The Handbook of Soap Manufacture

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W. H. SIMMONS, B.Sc. (Lond.), F.C.S.

WITH TWENTY-SEVEN ILLUSTRATIONS LONDON SCOTT, GREENWOOD & SON "THE OIL AND COLOUR TRADES JOURNAL" OFFICES 8 BROADWAY, LUDGATE HILL, E.C. 1908 [All rights reserved] Transcriber's note: Footnotes have been moved to the end of the chapter and minor typos have been corrected. [Pg iii]

In the general advance of technical knowledge and research during the last decade, the Soap Industry has not remained stationary. While there has not perhaps been anything of a very revolutionary character, steady progress has still been made in practically all branches, and the aim of the present work is to describe the manufacture of Household and Toilet Soaps as carried out today in an up-to-date and well-equipped factory. 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. We also venture to hope that the work may prove useful to Works' Chemists and other Analysts consulted in connection with this Industry. At the same time, in the greater part of the book no chemical knowledge is necessary, the subject being treated in such a way that it is hoped those who are not directly engaged in the manufacture of soap, but who desire a general idea of the subject, will find it of value. In the sections dealing with the composition and analysis of materials, temperatures are expressed in degrees Centigrade, these being now almost invariably used in scientific work. In the rest of the book, however, they are given in degrees Fahrenheit (the degrees Centigrade being also added in brackets), as in the majority of factories these are still used.

As regards strengths of solution, in some factories the use of Baumé degrees is preferred, whilst in others Twaddell degrees are the custom, and we have therefore given the two figures in all cases.[Pg iv] In the chapter dealing with Oils and Fats, their Saponification Equivalents are given in preference to Saponification Values, as it has been our practice for some years to express our results in this way, as suggested by Allen in Commercial Organic Analysis, and all our records, from which most of the figures for the chief oils and fats are taken, are so stated. For the illustrations, the authors are indebted to Messrs. E. Forshaw & Son, Ltd., H. D. Morgan, and W. J. Fraser & Co., Ltd. W. H. S. H. A. A. London, September, 1908. [Pg v]

PAGE CHAPTER I. Introduction. 1 Definition of Soap—Properties—Hydrolysis—Detergent Action. CHAPTER II. Constitution of Oils and Fats, and their Saponification 6 Researches of Chevreul and Berthelot—Mixed Glycerides—Modern Theories of Saponification— Hydrolysis accelerated by (1) Heat or Electricity, (2) Ferments, Castor-seed Ferment, Steapsin, Emulsin, and (3) Chemical Reagents, Sulphuric Acid, Twitchell's Reagent, Hydrochloric Acid, Lime, Magnesia, Zinc Oxide, Soda and Potash. CHAPTER III. Raw Materials used in Soap-making 24 Fats and Oils—Waste Fats—Fatty Acids—Less-known Oils and Fats of Limited Use—Various New Fats and Oils Suggested for Soap-making—Rosin—Alkali (Caustic and Carbonated)—Water—Salt —Soap-stock. CHAPTER IV. Bleaching and Treatment of Raw Materials intended for Soap-making 41 Palm Oil—Cotton-seed Oil—Cotton-seed "Foots"—Vegetable Oils—Animal Fats—Bone Fat—

Rosin. CHAPTER V. Perfume. Cotton and Silk Industries—Patent Textile Soaps—Miscellaneous Soaps. Glycerine Manufacture and Purification 111 Treatment of Lyes—Evaporation to Crude Glycerine—Distillation—Distilled and Dynamite Glycerine—Chemically Pure Glycerine—Animal Charcoal for Decolorisation—Glycerine obtained by other methods of Saponification—Yield of Glycerine from Fats and Oils. . Colouring and Perfuming— Disinfectant Soaps—Framing—Slabbing—Barring—Open and Close Piling—Drying—Stamping —Cooling. or Medicament—Perfume—Colouring matter —Neutralising and Superfatting Material—Compressing—Cutting—Stamping—Medicated Soaps —Ether Soap—Floating Soaps—Shaving Soaps—Textile Soaps—Soaps for Woollen. Smooth and [Pg vi]Marbled—Pasting or Saponification—Graining Out—Boiling on Strength—Fitting—Curd Soaps—Curd Mottled—Blue and Grey Mottled Soaps—Milling Base— Yellow Household Soaps—Resting of Pans and Settling of Soap—Utilisation of Nigres— Transparent soaps—Saponifying Mineral Oil—Electrical Production of Soap. Treatment of Settled Soap 60 Cleansing—Crutching—Liquoring of Soaps—Filling—Neutralising. CHAPTER VI. Toilet. CHAPTER X. Soap-making 45 Classification of Soaps—Direct combination of Fatty Acids with Alkali—Cold Process Soaps— Saponification under Increased or Diminished Pressure—Soft Soap—Marine Soap—Hydrated Soaps. CHAPTER IX. CHAPTER VII. Soap Perfumes 95 Essential Oils—Source and Preparation—Properties—Artificial and Synthetic Perfumes. Textile and Miscellaneous Soaps 77 Toilet Soaps—Cold Process soaps—Settled Boiled Soaps—Remelted Soaps—Milled Soaps— Drying—Milling and Incorporating Colour. CHAPTER VIII.

having been discovered by the Gauls. for according to Pliny (Nat. the use of soap has not always been coexistent with civilisation. who used the product obtained by mixing goats' tallow and beech ash for giving a bright hue to the hair.. 151 Index 153 [Pg 1] CHAPTER I. In West Central Africa. The manufacture of soap seems to have flourished during the eighth century in Italy and Spain. especially the Fanti race. but though this may perhaps be in a great measure correct at the present day. Twaddell and Baumé. when factories were established at . 51) soap was first introduced into Rome from Germany. the natives. It has been said that the use of soap is a gauge of the civilisation of a nation. and was introduced into France some five hundred years later.Analysis of Raw Materials. xxviii. 12. Soap. INTRODUCTION. [Pg vii] Comparison of Different Thermometric Scales 148 APPENDIX C. moreover. with Actual Densities 147 APPENDIX B. Hist. have been accustomed to wash themselves with soap prepared by mixing crude palm oil and water with the ashes of banana and plantain skins. Table of the Specific Gravities of Solutions of Caustic Soda 149 APPENDIX D. Statistics of the Soap Industry 140 APPENDIX A. and Glycerine 117 Fats and Oils—Alkalies and Alkali Salts—Essential Oils—Soap—Lyes—Crude Glycerine. Comparison of Degrees. Definition of Soap—Properties—Hydrolysis—Detergent Action. Table of Strength of Caustic Potash Solutions at 60° F.. CHAPTER XI.

