H. A. Appleton

“ Decomposition of Fats by Bacteria.—Though this subject is not of any practical interest in the preparation of fatty acids for soap-making, it may be mentioned, in passing, that some bacteria readily hydrolyse fats. Schriber (Arch. f. Hyg., 41, 328-347) has shown that in the presence of air many bacteria promote hydrolysis, under favourable conditions as to temperature and access of oxygen, the process going beyond the simple splitting up into fatty acid and glycerol, carbon dioxide and water being formed. ”

“ Tallow soaps are so slowly soluble that they are not applicable to the scouring of silk.
The dyer of silk requires soap, which is neutral and of a pleasant odour. The preference is given to neutral olive-oil soft soap, but hard soaps (made from olive oil, oleine, or palm oil) are used chiefly on account of cheapness. It is essential, however, that the soap [Pg 94] should be free from rosin on account of its frequent use and consequent decomposition in the acid dye bath, when any liberated rosin acids would cling to the silk fibres and produce disagreeable results. ”

“ The extent of dissociation occurring when a soap is dissolved in water depends upon the nature of the fatty acids from which the soap is made, and also on the concentration of the solution. The sodium salts of cocoa-nut fatty acids (capric, caproic and caprylic acids) are by far the most easily hydrolysed, those of oleic acid and the fatty acids from cotton-seed oil being dissociated more readily than those of stearic acid and tallow fatty acids. The decomposition increases with the amount of water employed. ”

“ II. Action of Enzymes.—It was discovered by Muntz in 1871 (Annales de Chemie, xxii.) that during germination of castor seeds a quantity of fatty acid was developed in the seeds, which he suggested might be due to the decomposition of the oil by the embryo acting as a ferment. Schutzenberger in 1876 showed that when castor seeds are steeped in water, fatty acids and glycerol are liberated, and attributed this to the hydrolytic action of an enzyme present in the seeds. ”

“ Colouring Matter.—During recent years an outcry has been made against highly coloured soaps, and the highest class soaps have been manufactured either colourless or at the most with only a very delicate tint. It is obvious that a white soap guarantees the use of only the highest grade oils and fats, and excludes the introduction of any rosin, and, so far, the desire for a white soap is doubtless justified. Many perfumes, however, tend to quickly discolour a soap, hence the advantage of giving it a slight tint. ”

“ The unsaponifiable matter naturally present as cholesterol, or phytosterol, ranges in the various oils and fats from 0.2 to 2.0 per cent. All oils and fats contain more or less free acidity; but excess of acidity, though it may be due to the decomposition of the glyceride, and does not always denote rancidity, is undesirable in soap-making material. Rancidity of fats and oils is entirely due to oxidation, in addition to free acid, aldehydes and ketones being formed, and it has been proposed to estimate rancidity by determining the amount of these latter produced. ”

“ From this time till the beginning of the nineteenth century the manufacture of soap developed very slowly, being essentially carried on by rule-of-thumb methods, but the classic researches of Chevreul on the constitution of fats at once placed the industry upon a scientific basis, and stimulated by Leblanc's discovery of a process for the commercial manufacture of caustic soda from common salt, the production of soap has advanced by leaps and bounds until it is now one of the most important of British industries. ”

“ Soda and Potash.—Unlike the preceding bases, the soaps formed by soda and potash are soluble in water, and constitute the soap of commerce. These reagents are always used in sufficient quantity to combine with the whole of the fatty acids contained in an oil or fat, though doubtless, by the use of considerably smaller quantities, under pressure, complete resolution of the fatty matter into fatty acids and glycerol could be accomplished. ”

“ Soap made from cocoa-nut oil and palm-kernel oil will admit of the incorporation of large quantities of a solution of either salt, carbonate of soda, or silicate of soda, without separation, and will retain its firmness. These materials are, therefore, particularly adapted for the manufacture of marine soaps, which often contain as much as 80 per cent. of water, and, being soluble in brine, are capable of use in sea-water. ”

“ For the same reason, cocoa-nut oil enters largely into the constitution of hydrated soaps, but the desired yield or grade of soap allows of a variation in the choice of materials. Whilst marine soap, for example, is usually made from cocoa-nut oil or palm-kernel oil only, a charge of 2/3 cocoa-nut oil and 1/3 tallow, or even 2/3 tallow and 1/3 cocoa-nut oil, will produce a paste which can carry the solutions of silicate, carbonate, and salt without separation, and yield a smooth, firm soap. ”

“ Another way in which it has been suggested that soap acts as a cleanser is that the soap itself or the alkali set free by hydrolysis serves as a lubricant, making the dirt less adherent, and thus promoting its removal. ”

“ For yellow soaps, containing a low percentage of fatty acids, [Pg 65] solutions of silicate of soda of varying strengths are generally used.
It is always advisable to have a test sample made with the soap to ascertain what proportion and what strength of sodium silicate solution is best suited for the grade of soap it is desired to produce. It is important that the soap to be "silicated" should be distinctly alkaline (i.e., have a distinct caustic taste) , or the resultant soap is liable to become like stone with age. ”

“ The soap-base or mixture of various kinds of soap is remelted in a steam-jacketed pan, or pan provided with steam coils, and agitated. The agitation must not be too vigorous or lengthy, or the soap will become aerated. When all the soap is molten, additions of pearl ash solution are made to give it a finer and smoother texture, render it more transparent, and increase its lathering properties. ”

