This class of examinations is particularly necessary when the crime of infanticide is suspected. As the complete incineration of a cadaver is a long and difficult operation, it frequently occurs that bones—partially or completely carbonized, but retaining their original form—are discovered by the careful examination of the ashes of the fire-place in which the combustion was accomplished.
When this is not the case and complete incineration and disaggregation have occurred, recourse must be had to the indications furnished by a chemical analysis. These indications are reliable, however, only when the certainty exists that bones of animals have not been consumed in the same fire-place; otherwise, the results obtained are entirely worthless, the reactions given by ashes of animal bones being identical with those produced by the ashes of a human body. Two tests are employed to detect the presence of bones in the residue left by the combustion of animal matter.
1. A portion of the ashes is placed in a silver crucible, heated with potassa, and the mass afterwards treated with cold water. If animal matter is contained in the consumed materials, cyanide of potassium will be present in the aqueous solution. In order to detect this salt, the fluid is acidulated with hydrochloric acid, and a solution of persulphate of iron added: the formation of a blue precipitate indicates the presence of the cyanide.
2. The ashes are next examined for phosphate of lime. As wood, coal, and the other substances usually employed for heating purposes contain none or little of this salt, its detection in a notable quantity would lead to the inference that bones have been consumed. The ashes are allowed to digest for twenty-four hours with one-quarter of their weight of sulphuric acid. Water is next added to the pasty mixture, and the fluid filtered. If phosphate of lime be present, it is converted by this treatment into a soluble acid phosphate, which passes into the filtrate. Upon adding ammonia to the filtrate, a precipitate of neutral phosphate of lime is formed, neutral phosphate of ammonia remaining in solution. The fluid is again filtered, the filtrate acidulated with nitric acid, and then boiled with a solution of molybdate of ammonia likewise acidulated with nitric acid: in presence of a phosphate, a yellow precipitate, or at least a yellow coloration of the fluid, will be produced. It has been stated that the disengagement of sulphuretted hydrogen, upon treating the ashes with sulphuric acid, is an indication that the combustion of a human body has occurred; this reaction is, however, valueless, inasmuch as coal and certain vegetable ashes likewise evolve the gas when subjected to the same treatment.
Contracts, checks, etc., are frequently altered with criminal intent, either by erasing the portion of the writing over the signature and substituting other matter, or by changing certain words, in order to modify the signification of a sentence.
Writings are altered either by erasure or by washing. Erasure, although more easily executed, is seldom employed, as it renders the paper thin in places, and in this way leaves effects apparent even to the naked eye, and, although the original thickness can be restored by application of sandarac or alum, these substances possess properties differing from those exhibited by paper, and may, moreover, be completely removed, thus exposing the thinning of the paper.
In case washing by means of chlorine has been resorted to, the sizing—which renders the paper non-bibulous, and which is only with difficulty replaced—may have been removed. Formerly paper was sized by immersion in a solution of gelatine; at present, however, a soap of resin, or wax, and alumina (a little starch being added) is more commonly used. In the latter case, the sizing is less easily removed by the action of water than when the gelatine preparation is employed; the detection of its attempted restoration is also a matter of less difficulty, as gelatine would be employed for this purpose, and this body possesses properties different from those exhibited by the substances normally contained in paper: iodine, for instance, which imparts a yellow color to gelatine, turns starch violet-blue. In order to detect the alteration of a writing, the following examinations are made:
1º. The paper is carefully examined in all of its parts, and in various positions, by aid of a lens. In this way, either thinned points, caused by erasure, or remaining traces of words, may possibly be discovered.
2º. The paper is next placed upon a perfectly clean piece of glass, and completely and uniformly moistened with water. The glass is then removed, and the transparency of the paper examined by aid of a lens. When uniform transparency is exhibited, and certain portions are neither more transparent nor more opaque than the rest of the paper, it is probable that erasure has not been attempted. If, on the other hand, opaque points are observed, it is almost certain that letters have been erased, and sandarac, which is not affected by water, subsequently applied. In case transparent points are detected, there is reason to suspect that words have been removed, and the spots either left intact or afterwards coated with a substance soluble in water, such as alum.
3º. The paper is dried and the above operation repeated with alcohol of 87 per cent. Indications may now be observed which failed to occur in the treatment with water; as well as these latter confirmed. As alcohol dissolves sandarac, the points that formerly appeared opaque may now become transparent.