206. Definition of Soap. however. based not upon its composition. they are generally regarded as legitimate constituents of soap." and that of Nuttall. among which may be mentioned that of Kingzett. a definition which includes not only sodium stearate. Chem. . The use of ammonia as an alkali for soap-making purposes has often been attempted. manganese. e. and various pharmaceutical preparations. Krafft (Journ. Soap does not appear to have been made in England until the fourteenth century. but upon its properties. Technically speaking. being essentially carried on by rule-of-thumb methods. H. Jackson has. commonly called rosin soap. due to hydrolysis (vide infra).g. with soda or potash. but the classic researches of Chevreul on the constitution of fats at once placed the industry upon a scientific basis. the molecules. In the case of soda soaps the colloidal character increases with the molecular weight of the fatty acids. From this time till the beginning of the nineteenth century the manufacture of soap developed very slowly. but also the linoleates of lead. or the fatty acids derived therefrom. In cold water they dissolve more slowly. together with a number of other metallic salts of fatty acids.—Both soda and potash soaps are readily soluble in either alcohol or hot water. but owing to the ease with which the resultant soap is decomposed. a property possessed by colloidal bodies. in contradistinction to substances which under the same conditions deposit crystals. or definite aggregates of molecules. and stimulated by Leblanc's discovery of a process for the commercial manufacture of caustic soda from common salt. although arranged differently to that of a crystal. the meaning of the term soap is considerably restricted. obtained by treating various animal or vegetable fatty matters. for the acid constituents of rosin have been shown to be aromatic. oleate and palmitate. the latter soft soaps. have investigated this property of soap solutions very fully. and 1902. and owing to slight decomposition. it can scarcely be looked upon as a product of much commercial value.. and receiving legislative sanction in Holland in 1875. however.Marseilles for the manufacture of olive-oil soap. 6. 691. due to diminished solubility of the salt at a lower temperature. who says that "Soap. the researches extending over several years. This detergent is prepared in the wash-tub at the time of use. but there is a definite structure. Other definitions of soap have been given. Ind. the former giving hard soaps. 601. 1899. Sodium oleate is peculiar in not undergoing hydrolysis except in very dilute solution and at a low temperature. mercury oleate (Hydrargyri oleatum). who defines soap as "an alkaline or unctuous substance used in washing and cleansing". 1896. etc. of solutions which become gelatinous on cooling move much more slowly than the molecules in the formation of a crystal. zinc oleate and lead plaster. the production of soap has advanced by leaps and bounds until it is now one of the most important of British industries. used as driers.. Wiglow. is a body which on treatment with water liberates alkali. the solution becomes distinctly turbid. 1301) and his collaborators. recently patented (Eng..712. Pat. tallow) appears to have been originally applied to the product obtained by treating tallow with ashes. In the light of their more recent work. Strutz and Funcke. which is cognate with Latin sebum. but in view of the analogous properties of these resinates to true soap. being generally[Pg 2] limited to the combinations of fatty acids and alkalies. which form the bulk of the soaps of commerce. Properties of Soap. 1906) the use of ammonium oleate for laundry work. and it is claimed that goods are cleansed by merely immersing them in this solution for a short time and rinsing in fresh water. and the first record of soap manufacture in London is in 1524.—The word soap (Latin sapo. In its strictly chemical sense it refers to combinations of fatty acids with metallic bases. considered commercially. Soc. Neither of the definitions given above includes the sodium and potassium salts of rosin. a jelly of more or less firm consistence results. having been used in Great Britain since 1827. such as starch and gelatine. On cooling a hot soap solution.

solution of sodium chloride.. and considered that the value of a soap depended upon the ease with which it yielded free alkali on solution in water. Addition of brine to a solution of potash soap. have been suggested. however.—The term "hydrolysis" is applied to any resolution of a body into its constituents where the decomposition is brought about by the action of water. on the other hand. and sodium caproate is not thrown out of solution even by a saturated solution. the reaction taking place being represented in its simplest form by the equation:— 2NaC18H35O2 + H2O = NaOH + HNa(C18H35O2)2 sodium acid sodium water caustic soda stearate stearate The actual reaction which occurs has been the subject of investigation by many chemists.—The property possessed by soap of removing dirt is one which it is difficult to satisfactorily explain. Detergent Action of Soap. He appears. thus:— C17H35COOK + NaCl = C17H35COONa + KCl potassium sodium potassium sodium stearate stearate chloride chloride The solubility of the different soaps in salt solution varies very considerably. as appears in the above equation. The sodium salts of cocoa-nut fatty acids (capric. the particles of dirt are loosened and easily washed off. sodium laurate requires a 17 per cent. Berzelius held this view. and very diverse conclusions have been arrived at.Soda soaps are insoluble in concentrated caustic lyes. the pioneer in the modern chemistry of oils and fats. hence when soap is treated with cold water. was resolved into a basic and an acid salt. The hydrolytic action of water on soap is affected very considerably[Pg 4] by the presence of certain substances dissolved in the water. 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. it is said to undergo hydrolysis. Chevreul. Ind. Soc. 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. considered that a neutral soap. 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. merely results in double decomposition. solution to precipitate it. and. who from experiments with pure sodium palmitate and stearate entirely confirm the conclusions arrived at by Chevreul. 1747 and 1755). 1894. particularly salts of calcium and magnesium. Hydrolysis of Soap.. to have been misled by the fact that sodium oleate is readily soluble in cold water. together with the formation of an acid salt. more or less complicated. Many theories. and only slightly soluble in hot water. Chem. 601). soda soap and potassium chloride being formed. on being dissolved in water. . and also on the concentration of the solution. Chem. and his views have been shown to be incorrect by Krafft and Stern (Ber. a very minute quantity of free fatty acid remaining in solution. found that a small amount of alkali was liberated. Whilst sodium stearate is insoluble in a 5 per cent. but even now the question cannot be regarded as solved. on the other hand. The explanation commonly accepted is that the alkali liberated by hydrolysis attacks any greasy matter on the surface to be cleansed. the former readily soluble in both hot and cold water. as the fat is dissolved. the latter insoluble in cold water. Rotondi (Journ. Ges. d. as do also ethyl and amyl alcohols and glycerol. 1885. and. in strong solutions of sodium chloride. caproic and caprylic acids) are by far the most easily hydrolysed. Caustic soda exerts a marked retarding effect on the hydrolysis. for the most part. The decomposition increases with the amount of water employed.

