine the kreatin should first be converted into kreatinin, by boiling with a little dilute H 2 S0 4 , then add a solution of sodic nitro-prusside and a little NaHO, and note the red color, which, however, soon disap- pears. For its quantitative estimation its product with zinc chloride is utilized. At least 300 c.c. urine will have to be em- ployed, and these are treated with milk of lime to alkalescence and subsequently with calcic chloride until no further precipi- tate occurs. After subsidence the precipitate is filtered off and washed out, the filtrate condensed to syrupy thickness, and while warm mixed with 40-50 c.c. of stronger alcohol. After this has subsided for 6-8 hours, it is filtered and IC-15 drops of an alcoholic zinc chlorine solution added and set aside for 2-3 days, when the whole is thrown on a tared filter, the pre- cipitate washed with alcohol and dried and weighed. 100 kreatinin-zinc-chloride = 62.44 kreatinin. Besides the aromatic ethyl-sulphuric acids, amongst which properly belongs " indican " as potassic indoxylsulphate, oxalic acid deserves mention not alone as a normal ingredient of urine, though in very small amounts, but also for the pathological im- portance when excreted in larger quantities as calcic oxalate, occasioning vesical concretes. For its determination, in urine 500-600 c.c. Urine are treated with Calcic chloride solution. This is rendered slightly alkaline with NH 4 HO, and the precipitate dissolved in acetic acid, avoiding excess. After 24 hours the precipitate of uric acid now formed is collected on a filter, washed and the calcic 104 APPLIED MEDICAL CHEMISTRY. oxalate dissolved in HC1, diluted and covered with NH 4 HO, when in 24 hours further all of the calcic oxalate will be sepa- rated in the vessel. URINARY COLORING BODIES. These bodies, by recent investigations have been reduced to only two important ones, of which one is claimed not to pre- exist in urine, but to owe its presence there to another sub- stance, and as a product of oxidation thereof (Urobilin, Hoppe-Seyler) while the other (indican) plainly belongs to the aromatic ethylsulphuric acid group. As they seem, however, to be the chief bodies from which urine derives its color they will be taken up here. Urobilin (hydrobilirubin) has been shown to be formed from bilirubin with sodiumamalgam as hydrobilirubin which is iden- tical with urobilin. A substance of the same properties was produced by Hoppe-Seyler from haematin, showing the succes- sive change of the blood-coloring matter to biliary and urinary pigments. According to the former, urobilin does not exist in the normal urine as such, but a substance is precipitated by basic lead acetate, which when liberated from the lead salt by H 2 S0 4 and alcohol, gradually oxidizes into urobilin. It forms a reddish-brown mass with green tint in reflected light, insol- uble in water, readily soluble in alcohol, ether or chloroform, and in alkalies; forming red solutions with green fluorescence, which if KHO or NaHO is employed, exhibits a characteristic absorption band in d between b and / 'of the spectrum, which is less marked if NH 4 HO is employed. The fluorescence is especially noticeable in theammoniacal zinc solutions of urobilin, being ruby red with transmitted and green with reflected light, which can be shown in urine containing it, by first adding NH 4 HO in excess, filtering and adding a little zinc chloride solution. To detect urobilin in urine the latter reaction is employed and observed in the spectroscope, or when it fails, urine is shaken with an equal volume of ether, which is decanted, evapo- rated, and the residue dissolved in alcohol. This solution gives the characteristic absorption band. In the urine of icterus urobilin can be readily detected after precipitating the biliary URINARY COLORING BODIES. 105 pigments with milk of lime and carbonic acid; also by precipi- tating urine with basic lead acetate solution, and drying the washed precipitate, extracting this with alcohol and treating with a little H 2 SO^ and filtering after 24 hours. Urobilin can be shown by its fluorescence if treated with NH 4 HO and zinc chloride, or if treated with water or chloroform. If the latter solution is treated with a little tincture of iodine and KHO, a marked brownish-yellow color is obtained, showing green efflorescence. Urochrome and uromelanin, already mentioned elsewhere, are urinary pigments of minor importance, belonging under this head. The most important and interesting urinary pigment, as it might be termed, is the Indigogen or indoxylsulphuric acid commonly named Indican [iiroxanthhi), potassic indoxylsulphate (C 8 H 6 NS0 4 K), which in the presence of slightly oxidizing bodies and HC1 splits into indigo and potassic sulphate, distinct from the indican of vegetable origin, which is a glucoside, and with acids or ferments forms indigo and indiglucin which reduces the alka- line cupric solution. In the normal urine 4.5 to 19.5 milli- grams of it are said to be present in 1500 c.c, or an average of 6.6 milligrams in 1000 c.c, which is increased in intestinal obstructions, where it was in one case on record increased to 98.4 milligrams. In acute peritonitis it is also increased, also in Addison's disease, progressive atrophy of the muscles, cholera, and in all chronic affections ; while in anaemia, chlorosis, leukaemia, it is diminished. In the tropics the urine is said to be especially rich in indican. To detect indican in urine it is mixed with equal volumes of HC1 to which is added a few drops of saturated solution of chloride of lime, until a red- violet or greenish-blue color appears, according to the amount present, which is imparted to chloroform if shaken well with it. For the quantitative determination of indican comparison of color tints is employed. To this purpose a standard solution containing a known strength of indigo in a certain volume of chloroform is made by dissolving finely pow T dered indigo in chloroform, and by weighing the residue of undissolved indigo,, the strength of the solution being noted. Then a known 8 106 APPLIED MEDICAL CHEMISTRY. volume of urine is treated with an equal volume of HC1, to which, gradually, a saturated solution of chloride of lime is added drop by drop, shaking each time until the maximum blue color is developed ; this is then shaken with chloroform until the latter has taken up all the color. This chloroform solution compared with an equal volume of the standard solu- tion which is brought with more well known quantities of chloroform to an equal shade, is then computed for the amount of volume, corresponding to the same amount of indigo, and this adapted to the known volume of urine. ABNORMAL CONSTITUENTS OF URINE. The principal of these are albumin, peptones, mucin, sugar, acetone, blood, biliary pigments and acids, cystin, leucin and tyrosin, allantoin, fats and fatty acids. Albumin. — Although this is not a normal constituent of urine, it has been shown to exist in normal urine, both temporarily as well as permanently in minute quantities (up to T \ per cent.). Its presence in urine indicates a pathic condition termed albu- minuria, which maybe true or false, according to its occurrence in consequence of renal disease, or as depending on the pres- ence of other albuminous substances, such as pus, blood, etc., which can be distinguished besides the chemical tests, common to both, by microscopic examination. The albumins present in urine are principally serum-albumin and globulin, of which the recognition of the former is of the greatest importance for the physician. Urine containing albumin is of pale color and low specific gravity, and according to the severity of the case, albumen may be found therein in quantities of from ^ to I and even 4 per cents. For testing, it should be clear or cleared by filtration and its reaction ascertained, which if alkaline or neutral, should be rendered slightly acid by a few drops of acetic acid. Should acetic acid produce a precipitate of mucin, this should be sepa- rated, and the urine then boiled in a test tube, when any albumin present will coagulate (serum-albumin coagulates at 72°-75°), and rendered readily perceptible. The character of the precipitate as albumin should be further confirmed by ABNORMAL CONSTITUENTS OF URINE. IO7 addition of a few drops of nitric acid, which, if the precipitates were phosphates, would rapidly dissolve it, but will not affect coagulated albumin (turbid urine, clearing up on heating, con- tains urates in excess). To test urine with HN0 3 , the latter should be admixed in I volume of the acid to 2 of urine, but with better success and greater delicacy the test is effected by putting a quantity of HN0 3 into a wide test-tube and allowing the urine to flow over the surface from the sides of the tube with a pipette, when albumin will be indicated by a well-defined white or opalescent zone between the acid and urine, which can be distinctly observed with reflected light, when the tube is placed against a dark background. Should another zone appear due to excess of urates, this latter will disappear when warmed. — Boedecker's