SOAP may in general terms be defined as a chemical compound resulting from the union of fatty oils and fats with alkaline bodies. In a scientific definition the compounds of fatty acids with basic metallic oxides, lime, magnesia, lead oxide, &c, should also be included under soap; but, as these compounds are insoluble in water, while the very essence of a soap in its industrial relations is solubility, it is better to speak of the insoluble compounds as " plasters," limiting the name " soap " to the compounds of fatty acids with soda and potash. Soap both as a medicinal and as a cleansing agent was known to Pliny (H.N., xxviii. 51), who speaks of two kinds—hard and soft—as used by the Germans. He mentions it as originally a Gallic invention for giving a bright hue to the hair ("rutilandis capillis "). There is reason to believe that soap came to the Bomans from Germany, and that the detergents in use in earlier times and mentioned as soap in the Old Testament (Jer. ii. 22 ; Mai. iii. 2, &c.) refer to the ashes of plants and other such purifying agents (comp. vol. x. p. 697).

Till Chevreul's classical researches on fatty bodies (1811-23) it was believed that soap consisted simply of a binary compound of fat and alkali. Claude J. Geoffroy in 1741 pointed out that the fat or oil recovered from a soap solution by neutralization with a mineral acid differs from the original fatty substance by dissolving readily in alcohol, which is not the case with ordinary fats and oils. The significance of this observation was overlooked; and equally unheeded was a not less important discovery by Scheele in 1783. In preparing lead plaster by boiling olive oil with oxide of lead and a little water—a process palpably analogous to that of the soap-boiler—he obtained a sweet substance which, called by himself " Oelsiiss" (" principium dulce oleorum"), is now known as "glycerin." These discoveries of Geoffroy and Scheele formed the basis of Chevreul's researches by which he laid bare the constitution of oils and the true nature of soap. (See OILS, vol. xvii. p. 740, and GLYCERIN, vol. x. p. 697.) In those articles it is pointed out that all fatty oils and fats are mixtures of glycerides, that is, of bodies related to the alcohol glycerin C3H6(OH)3, and some fatty acid such as palmitic acid (C1(iH310,)H. Under suitable conditions

== IMAGE ==

The corresponding decomposition of palmitin into palmitic acid and glycerin takes place when the glyceride is distilled in superheated steam, and similarly it can be realized by boiling in water mixed with a suitable proportion of caustic potash or soda. But in this case the fatty acid unites with the alkali into its potash or soda salt, forming a soap—

== IMAGE ==

Of the natural fats or glycerides contained in oils the most important in addition to palmitin are stearin and olein, and these it may be sufficient to regard as the principal fatty bodies concerned in soap-making.

The general characters of a soap are a certain greasiness to the touch, ready solubility in water, with formation of viscid solutions which on agitation yield a tenacious froth or "lather," an indisposition to crystallize, readiness to amalgamate with small proportions of hot water into homogeneous slimes, which on cooling set into jellies or more or less consistent pastes. Soaps give an alkaline reaction and have a decided acrid taste ; in a pure condition—a state never reached in practice—they have neither smell nor colour. Almost without exception potash soaps even if made from the solid fatty acids are " soft," and soda soaps, although made with fluid olein, are "hard"; but there are considerable variations according to the pre-vailing fatty acid in the compound. Almost all soda soaps are precipitated from their watery solutions by the addition of a sufficiency of common salt. Potash soap with the same reagent undergoes double decomposition—a proportion being changed into a soda soap with the forma-tion of chloride of potassium. Soap when dissolved in a large amount of water suffers hydrolysis, with formation of a precipitate of alkaliferous fatty acid and a solution containing free alkali. Its cleansing power is ordinarily explained by this reaction; but it is difficult to see why a solution wdiich has just thrown off most of its fatty acids should be disposed to take up even a glyceride. It is more likely that the cleansing power of soap is due to the inherent property of its solution to emulsionize fats.