and suggested that to this action of soap might be attributed much of its cleansing power. Quincke holds similar views.[Pg 5] 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. but. The most likely theory yet advanced is that based on the emulsifying power of soap solutions. 1903. of that of water. (1) it must have considerable viscosity. the liberated alkali would be far more likely to recombine with the acid or acid salt from which it has been separated. Yet another argument against the theory is that hydrolysis is greater in cold and dilute solutions. 1885. cit. and. but considers that no pure liquid will foam. based on the purely physical properties of soap solutions. 592) have made very complete researches on the emulsification and foaming of liquids and on the formation of bubbles. and (2) its surface tension must be low. no emulsion is produced with an oil from which all the acidity has been removed. and there can be little doubt that the ultimate solution of the problem lies in this direction.. Hillyer. 44) and Quincke (Wiedmann's. So far as viscosity is concerned. than to saponify a neutral glyceride. Chem.) show. Ann. Most of these are probably. found that the pedetic action was considerably increased by soap and sodium silicate. The former considers that there are two properties of a liquid which play an important part in the phenomenon. 524). however. The fact that these will readily form emulsions with oils has long been known. however. . Soc. making the dirt less adherent. that while N/10 solution of alkali will readily emulsify a cotton-seed oil containing free acidity. Experiments by Hillyer (loc. its surface tension being only about 40 per cent. as the result of a very large number of experiments. investigated the whole question of detergent action very exhaustively. and Knapp regarded the property of soap solutions themselves to facilitate contact of the water with the dirt. to whose work reference has already been made. Alder Wright considered that the alkali liberated by hydrolysis in some way promoted contact of the water with the substance to be cleansed. and it is doubtless to this property that its emulsifying power is chiefly due. solution of sodium oleate. is an excellent emulsifying agent. 35. whereas hot concentrated soap solutions are generally regarded as having the best detergent action. and his conclusions are therefore invalid. or with kerosene. as already pointed out. Soc. was alone responsible for the detergent action of soap. while its cohesion is also very small. at any rate in part. Chem. to be quite illogical. and carries it away in suspension with the other impurities. this can have but little influence... 141. and that the detergent action of soap will be found to depend on many of these properties. and thus promoting its removal. which has a viscosity very little different from that of pure water. his theory of the formation of a basic soap is now known to be incorrect. for a 1 per cent. Jevons in 1878 in some researches on the "Brownian movement" or "pedesis" of small particles. Amer. for. Rotondi (Journ. iron oxide. together with other factors not yet known. thus proving that the emulsification is due to the soap itself. as one of the chief causes of the efficacy of soap as a detergent.This theory is considered by Hillyer (Journ. unsaponifiable greasy matter is removed by soap as easily as saponifiable fat. Several explanations have been suggested. further. Ann. whereas a N/10 solution of sodium oleate will readily give an emulsion with either. Soap solution admirably fulfils Plateau's second condition. correct.. Plateau (Pogg. as he points out. the explanation given being that the alkali set free by the water emulsifies the fatty matter always adhering to dirt. a movement of the particles which is observed to take place when clay. this basic soap dissolving fatty matter by saponification. and not to the alkali. 601) was of the opinion that the basic soap. Ind. and the detergent action of soap has frequently been attributed to it. which he believed to be formed by hydrolysis. and there can be no question of any chemical action of the free alkali in its case. or other finely divided insoluble matter is suspended in water. while.

to form the soap. Researches of Chevreul and Berthelot—Mixed Glycerides—Modern Theories of Saponification— Hydrolysis accelerated by (1) Heat or Electricity. and the constitution of oils and fats was not properly understood. and of lubricating texture and impurities so that these may be removed easily. or other base. which together cause the low surface tension between soap solution and oil. and the glycerol remaining free. Hydrochloric Acid. [Pg 6] CHAPTER II. The term oil is of very wide significance. It was Chevreul who showed that the manufacture of soap involved a definite chemical decomposition of the oil or fat into fatty acid and glycerol. and their strong attraction or affinity to oily matter. Twitchell's Reagent. Soda and Potash. both organic and inorganic. being applied to substances of vastly different natures. Although Scheele in 1779 discovered that in the preparation of lead plaster glycerol is liberated. AND THEIR SAPONIFICATION. Sulphuric Acid.concludes that the cleansing power of soap is largely or entirely to be explained by the power which it has of emulsifying oily substances. Magnesia. Castor-seed Ferment. and may be regarded as frozen oils. CONSTITUTION OF OILS AND FATS. the fatty acid combining with soda. Lime. Zinc Oxide. Steapsin. potash. Fats readily become oils on heating beyond their melting points. soap at that time was regarded as a mere mechanical mixture. Emulsin. and (3) Chemical Reagents. It is thought that all these properties may be explained by taking into account the low cohesion of the soap solutions. The reactions with stearin and palmitin (of which tallow chiefly consists) and with olein (found largely in olive and cotton-seed oils) are as follows:— CH2OOC18H3 5 CH2OH | = 3NaOOC18H35 + CHOH | CH2OH sodium hydroxide sodium stearate glycerol | CHOOC18H35 + 3NaOH | CH2OOC18H3 5 stearin CH2OOC16H3 1 CH2OH | = 3NaOOC16H31 + CHOH | | CHOOC16H31 + 3NaOH | . but so far as soap-making materials are concerned. it may be restricted almost entirely to the products derived from animal and vegetable sources. (2) Ferments. though many attempts have been made during the last few years to also utilise mineral oils for the preparation of soap. of wetting and penetrating into oily textures.