4º. The paper is again dried, then placed under a sheet of very thin silk-paper, and a warm iron passed over it. This operation frequently causes the reappearance of words that have been partially obliterated. It is also advisable—as suggested by M. Lassaigne—to expose the paper to the action of iodine vapors. If alteration has not been attempted, the paper will acquire an uniform color; yellow, if sized with gelatine; violet blue, if sized with the mixture of soap, resin and starch. When, on the contrary, a subsequent sizing of gelatine has been applied in order to mask the alteration—the paper having been originally sized with the above mixture—it will assume in some portions a yellow, in others a violet-blue color.
5º. It is ascertained whether the paper possesses an acid reaction. If so, its acidity may result from the presence of hydrochloric acid, in case the paper was washed with chlorine, or of other acids. Alum, used to disguise erasure, would also cause an acid reaction. The mere detection of acidity is, in itself, of little importance, as, in the manufacture of paper, the pulp is bleached by means of chlorine, and this reagent may not have been entirely removed by washing. If, however, the paper is acid only in certain spots, and these points produce a red coloration upon blue litmus paper, having the form of letters, the indication is of value. In order to ascertain if this be the case, it is advisable, before wetting the paper, to slightly press it upon a sheet of moist litmus paper: the acid spots will then leave a reddish trace upon the latter.
6º. The manuscript under examination is again spread upon a glass-plate, and a solution of tannin (or preferably, a solution of ferrocyanide of potassium containing one per cent. of the salt, and acidulated with acetic acid) applied by means of a brush. If the original writing was executed with ordinary ink (which has as its base tannate of iron), and the washing has been but imperfectly performed, it is quite possible that a blue coloration will be produced by the action of the ferrocyanide. It is, however, often necessary to apply the above reagents several times before the original writing becomes apparent; indeed, in some cases months have elapsed before the reaction has occurred.
In case the alteration or destruction of the document is feared in the above test, it is well to previously provide the court with a certified copy, and then proceed with the examination.
7º. If the paper possesses a friable appearance, it has possibly been washed with sulphuric acid. This property may however originate from other causes, and the presence of the acid should be confirmed by washing the document with distilled water, and adding a solution of chloride of barium to the washings. The precipitate should form in a considerable quantity, as a slight cloudiness could be due to sulphates contained in the water used in the preparation of the pulp.
If much sulphuric acid be present, it may be so concentrated by heating as to cause the carbonization of the paper.
8º. It is also well, should washing with sulphuric acid be suspected, to ascertain, by aid of a lens, if the filaments on the surface of the manuscript possess an inflated appearance. This would be caused by the escape of carbonic acid, originating from the action of sulphuric acid upon the carbonates contained in the water used in the manufacture of the paper.
9º. Old ink is more difficult to remove than new, and it is therefore sometimes possible to cause the reappearance of old writings, over which words have been subsequently written. For this purpose, a solution containing 50 per cent. of oxalic acid is applied with a fine brush over the suspected points. As soon as the ink disappears, the acid is immediately removed by washing with water, and the paper dried. Upon now repeating the operation, the presence of a former writing may be detected after the complete disappearance of the words last written.
10º. According to M. Lassaigne, when the same ink has not been used throughout a document, washing with dilute hydrochloric acid will demonstrate the fact. This acid, while causing the gradual obliteration of characters written with ordinary ink—the shade of the paper not being altered—produces a red color, if ink containing log-wood has been employed, and a green coloration, in case the ink used contained Prussian blue.
The expert may possibly be called upon to give evidence as to the existence of a "trompe-l'oeil;" as was the case in the trial of M. de Preigne, which took place at Montpelier in 1852. A "trompe-l'oeil" consists of two sheets of paper, glued together at the edges, but having the upper sheet shorter than the other which therefore extends below it. This species of fraud is executed by writing unimportant matter on the uppermost sheet, and then obtaining the desired signature, care being taken that it is written on the portion of the paper projecting below. The signature having been procured, it is only necessary to detach the two sheets in order to obtain a blank paper containing the signature, over which whatever is desired can be inserted. The trial referred to above, was in reference to a receipt for 3,000 francs. The expert, upon placing pieces of moistened paper upon the suspected document, noticed that they adhered to certain points, and that these formed a border around the paper but passing above the signature. The fraudulency of the act was thus established, and so recognized by the court, although the accused was acquitted by the jury.
Numerous means have been proposed, in order to render the falsification of documents a matter of difficulty. The most reliable of these is the use of "Grimpe's safety-paper," containing microscopic figures, the reproduction of which is impossible. Unfortunately, up to the present, the government has adopted methods less sure.