“ Another operation in which soap is used, is that of milling or fulling, whereby the fabric is made to shrink and thus becomes more compact and closer in texture. The fabric is thoroughly cleansed, for which purpose the soap should be neutral and free from rosin and silicates, otherwise a harsh feeling or stickiness will be produced. Curd soaps or finely-fitted soaps made from tallow or bleached palm oil, with or without the addition of cocoa-nut oil, give the best results. All traces of soap must be carefully removed if the fabric is to be dyed. ”

“ As pointed out in Chapter II. the fatty acids, which, combined with soda or potash, form soap, occur in nature almost invariably in the form of glycerides, i.e., compounds of fatty acids with glycerol, and as the result of saponification of a fat or oil glycerine is set free.
In Chapter V. processes of soap-making are described in which (1) the glycerine is retained in the finished soap, and (2) the glycerine is contained in the lyes, in very dilute solution, contaminated with salt and other impurities. ”

“ It has long been known that whilst recently rendered animal fats are comparatively free from acidity, freshly prepared vegetable oils invariably contain small quantities of free fatty acid, and there can be no doubt that this must be attributed to the action of enzymes contained in the seeds or fruit from which the oils are expressed, hence the necessity for separating oils and fats from adhering albuminous matters as quickly as possible. ”

“ The most likely theory yet advanced is that based on the emulsifying power of soap solutions. The fact that these will readily form emulsions with oils has long been known, and the detergent action of soap has frequently been attributed to it, the explanation given being that the alkali set free by the water emulsifies the fatty matter always adhering to dirt, and carries it away in suspension with the other impurities. ”

“ In the more scientific portions of the book, an acquaintance with the principles of elementary chemistry is assumed, and in this we feel justified, as in these days of strenuous competition, no soap-maker can hope to compete successfully with his rivals unless he has a sound theoretical as well as practical knowledge of the nature of the raw materials he uses, and the reactions taking place in the pan, or at other stages of the manufacture. ”

“ There is a considerable distinction, however, often lost sight of, between an artificial and a synthetic oil. An artificial oil may be produced by separating various constituents from certain natural oils, and so blending these, with or without the addition of other substances, as to produce a desired odour, the perfume being, at any rate in part, obtained from natural oils. ”

“ The colour of the resulting fatty acids is also of no importance, as they are always subjected to distillation.
During the last few years, however, there has been a growing attempt to first separate the glycerol from the fatty acids, and then convert the latter into soap by treatment with the carbonates of soda or potash, which are of course considerably cheaper than the caustic alkalies, but cannot be used in the actual saponification of a neutral fat. The two processes chiefly used for this purpose are those in which the reaction is brought about by enzymes or by Twitchell's reagent. ”

“ Soda soaps are insoluble in concentrated caustic lyes, and, for the most part, in strong solutions of sodium chloride, hence the addition [Pg 3] of caustic soda or brine to a solution of soda soap causes the soap to separate out and rise to the surface. Addition of brine to a solution of potash soap, on the other hand, merely results in double decomposition, soda soap and potassium chloride being formed, thus:—
The solubility of the different soaps in salt solution varies very considerably. ”

“ Hillyer, to whose work reference has already been made, investigated the whole question of detergent action very exhaustively, and, as the result of a very large number of experiments, concludes that the cleansing power of soap is largely or entirely to be explained by the power which it has of emulsifying oily substances, of wetting and penetrating into oily textures, and of lubricating texture and impurities so that these may be removed easily. ”

“ Boric acid in aqueous or glycerine solutions, and borax (biborate of soda) are sometimes used, but care is necessary in employing these substances, as any excess is liable to decompose the soap.
The addition of cocoa-nut oil is unsatisfactory, the great objection being that complete saponification is difficult to ensure, and, further, there is always the liability of rancidity developing. Stearic and oleic acids are more suitable for the purpose, but oleic acid has the disadvantage that oleates are very liable to go rancid. ”

“ It is a matter of some difficulty to judge the purity of essential oils, not only because of their complex nature, but owing to the very great effect upon their properties produced by growing the plants in different soils and under varying climatic conditions, and still more to the highly scientific methods of adulteration adopted by unscrupulous vendors. ”

“ In the case of oils like bergamot oil, the odour value of which depends chiefly on their ester content, it is very important that these should not be added to soaps containing much free alkali, as these esters are readily decomposed thereby. Some perfumes possess the property of helping the soap to retain other and more delicate odours considerably longer than would otherwise be possible. ”

“ In the case of household soaps, where the resultant product must be of good appearance and have a firm texture, the difficulty is to produce a bar fit for sale after the cooling has been performed, as soap which has been suddenly chilled lacks the appearance of that treated in the ordinary way. Several patents have been granted for various methods of moulding into bars in tubes, where the hot soap is cooled by being either surrounded by running water in a machine of similar construction to a candle machine, or rotated through a cooling medium ”

“ Bone fat often contains calcium (lime) salts, which are very objectionable substances in a soap-pan. These impurities must be removed by a treatment with hydrochloric or sulphuric acid. The former acid is preferable, as the lime salt formed is readily soluble and easily removed. The fat is agitated with a weak solution of acid in a lead-lined tank by blowing in steam, and when the treatment is complete and the waste liquor withdrawn, the last traces of acid are well washed out of the liquid fat with hot water. ”

“ If simply mixed with the soap in the mill, reaction very quickly takes place between the mercury salt and the soap, with formation of the insoluble mercury compounds of the fatty acids, a change which can be readily seen to occur in such a soap by the rapid development on keeping, of a dull slaty-green appearance. ”