C3H6(C16H3102)

This article appears in Volume V25, Page 299 of the Encyclopedia Britannica.

Encyclopedia Britannica - Main :: BUN-CAL

C3H6(C16H3102) 3+3NaOH =3NaC16H3102+C,Hs(OH)3
Palmitin. Caustic Soda. Soap. Glycerin.
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 conditiona state never reached in practicethey 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 prevailing 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 decompositiona proportion being Changed into a soda soap with the formation of potassium chloride. Ammonia soaps have also been made, but with little commercial success; in 1906 H. Jackson patented the preparation of ammonium oleate directly in the washing water, and it is claimed that for cleansing articles it is only necessary to immerse them in the water containing the preparation and then rinse.
Soap when dissolved in a large amount of water suffers hydrolysis, with formation of a precipitate of acid salt and a solution containing free alkali. The reaction, however, is very complicated. Chevreul found that a neutral salt soap hydrolysed to an acid salt, free alkali, and a small amount of fatty acid. Rotondi in 1885, however, regarded a neutral soap as hydrolysing to a basic salt, soluble in both hot and cold water, and an acid salt, insoluble in cold and sparingly soluble in hot. Chevreul's views were confirmed in 1894 by Krafft and Stern. The extent to which a soap is hydrolysed depends upon the acid and on the concentration of the solution; it is also affected by the presence of metallic salts, e.g. of calcium and magnesium. As to the detergent action of a soap, Berzelius held that it was due to the free alkali liberated with water; but it is difficult to see why a solution which has just thrown off most of its fatty acids should be disposed to take up even a glyceride, and, moreover, on this theory, weak cold solutions, in which the hydrolysis is consider-able, should be the best cleansers, whilst experience points to the use of hot concentrated solutions. It is more likely that the cleansing power of soap is due to the inherent property of its solution to emulsionize fats. This view is supported by Hillyer (Jour. Amer. Chem. Soc., 1903, p. 524), who concluded that the cleansing power depended upon several factors, viz. the emulsionizing power, theproperty of penetrating oily fabrics, and lubricating impurities so that they can be readily washed away.
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 compound soaps.
Manufacture.Numerous varieties of soaps are made; 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 fat 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 3o% 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 6o to 7o% of water and kept present a firm hard texture.
Almost any fatty substance can be employed in soap-making; but the choice is naturally restricted by the price of the fat and also the quality of the soap desired. The most important of the animal fats are those of the ox and hog, and of the vegetable oils

cotton

-seed and coco-nut ; it is also to be remembered that resin, although not a fat, is also important in soap-making. Ox and sheep tallow, with the addition of resin, are the primary materials for making the hard yellow or primrose soaps; these tallows are often adulterated. The cheaper mottled and brown soaps have for their basis bone fat, obtained by treating bones with superheated steam or other methods. Lard yields lard oil, which is mainly applied in making hard toilet soaps. Curd soap and London grey mottled are prepared from kitchen or ship fat, whilst fuller's fat is employed in the manufacture of soft soaps. Of the vegetable oils, in addition to

cotton

-seed and coco-nut, olive oil is the basis of soaps for calico printers and silk dyers; castor oil yields transparent soaps (under suitable treatment), whilst crude palm oil, with bone fat, is employed for making brown soap, and after bleaching it yields ordinary pale or mottled. The alkalis are used almost exclusively in the condition of caustic lyessolutions 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 also may be bought direct, but in some cases they are sharpened or causticized by the soap-boiler himself from the carbonate.
The processes of soap manufacture may be classified (a) according to the temperatures employed into (I) cold processes and (2) boiling processes, or (b) according to the nature of the starting materialacid or oil and fatand the relative amount of alkali, into (1) direct saturation of the fatty acid with alkali, (2) treating the fat with a definite amount of alkali with no removal of unused lye, (3) treating the fat with an indefinite amount of alkali, also with no separation of unused lye, (4) treating the fat with an indefinite amount of alkali with separation of waste lye. In the second classification (2) is typical of the " cold " process, whilst (I), (3), (4) are effected by the " boiling " process.
The cold process, which is Dnly applicable to the manufacture of soaps from readily saponifiable oils, such as those of the coco-nut oil group and also from castor oil, is but little used. In it the oils at 35 C. are stirred with concentrated alkali in an iron or wooden tub, whereupon saponification ensues with a development of some heat; the mixture being well agitated. After a few hours the mixture becomes solid, and finally transparent; at this point the perfume is added, and the product framed and crutched (see under Marine Soap). By blending the coco-nut oil with other less saponifiable substances such as tallow, lard, cotton-seed oil, &c., and effecting the mixing and saponification at a slightly higher temperature, soaps are obtained which resemble milled toilet soaps. Soaps made by this process contain the glycerin originally present in the oil, but, in view
298
of their liability to contain free alkali and unsaponified oil, the appearance was formerly highly valued as an indication of freedom process has been largely given up.
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 3o tons or more. The pan proper is surmounted by a great

cone

CONE (Gr. Kwvos)