Test. — Consists in acidifying urine with acetic acid, when, if albumin is present, a precipitate will occur on the addition of a solution of potassic ferrocyanide. Picric acid Test (Galipe). — If, to albuminous urine, a few drops of a saturated solution of picric acid are added, a yellowish-white precipitate will occur. Peptones are also precipitated by it. Metaphosphoric acid. — Will precipitate albumin completely. If a crystal of trichloracetic acid is added to albuminous urine, it will dissolve and form a turbid zone. Tanrefs solution. — Con- taining potassic iodide 3.32 grams, mercuric chloride 1.35 grams, acetic acid 20 ex., and water 64 c.c, will give a white precipitate with albuminous urine. Phospho-Uingstic acid. — Precipitates even very small amounts of albumin, but also peptones. Comparative approximation of albumin can be effected by boiling acidulated urine in a test tube of the same capacity, and containing the same quantity, and after setting aside for a while, noting the volume of the deposit comparatively with the amount of urine tested. In this manner clinical observation may be conducted from day to day, with fair results, as to the increase or decrease of albumin in the urine. Quantitative determination of albumin is best conducted by precipitating it from a certain volume of urine, acidulated with a few drops of acetic acid, adding, if needed, a little more acetic acid to favor separation of precipitate, and throwing it on a well-dried (at I io°), and weighed filter ; the precipitate is washed with boiling water, rendered slightly alkaline with NH^HO, sub- 108 APPLIED MEDICAL CHEMISTRY. sequently washed with alcohol and ether dried at I io°, and weighed and the difference between filter, and filter -f- precipi- tate, noted as albumin. Albuminous urine may be analyzed by means of polarimetry, if no sugar is present, after being well cleared, first with acetic acid and then with milk of lime; but this is hardly applicable to urines containing only small quantities of albumin. For the volumetric estimation of albumin in urine, Tanret's solution (see above) is best suited, if no peptones or alkaloids are present therein. I c.c. corresponds to I decigram of albumin. It is added carefully, drop by drop, from a burette to the urine, stirring well and allowing precipitate to subside. When a drop added to the supernatant liquid, or some of the filtered urine fails to give a further precipitate the operation is completed. Peptones. — The presence of peptones in the urine after poisoning by phosphorus and in suppurative processes, in pneumonia and in reabsorption of fibrinous exudations, makes its detection in urine of some importance for the clinician. To do this, urine is acidulated with a little acetic acid and boiled to separate the albumin, if present. To completely do so, the filtrate may be treated with lead acetate, filtered, one-fifth volume of acetic acid added to filtrate, and then the peptone precipitated with sodic phospho-tungstate, acidified with acetic acid, also Tanret's test or picric acid. Its presence can be shown with any of these reagents in absence of albumin, or with Fehling's solution to which it gives a pinkish color. Mucin. — Though principally found suspended as secreted by the congested membranes of the urinary tract, it may also be found in solution in the urine, and is of importance principally on account of its interference with the detection of other abnor- mal constituents. As already stated, after separation of the flocculent mucin in the urine by filtration, the dissolved portion thereof is readily precipitated by acetic acid at ordinary tem- perature. Sugar. — The presence of grape sugar in urine, although claimed by some as a normal component of urine in minimal quantities, and probably present as such under certain con- ditions, is, when found therein in more than traces certainly ABNORMAL CONSTITUENTS OF URINE. IO9 indicative of grave lesions. Its detection and quantitative determination form a valuable diagnostic aid to medicine. The urine of diabetes mellitus or melituria is one of high specific gravity, 1030-1050, very pale color, voided in greatly increased quantities from 2500-5000, or 6000 c.c. in 24 hours, and, as a rule, it contains from 4-5 per cent, of sugar, but this may be increased to 8 or 10 per cent, and over. It has a pecu- liar odor, a persistent froth after shaking, and leaves a syrupy, sticky residue on evaporation. Qualitative Tests. — For the purpose of testing urine for sugar it should be filtered, and, if albumin is present, this should be separated. Moore's Test. — Requires the mixing of urine with an equal volume of potassic hydrate solution, when, if heated, it will turn yellow and brown, the latter if sugar is present in sufficient quantities, and an odor reminding of molasses will be noticeable. Mulder-Neiibauer 's Test. — Depends on rendering the urine alkaline with sodic carbonate and adding enough indigo solution (potassic sulphindigotate) to render it percep- tibly blue, which color will turn violet, and finally yellow on boiling, if sugar is present, and on cooling and agitation the blue color reappears. Boettgers Test. — If urine mixed with an equal volume of sodic carbonate (1-3) and a little bismuthyl nitrate (subnitrate) added, is boiled for a little while, it will turn brown and black if sugar is present, from the reduction of the bismuth salt. As this test may prove fallacious from the pres- ence of sulphur compounds, care is to be taken to separate all the albumin and testing the urine by boiling with potassic hydrate solution in the presence of lead acetate paper. If this is black- ened this test is not admissible. Trommer s Test. — Urine, some- what diluted and treated with an equal volume of potassic hydrate solution and a little cupric sulphate added to it, to render a blue solution, is boiled; when near the boiling point a yellowish-red precipitate is occasioned, sugar is present, cuprous oxide being formed. Fehling's solution (a.v.) may also be employed quali- tatively. Picric acid. — If added in saturated solution to an equal volume of urine, with an addition of a few drops of potassic hydrate solution, when heated will yield a reddish-brown color if sugar is present. 110 APPLIED MEDICAL CHEMISTRY. Quantitative estimation of sugar is accomplished by several methods. Saccharimetry by Polarization. — The urine for this purpose should be clear and not much colored, nor containing any albumin. When the container is filled, care must be taken that it is clear and contains no free water from cleaning, to which end it should be previously rinsed with a portion of the urine to be examined. Air bubbles must also be excluded from the container before it is put in place. The analyzer is then rotated until the two halves of the field separated by the dark line (which should be made distinct by adjustment of the telescope) assume again both the same tints as the polarimeter showed with a non-active fluid when at zero. To guard against error a number of observations are made and noted and the mean thereof set down as angle observed, = a, while W. would stand for weight of sugar in grams in I c.c. urine and /. for length of column in decimeters. Knowing the specific rotary power as 57.6 — -|- \_a] D , we can find W. by the following for- mula: W= ^ Thus if the angle observed were 2. =5°, the length of the column I decimeter, the amount of sugar con- 2 K tained in 1 c.c. urine would be — — = 0.043 grams, or in 57-6 xi 4J B 100 c.c. = 4.3 grams, which would be the percentage of sugar contained in this urine. To obtain the percentage at once the angle observed is multiplied by 1 00 and divided by the specific rotation if a one decimeter tube is used. Though apparently easy, the observations are not sufficiently reliable, especially with the unpracticed eye, to entitle this method to great accuracy, though it is for clinical purposes quite sufficient. Fermentation Test. — This, like the previous method, yields only approximate results, but sufficiently correct for medical purposes. It is utilized in three different manners; first, by fermenting a certain volume of saccharine urine by means of yeast, measuring the amount of carbonic acid gas liberated, and computing the corresponding weight of sugar to the meas- ure of the gas ; secondly, by fermenting a certain volume of saccharine urine by means of yeast and causing the carbonic ABNORMAL CONSTITUENTS OF URINE. I 1 1 acid gas liberated to be absorbed by a known quantity of potassic hydrate solution, and ascertaining the amount of carbonic acid, so absorbed, by weight ; 48.89 C0 2 , correspond to 100 sugar; and thirdly, by observing the specific gravity of saccharine urine, exposing it to fermentation with yeast at 25 ° until fer- mentation ceases, when the difference in each degree of spe- cific gravity will indicate 0.2196 grams grape sugar in 10 c.c. urine. The urine in the fermentation test should be slightly alkaline or rendered so by the addition of a little sodic carbon- ate ; the yeast should be fresh and the liquid kept at a tempera- ture of 25 ° for at least 24 hours. Fehling's Test. — This is undoubtedly the most accurate and most practical for clinical purposes. It depends upon the reduction by glucose of the cupric salt present in alkaline solu- tions to cuprous hydrate at the boiling point. The standard alkaline cupric solution for the volumetric analysis of glucose is unstable and should either be made fresh when wanted, or pre- ferably, kept in two separate solutions, to be mixed in equal volumes as needed. (1.) Copper solution : 34.65 grams of pure crystallized cupric sulphate, not effloresced, broken into small fragments which are deprived of any adhering water of crystallization by press- ing them gently with bibulous paper, are dissolved in suf- ficient warm water and the solution brought with water to 500 c.c. (2.) Alkaline solution: 173 grams pure crystallized sodium potassium tartrate are dissolved in 350 c.c. of solution of sodic hydrate, specific gravity 1.33, and diluted with water to make 500 c.c. The urine to be examined is first filtered, if not perfectly clear, and a certain quantity of it is diluted either with nine volumes of water, or if the specific gravity is very high with 19 volumes thereof. 