CH2OOC16H3 1 CH2OH sodium hydroxide sodium palmitate glycerol palmitin [Pg 7] CH2OOC18H3 3 CH2OH | = 3NaOOC18H33 + CHOH | CH2OH | CHOOC18H33 + 3NaOH | CH2OOC18H3 3 sodium sodium oleate glycerol hydroxide Berthelot subsequently confirmed Chevreul's investigations by directly synthesising the fats from fatty acids and glycerol.. the hydrogen atoms of which are displaceable by acid radicles. the above reaction may be supposed to take place in three stages. Thus. we may have:— (1) C18H35O2 H C18H35O2 H + C3H5(OH)3 = C3H5(OH)2C18H35O2 monostearin (2) + C3H5(OH)2C18H35O2 = C3H5(OH) (C18H35O2)2 distearin (3) C18H35O2 H + C3H5(OH) (C18H35O2)2 = C3H5(C18H35O2)3 + H2O + H2O + H2O tristearin There are two possible forms of monoglyceride and diglyceride. where R denotes the acid radicle:— Monoglyceride:— CH2OR | CH2OH | .e. and represented by the following formulæ. the method he adopted consisting in heating the fatty acids with glycerol in sealed tubes. for example:— olein 3C18H35O2 H + C3H5(OH) 3 = C3H5(C18H35O2) 3 stearic acid glycerol tristearin Since glycerol is a trihydric alcohol. contains three hydroxyl (OH) groups. these being termed alpha and beta respectively. i. Thus. according to the relative position of the acid radicle.

has shown the existence of several socalled mixed glycerides. In some cases the fatty acids are combined with other bases than glycerol. C3H5(OC18H35O)(OC18H35O)2. are given in the following table:— Glyceride.(alpha) CHOH and (beta) CHOR | CH2OH Diglyceride:— CH2OR | (alpha) CHOH and (beta) CHOR | CH2OR | CH2OH CH2OR | | CH2OH According to the relative proportions of fatty acid and glycerol used. however. di. As examples may be cited beeswax. and the temperature to which they were heated. which invariably occur in nature in the form of triglycerides. Hansen has since found that tallow contains oleodipalmitin. and herein lies the essential difference between fats and waxes. also in cod-liver. CH(OC16H31O)(OC18H35O)2. and Hehner and Mitchell have obtained indications of mixed glycerides in linseed oil (which they consider contains a compound of glycerol with two radicles of linolenic acid and one radicle of oleic acid). cod. Practically all the oils and fats used in soap-making consist of mixtures of these compounds of glycerol with fatty acids. though sometimes admixed with soap to accomplish some special object.and triglycerides of various fatty acids. Berthelot succeeded in preparing mono-. stearodipalmitin. oleopalmitostearin. and spermaceti. obtained by Heise in 1896 from Mkani fat. Recent work. Chief Melting Refractive Saponification . containing myricin or myricyl palmitate. consisting chiefly of cetin or cetyl palmitate. but as these substances are not soap-making materials. of oleodidaturin. whale and shark oils. while Holde and Stange have shown that olive oil contains from 1 to 2 per cent. with their formulæ and chief constants. C3H5(OC18H33O)(OC17H33O)2. C3H5(OC18H35O)(OC16H31O). the latter of which has also been obtained by Kreis and Hafner from lard. The first mixed glyceride to be discovered was oleodistearin. they do not require further consideration. corresponding to the formula— CH2OR | CHOR | CH2OR where R denotes the acid radicle. C3H5(OC18H35O)(OC16H31O). Formula. The principal pure triglycerides.[Pg 8] It was formerly considered that the three acid radicles in any naturally occurring glyceride were identical. in which the hydroxyls of the same molecule of glycerol are displaced by two or sometimes three different acid radicles. C3H5(OC18H33O)(OC16H31O) (OC18H35O) and palmitodistearin.

. . is the chief constituent. olive and cotton-seed. hence tallows and palm oils are solid.42715 1. Of the above the most important from a soap-maker's point of view are stearin.7 310.7 294.43316 1.6° C. Where olein.C4H7O Butter fat )3 Point. 1.. O)3 C3H5(O.Occurrence. When heated to 55° C. palmitin.43697 1.7 114.7 268. oils -6 3O)3 C3H5(O..C5H9O Porpoise.7 296. Liquid at -60 Index at 60° C.1 45 56. Stearin (Tristearin) can be prepared from tallow by crystallisation from a solution in ether. and allowed to cool. and again becomes liquid at 71. do.6 C3H5(O. solidification will occur at 70° C.C10H1 Do. 9O)3 C3H5(O. do. stearin liquefies.7 240. it will not solidify until 55° C. lard 1O)3 C3H5(O.C18H3 Castor oil 3O2)3 . Palmitin (Tripalmitin) may be obtained by heating together palmitic acid and glycerol.. is reached. we have softer fats. which is liquid. 3O)3 C3H5(O.C12H2 Do...C8H15 Do. dolphin .3 31. as almond.44285 .7 C3H5(O. firm fats.7 184. If this liquid be further heated to 76° C. The melting point of stearin appears to undergo changes and suggests the existence of distinct modifications.42015 . Equivalent. which are solid at the ordinary temperature...C16H3 Palm oil.. and allowing it to crystallise. forming small crystals which have a bright pearly lustre... lard.5 63-64 71. The presence of stearin and palmitin. Palmitin exists in . ... cacao butter 5O)3 -25 -8. and liquid oils. 1. be allowed to cool.44039 1.C18H3 Olive and almond Solidifies at . )3 C3H5(O.C18H3 Tallow. gives firmness to a fat.7 212. the harder the fat and the higher will be the melting point. as these predominate in the fats and oils generally used in that industry. but if the liquid at 71. olein and laurin. 100. with increase of temperature it becomes solid.C6H11 Cocoa-nut and O)3 palm-nut oils C3H5(O. °C.6° C.7 128. repeatedly boiling the resulting product with strong alcohol.7 156. the greater the percentage present..C14H2 Nutmeg butter 7O)3 C3H5(O.. do. Butyrin Isovalerin Caproin Caprylin Caprin Laurin Myristin Palmitin Stearin Olein Ricinolein [Pg 9] C3H5(O. such as lard.