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 perforated 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 provided, which in some cases, as in Morfit's steam " twirl," is formed of the steam-heating tubes geared to rotate. Autoclaves, in which the materials are boiled under pressure, are also employed for certain soaps.
The process of manufacturing soaps by boiling fatty acids with caustic alkalis or sodium carbonate came into practice with the development of the manufacture of candles by saponifying fats, for it provided a means whereby the oleic acid, which is valueless for candle making, could be worked up. The combination is effected in open vats heated by a steam coil and provided with a stirring appliance; if soda ash be used it is necessary to guard against boiling over. (See under Curd Soap.)
Curd Soap.This variety is manufactured by boiling the fat with alkali and removing the unused lye, which is afterwards worked up for glycerin. 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

CHIEF (from Fr. chef, head, Lat. caput)

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 i6 cwt. 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 produces 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 alkalinea test which indicates that the whole of the fatty acids have been taken up by and combined with the alkali. Then without 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. Suppose that a pure soap without resin is to be madea product little seen in the marketthe 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 impure materials have been used. The spent lye of the washing being drained off, the soap is now " boiled for strength." Steam is 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 coap, 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 subsequent " 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 curd soap prepared from kitchen fat or bone grease always carries with it into the cooling frame a considerable amount of coloured impurity, such as iron sulphate, &c. 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

DRAWN

. In this way curd, mottled or marbled soap is formed, and such mottled
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. Now, however, the mottled soaps, blue and grey, are produced by working colouring matter, ultramarine for blue, and manganese dioxide for grey, 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 4o% or moreof resin soap. That sub-stance by itself has a tenacious gluey consistence, and its inter-mixture 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, continuing the boil till by examination of a sample the proper consistency has been reached. On settling the product forms three layers: the uppermost is a thin crust of soap which is worked up again in the pan; the second is the desired soap; next there is a dark-coloured weak soap termed nigre, which, because it contains some soap and alkali is saved for future use; underneath these is a solution of alkaline salts with a little free alkali.
Treatment of Settled Soap.The upper layer having been removed, the desired soap is ladled out or ran off to a crutcher, which is an iron pan provided with hand or mechanical stirring appliances. It is here stirred till it becomes ropy, and the perfume, colour or any other substance desired in the soap is added. The soap is now ready for 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; wooden frames are used in the case of mottled soaps. 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 cat 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.
Marine Soap.These soaps are so named because they are not insoluble in a strong solution of salt; hence they form a lather and can be used for washing with sea-water. 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. Coco-nut soap (see above) is typical of this class. Its property of absorbing large proportions of water, up to 8o %, and yet present the appearance of a hard solid body, makes the material a basis for the hydrated soaps, smooth and marbled, in which water, sulphate of soda, and other alkaline solutions, soluble silicates, fuller's earth,