10 c.c. of the mixed solutions of the test are then placed in a porcelain capsule and diluted with 4 times its volume of water. The capsule, is placed on a wire gauze over the open flame, and the test brought to the boiling point ; the urine, as above diluted, is now allowed to flow into it, drop by drop, from a burette, which is filled to the topmost mark. After every few drops the contents of the capsule are allowed 112 APPLIED MEDICAL CHEMISTRY. to boil for a few seconds, amidst stirring, and the gradual dis- coloration of the cupric solution is to be closely observed, by allowing the deposit to settle and tilting the capsule slightly to discover the presence of blue coloration. At the point when the discoloration is complete the process is finished. This can be more accurately determined by taking a few drops of the clear supernatant liquid from the capsule on a small porcelain slab, adding a drop of acetic acid, when, on addition of a drop of potassic ferrocyanide, no brown precipitate should occur (absence of copper), or by filtering a portion and applying the same test. If, however, a little portion of Fehling's solution is added to the filtered or supernatant clear liquid and boiled, and a reduction takes place, the process has been continued too far and must be commenced over again. The amount of urine drawn from the burette during the test is now noted, and as this has decomposed 10 c.c. of the test, it contained 0.05 of grape sugar. Thus if 16 c.c. of the diluted urine (1 in 10) corre- sponded to 0.05 sugar, 1.6 c.c. urine contained that much. To obtain the percentage compute as following: 1.6: 0.05 = 100 : x; = 3.1 per cents. If the urine had been diluted with 19 volumes of water and 16 c.c. would represent 0.05 sugar, ] £' =0.8 urine would contain 0.05 and 0.8: 0.05 = 100 : x; x = 6.2 per cents. Acetone (C 3 H 6 0). — Dimethyl-carbon monoxide, CO^ pu' a colorless liquid of pleasant odor, soluble in water, alcohol, and ether, specific gravity 0.814. This is of importance to the physician owing to its occasional presence in the blood of melituria, attributed to a fermentation of grape sugar induced by a special ferment. While it is recognized by its odor when present in large quantities, it is necessary to show its existence in the urine when the symptoms indicate it. This is done by the addition of a little ferric chloride, which will turn it red- dish-brown. Blood. — The presence of blood in the urine, haematuria, may be due to different causes, and may be characterized by different color. This may be blood-red, brownish-red, black, and even dirty greenish-brown. The bright-red is due to fresh corpuscles and haemoglobin, the brownish to broken down cor- ABNORMAL CONSTITUENTS OF URINE. II3 puscles and methsemoglobin, the black to disoxidized haemo- globin, and the greenish-brown, strongly alkaline and ichorous in appearance, contains blood and pus in larger proportions. While the microscope must give information as to blood cor- puscles, as well as their condition and amount, the spectroscope will have to be employed to define their component parts. Thus, oxyhemoglobin, if present, will be noted by the two absorption bands in yellow and green between D and E of the spectrum. If the absorption band cannot be seen the urine is to be treated with lead acetate in excess, the precipitate filtered off and treated with a little water, in which it is decomposed with sodic carbonate, the precipitated lead carbonate removed and the filtrate examined with the spectroscope. Chemically the oxyhemoglobin can be confirmed by shaking well together equal volumes of old spirits of turpentine and fresh tincture of guaiac ; if some of this is poured into a little urine containing blood, a blue resinous precipitate will ensue. Also, if to a little urine a few drops of tincture of guaiac are added and the mix- ture shaken with ozonic ether, an ethereal solution of hydrogen peroxide, the presence of blood will be proven by the blue col- oration of the ether. The presence of hcematin is established by Heller's test, as following: Two volumes of urine are mixed with one KHO solution, 1 : 3. On warming this a precipitate of the earthy phosphates will take place, which, while white or grayish in normal urine, will be found of a red or rosy tint if hsematin is present. Hcemin can be proven by preparing haemin-crystals for mi- croscopic examination as follows : The precipitate obtained to show the haematin, or even the albuminous coagulation from boiling urine containing blood, is spread on a microscopic slide and dried with gentle heat. Add a few morsels of NaCl and rub with a knife into the sediment until the salt is finely divided, blowing off the surplus and adding a drop of glacial acetic acid to the slide; cover them with a cover glass, adding a few more drops acetic acid to float the cover glass, and warm the slide until the acid begins to boil, adding glacial acetic acid subsequently as long as it evaporates; when cool examine 114 APPLIED MEDICAL CHEMISTRY. under microscope, when dark-brown long rhombic lamellae of haemin will be seen. Biliary Pigments and Acids. — The diagnosis of icterus makes it at times desirable to show the presence of these in this condition. The urine under such circumstances presents a dark yellowish-brown color, at times more extensively yel- low or brown, and on shaking has a more than usual lasting yellow froth. The quantity remains about as usual; in reac- tion it is acid, clear, and free from albumin. The appearance of froth, color, and reaction is largely due to the presence of the biliary pigments and acids. The presence of the pigments can be demonstrated by the Gmelin's test, which depends on the oxidation of the bilirubin by nitric acid and the play of colors occasioned by it. If a little of such urine is touched with nitric acid on a plate or porcelain slab, there will be a play of colors from red to violet into green, perceptible at the points of contact. The addition of a little H^SO^ will improve the reaction, as the presence of a little nitrous acid is nec- essary to show it well. The same play of colors will be noticed if the filter, still wet with urine, is touched with a drop of HN0 3 . The Gmelin's test is occasionally not noticeable at once. Heller's test is to add albumin to the urine before add- ing HN0 3 , and noting the green or bluish color of precipitate. The pigments may be precipitated with either basic lead acetate or milk of lime; if with the former, after separating the precipi- tate, this is decomposed with H 2 S ; with the latter it is acidu- lated with H 2 S0 4 ; if treated either with alcohol or chloroform, it imparts a beautiful green color by the lime process, while the chloroform extracted from the lead precipitate is distinctly yel- low, turned green by H 2 S0 4 , answers the Gmelin's test, and ex- hibits a play of colors on addition of a little bromine water. The biliary acids are not as readily detected and need isola- tion in case of doubt to establish their identity. Generally the application of Pettenkofer's reaction will suffice. This is easily applied by dissolving some cane sugar in the urine and filter- ing. The filter is allowed to dry, and touched with a drop of H 2 S0 4 , when a beautiful violet color will appear, growing darker and purple. This is a very delicate test. To isolate the biliary acids treat the urine with basic lead acetate and a ABNORMAL CONSTITUENTS OF URINE. I I 5 little NH 4 HO, filter and wash precipitate with hot alcohol, which dissolves the biliary lead salts. The alcoholic extracts are then decomposed with sodic carbonate and evaporated to dryness. The dry residue is extracted again with boiling alcohol and concentrated, then a little ether added to it ; set aside in a vial it will soon exhibit the precipitation of the biliary acids, which can be confirmed and recognized by the other tests. Cy stin. — The presence of this body in urine characterizes a