Ricinoleic series CnH2n-7COOH I. Linolic series CnH2n-3COOH IV.. with separation of crystalline particles. All the acids naturally present in oils and fats. After melting and solidifying. butyric. °C. Butter. Limburg cheese. after clarifying by warming[Pg 10] and washing free from mineral acid. CH3COOH C3H7COOH C4H9COOH C5H11COOH C7H15COOH C9H19COOH C11H23COOH Melting Point. colourless. palm-kernel oil. and the initial temperature of the mass when previously cool. but only slightly so in cold absolute alcohol. The more important fatty acids may be classified according to their chemical constitution into five homologous series. it is quite clear. such as rate at which the temperature is raised. and becoming cloudy. and may be obtained by submitting olive oil to a low temperature for several days. tasteless oil. Linolenic series CnH2n-5COOH V. which rapidly absorbs oxygen and becomes rancid. It has been prepared synthetically by heating glycerol and oleic acid together. Fatty Acids. is soluble in alcohol and reddens blue litmus paper. At 63° C. Butter. 15 30 44 Found in Macassar oil. an oily layer gradually rises to the surface of the liquid. Scheij gives its specific gravity. and also one of the principal components of cocoa-nut oil. It crystallises in needles. Laurin is the chief constituent of palm-kernel oil.. cocoa-nut oil.OH group. again liquefying when 61. together with their melting points and chief sources. Cocoa-nut oil. are monobasic in character. Stearic series CnH2n+1COOH II. cocoa-nut oil. the resulting soap dissolved in hot water.. Stearic Series. which are all more or less readily soluble in water. Laurin (Trilaurin) may be prepared synthetically from glycerol and lauric acid.. melting at 45°-46° C. and sufficient dilute sulphuric acid added to decompose the soap.8944. remaining for the most part dissolved in the aqueous portion.7° C. and are greasy to the touch.—The principal acids of this series. 17 . Acetic Butyric Isovaleric Caproic Caprylic Capric Lauric Formula.. d60°/4° = 0. Butter. Butter. It has been suggested that the different changes at the temperatures mentioned are due to varying manipulation.. . when heated to 46° C. it melts to a liquid which becomes solid on further heating. that is to say. caprylic and capric. which. palmitin shows no crystalline fracture. are given in the following table:— Acid. contain only one carboxyl—CO. having the general formulæ:— I. Olein may be distilled in vacuo without decomposition taking place. Porpoise and dolphin oils. . acids like acetic. Oleic series CnH2n-1COOH III. whether free or combined. cocoa-nut oil.. is reached. when the liquid portion may be further deprived of any traces of stearin and palmitin by dissolving in alcohol.—When a fat or oil is saponified with soda or potash. This oily layer consists of the "fatty acids" or rather those insoluble in water.scales. Macassar oil. caproic. . which have a peculiar pearly appearance. propionic. and this temperature is taken as the true melting point. which are readily soluble in ether. Olein (Triolein) is an odourless.

.. Ben oil. 69 75 .5 ... Most oils and fats.5 Croton oil. cocoa-nut oil. and will not combine directly with iodine or bromine. rape oil. most animal fats. . Sperm oil... Tiglic Moringic Formula. Pisang wax. Cacao butter Psyllostearylic C32H65COOH Theobromic C63H127COOH ..Ficocerylic Myristic Palmitic Daturic Stearic Arachidic Behenic Lignoceric Carnaubic Pisangcerylic Hyænic Cerotic Melissic C12H25COOH C13H27COOH C15H31COOH C16H33COOH C17H35COOH C19H39COOH C21H43COOH C23H47COOH C23H47COOH C23H47COOH C24H49COOH C25H51COOH C29H59COOH . which is almost insoluble in cold water. croton oil.. Arachis oil.. °C.. Psylla wax. Hyæna fat. and stearic palmitic and oleic acids respectively.[Pg 11] The acids of this group are saturated compounds. distil without decomposition.. Oleic Series:— Acid. The two first are liquid at ordinary temperatures. Oil of Datura Stramonium. The higher acids of the series are solid.. most solid animal fats. and are completely insoluble in water.. II. rape and mustard-seed oils.. lard. and are miscible with water in all proportions. Carnauba wax. which were formerly included in this series. Pisang wax.. Ben oil. Found in 64. . Beeswax. black mustard-seed oil.. liver fat. dika fat. Palm oil. Tallow. the next four are more or less soluble in water and distil unchanged in the presence of water. C4H7COOH Melting Point. Nutmeg butter. and only slightly dissolved by boiling water. C14H27COOH 0 Physetoleic C15H29COOH 30 Hypogæic Oleic Rapic C15H29COOH 33 C17H33COOH 14 C17H33COOH . China wax. have now been shown to consist of mixtures of stearic and palmitic. Arachis or earth-nut oil.. 54 62. Arachis and maize oils. Beeswax. All these acids are soluble in warm alcohol.. as does also lauric acid. and on being heated with solid caustic alkali undergo no change.5 .. Medullic and margaric acids. 80. Rape oil. spermaceti. 78 89 .

515. as Edmed has pointed out. may also be converted into saturated acids by heating to 300°C..Doeglic Erucic C18H35COOH . Melting Point. 1903) for the conversion of unsaturated fatty acids of Series II. and that the melting point of tallow fatty acids is raised thereby about 12° C. of iodine in autoclaves up to 270°-280° C. though it must be really more complex than this indicates. with solid caustic potash.. on treatment with sodium amalgam in alkaline solution. melting at 45°. Linolic Series:— Acid. olein being converted into elaidin. Acids of Series II. Found in Chinese-wood oil. and the lithium salts more soluble in alcohol than those of the stearic series. The lead salts of the acids of this series are much more soluble in ether. °C. with oleic acid. III. for example. Formula. oxalic acid is also formed in considerable quantity.. for. which melts at 32°C. Elæostearic Linolic C16H29COOH 71 C17H31COOH Fluid . and erucic acid gives brassic acid. Thus. One of the most important properties of this group of acids is the formation of isomeric acids of higher melting point on treatment with nitrous acid.. This reaction. C21H41COOH 34 Bottle-nose oil. Oleic acid. cobalt or iron. which effects its reduction to stearin. Stearic acid is also formed by treating oleic acid with fuming hydriodic acid in the presence of phosphorus. upon both of which properties processes have been based for the separation of the solid from the liquid fatty acids. yields elaidic acid. and Zürer has devised (German Patent 62. is converted into stearic acid. but as the conversion of the latter into solid acids is a matter of some technical importance from the point of view of the candle-maker. which decomposes them into acids of the stearic series with liberation of hydrogen.. It is claimed that by this method oleic acid is completely transformed into stearic acid. about 70 per cent. marine animal oils. Unfortunately. acted upon by nitrous acid. is generally represented by the equation— C18H34O2 + 2KOH = KC2H3O2 + KC16H31O2 + H2. rape oil. The process on a commercial scale has now been abandoned. into the saturated compounds of Series I. Elæomargaric C16H29COOH . Mustard oils. More recently Norman has secured a patent (English Patent 1. Linseed. Another method which has been proposed is to run the liquid[Pg 12] olein over a series of electrically charged plates. they readily combine with bromine or iodine to form addition compounds. which is then reduced with nascent hydrogen. this reaction does not apply to the higher acids such as oleic acid. generally termed the elaidin reaction. by reduction with hydrogen or water-gas in the presence of finely divided nickel. melting at 60°C. and the lower members of the series are at once reduced. This reaction also occurs with the neutral glycerides of these acids.407) a process whereby the oleic acid is first converted by the action of chlorine into the dichloride. for example. while other solid acids are obtained by the action of sulphuric acid or zinc chloride on oleic acid.. to the corresponding saturated acids of Series I. cotton-seed and maize oils. a number of attempts have been made to effect this by other methods. De Wilde and Reychler have shown that by heating oleic acid with 1 per cent. The unsaturated nature of these acids renders their behaviour with various reagents entirely different from that of the preceding series. Chinese-wood oil.

