GLYCERIN, Glycerine or Glycerol (in pharmacy Glycerinum) (from Gr. γλυκύς, sweet), a trihydric alcohol, trihydroxypropane, C3H5(OH)3. It is obtainable from most natural fatty bodies by the action of alkalis and similar reagents, whereby the fats are decomposed, water being taken up, and glycerin being formed together with the alkaline salt of some particular acid (varying with the nature of the fat). Owing to their possession of this common property, these natural fatty bodies and various artificial derivatives of glycerin, which behave in the same way when treated with alkalis, are known as glycerides. In the ordinary process of soap-making the glycerin remains dissolved in the aqueous liquors from which the soap is separated.
Glycerin was discovered in 1779 by K. W. Scheele and named Ölsüss (principe doux des huiles—sweet principle of oils), and more fully investigated subsequently by M. E. Chevreul, who named it glycerin, M. P. E. Berthelot, and many other chemists, from whose researches it results that glycerin is a trihydric alcohol indicated by the formula C3H5(OH)3, the natural fats and oils, and the glycerides generally, being substances of the nature of compound esters formed from glycerin by the replacement of the hydrogen of the OH groups by the radicals of certain acids, called for that reason “fatty acids.” The relationship of these glycerides to glycerin is shown by the series of bodies formed from glycerin by replacement of hydrogen by “stearyl” (C18H35O), the radical of stearic acid (C18H35O·OH):—
| Glycerin. | Monostearin. | Distearin. | Tristearin. |
| CH2·OH | CH·OH | CH2·OH |
CH2·O(C18H35O) | CH·OH | CH2·OH |
CH2·O(C18H35O) | CH·O(C18H35O) | CH2·OH |
CH2·O(C18H35O) | CH·O(C18H35O) | CH2·O(C18H35O) |
The process of saponification may be viewed as the gradual progressive transformation of tristearin, or some analogously constituted substance, into distearin, monostearin and glycerin, or as the similar transformation of a substance analogous to distearin or to monostearin into glycerin. If the reaction is brought about in presence of an alkali, the acid set free becomes transformed into the corresponding alkaline salt; but if the decomposition is effected without the presence of an alkali (i.e. by means of water alone or by an acid), the acid set free and the glycerin are obtained together in a form which usually admits of their ready separation. It is noticeable that with few exceptions the fatty and oily matters occurring in nature are substances analogous to tristearin, i.e. they are trebly replaced glycerins. Amongst these glycerides may be mentioned the following:
Tristearin—C3H5(O·C18H35O)3. The chief constituent of hard animal fats, such as beef and mutton tallow, &c.; also contained in many vegetable fats in smaller quantity.
Triolein—C3H5(O·C18H33O)3. Largely present in olive oil and other saponifiable vegetable oils and soft fats; also present in animal fats, especially hog's lard.
Tripalmitin—C3H5(O·C16H31O)3. The chief constituent of palm oil; also contained in greater or less quantities in human fat, olive oil, and other animal and vegetable fats.
Triricinolein—C3H5(O·C18H23O2)3. The main constituent of castor oil.
Other analogous glycerides are apparently contained in greater or smaller quantity in certain other oils. Thus in cows’ butter, tributyrin, C3H5(O·C4H7O)3, and the analogous glycerides of other readily volatile acids closely resembling butyric acid, are present in small quantity; the production of these acids on saponification and distillation with dilute sulphuric acid is utilized as a test of a purity of butter as sold. Triacetin, C3H5(O·C2H3O)3, is apparently contained in cod-liver oil. Some other glycerides isolated from natural sources are analogous in composition to tristearin, but with this difference, that the three radicals which replace hydrogen in glycerin are not all identical; thus kephalin, myelin and lecithin are glycerides in which two hydrogens are replaced by fatty acid radicals, and the third by a complex phosphoric acid derivative.
Glycerin is also a product of certain kinds of fermentation, especially of the alcoholic fermentation of sugar; consequently it is a constituent of many wines and other fermented liquors. According to Louis Pasteur, about 130th of the sugar transformed under ordinary conditions in the fermentation of grape juice and similar saccharine liquids into alcohol and other products becomes converted into glycerin. In certain natural fatty substances, e.g. palm oil, it exists in the free state, so that it can be separated by washing with boiling water, which dissolves the glycerin but not the fatty glycerides.