condition known as cystinuria, which, as a hereditaiy tendency for the formation of cystic calculi, is of some importance to the physician. It is, by far, more prevalent as a urinary sediment and urinary concretion (q.v.). To demonstrate cystin in urine in solution, the urine is treated with a little acetic acid which soon produces a turbidity, and after twelve to twenty-four hours, fine crystals of cystin will be formed at the bottom of the vessel, which can readily be distin- guished by the microscope. Quantitatively cystin may be deter- mined by treating 500 c.c. urine with 20 c.c. acetic acid (20 per cent), and setting the mixture aside for twenty -four hours, when the cystin will have separated in crystals, along with some uric acid, calcic oxalate, and also sodic urate. The sediment is gathered on a tared filter, washed with dilute acetic acid, and then dried and weighed. The cystin left on the filter is now dissolved with dilute HC1, and the amount determined by the difference between the dried filter containing it and the dried filter from which it has been dissolved. Leucin and Tyrosin. — The presence of leucin and tyrosin in the urine points to an imperfect oxidation of the albuminoids. To detect them in the fresh urine, this is precipitated with basic lead acetate ; separate the precipitate by filtration, and treat the filtrate with H 2 S, until all the lead is separated ; filter again and evaporate filtrate to syrupy consistence ; set aside in a cool place until the leucin and tyrosin have separated into crystalline warty masses. To separate the tyrosin, treat the latter with boiling alcohol, filter, when on cooling the leucin will crystallize out. Allantoin. — This is found in the urine of the new-born, within the first eight days, and in the urine of pregnant women. It is Il6 APPLIED MEDICAL CHEMISTRY. detected by treating urine with baryta water, separating the baryta by exact saturation with H 2 S0 4 , and treating the alkaline filtrate with sufficient mercuric chloride to produce a precipitate. If acid, it is neutralized with NaHO. The precipitates are then treated with H 2 S ; evaporated, when, on cooling, allantoin will crystallize out, which can be recrystallized from hot water for microscopic inspection. Fats are, at times, present in the urine, either in solution, emul- sified, or in suspension as globules. It has been shown in chyluria, in fatty degeneration of the kidneys, and in some vesical affections ; also, in phthisis and affections of the pan- creas and liver, as the result of certain poisons (phosphorus), and along with diabetes. Besides their detection under the microscope, they can be demonstrated by evaporating the urine, and incinerating the residue, when the presence of fat will give rise to the irritating vapors of acreolin. From the dry evaporate, the fats can also be readily separated with petroleum-benzin, and on the evapora- tion thereof quantitatively determined. ADVENTITIOUS SUBSTANCES IN URINE. Under this head must be considered all such substances of diet or therapeutic agents which are eliminated from the body, to a greater or less extent, by the urinary apparatus. Their detection is not alone of importance in toxicology, but also to determine the efficiency and sufficiency of medicinal agents and their doses. While many of these bodies are not eliminated directly, but as compounds with other material in the system, and as oxidation or reduction products, others can be recovered from the urine, without having undergone any chemical change. Thus, while the chlorates of the alkalies can, already ten minutes after ingestion, be traced in the urine, when taken in sufficient doses, they are, when taken in small quantities, sometimes eliminated as chlorides, while the bromates and iodates reappear in the urine as iodides and bromides, and the chlorides, bromides and iodides are eliminated unchanged. The carbonates of the alkalies reappear in the urine when taken in sufficient quantities, and render it alkaline ; the acids as neutral salts, sulphur and sulphides as sulphates, while the alkaline ADVENTITIOUS SUBSTANCES IN URINE. 11/ earths and the metals are eliminated with the urine only to a slight extent. Alcohol reappears only in small quantities in the urine, being oxidized in the body ; chloroform, when administered for some time, and chloral are eliminated as urochloralic acid, and, while oxalic, citric and tartaric acids are oxidized and render the urine alkaline, tannic acid is eliminated as gallic acid, whereas the latter and pyrogallic acid reappear in the urine unchanged, as well as many of the odorifera, and most of the alkaloids. The Chlorides are shown by the usual reactions already dwelt upon under the normal constituents of urine, their increased presence by their quantitative determination. Chlorates. — Of these the most important is potassic chlorate, which is detected by adding a few drops of indigo solution. If to this mixture, acidulated with H 2 S0 4 , a few drops of sulphur- ous acid are carefully added, chlorine is liberated, which will decolorize the indigo. Bromides are detected by evaporating 500 c.c. urine with about 3 grams sodic hydrate or carbonate. The incinerated residue is then dissolved, filtered, and, if treated either with chlorine or chlorine water, and shaken with ether, the latter is colored yellow from free bromine, which, upon shaking with an alkaline hydrate, is decolorized. If, instead of ether, chloro- form or carbon bisulphide is used, they will be colored yellowish- red. Iodides. — Urine, to be tested for them, is treated as in the test for bromides, but to the watery solution of the ashes a little starch mucilage is added, and subsequently chlorine water, or a few drops of nitric acid. In either case, if iodides are present, the characteristic, dark-blue color of starch iodide will be de- veloped; or, if the solution of the ashes is treated with chlorine water, chlorine, or HN0 3 , in the presence of chloroform or carbon bisulphide, and these are well shaken and then allowed to separate, the latter will show a beautiful violet color. Arsenic. — This is found in the urine in cases of poisoning, as well as after continued medication with that substance, and oc- curs therein as an alkaline arsenite. To detect it, the urine is evaporated to syrupy consistence, to which about 20 per cent. HC1 is added, and then potassic chlorate in small doses until Il8 APPLIED MEDICAL CHEMISTRY. decolorized, while the mixture is kept on a water-bath. After all the free chlorine has been liberated, it is filtered, and the filtrate tested by the Fleitmann's or Marsh's test. Mercury. — To demonstrate its presence in urine, the quantity voided in several days is condensed, treated with HC1 and po- tassic chlorate, until all organic admixtures are oxidized ; after this it is filtered, and the filtrate treated by electrolysis for about twenty-four hours, with a gold wire as cathode and a platinum slip as anode. The mercury present will be deposited on the golden cathode, which is clipped off, introduced in a hard glass tube drawn out fine at one end. After the wire is entered into this, the other end is closed, and the part containing the wire heated until the volatilized mercury is deposited on the cooler portion of the tube, when it can be recognized by the introduc- tion of a little iodine, which, if vaporized, forms mercuric iodide with mercury if present. Lead. — The detection of this in urine is often of great im- portance, in connection with the diagnosis of lead-poisoning. It is accomplished by concentrating the urine over the water-bath, oxidizing the organic ingredients as above, and treating the residue with H 2 S ; or by incinerating the residue of the water- bath, dissolving in HN0 3 , diluting and testing also by H 2 S. The alkaloids, as already stated, are generally eliminated without chemical change, and can be detected by their special tests given under the respective headings, the urine being duly concentrated, and the alkaloid to be tested for, separated by its best solvent. URINARY SEDIMENTS. While often of importance in a diagnostic way, they are of more interest to the pathologist and microscopist than the chemist, as their form, generally distinguishable under the microscope, would readily indicate their composition, with- out chemical tests. They are classified as organized and un- organized ; the former comprise mucin, blood, with its red and pale corpuscles, pus and the corpuscles thereof, epithelium in its various forms, according to their respective sources, and the cylinder casts of the various renal affections. Another feature of urinary sediments form the micro-organisms abounding URINARY SEDIMENTS. I I9 therein very often, and known as micrococci, bacteria, bacilli, schistomycetes, saccharomycetes, etc., the recognition of which under the microscope forms a special part of modern pathology. The unorganized sediments differ according to the media in which they occur. Thus, in urine of acid reaction the following may be found in amorphous form: sodic and potassic urate; in crystals: uric acid, calcic oxalate, cystin, leucin, and tyrosin. In urine, of alkaline reaction, the following may occur : amorphous : neutral calcic phosphate, calcic carbonate ; crystal- line: ammonic urate, ammonio-magnesic phosphate (triple phos- phate), secondary calcic phosphate, and magnesic phosphate. To obtain the sediments, urine should be allowed to subside for twenty-four hours in a conical glass, when it can be either separated by decantation, or preferably by means of a pipette, transferred to the slide of a microscope and then examined. Their behavior with acetic acid or potassic hydrate solution is as follows : Soluble in Acetic Acid. — Triple phosphate. Calcic phosphate, without effer- vescence. Calcic carbonate, with effer- vescence. Urates, with subsequent ap- pearance of uric acid crystals. Insoluble in Acetic Acid. — Uric acid. Calcic oxalate. Tyrosin. Leucin. Cystin. Hippuric acid. Fats. With Acetic Acid. — i?