Sympathetic inks are those which, although invisible at the time of writing, become apparent by the application of certain agents. They are of two classes: those which are rendered visible by the mere application of heat, such as chloride of cobalt, or the juice of onions; and those which are brought out only by the action of a reagent. The inks of the second class most frequently used are solutions of acetates of lead, and other metals which give a colored sulphide when treated with sulphuretted hydrogen. Characters written with a solution of ferrocyanide of potassium acquire a blue color, if washed with a solution of perchloride of iron. It is scarcely necessary to add that the latter solution can be used as the ink, and the ferrocyanide as the developer.
When the presence of characters written with a sympathetic ink is suspected, the document is examined as follows:
1. The paper is at first warmed: if the ink used is of the first class, the characters will now become legible; otherwise the examination is continued as below.
2. The paper is exposed to the action of steam, in order to moisten the ink present (care being taken to avoid dissolving the characters), and a current of sulphuretted hydrogen allowed to act upon it. If the ink used consists of a lead, bismuth, or gold salt, a black coloration will ensue; if salts of cadmium or arsenic were employed, the characters will acquire a yellow color; if, finally, a salt of antimony was used, a red coloration will be produced.
3. If no coloration was caused by the action of sulphuretted hydrogen, it is probably that either a solution of ferrocyanide of potassium or a persalt of iron has been resorted to. Each of these solutions is separately applied on a small portion of paper by means of a brush, and notice taken if the characters become visible. The solution that produced the change is then applied over the entire sheet.
4. In case only negative results were obtained in the preceding operations, it must not yet be concluded that a sympathetic ink has not been used, although we are left without further recourse to chemical tests. Numerous organic compounds may have been resorted to, the detection of which is almost impossible; moreover, if a mistake was made in regard to the preparation supposed to have been used, the reagents employed for its detection may render the discovery of another ink absolutely impossible. It is therefore often necessary to apply mechanical tests. For this purpose, the paper is spread upon a glass plate, uniformly moistened with water, and a second plate placed over it: if the characters were written with a pulverulent substance suspended in water or mucilage, they may often be observed upon examining the transparency of the paper. In case the substance used is both colorless and soluble, the detection of the written characters will be more difficult; still, indelible traces may possibly have been left by the pen. If, however, the ink employed is a colorless and transparent organic compound of rare occurrence, and was applied with a fine pencil-brush which failed to affect the paper, it must be acknowledged that little or nothing can be definitely determined as to its presence or absence.
In all civilized countries a fixed standard for coins and precious alloys is established by law, in order to prevent the perpetration of frauds which would be of serious injury to the public welfare. The substitution of coins consisting of an alloy inferior in value to the standard fixed by law, is too advantageous a fraud not to be often attempted.
Coins are most frequently altered by clipping; by stuffing, that is, by boring the coin and inserting an alloy of small value; by doubling, which operation consists in covering its face with two thin laminæ taken from a genuine coin; and by applying a coating of gold or silver by means of electro-plating.
In order to ascertain if a coin has been counterfeited, its weight should at first be determined. If it has been clipped, or consists of an alloy possessing a density less than that of silver or gold, the fact is immediately demonstrated by its decreased gravity.
The coin is further tested by throwing it down upon a hard substance: gold and silver give a ringing sound, whereas the majority of other metals produce a dull sound.
The result obtained by this latter test often fails to be reliable. A skilful counterfeiter may prepare an alloy equally sonorous and heavy as silver or gold; in fact, M. Duloz exhibited to the author an alloy, prepared by him, possessing the density, sonorousness and lustre of silver; the composition of which, for obvious reasons, has not been published.
In instances of this nature the fusibility of the coin should be determined, and the result obtained compared with the melting point of the legal alloy, or, this failing, a chemical analysis executed. In order to perform the latter test, the coin under examination is boiled with nitric acid: all metals are dissolved, with exception of gold and platinum, which remain unaltered, and tin and antimony, which are converted respectively into metastannic and antimonic acids. The fluid is filtered, the insoluble residue well washed, and then boiled with hydrochloric acid, which dissolves the metastannic and antimonic acids. The solution is again filtered, and the second residue dissolved in aqua regia. The metals dissolved in the several filtrates are then detected, either by the processes previously given for the detection of metallic poisons, or by the more complete methods contained in works on chemical analysis. This qualitative test is, however, insufficient, in case the falsification consisted in merely diminishing the proportions of the valuable metals contained in the alloy, without changing its qualitative composition: it is then necessary to execute a quantitative estimation of the metals present. As this operation requires considerable practice and the methods employed are to be found in all treatises on quantitative analysis, we will not reproduce them here.