Properties.—Glycerin is a viscid, colourless liquid of sp. gr. 1.265 at 15° C., possessing a somewhat sweet taste; below 0° C. it solidifies to a white crystalline mass, which melts at 17° C. When heated alone it partially volatilizes, but the greater part decomposes; under a pressure of 12 mm. of mercury it boils at 170° C. In an atmosphere of steam it distils without decomposition under ordinary barometric pressure. It dissolves readily in water and alcohol in all proportions, but is insoluble in ether. It possesses considerable solvent powers, whence it is employed for numerous purposes in pharmacy and the arts. Its viscid character, and its non-liability to dry and harden by exposure to air, also fit it for various other uses, such as lubrication, &c., whilst its peculiar physical characters, enabling it to blend with either aqueous or oily matters under certain circumstances, render it a useful ingredient in a large number of products of varied kinds.
Manufacture.—The simplest modes of preparing pure glycerin are based on the saponification of fats, either by alkalis or by superheated steam, and on the circumstance that, although glycerin cannot be distilled by itself under the ordinary pressure without decomposition, it can be readily volatilized in a current of superheated steam. Commercial glycerin is mostly obtained from the “spent lyes” of the soap-maker. In the van Ruymbeke process the spent lyes are allowed to settle, and then treated with “persulphate of iron,” the exact composition of which is a trade secret, but it is possibly a mixture of ferric and ferrous sulphates. Ferric hydrate, iron soaps and all insoluble impurities are precipitated. The liquid is filter-pressed, and any excess of iron in the filtrate is precipitated by the careful addition of caustic soda and then removed. The liquid is then evaporated under a vacuum of 27 to 28 in. of mercury, and, when of specific gravity 1.295 (corresponding to about 80% of glycerin), it is distilled under a vacuum of 28 to 29 in. In the Glatz process the lye is treated with a little milk of lime, the liquid then neutralized with hydrochloric acid, and the liquid filtered. Evaporation and subsequent distillation under a high vacuum gives crude glycerin. The impure glycerin obtained as above is purified by redistillation in steam and evaporation in vacuum pans.
Technical Uses.—Besides its use as a starting-point in the production of “nitroglycerin” (q.v.) and other chemical products, glycerin is largely employed for a number of purposes in the arts, its application thereto being due to its peculiar physical properties. Thus its non-liability to freeze (when not absolutely anhydrous, which it practically never is when freely exposed to the air) and its non-volatility at ordinary temperatures, combined with its power of always keeping fluid and not drying up and hardening, render it valuable as a lubricating agent for clockwork, watches, &c., as a substitute for water in wet gas-meters, and as an ingredient in cataplasms, plasters, modelling clay, pasty colouring matters, dyeing materials, moist colours for artists, and numerous other analogous substances which are required to be kept in a permanently soft condition. Glycerin acts as a preservative against decomposition, owing to its antiseptic qualities, which also led to its being employed to preserve untanned leather (especially during transit when exported, the hides being, moreover, kept soft and supple); to make solutions of gelatin, albumen, gum, paste, cements, &c. which will keep without decomposition; to preserve meat and other edibles; to mount anatomical preparations; to preserve vaccine lymph unchanged; and for many similar purposes. Its solvent power is also utilized in the production of various colouring fluids, where the colouring matter would not dissolve in water alone; thus aniline violet, the tinctorial constituents of madder, and various allied colouring matters dissolve in glycerin, forming liquids which remain coloured even when diluted with water, the colouring matters being either retained in suspension or dissolved by the glycerin present in the diluted fluid. Glycerin is also employed in the manufacture of formic acid (q.v.). Certain kinds of copying inks are greatly improved by the substitution of glycerin, in part or entirely, for the sugar or honey usually added.
In its medicinal use glycerin is an excellent solvent for such substances as iodine, alkaloids, alkalis, &c., and is therefore used for applying them to diseased surfaces, especially as it aids in their absorption. It does not evaporate or turn rancid, whilst its marked hygroscopic action ensures the moistness and softness of any surface that it covers. Given by the mouth glycerin produces purging if large doses are administered, and has the same action if only a small quantity be introduced into the rectum. For this purpose it is very largely used either as a suppository or in the fluid form (one or two drachms). The result is prompt, safe and painless. Glycerin is useless as a food and is not in any sense a substitute for cod-liver oil. Very large doses in animals cause lethargy, collapse and death.