/<%> C 17 H 23 N0 3 . — A fragment of potassic bichromate, or ammonium molybdate dissolved in H 2 S0 4 c. and warmed, gives, upon the addition of atropine and afterwards a few drops of H 2 0, rise to an odor variously compared to orange blossoms and oil of bitter almonds. Caffeine, C 8 H 10 N 4 O 2 + H 2 0. — With hot fuming nitric acid it gives a yellow liquid, turning purple on addition of ammonia. Caffeine is not precipitated by picric acid nor potassio-mercuric iodide. Cinchonidine ', C 19 H 22 N 2 0, laevogyrous = 144.61 °. No change in color with concentrated H 2 S 4 or HN0 3 (distinction from morphine, salicin, etc.). No coloration with H 2 S0 4 and po- tassic dichromate (distinction from strychnine) ; on addition of PHARMACEUTICAL PREPARATIONS, ETC. I 57 chlorine water and ammonia, no coloration (distinction from quinine and quinidine). CincJwnine, C 19 H 22 N 2 0, dextrogyrous = 190.4 no change in color with H 2 S0 4 or HN0 3 , no color with H 2 S0 4 and po- tassic dichromate, no color with chlorine water and ammonia. Codeine. — C 18 H 21 N0 3 -f- H 2 laevogyrous = 1 18.2 . Not pre- cipitated by ammonia from its solutions. Its solution in cold H 2 S0 4 is at first colorless, but turning blue on being warmed; does not reduce iodic acid. With H 2 S0 4 containing a little ammonium molybdate, it gives a green solution, soon changing to blue, gradually changing to yellow. If dissolved in chlorine- water and addition of ammonia, it gives a yellowish-red color. Colchicine. — C ]7 H 19 N0 5 . — H 2 S0 4 colors it first yellow, then green; HN0 3 first violet then green. H 2 S0 4 -f- HN0 3 turns it violet, and on addition of alkali, orange-yellow. Coniine. — C 8 H 15 N liquid ; specific gravity, 0.878. Produces white fumes with vapors of HC1 and HN0 3 ; with H 2 S0 4 it produces a purplish-red color, changing to olive green, giving off odor of butyric acid. With iodic acid its solution in alcohol gives a white precipitate. Emetine. — C 28 H 40 N 2 O 5 — H 2 S0 4 forms greenish-brown solu- tion. H 2 S0 4 -+- HN0 3 green, changing to yellow. When a little chlorinated lime is added to it, a drop or two of acetic acid will give therewith an orange-yellow. Hyoscy amine. — C 17 H 23 N0 3 laevogyrous = 14.5 . With auric chloride precipitate, which when crystallized from H 2 with HC1, forms brilliant, lustrous, golden-yellow scales, without rendering the liquid turbid (distinction from atropine.) Morphine. — C 17 H 19 N0 3 .H 2 laevogyrous = 88.04 . Its acid solutions yields precipitates with alkalies and alkaline carbo- nates, soluble in excess of alkali, but less so with ammonia. Morphine is not precipitated by tannic acid, but by potassio- mercuric iodide. H 2 S0 4 dissolves it colorless, but upon addition of HN0 3 a red color is developed. With HN0 3 a red color is produced, changing to yellow ; this is changed to violet on addition of stannous chloride or ammonic sulphydrate. A mixture of mor- phine and four times its weight of cane-sugar, moistened with H 2 S0 4 , gives a dark red color, or if a small amount of the alka- 158 APPLIED MEDICAL CHEMISTRY. loid only is present, wine or rose red. If a fresh solution of molybdic acid is added, or amnionic molybdate dissolved in H 2 S0 4 , a beautiful violet color is produced, changing to blue and dirty green before disappearing ; the addition of water de- stroys this color. Its most characteristic test consists in its power to reduce iodic acid, giving it a yellowish-brown color, which, when shaken with chloroform or carbon bisulphide, gives these a fine purple coloration. The neutral solution of its salts gives a blue color on addition of a little ferric chloride. If to a diluted solution of potassic ferricyanide a little ferric chloride solution be added, and, finally, a drop of morphine solution, a deep blue coloration will ensue. Narceine. — C 23 H 29 N0 9 -\- H 2 laevogyrous = 6.y° ; blue on addition of iodine-water ; with H^O^ grayish-brown, turning to blood-red on warming. Dissolved in chlorine-water and ammonia added, blood-red. Narcotine. — C 22 H 23 N0 7 laevogyrous = 103.5. Colorless with H 2 S0 4 , gradually turning yellow, and on addition of HN0 3 blood-red. With dilute H 2 S0 4 gradually evaporated, it turns first orange-red, then from without bluish-violet, and finally red. H 2 S0 4 with a trace of sodium molybdate, green ; if more molyb- date be added, cherry-red. Chlorine-water turns its salts greenish-yellow, changing on addition of ammonia to a tran- sient cherry-red. Physostigmine. — Eserine C 15 H 21 N 3 2 . Yellow with H 2 S0 4 , gradually changing to red, or reddish-brown, on addition of bromine-water. With small amount of chlorinated lime red- dish, which, on addition of more, passes off Pilocarpine. — C u H 16 N 2 2 . The hydrochlorate with H 2 S0 4 yellow; with HN0 3 , faintly greenish-violet; with H 2 S0 4 and potassic bichromate, emerald-green. Quinine. — C 20 H 24 N 2 O 2 -f 3 H 2 laevogyrous = 126.7 . Solu- tions of quinine and its salts, when mixed with chlorine-water, and afterwards with an excess of ammonia, give a bright emerald- green color (Thalleiochin). The green color passes to red by addition of potassic ferrocyanide, or better, if the latter is added before the ammonia. Owing to the frequent adulterations of quinine sulphate, the following tests for its purity should be employed. One gram if dried at ioo° C. for three hours, SYLLABUS TO PART V. 1 59 or until it ceases to lose weight, should not weigh less than 0.838 ; if less, it contains more than 8 molecules of water. If I gram of it be shaken in a test-tube with 15 c. c. of ether and 2 c. c. of aqua ammonia is added, the liquid should separate into two clear layers, without milky zone or crystals (Cincho- nine). When dissolved in hot water, precipitated with an alka- line oxalate and filtered, there should be no precipitate with am- monia and the filtrate (Quinidine). It should not turn yellow or red on addition of H 2 S0 4 (Salicin and Phlorizin). Its solu- bility in acidulated waters, boiling dilute alcohol, complete com- bustion would prove the absence of fats, resins, gum, starches, and mineral substances. Strychnine. — C 21 H. 22 N 2 2 laevogyrous = 132.07 . Dissolves in a little H 2 S0 4 without color, but upon addition of a small fragment of potassic dichromate, or if potassic permanganate is added, a beautiful deep violet or blue color is devoloped, chang- ing to red, and finally to yellow. A solution of iodic acid in H 2 S0 4 if added to strychnine or a residue containing it, a yellow color appears, changing to brick-red, and finally to violet-red. HNO3 gives it yellow color in the cold. Pink or red would indicate presence of brucine. Physiological test by injecting the solution hypodermically into a small frog for the develop- ment of tetanic spasms. Veratrine. — C 32 H 52 N 2 8 — H 2 S0 4 first turns it yellow, then red, and finally purple. Bromine-water colors it violet or purple- red. Dissolved in HC1 it is colorless, but on heating turns red # SYLLABUS TO PART V. (1.) Determine the amount of oxygen present in atmospheric air by means of pyrogallic acid, also in the same process, the carbon dioxide with potassic hydrate. (2.) Determine hardness of water, temporary and permanent, with soap test. (3.) Determine ammonia in water with Nessler's test. (4.) Determine organic matter in water by the permanganate test. (5.) Examine a specimen of carbonic acid water for copper. (6.) Examine water for lead. (7.) Determine, approximately, amount of cream in milk. l60 APPLIED MEDICAL CHEMISTRY. (8.) Determine casein, fat, and lactose in a specimen of milk. (9.) Determine amount of water in a specimen of flour, also amount of ashes thereof and mineral contaminants by the chloroform test, also for ergot. (10.) Examine a specimen of bread for alum. (11.) Examine a specimen of candy for arsenic, lead, and fuchsin. (12.) Determine alcohol in a specimen of wine. (13.) Test a specimen of beer for glycerin, and picric acid, and bitter alkaloids. (14.) Take specific gravity of a specimen of whiskey and brandy and determine amount of alcohol present by weight. (15.) Examine whiskey or brandy for presence of fusel oil, also by Molnar's test for other ethers present. (16.) Determine amount of