We will next enumerate the methods employed in the detection of the principal adulterations to which flour, bread, oils of seeds, milk, wines, vinegar and the sulphate of quinine are subjected. These researches, united with those preceding, fail to embrace all the diverse examinations which the chemical expert may be expected to execute; but we do not claim to foresee all the contingencies that may arise, and will describe the steps to be pursued in instances which are anticipated, at the same time indicating general methods applicable to cases not here included.
The adulterations to which flour and bread are exposed usually consist in adding damaged or an inferior grade of flour to wheaten flour, or in disguising the presence of a poor quality of flour by the addition of mineral substances, such as: plaster, chalk, lime, alum, and sulphate of copper.
Good flour has a white color, possessing a slightly yellow tinge, but is entirely free from red, grey or black specks. It is soft to the touch and adheres to the fingers, acquiring, when compressed in the hand, a soft cushion-like form. If mixed with water, it forms an elastic, homogeneous, but slightly coherent dough, which can be extended out in thin layers.
Flour of an inferior quality possess a dull white color, and does not assume the cushion-like condition mentioned above, when pressed in the hand, but escapes between the fingers: the dough formed is of a poorer quality.
Flour which has been damaged by moisture has a dull or reddish-white hue, and possesses a mouldy, or even a noxious, odor, as well as a bitter and nauseous taste which produces a marked acid sensation in the throat. Occasionally the presence of moisture causes the growth of fungi, the introduction of which in the digestive organs would cause serious results.
The constituents of pure flour are:
In the process of bread-making, the gluten undergoes fermentation by the action of the leaven and liberates carbonic acid, which causes the dough to become porous and swell up, or, as it is termed, to rise. Bread contains the same substances as flour, but gluten and starch are present in a state that does not admit of their separation by mechanical means, and glucose, if present at all, exists in a smaller quantity: the proportion of dextrine and water is, on the other hand, considerably increased. The bread of the Paris city bakeries contains 40 per cent. of water—the crumb, which forms 5/6 of the weight of the bread, containing 45 per cent.; the crust, which constitutes the remaining 1/6, containing 15 per cent. In army bread 43 per cent. of water are contained—the crumb, which constitutes 4/5 of the weight of the bread, holding 50 per cent.; the crust which forms the remaining 1/5, containing 15 per cent.
The addition of common salt naturally increases the proportion of ash left upon calcining bread.
Water is contained in stale bread in the same quantity as in fresh bread; but exists in a modified molecular condition: upon heating stale bread, it acquires the properties of fresh bread.
The following substances are used in the adulteration of wheaten flour:[P]
In order to detect these substances, the gluten, the starch, and the ash are separately examined.
In order to separate the gluten, two parts of the flour to be examined and one part of water are mixed into a paste, and this is placed in a fine linen sack, in which it is kneaded under a stream of water so long as the washings have a turbid appearance: these are preserved. The gluten obtained from good wheaten flour possesses a light-yellow color; emits a stale odor; and spreads out, when placed in a saucer. In case the flour has been too strongly heated in the grinding, or otherwise badly prepared, the gluten is granulous, difficult to collect in the hand, and somewhat resembles flint-stone in appearance.
Gluten prepared from a mixture of equal parts of wheat and rye is adhesive, blackish, without homogeneousness, spreads out more readily than pure wheaten gluten, separates easily and adheres somewhat to the fingers.
Gluten obtained from a mixture of wheat and barley is non-adhesive, of a dirty reddish-brown color, and appears to be formed of intertwined vermicular filaments.
Gluten formed from a mixture of equal parts of wheat and oats has a blackish-yellow color and exhibits, at the surface, numerous small white specks.
The gluten from a mixture of wheat and corn has a yellowish color, is non-adhesive, but firm, and does not readily spread.
Gluten prepared from a mixture of wheat and leguminous flour is neither cohesive nor elastic, and, if the proportion of the latter present be considerable, can be separated and passed through a sieve, like starch.
The gluten obtained from a mixture of equal parts of wheat and buckwheat flour is very homogeneous, and is as easily prepared as the gluten from pure wheaten flour. It possesses when moist a dark-grey color; which changes to a deep black upon drying. The proportion of gluten in flour is exceedingly variable: good flour contains from 10 to 11 per cent. of dry gluten; poor flour from 8 to 9 per cent. of moist gluten, equal to about one-third of its weight of the dry compound.