Resin soaps are compounds of soda or potash with the complex acids (chiefly abietic) of which coniferous resins consist. Their formation is not due to a true process of saponification ; but they occupy an important place in conqjound soaps.

MANUFACTURE.—The varieties of soaps made are numerous ; the purposes to which they are applied are varied ; the materials employed embrace a considerable range of oils, fats, and other bodies ; and the processes adopted undergo many modifications. As regards processes of manufacture soaps may be made by the direct combination of fatty acids, separated from oils, with alkaline solutions. In the manufacture of stearin for candles, &c., the fatty matter is decomposed, and the liquid olein, separated from the solid fatty acids, is employed as an ingredient in soap-making. A soap so made is not the result of saponification but of a simple combination, as is the case also with resin soaps. All other soaps result from the combination of fatty oils and fats with potash or soda solutions under conditions which favour saponification. The soap solution which results from the combination forms soap-size and is a mixture of soap with water, the excess alkali, and the glycerin liberated from the oil. In such condition ordinary soft soaps and certain kinds of hard soap are brought to the market. In curd soaps, however, which form the basis of most household soap, the uncombined alkali and the glycerin are separated by "salting out," and the soap in this condition contains about 30 per cent, of water. Soap may be framed and finished in this state, but almost invariably it receives a further treatment called "refining" or "fitting," in which by remelting with water, with or without the subsequent addition of other agents to harden the finished product, the soap may be made to contain from 60 to 70 per cent, of water and yet present a firm hard texture.





Among the raw materials used by the soap-boiler the principal fatty bodies are tallow, lard, palm oil, palm-kernel oil, olive oil, cotton-seed oil, sesame oil, and cocoa-nut oil for hard soaps, and fish oils, linseed oil, marrow fat, and the lower qualities of other oils obtained by extraction, &c., for potash or soft soaps. Almond oil, spermaceti, cocoa-butter, ground-nut oil, and some others form the basis of certain toilet and medicinal soaps. Resin and colophony form essential ingredients in yellow soaps. The alkalis are used almost exclusively in the condition of caustic lyes,—solutions of their respective hydrates in water. Caustic soda is now obtained direct from the soda manufacturer, and one operation, causticizing the soda, is thus spared the soap-boiler. Potash lyes are, however, principally sharpened or causticized by the soap-boiler himself from potash carbonate, the process for which is described under POTASSIUM METALS (vol. xix. p. 589).

The process of soap-boiling is carried out in large iron boilers called " soap pans " or " coppers," some of which have capacity for a charge of 30 tons or more. The pan proper is surmounted by. a great cone or hopper called a curb, to provide for the foaming up of the boiling mass and to prevent loss from overflowing. Formerly the pans were heated by open firing from below; but now the almost universal practice is to boil by steam injected from per-forated pipes coiled within the pan, such injection favouring the uniform heating of the mass and causing an agitation favourable to the ultimate mixture and saponification of the materials. Direct firing is used for the second boiling of the soap mixture ; but for this superheated steam may with advantage be substituted, either applied by a steam-jacket round the pan or by a closed coil of pipe within it. In large pans a mechanical stirring apparatus is pro-vided, which in some cases, as in Morfit's steam "twirl," is formed of the steam-heating tubes geared to rotate. Closed cylinders in which the materials are boiled under pressure are also employed for certain soaps.