the above equation may be regarded as a summary of the following three:— { OR { OH (i. their saponification can be supposed to take place in three successive stages. 6 and 7)— C3H5(OR) + 3NaOH = C3H5(OH)3 + 3RONa. V.. C17H29COOH Cod-liver and marine animal oils. is not by any means such a simple reaction. though generally represented by the equation already given (pp. the presence of the latter is found to be indispensable for saponification to take place. obtained from castor oil. They are unaffected by nitrous acid. Formula. These acids readily combine with bromine. Ricinoleic Series:— Acid. Found in Castor oil. °C. caustic soda or potash merely acting as a catalytic agent. which melts at 52°-53° C. its rotation being αd +6° 25'.Tariric Telfairic C17H31COOH 50.—The decomposition of a triglyceride. brought about by caustic alkalies in the formation of soap. and their lead salts are soluble in ether. which are the converse of the formation of mono.and diglycerides in the synthesis of triglycerides from fatty acids and glycerine. Hydrolysis or Saponification of Oils and Fats.) C3H5 { OR + NaOH = C3H5 { OR + RONa { OR { OH { OR { OH (ii. is optically active. or oxygen. and is converted by nitrous acid into the isomeric ricinelaidic acid. Further. in fact.) C3H5 { OR + NaOH = C3H5 { OR + RONa { OR { OH . the water must be regarded as actually decomposing the oil or fat. though in this equation no water appears. Linolenic Formula. Ricinoleic C17H22(OH)COOH 4-5 This acid combines with two atoms of bromine or iodine. Found in C17H29COOH Linseed oil. Thus. IV. In the first place. Jecoric [Pg 13] These acids are similar in properties to those of Class III. Telfairia oil. iodine. Linolenic Series:— Acid.5 C17H31COOH Fluid Tariri-seed oil. whereas the latter combine with only four atoms. Isolinolenic C17H29COOH Linseed oil. but combine with six atoms of bromine or iodine. Pure ricinoleic acid. Melting Point. since in the glycerides there are three acid radicles to be separated from glycerol.

the rate of hydrolysis being thereby. which include (i. (ii. and to yield a dark soap. but by passing superheated steam through fatty matter heated to 200°-300° C. on the other hand. the temperature not . the accelerating effect of the two latter methods is due to their emulsifying power. During the last few years.OH = C3H5(OH)3 + 3ROH.111) a process whereby steam under a pressure of 8 to 10 atmospheres is projected against a baffle plate mounted in a closed vessel. since the fatty matter is usually subjected to a second treatment with sulphuric acid to increase the proportion of solid fatty acids. but as the process is extremely slow. glycerol and soap. the fatty acids liberated at the same time combining with the catalyst. experimenting on the saponification of olive oil with caustic potash. The two processes chiefly used for this purpose are those in which the reaction is brought about by enzymes or by Twitchell's reagent. are obtained almost alone in the earlier ones. which are of course considerably cheaper than the caustic alkalies. who have studied this question from the physical and chemical point of view respectively. and Fanto. Pat. for which purpose complete separation of the glycerol in the first hydrolysis is not essential. which condense first. however. Hydrolysis can be brought about by water alone. there has been a growing attempt to first separate the glycerol from the fatty acids. Simpson (Fr. and concludes that in homogeneous solution the saponification is practically quadrimolecular. 364. these three reactions do actually occur side by side.) the application of heat or electricity. soda or potash. The colour of the resulting fatty acids is also of no importance. Pat. and by arranging a series of condensers. and an aqueous solution of glycerine in the later ones. the matter cannot be regarded as yet definitely settled. the soap-pan containing at the same time unsaponified triglyceride.) action of enzymes. Application of Heat or Electricity.{ OH { OH (iii. Mannig has patented (Germ. and though the evidence seems to favour this theory. and then convert the latter into soap by treatment with the carbonates of soda or potash. from physico-chemical data. and so prevent discoloration. diglyceride. in which are immersed the two electrodes connected with a dynamo or battery. the effect of water on oils and fats is very slight.) treatment with chemicals. monoglyceride.e. it is claimed. i. is unable to detect the intermediate formation of any mono. To expose the acids to heat for a minimum of time. This method of preparation of fatty acids is extensively used in France for the production[Pg 15] of stearine for candle-manufacture.587) has attempted to accelerate further the decomposition by subjecting oils or fats to the simultaneous action of heat and electricity. This theory is not accepted.. but cannot be used in the actual saponification of a neutral fat. where it mixes with the fat or oil in the form of a spray. Hitherto the other processes of hydrolysis have been employed chiefly for the preparation of material for candles. Kreeman. and (iii. are of opinion that[Pg 14] when an oil or fat is saponified. The most usual method adopted in the manufacture of soap is to hydrolyse the fat or oil by caustic soda or potash. but the resulting product is liable to be dark coloured. I. as they are always subjected to distillation. 160. much increased.) C3H5 { OR + NaOH = C3H5 { OH + RONa { OH { OH Geitel and Lewkowitsch.or diglyceride. however. The fatty acids and glycerol formed distil over with the excess of steam. it is customary in practice to accelerate the reaction by the use of various methods. to form soap. the former. if sufficient time is allowed.—Up to temperatures of 150° C. by all investigators. Balbiano and Marcusson doubt the validity of Lewkowitsch's conclusions. Superheated steam is passed into the oil. supports the view of Geitel and Lewkowitsch that saponification is bimolecular. the neutral glycerides are completely decomposed into glycerol and fatty acids according to the equation— C3H5(OR)3 + 3H.