The washings of the flour are allowed to stand for some time in a conical-shaped vessel. As soon as the amylaceous matter has entirely settled to the bottom of the vessel, the greater portion of the water is decanted, and the residual mass brought upon a small filter and allowed to dry. The residue is then examined for potato and rice starch.
Potato starch. The grains of potato starch are much larger than those of wheaten starch. If a portion of the residue mentioned above is crushed in an agate mortar, the granules of potato starch present are ruptured, and their contents liberated; the wheaten starch remaining unaltered. The mass is then taken up with water, and the fluid filtered. If potato starch be present, the filtrate will acquire a blue color upon addition of an aqueous solution of iodine; otherwise, a yellow or violet-rose coloration is produced. It is necessary to avoid crushing the residue for too long a time, as the granules of wheaten starch would also become ruptured by prolonged comminution.
Besides the difference presented by potato starch in the size of the granules in comparison to those of wheaten starch, the former swell to ten or fifteen times the volume of the latter, when treated with a solution of potassa: wheaten starch granules are not affected by the treatment, if the solution used does not contain more than 2 per cent. of the salt. The results obtained by the above operation should be confirmed by a microscopic examination.
A portion of the residue is moistened with solution of iodine, then carefully dried, and placed on the slide of a microscope. The mass is next moistened with a solution containing 2 per cent. of potassa, and examined. The addition of iodine causes the potato starch granules to acquire a blue color, and renders their shape and volume more easily perceptible; thus allowing the two varieties of starch to be readily distinguished. Fig. 13 represents the relative size of the granules as observed under the microscope.[Q]
The presence of potato starch in bread is also detected by crushing a small portion of the sample under examination on the glass, and then adding a few drops of the alkaline solution.
Rice and Corn.—If rice or corn meal have been mixed with the flour, angular and translucent fragments (Fig. 14) are observed in the microscopic examination. Corn meal acquires a yellow color, if treated with dilute potassa solution.
Linseed and rye meals.—If linseed meal is moistened with an aqueous solution containing 14 per cent. of potassa and examined under the microscope, numerous minute characteristic granules, smaller than the grains of potato-starch, are observed. These possess a vitreous appearance, sometimes a reddish color, and usually form in squares or very regular rectangles. The test is equally applicable to bread. The detection of linseed and rye meals is simultaneously effected by exhausting the suspected flour with ether, then filtering the solution and allowing it to evaporate. If the flour contains rye, the oil left by the evaporation, when heated with a solution of mercury in concentrated nitric acid, is converted into a solid substance having a fine red color; but it remains unaltered, if entirely due to linseed. In case the oil becomes solidified, the mercury salt present should be removed by washing with water, the residue taken up with boiling alcohol of 36° B. and the solution filtered: upon evaporating the alcoholic filtrate, a residue is obtained consisting of the linseed oil present.
Buckwheat.—Flour adulterated with buckwheat is less soft to the touch, does not pack as easily, and passes more readily through a sieve than pure wheaten flour. It presents, here and there, blackish particles, due to the perisperm of the grain, and has a dirty-white color. As previously remarked, the gluten obtained from a mixture of buckwheat and wheaten flour possesses a grey or even a black color. The starch furnished by buckwheat flour exhibits polyhedral agglomerations, analogous to those presented by corn.
Darnel.—The use of darnel in the adulteration of wheaten flour may give rise to serious sanitary results. To effect its detection, the flour to be examined is digested with alcohol of 35° B.: if the flour be pure, the alcohol remains limpid: it acquires a straw-yellow tint, due to traces of bran present, but—although a peculiar resin may be dissolved—the solution does not possess a disagreeable taste. When, on the contrary, darnel is present, the alcohol assumes a green tint, which gradually deepens, and possesses a bitter and nauseous taste; the residue, left by the evaporation of the tincture to dryness, has a greenish-yellow color, and a still more disagreeable flavor than the alcoholic solution.