Curd Soap. —The oil mixture used differs in the several manufacturing countries, and the commercial name of the product is correspondingly varied. In Germany tallow is the principal fat; in France olive oil occupies the chief place and the product is known as Marseilles or Castile soap ; and in England tallow and palm oil are largely used. But in all countries a mixture of several oils enters into the composition of curd soaps and the proportions used have no fixity. For each ton of soap to be made from 12 to 16 cwts. of oil is required. The soap pan is charged with the tallow or other fat, and open steam is turned on. So soon as the tallow is melted a quantity of weak lye is added, and the agitation of the injected steam causes the fat and lye to become intimately mixed and pro-duces a milky emulsion. As the lye becomes absorbed, a condition indicated by the taste of the goods, additional quantities of lye of increasing strength are added. After some time, the contents of the pan begin to clear and become in the end very transparent. Lye still continues to be poured in till a sample tastes distinctly alkaline,—a test which indicates that the whole of the fatty acids have been taken up by and combined with the alkali. Then with-out further addition of alkali the boiling is continued for a few minutes, when the soap is ready for salting out or " graining." Either common salt or strong brine in measured quantity is added to the charge, and, the soap being insoluble in such salt solution, a separation of constituents takes place: the soap collects on the surface in an open granular condition, and the spent lye sinks to the bottom after it has been left for a short time to settle. Suppos-ing now that a pure soap without resin is to be made—a product little seen in the market—the spent lye is run off, steam is again turned on, pure water or very weak lye run in, and the contents boiled up till the whole is thin, close, and clear. The soap is from this again grained off or salted out, and the underlye so thrown down carries with it coloured impurities which may have been in the materials or which arise from contact with the boiler. Such washing process may have to be repeated several times when im-pure materials have been used. The spent lye of the washing being drained off, the soap now receives its strengthening boil. Steam ris turned on, and, the mass being brought to a clear condition with weak lye or water, strong lye is added and the boiling continued with close steam till the lye attains such a state, of concentration that the soap is no longer soluble in it, and it will separate from the caustic lye as from a common salt solution. The contents of the pan are once more allowed to cool and settle, and the soap as now formed constitutes a pure curd soap, carrying with it some pro-portion of uncombined alkali, but containing the minimum amount of water. It may be skimmed off the underlye and placed direct in the frames for solidification ; but that is a practice scarcely at all followed, the addition of resin soap in the pan and the sub-sequent '' crutching in " of silicate of soda and adulterant mixings being features common to the manufacture. The lye from the strengthening boil contains much alkali and is used in connexion with other boilings.

Mottled Soap.—A pure curd soap always carries with it into the cooling frame a considerable amount of coloured impurity, such as iron sulphate, &e. When it is permitted to cool rapidly the colouring matter remains uniformly disseminated throughout the mass ; but when means are taken to cause the soap to cool and solidify slowly a segregation takes place : the stearate and palmitate form a semi-crystalline solid, while the oleate, solidifying more slowly, comes by itself into translucent veins, in which the greater part of the coloured matter is drawn. In this way mottled or marbled soap is formed, and such mottled appearance was formerly highly valued as an indication of freedom from excess of water or other adulteration, because in fitted soaps the impurities are either washed out or fall to the bottom of the mass in cooling. Wow, however, the most perfect mottle can be produced by working colouring matter into the soap in the frame, and mottling is very far from being a certificate of excellence of quality.

Yellow Soap consists of a mixture of any hard fatty soap with a variable proportion—up to 40 per cent, or more—of resin soap. That substance by itself has a tenacious gluey consistence, and its intermixture in excess renders the resulting compound soft and greasy. The ordinary method of adding resin consists in stirring it in small fragments into the fatty soap in the stage of clear-boiling ; but a better result is obtained by separately preparing a fatty soap and the resin soap, and combining the two in the pan after the underlye has been salted out and removed from the fatty soap. The compound then receives its strengthening boil, after which it is fitted by boiling with added water or weak lye, continu-ing the boil till by examination of a sample the proper consistency has been reached. On settling a dark-coloured "nigger" or under-lye separates out, which, because it contains some soap and alkali, is saved for future use.





