This section is from "Scientific American Supplement". Also available from Amazon: Scientific American Reference Book.
The methods employed up to the present in examination of fats, animal and vegetable, are mere reactions lacking general application; scattered throughout the literature, and doubtful with regard to reliability, they are of little or no value to the experimenter - an approximate quantitative examination even of a simple mixture being exceedingly difficult if not impossible, since the qualitative composition of fatty substances is the same, and the separation of the nearer components impracticable. The object of analysis consisted in estimating the accompanying impurities of fat, as, resin, albuminoids, and pigments. The nature of these substances depends on the mode of extraction and preservation of the fat, and are subject in the course of time to alteration. The only reaction based upon the chemical constitution of fat is produced by treatment of oleic or linoleic acid with nitrous acid, which therefore is of some value in the examination of drying oils. Of general application are the methods which correspond to the chemical constitution of fats, and thus determine the relative quantity of the components; advantage can then be derived from qualitative reactions, inasmuch as they further affirm the result of the quantitative test, or dispel any doubt with regard to the correctness of the result.
The principal methods which comply with these demands have been carefully studied by Hueble for the purpose of discovering a process of general application; methods founded on the determination of density, freezing, and melting point were compared with those dependent on the solubility of fatty substances in glacial acetic acid or a mixture of alcohol and acetic acid; also the method of Hehner for testing of butter, the determination of glycerine and oleic acid, and at length the process of saponification. Nearly all fats contain members belonging to one of the three series of fatty acids, e.g., acids of the type of acetic acid (stearic and palmitic acids); such as are derivatives of acrylic acid (oleic and erucic acids); and such as are homologues of tetrolic acid (linoleic acid). It is likely that the relative quantity of each of these acids is variable, with regard to the same fat, within definite limits, and changes with the nature of the fatty substance. The groups of fatty acids are distinguished by a characteristic deportment toward halogens; while members of the first series are indifferent to haloids, those of the second and third class combine readily, without suffering substitution, with two respectively four atoms of a haloid.
In view of this behavior the first series is termed saturated, the second and third that of unsaturated acids. Addition of halogen to one of the unsaturated acids yields on subsequent examination an invariable quantity of the former, representing two or four atoms, according to one or the other of unsaturated groups; and as the molecular weights of fatty acids are unequal, the percentage quantity of halogen will be found varying with regard to members belonging to the same series. The amount of iodine absorbed by some of the fatty acids is illustrated by the following items:
| Hypogallic acid, | CHO, | combines | with | 100.00 | grammes. | iodine. |
| Oleic acid, | CHO | " | " | 90.07 | " | " |
| Erucic acid, | CHO | " | " | 75.15 | " | " |
| Ricinoleic acid, | CHO | " | " | 85.24 | " | " |
| Linoleic acid, | CHO | " | " | 201.59 | " | " |
Of the halogens employed in the examination, iodine is preferable to either chlorine or bromine; it acts but slowly at ordinary, but energetically at elevated temperatures. The reagents are solution of mercury iodo-chloride prepared by dissolving of 25 grms. iodine, 500 c.c. alcohol of 95 per cent., and of 30 grms. mercury chloride in an equal measure of the same solvent; both liquids are filtered and united; a standard solution of sodium hyposulphite produced by digestion of 24 grms. of the dry salt with 1 liter water and titration with iodine solution; solution of potassium iodide of 1:10; chloroform, and finally a solution of starch. The above solution of mercury iodo-chloride acts on both free unsaturated acids and glycerides, producing addition products. For testing a sample of 0.2 to 0.4 grm. of a liquid, and from 0.8 to 1.0 grm. of a solid fat being used, which is dissolved in 10 c.c. chloroform and treated with 20 c.c. mercury iodo-chloride solution run into it from a burette, if the liquid appear opalescent a further measure of chloroform is introduced, while the amount of mercury iodo-chloride must be such as to produce a brownish coloration of the chloroform for two subsequent hours.
The excess of iodine is determined, on addition of from 10 to 15 c.c. potassium iodide solution and 150 c.c. distilled water, by means of caustic soda. From a burette divided into 0.1 c.c. a solution of caustic soda is poured with continual gyration of the flask into the tinged liquid, and the percentage of combined iodine ascertained by difference; for this purpose 20 c.c. of mercury iodo-chloride are tested, on introduction of a solution of potassium iodide and starch, previously to its use as reagent. Adulteration of solid or semi-liquid fats, especially lard, butter, and tallow, with vegetable oils are readily detected by this method, since the latter yield on examination a high percentage of iodine. Animal fats, absorb comparatively less halogen than vegetable fats, and the power to combine with iodine increases with the transition from the solid to the liquid state, and attains its maximum with vegetable oils - the method being adapted to the examination of fat mixtures containing glycerides and free saturated fatty acids, provided that substances which under similar conditions combine with iodine are absent. These conditions are fulfilled with regard to the examination of animal fats and soap.
Ethereal oils are also acted upon by iodine; the reaction proceeds similar to that observed in ordinary fat mixtures. Alcoholic mercury iodo-chloride can probably be used with success in synthetical chemistry, as it allows determination of the free affinities of the molecule and conversion of unsaturated compounds into saturated chlorine-iodo addition products. - Rundschau.
 
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