Legumens.—Leguminous meals cannot be added otherwise than in small proportions to wheaten flour, owing to the rapidity with which they change the properties of the latter, and communicate to it their characteristic odor—noticeable upon treating the flour with a little boiling water. Their presence is also easily detected by the distinctive properties of the vegetable itself, and by the appearance of the amylaceous residue in the microscopic examination. In order to decide as to the presence of legumens, the washings containing the starchy matter of the flour, after the particles of gluten present have been separated by passing the fluid through a silk sieve, are divided into two portions. One portion is allowed to undergo fermentation, at a temperature of 18° to 20°: in case leguminous substances are not present, lactic fermentation occurs and the odor of sour milk is alone perceptible; if, on the other hand, legumens are contained in the fluid, rancid fermentation takes place, and an odor is emitted resembling that of decayed cheese. The remaining portion of the washings, after being decanted from the residue of amylaceous matter, is filtered and evaporated until a yellowish translucent pellicle appears upon its surface. The fluid is then again filtered from the coagulated albumen common to all flours, and the leguminous substances present coagulated by the addition, drop by drop, of acetic acid.
The leguminous deposit produced appears white and flaky; when examined under the microscope, it presents lamilla emarginated at the border; it is odorless and tasteless; when dried, it assumes a horny appearance; it is insoluble, both in water and alcohol, and does not become gelatinous when treated with boiling water; it is readily soluble in potassa and other alkaline solutions, from which it is precipitated upon addition of nitric, hydrochloric, acetic, oxalic, and citric acids; upon protracted boiling in water, it loses its property of being soluble in ammonia. The above tests having been applied, the residue containing the starch is next examined. For this purpose, a small portion is moistened with a little water, a few drops of iodine solution added, and the mixture placed on the side of the microscope: the bluish grains contained in the polyhedral and cellular envelope (Fig. 15) are easily recognized. The mixture on the glass may also be treated with an aqueous solution of potassa (containing 10 per cent. of the salt), or with dilute hydrochloric acid: these reagents dissolve the starch present, leaving the reticulated tissue intact. Should this examination fail to give a definite result, the remaining portion of the amylaceous residue is subjected to a sort of levigation, and the part most slowly deposited separated. In this portion the reticulated tissues of the leguminous substances present are contained, and, as they are comparatively free from foreign matters, their identification is a matter of comparative ease. In case the presence of reticulated tissue is indicated, it is still necessary to apply confirmatory chemical tests.
Meals prepared from beans, horse-beans, and lentils, contain a tannin which imparts a green or black color to salts of iron. The coloration is rendered very sensitive if a rather considerable quantity of the flour to be examined is passed through a silk sieve, and the remaining bran treated with a solution of sulphate of iron (ferrico-ferrous sulphate): the reaction immediately occurs, even if the sample contains but 10 per cent. of bean meal. The meals of horse-beans and of vetches acquire a red color, when exposed to the successive action of nitric acid and of ammonia vapors. In order to apply this test, the suspected flour is placed upon the edge of a capsule containing nitric acid, the latter heated, and, as a yellow coloration appears, the acid removed and replaced by ammonia. The capsule is then set aside: if the flour is adulterated with either of the above vegetables, reddish spots, which are easily perceptible by aid of a magnifying glass, are soon produced.
In case bread is to be examined, it is exhausted with water, the fluid passed through a sieve, the upper layer decanted, then evaporated, and the residue taken up with alcohol. The tincture so obtained is evaporated, and the second residuum treated with nitric acid and ammonia, as directed above. When meals prepared from beans, vetches, or lentils are heated on a water-bath with hydrochloric acid, diluted with three to four times its volume of water, a cellular tissue, possessing the color of wine-dregs, remains behind; flours of wheat, peas, and kidney-beans leave a colorless residue, when subjected to the same treatment.
Finally; the grains of the starch (fecula) of legumens possess a volume about equal to that of potato granules, and exhibit either a longitudinal furrow in the direction of their longer axis, or a double furrow arranged in a star-like form.
Leguminous substances, and more particularly mineral salts, are detected by the examination of the ash left upon the incineration of the flour.
Detection of Legumens.—Pure wheaten flour furnishes an ash consisting of about 2 per cent. of its weight; whereas meals of legumens leave from 3 to 4 per cent. of their weight in ash. This difference is, however, too slight to furnish conclusive results; the analysis of the ash is also necessary. The ash of wheaten flour is non-deliquescent, dry, semi-fused, and chiefly consists of phosphates of potassa, soda, magnesia and lime, of sulphates, and of silica. The solution obtained by treating the ash with water has an alkaline reaction. The phosphates of the alkalies, present in the ash of wheat, exist in the state of pyrophosphates, and, as chlorides are absent, the addition of nitrate of silver to the aqueous solution of the ash produces a white precipitate, consisting entirely of pyrophosphate of silver, which is not affected by exposure to the light.