acetic acid present in vinegar; also show admixtures of sulphuric acid and capsicum. (17.) Show the presence of an alkaloid (morphine) in a solu- tion, and determine the amount of morphine present therein. (18.) Show color-reaction for picrotoxin and digitalin. (19.) Determine the presence of aconitine by test. (20.) Show the test for coniine. (21.) Show tests for morphine and how to distinguish it from quinine. (22.) Examine a specimen of quinine for its purity. (23.) Apply the tests for strychnine and veratrine. (24.) Recognize atropine by its chemical test. APPENDIX. PTOMAINES. The source of these interesting compounds, as indicated by their name, are cadavers (nrw/ia^ in the state of putrescence. Chemically they are amines, and as they resemble the alkaloids of the previous part in many respects, they are in contradistinc- tion to those of vegetable origin, termed " cadaveric alkaloids." They cannot be limited in number and variety, and depend for their chemical character and physiological action on the prog- ress and degree of putrescence, and the conditions under which this takes place. When speaking of their source as cadavers, this must not be construed to apply to corpses alone, but to all diseased organic bodies containing albuminoid mate- rial. The decaying cheese and sausage, fish, fowl, or meat, the albumins and peptones, all are capable of developing alka- loidal substances, which, in their character, closely simulate those of vegetable origin, and while many of them exert no deleterious effect on the human organism, others, like many vegetable alkaloids, are possessed of powerful toxic properties. Their presence is of the greatest interest and value to the physician, not alone in a sanitarian and forensic sense, but ac- cording to recent researches, also as pathogenic elements. It has been long known * that putrid meats, fish, cheese, and fowl, are capable of producing most alarming and often fatal effects, not alone as gastro- intestinal irritants, but also at times by giving rise to neurotic symptoms. Salads from decaying fowls are a well-known source of disease, as are those of stale lobsters and other similar material; affections arising from the consume of partly decayed or decaying meats are almost of daily occurrence, while choleraic attacks can be frequently traced to them, and cases are on record where poisoning by 1 62 APPENDIX. alkaloidal substances was suspected when the fatal effect had to be looked for in the decaying food. It is especially claimed that slow decay, in the presence of little or no oxygen, is pro- ductive of decidedly poisonous basic products, and that view would be borne out by the many ill effects experienced after eating canned and badly preserved meats, fish, etc. The toxicologist finds in the ptomaines the most difficult subject in his differentiation between them and the poisonous alkaloidal substances introduced into the system with criminal intent. Not alone that the ptomaines closely resemble the vegetable alkaloids in their physical characters, but also in their chemical reactions and physiological effects there exists often great similarity. In view that they are comparatively little known, and that many of them possessing even closer resem- blance, than those we are already acquainted with, may yet be detected, the toxicologist must act with the greatest reserve when deciding on the origin of organic poisons, especially as their extraction is obtained in much the same way as the known vegetable alkaloids. It is only the closest comparison of the physiological effects that would, in such cases, aid a decision, along with the close correspondence of all the chemical reac- tions in confirmation thereof. In many instances the ptomaines correspond with the alkaloids in some special reactions, while in others they differ. Some of them have been observed which exhibit the same reaction with H 2 S0 4 and potassic bichromate as strychnine, while others show the color reaction of veratrine with H 2 S0 4 , and like it turn red with HC1; others exhibit some of the digitalin reactions, and again, there are some extracted with amylic alcohol from alkaline solutions, which show the reduction of iodic acid like morphine. Their reductive power might be utilized as a general reaction by the reduction of potassic ferricyanide to ferrocyanide, which, in the presence of a ferric salt, gives rapidly a dark blue pre- cipitate of ferric ferrocyanide ; but even this is inadmissible, as well known to pertain to some vegetable alkaloids as well, although not in as decided degree, and as not even characteristic of all ptomaines. The color, odor, and character of some liquid volatile ptomaines closely correspond to those of coniine and nicotine, while others show a mydriatic effect, and still others PTOMAINES. 163 produce tetanic spasms. Those resembling strychnine, how- ever, are not crystalline (at least not yet so obtained), and are not as intensely bitter as that vegetable alkaloid. Those giving the veratrine reaction lack its physiological effect, while that apparently analogous with digitalin fails to give a reaction with H 2 S0 4 and bromine ; the cadaveric morphine does not give the blue color with ferric chlqride like vegetable morphine, and the mydriatic ptomaine fails to give the characteristic odor pro- duced by atropine when heated with sulphuric or phosphoric acid. Besides this, as has been shown, the vegetable alkaloids exert a rotary power on polarized light, whereas the ptomaines are said to be optically inactive. It is evident, therefore, that though a differentiation between ptomaines and vegetable alka- loids may be satisfactorily arrived at, this can be done only after careful observation and experimentation with every known test, and its confirmation by the physiological action, and then only those who have the necessary experience and experimental skill required for this purpose. 164 APPENDIX. Table of Elements. a CO Aluminium Al Antimony (Stibium) Sb Arsenic As Barium Ba Beryllium (Glucinum)... Be Bismuth Bi Boron B Bromine Br Cadmium.. Cd Caesium Cs Calcium Ca Carbon C Cerium Ce Chlorine CI Chromium iCr Cobalt Co Copper (Cuprum) Cu Didymium D Erbium Eb Fluorine V Gallium Ga Gold (Aurum) .. Au Hydrogen H Indium In Iodine I Iridium Ir Iron (Ferrum ) .. Fe Lanthanum La Lead (Plumbum)... Pb Lithium Li Magnesium Mg Manganesium... Mn Mercury (Hydrargyrum) Ilg Atomic valence. Ill, V iii, V ii, iv ii iii, v iii i, iii, v, vii ii i ii ii, iv iii, iv i, iii, v, vii iii, vi ii, iii, vi i, ii, iii iii i iii i, iii i iii i, iii, v, vii 126.6 ii, iv. vi 192.7 ii, iii, vi iii < £ 27 11, IV i ii ii, iv, vi ii 120 74-9 U6.8 9 210 11 79.8 111.8 132.6 40 12 141 354 5 2 -4 58.9 63.2 144.6 165.9 19 68.8 196.2 1 "3 4 55-9 I38-5 206.5 7 24 54 199.7 CO Molvbdenum Mo Nickel Ni Niobium Nb Nitrogen N Osmium Os Oxygen O Palladium Pd Phosphorus P Platinum Pt Potassium (Kalium) K Rhodium Rh Rubidium Rb Ruthenium Ru Scandium Sc Selenium Se Silicium Si Silver (Argentum) .. Ag Sodium i Natrium) Na Strontium Sr Sulphur S Tantalum Ta Tellurium Te Thallium Tl Thorium Th Tin (Stannum).. Sn Titanium Ti Tungsten or Wolfram W Uranium U Vanadium V Ytterbium Yb Yttrium Y Zinc Zn Zirconium Zr Atomic valence. w 4J t he 11, iv, vi 95.5 ii, vi 58.1 iii, v I 94 i, iii, v ' 14 ii,iv, vi,viii 198.5 ii 16 ii, iv 105.7 iii, v ^1 ii, iv 194.4 11, 111, IV i 39 104. 1 85-3 11, iv, vi, vm 104.2 iii 44 11, iv, vi 78.8 iv 28 107.7 1 23 11, IV 87.4 11, IV, VI S2 V 182 11, IV, VI 128 1, 111 203.7 IV 233 11, IV II7.7 . iv 48 ii, iv, vi 183.6 IV, VI 238.5 111, V 5i-3 111 172.7 in 89.8 11 64.9 IV 90 WEIGHTS AND MEASURES. 165 Weights and Measures. METRIC AND ENGLISH WEIGHTS. 1 milligram = 0.001 gram. = 1 centigram = 0.01 " 1 decigram =0.1 " 1 gram = 1 decagram = 10 grams 1 hectogram = 100 '' 1 kilogram = 1000 '' = 0.015 gr. Troy. = 0.154 " 1 grain Troy, 1 drachm Troy. = 0.0648 gram, = 3.888 grams, = 1-543 " " 1 ounce " = 3 x - io 3 " = 15-434 g". " = 154-34 '' " 1 " Br. P. 1 " Avoird. = 28.35 " = 28.35 " = 3-53 ° 2S - '' = 35-27 " " 1 pound Troy, 12 oz. 1 " Avoird. = 373.242 " = 453-6 METRIC AND ENGLISH MEASURES. 1 millimetre = 0.001 metre = 1 centimetre =0.01 " = 1 decimetre =0.1 " = 1 metre = = 1 decametre = 10 metres = 1 hectometre = 100 '* = 1 kilometre = 1000 " = 32 0.03937 inch. 1 inch = 0.0254 metre, 0-3937 " 3.937 inches. 1 foot 1 yard == 0.3048 " 0.9144 " 39.3704 32 ft. 9.7 " 1 rod 1 turlong = 5.0292 metres. 201.1662 " 328 " 1 inch. 280 " 10.4 inches. 1 mile = 1609.3297 " METRIC AND APOTHECARIES' FLUID MEASURES. 1 millilitre, cubic centimetre 1 minim = 0.061 c. c. or C. C. = 0.001 litre = 16.23 minims. 1 fluiddrachm = 3-7 1 centilitre = 0.01 " = 2.71 fluiddrachms. 1 fluidounce — 29.6 " 1 decilitre =0.1 " = 3.38 fluidounces. 1 pint = 0.47 litre. 1 litre = 1 decalitre = 10 litres 1 hectolitre = 100 " = 33.81 fluidounces. = 2.6417 galls. == 26.417 "' 1 quart 1 gallon = 0.946 " = 3.785 litres. i kilolitre = 1000 " = 264.17 Rules for Converting Apothecaries' into Metric Weights and Measures, according to Oldberg. 