starch

STARCH

, &c. play an important and bulky part. Coco-nut soap also forms a principal ingredient in compound soaps meant to imitate curd and yellow soaps. Two principal methods of preparingsuch compound soaps are employed. In the first way the ordinary oil and the coco nut oil are mixed and saponified together as de-scribed above. According to the second plan, the ordinary oil is treated as for the preparation of a curd soap, and to this the coconut soap separately saponified is added in the pan and both are boiled together 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 saponification, 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.
Soft Soap.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 soap, consequently the product contains the whole constituents 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 potassium chloride. Owing to this circumstance it is impossible to
potassium 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 condition 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 coco-nut oil, castor oil and sugar. It generally contains a large amount of uncombined alkali, and that, with its unpleasant odour of coco-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. The greater quantity of high-class toilet soaps are now made by a milling process. A high class soap, which after framing contains about 30 %b of water, is brought down to a water content of II-14 % by drying in chambers through which warm air is circulated. The soap is now milled in the form of ribbons with the perfume and colouring matter, and the resulting strips are welded into bars by forcing through a heated nozzle. The bars are then cut or moulded into tablets, according to the practice of the manufacturer.
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, first investigated scientifically by liana of Hamburg in 1886, contain certain substances which exercise a specific influence on the skin. A few medicated soaps are prepared for internal use, among which are croton 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, as prophylactic washes and as disinfectant soaps. Among the principal varieties are those which contain carbolic acid and other ingredients of coal tar, salicylic acid, petroleum, borax, camphor, iodine, mercurial salts, sulphur and tannin. Arsenical soap is very much employed by taxidermists for the preservation of the skins of birds and mammals.
Miscellaneous Soaps.The so-called " floating soaps " are soaps made lighter than water either by inserting cork or a metallic plate so as to form an air space within the tablet. The more usual method is to take milling soap, neutralize it with sodium bicarbonate or a mixture of fatty acids, and, after perfuming, it is aerated by mixing the hot soap with air in a specially designed crutcher. Shaving soaps, which must obviously be free from alkali or any substance which irritates the skin, are characterized by readily forming a permanent lather. This property is usually obtained by mixing soft and hard soaps, or, more rarely, by adding gum tragacanth to a hard soap. In the textile trades the wool scourer employs a neutral olive-oil soap, or, on account of its cheapness, a neutral curd or curd mottled brand ; the cotton cleanser, on the other hand, uses an alkaline soap, but for cleaning printed cottons a neutral olive-oil curd soap is used, for, in this case, free alkali and resin are objectionable; olive-oil soap, free from caustic alkali, but often with sodium carbonate, is also used in cleansing silk fibres, although hard soaps free from resin are frequently employed for their cheapness. Soaps of smaller moment are the pearl ash soaps used for removing tarry stains; ox-gall soaps for cleaning carpets; magnesia, rouge and chalk soaps for cleaning plate, &c.
Soap Analysis.The most important points in soap analysis are (I) determination of the fatty matter, (2) of the total alkali, (3) of the substances insoluble in water, (4) of the water. The first is carried out by saponifying the soap with acid in the heat when the fatty acids come to the surface. If it fails to form a hard cake on cooling, a known weight of wax may be added and the product re-heated. The cake on weighing gives the free acid. The total alkali is determined by incinerating a weighed sample in a platinum dish, dissolving the residue in water, filtering and titrating the filtrate with standard acid. The residue on the filter paper gives (3) the sub-stances insoluble in water. The water in a soap is rarely directly determined; when it is, the soap, in the form of shavings, is heated to 105 C. until the weight is constant, the loss giving the amount of
' " Soap powders " and " soap extracts " are powdered mixtures of soaps, soda ash or ordinary sodium carbonate.water, With genuine soaps, however, it suffices to calculate the fatty acids as anhydrides and add to this the amount of alkalis, and estimate the water by difference. The complete analysis involves an examination of the fatty matter, of the various forms in which the alkalis are presentfree and combined glycerin, &c.
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 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, during the reign of Charles I., a monopoly of soap-making was farmed to a

corporation

CORPORATION (from Lat. corporare, to form into a body, corpus, corporis)

of soap-boilers in Londona proceeding 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 cost) greatly impeded the development of the industry. In 1793, when the excise duty was 2'-,d. on hard and 1;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 rid. and Id. respectively (and when a drawback was allowed for soap used in manufactures), the revenue was almost ',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.
Medicine.Two preparations of hard soap (sodium oleate), made by acting on olive oil with caustic soda, are used in medicine: (I) Emplastrumsaponis, made with lead plaster; (2) Pilula saponis composita, which contains one in five parts of opium. Soft or green soap (potassium oleate), made by acting on olive oil with caustic potash, is also used ; its preparation (Linamentum saponis) is known as opodeldoc. Curd soap is also used, and is chiefly a stearate of sodium. The

chief

CHIEF (from Fr. chef, head, Lat. caput)

use of hard soap is in enemata, and as a suppository in children suffering from constipation; it also forms the basis of many pills; given in warm water It forms a ready emetic in cases of poisoning. Soft soap is used by dermatologists in the treatment of chronic eczema, and opodeldoc is a domestic remedy for stiffness and sprains. Medicated soaps are made by adding the drug to either hard soap or curd soap in the desired proportions. Useful combinations are: borax Io %, carbolic acid 5 %, ichthyol 5%, sublimed sulphur '0 %, thymol 24 %, &c.
See L. L. Lamborn, Modern Soaps, Candles and Glycerin (1906); W. H. Simmons and H. A. Appleton, The Handbook of Soap Manufacture (1908); also J. Lewkowitsch, Oils, Fats and Waxes.
SOAP-BARK, the inner bark of Quillaja saponaria, a large tree which grows in Chile. Reduced to powder, it is employed as a substitute for soap, since it forms a lather with water, owing to the presence of a glucoside saponin, sometimes distinguished as Quillai saponin. The same, or a closely similar substance, is found in soapwort (Saponaria ojcinalis), in senega root (Polygala senega) and in

sarsaparilla

SARSAPARILLA

; it appears to be chemically related to 'digitonin, which occurs in digitalis. The saponins (with few exceptions) have the general formula (C0Hs,,_sO1o,-and by the action of dilute acids they are hydrolysed into sugars and sapogenins, which are usually inert pharmacologically. An alternative name for them, and especially for those which are pharmacologically active, is sapotoxins; on this nomenclature the hydrolytic products are termed saponins. Applied as a snuff to the mucous membrane of the nose, saponin (either in soap-bark or in senega root) promotes a violent

sneezing

SNEEZING (0. Eng. fneosung, from fneosan, to sneeze, cf. Dutch fniezen, allied to the obsolete neeze, and ultimately to be referred to root seen in Gr. irveiv, to breathe; the initial s is due to association with numerous words, such as snort, snuff, snor

. Solutions injected under the skin are violent local irritants and general depressants. -

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