The ash of leguminous meals is deliquescent and soluble in water, forming a strongly alkaline solution, which contains both chlorides and neutral phosphates. The latter give a clear yellow precipitate with nitrate of silver. Upon adding a solution of this salt to the aqueous solution of the ash, a pale yellow precipitate, which turns violet if exposed to the light, is therefore produced.
Detection of mineral substances.—The principal mineral substances, that are fraudulently added to flour, are ground calcined bones, sand, lime, plaster, alum, and sulphate of copper. The two last named salts are almost invariably added in small quantities; alum renders the flour white, even when used in the proportion of one per cent.; sulphate of copper is added to impart a good appearance to bread made from a damaged flour.
a. Ground bones (carbonate and phosphate of lime).—The washings of the gluten are placed in a conical vessel, and, after some time has elapsed, the clear supernatant fluid is removed by means of a syphon, a conical shaped deposit remaining on the bottom of the vessel: two hours later, the fresh layer of fluid that has formed is removed with a pipette. As soon as the residue becomes nearly solid, it is detached from the vessel, placed upon a fragment of plaster, and allowed to dry. The bones, being heavier than the amylaceous substances, are to be found in the apex of the cone formed by the residue. This is detached, and incinerated: in case the ash obtained contains phosphate and carbonate of lime, the addition of hydrochloric acid will cause effervescence, and, upon adding ammonia to the acid solution, a white precipitate will be formed. If the solution is then filtered and oxalate of ammonia added to the filtrate, a precipitate will be produced which, when heated to redness, leaves a residue of caustic lime possessing an alkaline reaction.
b. Sand.—As this substance possesses a much greater specific gravity than the usual constituents of flour, it is only necessary, in order to accomplish its separation, to repeatedly stir the flour with water, and remove the deposit at first formed, which, if consisting of sand, will be insoluble in acids, and will grate, when placed between the teeth.
c. Carbonates of lime and magnesia; vegetable ashes.—Carbonic acid is always evolved, upon treating flour with hydrochloric acid. If the base present be calcium, upon adding oxalate of ammonia to the filtered solution—which has previously been neutralized with ammonia—a white precipitate, possessing the properties mentioned above, will be formed; in case the base is magnesia, the addition of oxalate of ammonia will fail to cause a precipitate, but upon adding solution of phosphate of ammonia to the fluid a granular precipitate of phosphate of ammonia and magnesia is produced; if, finally, the flour contains vegetable ashes—i. e. carbonates of the alkalies—bichloride of platinum will produce in the acid solution a yellow precipitate: the addition of vegetable ashes, moreover, would render the ash of the flour deliquescent and very strongly alkaline.
d. Lime.—In presence of lime, carbonic acid produces a white precipitate, when conducted into the filtered aqueous extract of the flour.
e. Plaster.—The flour is boiled with water acidulated with hydrochloric acid, the fluid filtered, and lime detected in the filtrate by means of ammonia and oxalate of ammonia. The presence of sulphuric acid is indicated by the formation of a precipitate insoluble in acids, upon addition of solution of chloride of barium. Upon calcining the flour without access of air, sulphate of lime is converted into the corresponding sulphide: the residue of the calcination, when treated with hydrochloric acid, evolves sulphuretted hydrogen, and the lime present in the filtered acid solution is likewise precipitated by the addition of ammonia and oxalate of ammonia.
f. Alum.—A portion of the flour to be examined is treated with water, the fluid filtered, and the filtrate divided in two portions: in one, sulphuric acid is detected by means of chloride of barium; in the other, alumina by adding a solution of potassa, which gives with its salts a white gelatinous precipitate, soluble in an excess of the reagent.[R]
g. Sulphate of copper.—About 200 grammes of the bread under examination are incinerated; the ash treated with nitric acid; the mixture evaporated until it acquires a sticky consistence, and the mass then taken up with water. The aqueous solution is next filtered; an excess of ammonia and several drops of solution of carbonate of ammonia added; the fluid again filtered, the filtrate slightly acidulated with nitric acid, and divided into two parts. It is then ascertained if sulphuretted hydrogen produces in one portion of the solution a brown precipitate of sulphide of copper, and if solution of ferrocyanide of potassium produces in the other a reddish-brown precipitate of ferrocyanide of copper.[S]
Olive oil designed for table use is frequently adulterated with the oils of poppy, sesamé, cotton-seed, pea-nuts, and other nuts; olive oil, intended for manufacturing purposes, is often mixed with colza and nut oils.