1. To express quantities by weight of the Apothecaries' system in metric terms, or to write medical prescriptions in metric weights. Rule A. Reduce each quantity to grains ; then divide the number by 10 (or move the decimal point one place to the left), and from the quotient subtract one- third. The remainder is in each case the number of grams representing (nearly) the same quantity. Or, Rule B. Reduce each quantity to drachms, and multiply the number by 4. The product is in each case the number of grams representing (nearly) the same quantity. Or, Rule C. Reduce each quantity to ounces, and multiply the number by 32. The product is in each case the number of grams representing (nearly) the same quantity 2. To express quantities by measure of the Apothecaries' system in metric terms, or to write medical prescriptions in metric cubic measures. Rule D. Reduce each quantity to minims ; then divide the number by 10 (or move the decimal point one place to the left/, and from the quotient subtract one- third. The remainder is in each case the number of cubic centimetres represent- ing (nearly) the same quantity. Or, Rule E. Reduce each quantity to fluid drachms, and multiply the number by 4. The product is in each case the number of cubic centimetres representing (nearly) the same quantity. Or, Rule F. Reduce each quantity to fluid ounces, and multiply the number by 32. The product is in each case the number of cubic centimetres representing (nearly) the same quantity. 1 66 APPENDIX. Table of Equivalents of Centigrade and Fahrenheit Thermo- metry Scales. Cent. Fahr. Cent. Fahr. Cent. Fahr. Cent. Fahr. Cent. Fahr. o c —40 — 40.0 — II -j-12.2 + I8 +64.4 +47 -fll6.6 + 76 4-168.8 39 38.2 IO I4.O 19 66.2 48 1 18.4 77 I70.6 38 36.4 9 15.8 20 68.0 49 I20.2 78 I72.4 37 34-6 8 17.6 21 69.8 5° I22.0 79 174.2 36 32.8 7 I9.4 22 71.6 5i I23.8 80 I76.O 35 31.0 6 21.2 23 73-4 52 I25.6 81 177.8 34 29.2 5 23.O 24 75-2 53 I27.4 82 I79.6 33 27.4 4 24.8 25 77.0 54 I29.2 83 181.4 32 25.6 5 j 26.6 26 78.8 55 I3I.O 84 183.2 3i 23.8 2 28.4 27 80.6 56 132.8 85 185.O 30 22 1 30.2 28 82.4 57 I34.6 86 186.8 29 20.2 32.O 29 84.2 58 I36.4 87 188.6 28 18.4 + 1 33-8 3° 86.0 59 138,2 88 I9O.4 27 16.6 2 35- 6 31 87.8 60 I4O.O 89 192.2 26 14.8 3 37-4 32 89.6 61 141. 8 90 194.O 25 13.0 4 39-2 33 91.4 62 143.6 91 I95.8 24 11. 2 5 41.0 34 93-2 63 145-4 92 I97.6 23 9.4 6 42.8 35 95-o 64 147.2 93 I99.4 22 7.6 7 44.6 36 96.8 65 149.0 94 20I.2 21 5.8 8 46.4 37 98.6 66 150.8 95 203.O 20 4.0 9 48.2 38 100.4 67 152.6 96 204.8 19 2.2 10 50.0 39 102.2 68 154-4 97 206.6 18 0.4 11 51.8 40 104.0 69 156.2 98 208.4 17 + 1.4 12 53-6 41 105.8 70 158.0 99 2I0.2 16 3-2 13 55-4 42 107.6 7i 159.8 100 2I2.0 15 5-o 14 57-2 43 109.4 72 161. 6 IOI 213.8 14 6.8 15 59.o 44 HI. 2 73 163.4 102 215.6 13 8.6 16 60.8 45 113.0 74 165.2 103 217.4 12 10.4 17 62.6 46 1148 75 167.0 104 219.2 Rules for Converting Centigrade into Fahrenheit. (D to stand for the degree to be converted.) If above the freezing point of water, 32 F. (o° C), — X 9 4- 32. If below freezing, but above o°F. ( — iy.jj C.), 32 — ( — ) If below o°F. (—17.770c.) ~V7 x q) _3: Rules for Converting Fahrenheit into Centigrade. (D 72) If above the freezing point of water, 32° F. (o° C.) > — X 5. (-12 D^ If below freezing, but above o° F. (—17.77° C.) — X2 — < 5. If below o° F. (—1777° C.) 9 (D432) X5- TABLE OF THE TENSION OF AQUEOUS VAPOR. 167 Table of the Tension of Aqueous Vapor {after Bunse'i). °c. Milli- °C. Milli- °c. Milli- °C. Milli- metres. metres. metres. metres. — 2.0 3-955 6.2 7-095 14.4 I2.220 22.6 20.389 — 1.8 4.016 6.4 7-193 14.6 I2.378 22.8 20.639 —1.6 4.078 6.6 7.292 14.8 12.538 23.0 20.888 —1.4 4.140 6.8 7-392 15.0 I2.699 23.2 2I.I44 — 1.2 4.203 7.0 7.492 15.2 12.864 234 21.4OO — 1.0 4.267 7.2 7-595 154 I3.O29 23-6 21.659 —0.8 4-331 7-4 7.699 15.6 I3-J97 23.8 2I.92I —0.6 4-397 7-6 7.840 15.8 13.366. 24.0 22.184 —0.4 4-463 7-8 7.910 16.0 I3-536 24.2 22.453 — 0.2 4.531 8.0 8.017 16.2 13.710 24.4 22.723 — 0.0 4.600 8.2 8.126 16.4 13.885 24.6 22.996 -(-0.2 4.667 8.4 8.236 16.6 14.062 24.8 23.273 0.4 4-733 8.6 8-347 16.8 14.241 25.0 23.550 0.6 4.801 8.8 8.461 17.0 14.421 25.2 23.834 0.8 4.871 9.0 8-574 17.2 14.605 254 24.II9 1.0 4.940 9.2 8.690 174 14.790 25.6 24.406 1.2 5.011 9.4 8.807 176 14-977 25.8 24.697 I.4 5.082 9-6 8.925 17.8 15.167 26.0 24.988 1.6 5-155 9.8 9-°45 18.0 15-357 26.2 25.288 1.8 5.228 10.0 9.165 18.2 I5-552 26.4 25.588 2.0 5-302 10.2 9.288 18.4 15-747 26.6 25.89I 2.2 5-378 10.4 9.412 18.6 15-945 26.8 26.I98 2.4 5-454 10.6 9-537 18.8 16.145 27.0 26.505 2.6 5-53o 10.8 9.665 19.0 16.346 27.2 26.82O 2.8 5.608 11. 9.792 19.2 16.552 27.4 27.136 3° 5.687 11. 2 9-923 19.4 16.758 27.6 27455 3-2 5-767 11.4 10.054 19.6 16.967 27.8 27778 3-4 5.848 11.6 10.187 19.8 17.179 28.0 28.IOI 3-6 5-93° 11. 8 10.322 20.0 I7.39I 28.2 28.433 3-8 6.014 12.0 10.457 20.2 17.608 28.4 28.765 4.0 6.097 12.2 10.596 20.4 17.826 28.6 29.IOI 4.2 6.183 12.4 10.734 20.6 18.047 28.8 29.441 4.4 6.270 12.6 10.875 20.8 18.271 29.0 29.782 4.6 6 -35o 12.8 11.019 21.0 18.495 29.2 30.I3I 4.8 6-445 13.0 1 1. 1 62 21.2 18.724 29.4 30.479 5.o 6-534 13.2 11.309 21.4. 18.954 29.6 30.833 5- 2 6.625 13-4 11.456 21.6 19.187 29.8 31 I90 5-4 6.717 13.6 11.605 21.8 19423 30.0 3I-548 5.6 6.810 13-8 "•757 22.0 19.659 5.8 6.904 14.0 11.908 22.2 19.901 6.0 6.998 14.2 12.064 22.4 20.143 INDEX. Acetone in urine, 112 Acetyl hydrate, 84 Aconitine, 156 Acid albumin, 64 acetic, 84 acetic (as test), 23 amido-acetic, 77 amido-caproic, 67 arsenic, 38 arsenious, 38 benzoylamido-acetic, 77 butyric, 84 carbolic, 56 caproic, 85 cholic, 78 ethalic, 85 formic, 84 glycocholic, 77 hippuric, 77 hydrochloric, 55 hydrochloric (as test 1 ), 23 hydrocyanic, 56 hypophosphorous, 49 metaphosphoric, 50 metaphosphoric, as test for albumin in urine, 107 nitric, 54 nitric (as test), 23 ortho-phosphoric, 50 oleic, 86 oxalic, 56 oxalic (as test), 23 palmitic, 85 parabanic, 76 phosphoric, glacial, 50 phospho-tungstic, as test for albu- min in urine, 107 picric (as test), 23 picric, as test for albumin in urine, 107 picric, as test for sugar in urine, 109 propionic, 84 pyro-phosphoric, 50 stearic, 85 succinic, 86 sulphuric, 53 Acid, sulphuric (as test), 23 sulphurous (as test), 23 tannic (as test), 24 tartaric (as test), 24 taurocholic, 78 valerianic, 85 Albumin (as test), 24 determination of, in urine, 106 Albuminoids, 61 Albumose, 64 Alcohol (as test), 24 absolute (as test), 24 cholesteric, 83 ethylic, 83 propenylic, 83 Allantoin, 76 its detection in urine, 1 15 Alloxantin, 75 Alkali albumin, 65 Alkaloids, 153 in urine, 118 picric acid as precipitant of, 154 phospho-molybdic acid as precipi- tant of, 1 54 potassio-bismuthic iodide as pre- cipitant of, 154 potassio-mercuric iodide as precipi- tant of, 154 precipitants of, 153 separation of, by Stas-Otto method. tannic acid as precipitant of, 153 volumetric determination of, 154 Aluminium (as test), 24 alkaline test, 41 Amnionic carbonate (as test), 24 chloride (as test), 24 Amido-mercuric chloride, 45 Ammonia-water (as test), 24 Ammonic hydrate, 53 oxalate (as test), 24 phosphate (as test), 24 purpurate, 75 sulphydrate (as test), 24 urate, acid, 75 urate in urinary calculi, 123 Ammonio-cupric sulphate, 43 12 170 INDEX. Amygdalin, 155 Amyloid substance, 66 Atnyloses, 79 Analysis, 19 volumetric, 19 Aniline sulphate (as test), 24 Antimony, 35 golden sulphide of,. 37 oxide, 36 pentasulphide, ^7 trichloride, 36 trisulphide, 37 Apomorphine, 156 Argentic nitrate (as test), 24 nitrate, ammoniated (as test), 24 Arsenic, 37 its detection in urine, 117 pentasulphide, 38 pentoxide, 38 tribromide, 38 trichloride, 38 triodide, 38 trioxide, 38 trisulphide, 38 Atmospheric air, 132 analysis of, 132 determination of aqueous va- por in, 132 determination of carbon diox- ide in, 132 determination of oxygen in, 133 Atropine, 156 Auric chloride (as test), 24 Baric chloride (as test), 24 hydrate (as test), 24 nitrate (as test), 24 Barometer, 10 Basic cupric acetate, 43 Benzin (as test), 24 Benzoyl glycocin, 77 Biliary acids, tests for, 78 their detection in urine, 1 14 concretions, 124 pigments and acids, their detection in urine, 1 14 Bilifulvin, 70 Bilifusin, 71 Bilineurine, 73 Bilphsein, 70 Biliprasin, 71 in biliary concretions, 125 Bilirubin, 70 in biliary concretions-, 125 Biliverdin, 71 in biliary concretions, 125 Blood ferment, 66 in urine, 1 12 tests, 70 Borax (as test), 24 Boedecker's test, 107 Boettger's test for sugar in- urine, 109 Brandy, 151 acidity of, 152 acloholic strength of, 152 Molnar's test for, 152 Bread, 145 composition of, 145 detection of alum in, 146 examination of, 146 Bromides, their detection in urine, 1 17 Bromine-water (as test), 24 Caffeine, 156 Calcic carbonate in urinary calculi, 124 chloride (as test), 24 glycocholate in biliary concretions, 125 hydrate (as test), 24 phosphate, neutral, in urinary cal- culi, 124 oxalate in urinary calculi, 124 urate acid, 75 urate in urinary calculi, 123 Calomel, 45 Cane-sugar, 81 Carbamide, 73 Carbohydrates, 79 Carbon bisulphide (as test\24 Carnin, 76 Casein, 65 Chlorine-water (as test), 24 Chloroform (as test), 24 Chlorates, their detection in urine, 1 17 Cholepyrrhin, 70 Cholesterin, 83 in biliary concretions, 125 Choline, "JT, Chondrin, 68 Chondrogen, 68 Chondroglucose, 68 Cinchonidine, 156 Cinchonine, 157 Coagulated albumins, 66 Codeine, 157 Colchicine, 157 Collagens, 68 Confections and candies, 147 examination for poisonous pig- ments in, 147 Coniine, 157 Correction of gases for temperature, 2>3 Corrosive sublimate, 45 Copper, 42 (as test), 24 Crystallin, 64 Crystallization, 16 Cruorin, 69 Cupric carbonate, 43 INDEX. 