Marine Soap.—Cocoa-nut oil behaves as regards saponification quite differently from all other oils and fats in relation to the caustic alkalis. It does not form an emulsion with weak alkalis; these even under prolonged boiling have no influence on the fat. With strong alkaline solutions, on the other hand, it saponifies with the utmost readiness even without heat, and forms without the separation of any underlye a soap of stiff firm consistence notwith-standing the presence of a very large percentage of water. Such soap is not insoluble in a strong solution of salt; hence it forms a lather and can be used for washing with sea-water, from which peculiarity it derives its name " marine soap." Being thus soluble in salt water it cannot of course be salted out like common soaps ; but if a very concentrated salt solution is used precipitation is effected, and a curd soap is separated so hard and refractory as to be practically useless. Cocoa-nut soap is usually prepared by the so-called cold method, in which the fat heated to 80° C. is treated with a calculated quantity of caustic soda solution of sp. gr. 1.350, the two constituents being stirred together till the setting and hardening of the combination prevents further agitation. The property that cocoa-nut soap possesses of absorbing large proportions of water, and yet presenting the appearance of a hard solid body, makes the material a favourite basis for highly sophisticated compounds, in which water, sulphate of soda, and other alkaline solutions, soluble silicates, fuller's earth, starch, &c, play an im-portant and bulky part. Cocoa-nut soap is little prepared by itself; but it forms a principal ingredient in compound soaps meant to imitate curd and yellow soaps. Two principal methods of prepar-ing such compound soaps are employed. In the first way the ordinary oil and the cocoa-nut oil are mixed and saponified together with such a measured quantity of alkaline solution as serves to produce a hard soap without any salting out or separation of under-lye. According to the second plan, the ordinary oil is treated as for the preparation of a curd soap, and to this the cocoa-nut soap separately saponified is added in the pan and both are boiled to-gether till they form a homogeneous soap.

Silicate Soaps.—A further means of enabling a soap to contain large proportions of water and yet present a firm consistence is found in the use of silicate of soda. The silicate in the form of a concentrated solution is crutched or stirred into the soap in a mechanical mixing machine after the completion of the saponifica-tion, and it appears to enter into a distinct chemical combination with the soap. While silicate soaps bear heavy watering, the soluble silicate itself is a powerful detergent, and it possesses certain advantages when used with hard waters, so that, taking its cheapness into account, the question whether its introduction into soap is a fraud may be fairly discussed and much said in its defence.

Framing.—The frames into which hard soaps are ladled for cooling and solidification consist of rectangular boxes made of iron plates and bound and clamped together in a way that allows the sides to be removed when required. The solidification is a very gradual process, depending, of course, for its completion on the size of the block; but before cutting into bars it is essential that the whole should be set and hardened through and through, else the cut bars would not hold together. Many ingenious devices for forming bars have been produced ; but generally a strong frame is used, across which steel wires are stretched at distances equal to the size of the bars to be made, the blocks being first cut into slabs and then into bars.

Soft Soap.—As already said, soft soaps are made with potash lyes, although in practice a small quantity of soda is also used to give the soap some consistence. There is no separation of underlyes in potash soaji, consequently the product contains the whole consti-tuents of the oils used, as the operation of salting out is quite impracticable owing to the double decomposition which results from the action of salt, producing thereby a hard principally soda soap with formation of chloride of potassium. Owing to this circumstance it is impossible to "fit" or in any way purify soft soap, and all impurities which go into the pan of necessity enter into the finished product. The making of soft soap, although thus a much less complex process than hard soap making, is one that demands much skill and experience for its success. From the conditions of the manufacture care must be taken to regulate the amount and strength of the alkali in proportion to the oil used, and the degree of concentration to which the boiling ought to be continued has to be determined with close observation.

Toilet Soaps, &c.—Soaps used in personal ablution in no way differ from the soaps previously alluded to, and may consist of any of the varieties. It is of consequence that they should, as far as possible, be free from excess of alkali and all other salts and foreign ingredients which may have an injurious effect on the skin. The manufacturer of toilet soap generally takes care to present his wares in convenient form and of agreeable appearance and smell; the more weighty duty of having them free from uncombined alkali is in many cases entirely overlooked. Transparent soaps are prepared by dissolving ordinary soap in strong alcohol and distilling off the greater portion of the alcohol till the residue comes to the condi-tion of a thick transparent jelly. This, when cast into forms and allowed to harden and dry slowly, comes out as transparent soap. A class of transparent soap may also be made by the cold process, with the use of cocoa-nut oil, castor oil, and sugar. It generally contains a large amount of uncombined alkali, and that, with its unpleasant odour of cocoa-nut oil, makes it a most undesirable soap for personal use. Toilet soaps of common quality are perfumed by simple melting and stirring into the mass some cheap odorous body that is not affected by alkalis under the influence of heat. The finer soaps are perfumed by the cold method ; the soap is shaved down to thin slices, and the essential oil kneaded into and mixed with it by special machinery, after which it is formed into cakes by pressure in suitable moulds.