and 50 to 60 parts of acetic acid. Neither emulsin. but that cocoa-nut and palm-kernel oils only decomposed with difficulty. Several investigators have since examined the hydrolysing power of various other seeds. Sulphuric. as originally devised by Connstein and his collaborators. but in practice is too expensive. They found that tallow. the action is weakened. The high percentage of free acids found in rice oil has led C. No evidence of the existence of such a ferment was adduced. phosphoric.—It was discovered by Muntz in 1871 (Annales de Chemie. which he suggested might be due to the decomposition of the oil by the embryo acting as a ferment. (Journ. cotton-seed. Schutzenberger in 1876 showed that when castor seeds are steeped in water. u. the leaves of Arctostaphylos Uva Ursi. 25.. and the degree of hydrolysis is proportional to the quantity of ferment present. who. when no decomposition occurs. II. but myrosin is about half as active as castor seeds. 1142-1145. Butyric acid is stated to be the best. The presence of acidity is essential for the hydrolysis to take place. but those of Linaria are much weaker. belonging to some thirty different families. phys. Action of Enzymes. but only caused decomposition of castor oil after the initial acidity was first neutralised with alkali. Amer. is the action due to enzymes. The process for the utilisation of enzymic hydrolysis in the separation of fatty acids from glycerine on the industrial scale. Proc. were readily hydrolysed by the castor-seed ferment in the presence of dilute acid. Jequirity seeds were found to have a stronger decomposing action on lanoline and carnauba wax than the castor seed. and Chem. and at 100° C. 30 et seq. till 1890.) that during germination of castor seeds a quantity of fatty acid was developed in the seeds. 948-954).) has examined the hydrolytic action of a large number of Russian seeds. acetic or butyric acids. 1903.. The seeds of Chelidonium majus were found to have as great. at 50° C. The first experimenters to suggest any industrial application of this enzymic hydrolysis were Connstein. of fat. 1903. 370) definitely proved the presence in the seeds of a ferment capable of splitting up the oil into fatty acid and glycerol. while in many instances hydrolysis was not produced when the seeds were old. almond. then adding the rest of the oil. pp. Hoyer and Wartenburg. Soc. when Green (Roy. may be used without much influence on the result. Brown. to examine the rice bran. twenty to thirty parts having only the same lipolytic activity as four to five parts of castor seeds.. have made similar experiments with jequirity seeds (Abrus peccatorius) containing the enzyme abrin. and possibly greater. Harz. fatty acids and glycerol are liberated. gold lac (Cheirantus cheiri) and crotin from croton seeds. S. Ges. jun. Soc. and attributed this to the hydrolytic action of an enzyme present in the seeds. Hoyer and Wartenburg's work with castor seeds. in addition to confirming Connstein. and 3003-3005)..[Pg 16] myrosin from black mustard-seed. 1900-1901. consisted in rubbing a quantity of the coarsely crushed castor seeds with part of the oil or fat. notably Braun and Behrendt (Berichte. which proves to have considerable enzymic activity. but although more than half of these brought about the hydrolysis of over 10 per cent. except in the presence of potassium myronate.being allowed to exceed 270° C. 1902. ceases altogether.. russ. enzymic activity than castor seeds. xxii. Fett. 3988-4006) published the results of a lengthy investigation of the whole subject. palm. Chem. viz. containing the glucoside arbutin. Fokin (J. and rapidly effects the hydrolysis of glycerides. 36. A. 1904. or sodium bisulphate. . The quantities employed were 6-1/2 parts of decorticated castor beans for every 100 parts of oil or fat. together with acidified water (N/10 acetic acid). and acetic acid is usually adopted. emulsin from crushed almonds. olive. who (Berichte. the seeds of Chelidonium majus and Linaria vulgaris. he considers that in only two cases. arbutin nor crotin have any marked hydrolytic action on castor oil. 831-835. 35.. The emulsified mixture should be allowed to stand for twenty-four hours. however. 48. these being the only two seeds for which the yield of fatty acids is proportional to the amount of seed employed. the most suitable strength being one-tenth normal. chem. and many other oils. Ind. Rev. and the temperature should not exceed 40° C. 35.