171 Cupric di- acetate, 43 nitrate, 42 oxide, 42 sulphate, 42 sulphate (as test), 25 sulphate, ammoniated (as test), 25 sulphide, 43 Cuprous oxide, 42 sulphide, 43 Cursory examination of urine, 120 Cystin, 79 detection in urine, 115 in urinary calculi, 123 Decantation, 17 Dessication, 17 Dextrin, 80 Dextrose, 82 Di-cupric carbonate, 43 Digitalin, 156 Distillation, 18 Egg albumen, 63 Elastin, 69 Emetine, 157 Erythrocruorin, 69 Ether (as test), 25 Evaporation, 18 Excretin, 129 Faeces and their analyst, 126 Fats, their detection in urine, 1 16 Fehling's standard solution, 29 test for sugar in urine, 1 10 Feme chloride (as test), 25 hydrate, 39 Ferrous sulphate (as test), 25 sulphide (as test), 25 Fermentation test for sugar in urine, 1 10 Fibrin, 65 Fibrinogen, 63 Fibrinoplastin, 64 Filtration, 17 Flame tests, 22 Fleitmann's test, 42 Flour, 144 composition of, 144 detection of ergot in, 145 detection of mineral contaminants in, 145 examination of, 145 Frohde's test, 26 Galvanism, 10 Gases, measurement of, ^2 Gelatin, 68 (as test), 25 Globulin, 64 Globulins, 63 Glucoses, 79 Glucosides, 155 Glycerides, 86 Glycerin, 83 Glycin, 77 Glycocin, 77 Glycocol, 77 Glycogen, 80 Glyoxyldiurea, 76 Gmelin's test, 114 Gold (as test), 25 Grape -sugar, 82 Gravity, 9 Guanin, 76 Haematin, 70 its detection in urine, 113 Haemato-crystallin, 69 Haemato-globulin, 69 Haematoporphyrin, 70 Haemm, 70 its detection in urine, 113 Haemochromogen, 70 Haemoglobin, 69 Hippuric acid, determination of, urine, 102 Hydrobilirubin, 71 Hydrogen (as test), 25 antimonide, 36 arsenide, 38 phosphide, 49 sulphide (as test), 25 sulphide-water (as test), 25 Hydrometers, 13 Hyoscyamine, 157 Hypobromite solution, 99 Hypochlorite solution, 99 Hypoxanthin, 76 Incineration, 18 Indican, 71 determination of, in urine, 105 Indicators, 30 Indigo in urinary calculi, 123 solution (as test), 25 Indigogen, 71 Indol, 126 Inosit, 82 Iodides, their detection in urine, 117 Iodine tincture (as test), 25 water (as test), 25 Iodinized potassic iodide (as test), 25 Keratin, 69 Kermes mineral, 37 Kreatin, 79 172 INDEX. Kreatinin, 79 determination of, in urine, 103 Lactine, 81 Lactometer, 143 Lactose, 81 Lardacein, 66 Lead, 47 acetate, neutral, 48 basic, acetates of, 48 carbonate, 48 chromate, 48 iodide, 48 its detection in urine, 118 monoxide, 47 nitrate, 48 ortho-plumbate, 47 sulphate, neutral, 48 sulphide, 49 Lecithin, 87 Leucin, 67 and tyrosin, their detection in urine, 1 15 Litmus-paper, blue, 27 red, 27 Magnesic-carbonate in urinary calculi, 124 sulphate (as test), 25 urate in urinary calculi, 124 Magnesium (as test), 25 mixture (as test), 25 Malt liquors, 149 alcoholic strength of, 149 adulterations of, 149 extractives in, 149 glycerin in, 149 picric acid in, 150 picrotoxine in, 150 specific beer test for, 149 strychnine in, 150 sugar in, 149 Maltose, 81 Marsh's test, 41 Melanin, 72 Mercury, 44 its detection in urine, 11S Mercuric chloride, 45 chloride (as test), 25 cyanide, 45 iodide, 45 nitrates, 45 oxide, 44 sulphate, 45 sulphide, 45 Mercurous chloride, 45 chloride (as test), 25 iodide, 45 nitrates, 45 Mercurous oxide, 44 sulphate, 45 sulphide, 45 Mesoxalyl-tartronyldiurea, 75 Mesoxalylurea, 75 Metaglobulin, 63 Metric and apothecaries' fluid measures, 165 and English measure, 165 and English weights, 165 Millon's reagent, 25 Milk, 141 butter in, 142 casein in, 142 composition of, 142 composition of ashes, 142 contaminants of, 143 determination of cream in, 144 examination of, 142 gases in, 142 sugar of, 142 Morphine, 157 Moore's test for sugar in urine, 109 Mucin, 69 its detection in urine, 108 Mulder-Neubauer's test for sugar in urine, 109 Muscle-fibrin, 64 Muscle-sugar, 82 Murexid, 75 test, 101 Myosin, 64 Narceine, 158 Narcotine, 158 Nessler's test, 26 Neurine, 73 Olein, 87 Osmosis, 12 Ossein, 68 Ov-albumen, 63 Oxalic acid, determination of, in urine, 103 Oxalylurea, 76 Oxyhemoglobin, its detection in urine, 113 Palmitin, 86 Pancreatic concretions, 125 Pancreatin, 73 Paraglobulin, 64 Parapeptone, 64 Paris green, 39 Pepsin, 72 Peptones, 63 their detection in urine, 108 Pettenkofer's test, 78 INDEX. 173 Pharmaceutical preparations and their active principles, 152 determination of resins in, 153 Phenolphtalein (as test), 26 Phosphates in urine, 93 Phosphorus, white, 49 red, 49 pentoxide, 49 trioxide, 49 Physostigmine, 158 Picnometer, 12 Picrotoxin, 156 Pilocarpine, 158 Platinic chloride (as test), 26 Plumbic acetate (as test), 26 basic (as test), 26 paper, 27 Polarimetry, 11 Potassio-antimony tartrate, 36 Potassic arsenite, 39 bichromate (as test), 26 chromate, neutral (as test), 26 cyanide (as test), 26 ferricyanide (as test), 26 ferrocyanide (as test), 26 hydrate, 52 hydrate (as test), 26 iodide (as test), 26 nitrate (as test), 26 n trite (as test), 26 permanganate (as test), 26 sulphocyanide (as test), 26 urate in urinary calculi, 123 Potassio-mercuric iodide (as test), 26 with potassic hydrate (as test), 26 Precipitate, weighing of, 17 Precipitation, 16 Preserved fruits and vegetables, 146 examination for metallic contaminants, 147 Protagon, 87 Proteid substances in urinary calculi, 123 Ptomaines, 161 Ptyalin, 72 Quinine, 158 Reinsch's test, 38 Rules for converting degrees of ther- mometric scale, 166 for converting measures and weights, 165 Saccharimetry by polarization, no Saccharoses, 79 Salicin, 156 Sanitary chemistry, 131 Santonin, 156 Sarkin, 76 Scheele's green, 39 Seralbumin, 62 Serine, 62 Serum albumin, 62 Skatol, 126 Soap test, Clarke's, 26 Soda-lime (as test), 26 Sodic acetate (as test), 26 arsenate, 39 bicarbonate (as test), 26 bitartrate (as test), 26 chloride in urine, 93 glycocholate, 78 hydrate, 52 hydrate (as test), 26 hypochlorite (as test), 26 hyposulphite (as test), 26 molybdate (as test), 26 phosphate (as test), 26 urate acid, 75 urate in urinary calculi, 123 Solutions, 15 Solution, argentic nitrate, standard, 29 potassic hydrate, standard, 28 oxalic acid, standard, 27 Specific gravity, 12 Spectroscopy, n Starch, 79 mucilage (as test), 26 paper, 27 Stercobilin, 71 Stearin, 86 Stibamine, 36 Strychnine, 159 Sugar, its determination in urine, 108 of lead, 48 Sulphates in urine, 96 Syntonin, 64 Table of Dietrich, 100 of elements, 164 of tension of aqueous vapor, 167 Tanret's solution as volumetric test for albumin in urine, 107, 108 Tartar emetic, 36 Taurin, 78 Thermometers, 10 Thermometric equivalents, 166 Trommer's test for sugar in urine, 109 Turmeric paper, 27 Tyrosin, 67, 73 Urea, 73 determination of, in lime, 98 in urine, 97 nitrate, 74 174 INDEX. Urea oxalate, 74 Ureostealith, 123 Uric acid, 74 determination of, in urine, 101 in urinary calculi, 122 Urine, 89 analysis of, 93 color of, 92 gases of, 93 normal composition, 92 normal constituents of, 93 reaction of, 93 specific gravity, 91 Urinary calculi, combustible, 122 incombustible, 1 24 partially combustible, 123 concretions, 121 their chemical examination, 122 sediments, 119 Urobilin, 71 detection in urine, 104 Urochrome, 71 Uromelanin, 71 Uropittin, 71 Uroxanthin, 71 Veratrine, 159 Vinegar, 152 acidity of, 152 detection of capsicum in, 152 detection of sulphuric acid in, I5 2 metallic contaminations of, 152 Vitellin, 64 Water, 135 ammonia in, 1 37 analysis of, 135 chlorides in, 137 copper in, 139 determination of metallic contami- nants in, 140 hardness of, 136 lead in, 139 metallic contaminations of, 139 nitrites in, 137 organic matter in, 137 temporary hardness of, 136 purification of, 141 iron in, 139 Weight, 9 Whiskey, 150 acidity of, 151 alcohol in, 151 fusel oil in, 151 Molnar's test for, 151 White precipitate, 45 Wines, 147 alcoholic strength of, 148 determination of acidity of, 148 examination for fuchsin in red, 148 examination for lead in, 148 sugar in, 148 Xanthin, 76 in urinary calculi, 123 Zinc (as test), 26 chloride, determination of kreati- nin in urine by, 103 SEPTEMBER, 1885. 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Armatage's Pocket-book of. 1.25 Tuson's Vet. Pharmacopoeia. 2.50 WATER. Fox. Water, Air, Food. 4.00 Frankland. Analysis of. 1.00 MacDonald. " " 2.75 WOMEN, DISEASES OF. Byford's Text-book. - 5.00 Uterus. - - - 1.25 Courty. Uterus, Ovaries, etc. 6.00 Dillnberger. and Children. 1.50 Duncan. Sterility. - 2.00 Gallabin. Diseases of. - Savage. Surgery of Female Pelvic Organs. - - 12.00 Tilt. Change of Life. - 1.25 THE LATEST AND Most Important Books. GOODHART AND STARR. A MANUAL OF THE DIS- EASES OF CHILDREN. By J. F. Goodhart, m.d., Physician to the Evelina Hospital for Children ; Assistant Physician to Guy's Hospital, London. American Edition, revised and edited by Louis Starr, m d., Clinical Professor of Diseases of Children in the Hospital of the University of Pennsylvania; Physician to the Children's Hospital, Philadelphia. With Formulae. 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