The tests used are of a rather unsatisfactory character. In all instances, when the chemist is called upon to pronounce as to the adulteration of an oil, it is necessary to execute comparative experiments with the pure oil, and with admixtures arbitrarily prepared: it is only when this is done that the indications obtained are of value.
a. The density of the oil is determined by means of a hydrometer (oleometer) provided with a scale giving the densities from 0.8 to 0.94, for the temperature of 15.° Pure olive oil possesses a specific gravity of 0.917; poppy oil one of 0.925; a mixture of the two, an intermediate density. Since the fixed oils are not definite chemical compounds, this test is seldom conclusive.
b. Two or three cubic centimetres of concentrated nitric acid, containing nitric peroxide in solution (or a solution of mercury in strong nitric acid), are added to the oil to be examined, as well as to a sample of pure olive oil. The two samples are then allowed to stand in a room where the temperature does not exceed 10.° The oleine of the olive oil is converted into solid elaidine, and the mixture after some time becomes sufficiently thick to remain in the vessel upon inversion. If the sample under examination is free from adulteration, it will solidify at the same time as the pure oil; whereas, the presence of one per cent. of poppy oil, or of other drying oils, suffices to retard the solidification for forty minutes.
c. Fifteen grammes of the oil are mixed in a glass vessel with the same amount of strong sulphuric acid, the temperature of the two liquids being previously observed. The mixture is stirred with a thermometer, and the maximum temperature noted: pure olive oil produces an elevation of temperature of 37.°7; pure poppy oil, an elevation of 70.°5; and a mixture of the two an elevation of temperature intermediate between 37.°7 and 70.°5.
d. One volume of nitric acid of sp. gr. 1.33 is agitated with 5 grammes of the oil, and notice taken of the coloration produced after the lapse of five minutes. If the olive oil is pure, it acquires a pale green color; in case it is mixed with sesamé or nut oil, a deep-red color appears: poppy oil also communicates a reddish coloration, but one less deep than the preceding.
If an acid of sp. gr. 1.22 is taken, it is still less difficult to distinguish between sesamé, nut and poppy oils; the latter assumes, in this case, a pale yellowish-red color.
Pea-nut oil fails to exhibit a coloration; but can be recognized by its conversion into a white solid, when mixed with 1/5 of its volume of a solution of caustic soda of sp. gr. 1.34.
The chief adulterations are colza and nut oils. The latter is detected by means of the reaction with nitric acid, as described above. Colza oil is recognized by mixing 5 volumes of the sample to be examined, with 1 volume of sulphuric acid of sp. gr. 1.655: if colza or nut oils are present, a brown coloration ensues; under the same circumstances, pure olive oil assumes a pale greenish hue. In case the sample acquires a brown color when treated with sulphuric acid, and a red coloration is produced by the addition of nitric acid, it contains nut oil; if sulphuric acid produces a brown coloration, and nitric acid fails to change it, the presence of oil of colza is indicated.
This oil is frequently adulterated with linseed oil. The reactions exhibited by these oils are nearly identical, and the detection of the admixture is extremely difficult. It is advisable to mix the suspected oil with sulphuric acid, notice being taken of the elevation of temperature produced, and to treat it with nitric acid and with dilute potassa solution, subjecting, at the same time, an artificial mixture of the two pure oils to the same treatment, and comparing the results obtained.
Among alimentary substances probably no article is subjected to more adulteration than tea. The sophistications practised may be conveniently divided into three classes:
1. Additions made for the purpose of giving increased bulk and weight, which include foreign leaves and exhausted tea-leaves, and also certain mineral substances, such as metallic iron, sand, brick-dust, etc.
2. Substances added in order to produce an artificial appearance of strength in the tea decoction, catechu, or other bodies rich in tannin, and iron salts being chiefly resorted to for this purpose.
3. The imparting of a bright and shining appearance to the tea by means of various coloring mixtures or "facings," which adulteration, while sometimes practised upon black tea, is much more common with the green variety. This sophistication involves the use of steatite (soap-stone), sulphate of lime, China clay, Prussian blue, indigo, turmeric, and graphite; chromate of lead and copper salts being but very rarely employed. The compound most frequently used consists of a mixture of soap-stone (or gypsum) with Prussian blue, to which a little turmeric is sometimes added.
Genuine tea is the prepared leaf of Thea sinensis. It contains: moisture, 6% to 10%; theine, 0.4% to 4.0%; tannin, (green) 20%, (black) 10%; ash, 5% to 6%; soluble extractive matters, 32% to 50%; and insoluble leaf, 47% to 54%.