Glycerin soap ordinarily consists of about equal parts of pure hard soap and glycerin (the latter valuable for its emollient properties). The soap is melted by heat, the glycerin is stirred in, and the mixture strained and poured into forms, in which it hardens but slowly into a transparent mass. With excess of glycerin a fluid soap is formed, soap being soluble in that body, and such fluid soap has only feeble lathering properties. Soap containing small proportions of glycerin, on the other hand, forms a very tenacious lather, and when soap bubbles of an enduring character are desired glycerin is added to the solution. Soaps are also prepared in which large proportions of fine sharp sand, or of powdered pumice, are incorporated, and these substances, by their abrading action, powerfully assist the detergent influence of the soap on hands much begrimed by manufacturing operations.

Medicated soaps contain certain substances which exercise a specific influence on the skin. A few medicated soaps are prepared for internal use, among which are crotón soap and jalap soap), both gentler cathartics than the uncompounded medicinal principles. Medicated soaps for external use are only employed in cases of skin ailments and as prophylactic washes. Among the principal varieties are those which contain carbolic acid, petroleum, borax, camphor, chlorine, iodine, mercurial salts, sulphur, and tannin. Arsenical soap is very much employed by taxider-mists for the preservation of the skins of birds and mammals. It consists of a mixture of white arsenic, hard soap, and slaked lime, say 4 oz. of each, with 12 oz. of carbonate of potash, the wdiole being made into a stiff paste with water.

The following table indicates the average composition of several commercial soaps:—

== TABLE ==

Soap Analysis.—Here it will be sufficient to mention a few tests which can be executed without special chemical knowledge. To determine the water in a soap—a most important question—a few thin-slices are weighed and dried in a stove at 105°C. so long as loss of weight continues. The loss of weight is the measure of uncombined water in the sample. Added salts, such as alkaline silicates, sulphates, &c. and insoluble earthy admixtures are detected by boiling a sample with alcohol, in which only the soap proper dissolves. The residue is collected in a filter, washed with hot alcohol, and weighed. An excessive proportion of surplus alkali can be detected by dissolving the soap in hot water and adding a sufficiency of saturated solution of common salt to salt it out. The alkali remains: in solution and can be determined by the amount of a standard acid solution it neutralizes.

Commerce.—Marseilles has long been recognized as the most important centre of the soap trade, a position that city originally achieved through its ready command of the supplies of olive oil. The city is still very favourably situated for obtaining supplies, of oils both local and foreign, including sesame, ground nut, castor oil, &c. In England the soap trade did not exist till the 16th century. In the reign of Charles I. a monoply of soap-making was farmed to a corporation of soap-boilers in London, —a proceed-ing which led to serious complications. From 1712 to 1853 an excise duty ranging from Id. to 3d. was levied on soap made in the United Kingdom, and that heavy impost (equal when 3d. to-more than 100 per cent.) greatly impeded the development of the' industry. In 1793, when the excise duty was 2 1/4 d. on hard and 1 3/4 d. on soft soap, the revenue yielded was a little over £400,000; in 1815 it was almost £750,000; in 1835, when the duty was levied at 1 1/2 d. and 1d. respectively (and when a drawback was allowed for soap used in manufactures), the revenue was almost £1,000,000 ;; and in 1852, the last year in which the duty was levied, it amounted to £1,126,046, with a drawback on exportation amounting to £271,000. What the manufacture has risen to since that time there is no accurate way of estimating. (W. D.—J. PA.)



The above article was written by: Prof. Dittmar and James Paton.