Journ. The former.213. and the bottom one consisting of the aqueous glycerine. This active substance.304. Nicloux (Comptes Rendus. Hoyer. 1904) the preparation of an "extract" by triturating crushed castor or other seeds with castor oil. which now covers the use of vegetable ferments in the presence of water and manganese sulphate or other metallic salt. and a 25 per cent. or use may be made of that formed during the process. 1904) states that the use of an acid medium is unnecessary. lipase from pig's liver. Pat. its activity is destroyed by contact with water in the absence of oil. and steapsin from the pig or ox pancreas. The temperature is then raised to 70°-80° C. Werke have extended their original patent (addition dated 11th December. the proportion of salts not exceeding 0. of oil. Soc. Pat. and then filter. Pat. or to obtain[Pg 17] it in a purer and more concentrated form than is furnished by the seeds themselves. is found to have . the washings being added to glycerine water. or preferably by neutralising with carbonate of soda and removing the resulting soap. together with about 80 per cent. for eight days. The process has been the subject of a considerable amount of investigation. 1112. while in yet another patent. 77 B. and the middle layer between the glycerine solution and fatty acids is smaller and can be saponified directly for the production of curd soap." is considered to be not an enzyme. though in the latter case hydrolysis is somewhat slower. 1905. By the use of such an extract. the mixture is allowed to stand for twenty-four hours. In a subsequent addition to this patent. Pat. the one at the top consisting of the clear fatty acids. the middle one an emulsion containing portions of the seeds. numerous attempts having been made to actually separate the active fat-splitting constituent of the seeds. Lombard (Fr. 328. Soc. it is generally washed twice with water. 349. Soc.179. This observer has patented (Eng. and subjecting it to centrifugal force. the quantity of albuminoids brought into contact with the fat is reduced to about 10 per cent. and Roy. 349. has obtained a product of great activity. The Verein Chem. 454) has shown that the hydrolytic activity of castor seeds is due entirely to the cytoplasm. viz. the filtrate obtained being used in place of water in the enzymic process. 1902).. solution of sulphuric acid. following the ordinary laws of enzyme action. who has made a large number of experiments in the attempt to isolate the lipolytic substance from castor seeds.. The deposit consists of aleurone and the active enzymic substance. though it acts as such.After stirring until an emulsion is formed. of that in the original seeds. 350. and Proc. while the glycerine solution also is purer. 1903. and one part of it will effect nearly complete hydrolysis of 100 parts of oil in twenty-four hours. the active agent is separated from the aleurone by extraction with benzene and centrifugal force. fatty acids and glycerine. 1906. filtering the oily extract. 1900. it is claimed that the process is accelerated by the removal of acids from the oil or fat to be treated. allow the mixture to undergo spontaneous proteolytic hydrolysis at 40° C. during which hydrolysis takes place. 1903. although it has been shown by Kastle and Loevenhart (Amer. In this way three layers are formed..942. equal in amount to one-fiftieth of the total quantity of fat originally taken. 1904).. In a further patent Nicloux (Fr. Experiments have been carried out by Lewkowitsch and Macleod (Journ. 49) to readily hydrolyse ethyl butyrate. which may be accomplished by either washing first with acidulated water. then with pure water.101. 68. Proc. which it is possible to separate by mechanical means from the aleurone grains and all other cellular matter. which he terms "lipaseidine. Chem. Pat. It is further[Pg 18] stated that acetic acid may be added at the beginning of the operation. of the fat. and further that a simple method of obtaining the active product is to triturate oil cake with its own weight of water. to Fr.." by extracting the crushed seeds with a solvent for oils.. Oct. 1904. Chem.. 8. Roy. 1904) claims that acids act as stimulating agents in the enzymic hydrolysis of oils. jointly with Urbain (Fr. and claims that even better results are obtained by employing a neutral solution of calcium sulphate containing a small amount of magnesium sulphate. Ind. and the fatty mixture saponified and the resultant soap utilised.5 per cent. The intermediate layer is difficult to treat satisfactorily. 31) with ferments derived from animal sources. added to promote separation of the fatty acids. which destroys the enzyme. which he terms "ferment-oil.

were produced in the same time. but with steapsin more favourable results have been obtained. Rev. Addition of dilute acid or alkali appeared to exert no influence on the decomposition of the cotton-seed oil. Ind. or less appears to be practically useless as a hydrolysing agent. but the process proved too slow and too costly to have any practical use. Fett. 1903.7 per cent. 1904.. though afterwards to retard it. had a marked hydrolytic action and decomposed oleic acid. 795 et seq. III. 41. while with 70 per cent. With cotton-seed oil. Soc. soda and potash. Harz. zinc oxide. the glycerol remaining partly in the form of glycero-sulphuric acid. Hyg. Acid of 60 per cent. 69) there is a distinct increase in the amount of free fatty acids in a sewage after passage through a septic tank. Experiments have also been made on this subject by Rahn (Centralb. while experiments have also been made with hydrochloric acid (Journ. H2SO4.. but not identified. u. By this method. sulphuric acid. The name "lipobacter" has been proposed by De Kruyff for bacteria which hydrolyse fats. 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. Rancidity. which readily emulsify with water. Schriber (Arch. hence the necessity for separating oils and fats from adhering albuminous matters as quickly as possible. magnesia.. Ind..—The hydrolysing power of enzymes throws a good deal of light on the development of rancidity in oils and fats. lime. Chem. though not oleic acid. liberate fatty acids.—The hydrolysing action of concentrated sulphuric acid upon oils and fats has been known since the latter part of the eighteenth century. Use of Chemical Reagents. the process going beyond the simple splitting up into fatty acid and glycerol. of sulphuric acid of varying strengths. carbon dioxide and water being formed. and the use of sulphurous acid. Sulphuric Acid. ammonia. which is now generally regarded as due to the oxidation by air in the presence of light and moisture of the free fatty acids contained by the oil or fat. Decomposition of Fats by Bacteria. "Cantor Lectures. though the yield of fatty acids in this case is considerably inferior to that given by castor seeds. on treatment with steam. attacking the glycerol and lower fatty acids. but in the case of the lard. Fokin (Chem. It has long been known that whilst recently rendered animal fats are comparatively free from acidity. containing from 58 to 90 per cent.—Though this subject is not of any practical interest in the preparation of fatty acids for soap-making.—Among the chief accelerators employed in the hydrolysis of oils are sulphuric acid and Twitchell's reagent (benzene. and. 328-347) has shown that in the presence of air many bacteria promote hydrolysis. only a slight primary hydrolysis was found to take place. it may be mentioned. Bakteriol. 1903. but with lard only 46 per cent. and more recently by Lewkowitsch (J.) has attempted to utilise the pancreatic juice on a technical scale. under favourable conditions as to temperature and access of oxygen. who finds that Penicillium glaucum and other penicillia have considerable action on fats. 83-86 per cent.very little fat-splitting power. however. though according to Rideal (Journ. 422). Soc. Soc. producing a green fluorescent colouring matter. 67) with fairly satisfactory results. Under anærobic conditions. Ind. The process has been investigated by Fremy. 1905. 118-120 et seq. the latter being subsequently purified by steam distillation. though these latter substances differ from the former in that they subsequently combine with the fatty acids liberated to form soaps. of Arts. has been patented in Germany. freshly prepared vegetable oils invariably contain small quantities of free fatty acid. that some bacteria readily hydrolyse fats. A motile[Pg 19] bacillus. fatty acids were developed after twenty-two hours' . who has conducted a series of experiments on the hydrolysis of tallow with 4 per cent. f. dilute alkali seemed at first to promote hydrolysis. in passing. Geitel.)." 1904.or naphthalene-stearosulphonic acid). of fatty acids were liberated as a maximum after fifty-six days. or an alkaline bisulphite as catalyst. sulpho-compounds of the glyceride are first formed. but was not applied on a practical scale till 1840 when Gwynne patented a process in which sulphuric acid was used to liberate the fatty acids. acid only 47. Chem. To this class belong also the bases.

This. whale. In the one case. Dreymann has recently patented (Eng. carbonate. of sulphuric acid (141° Tw. the lower one consisting of a clear aqueous solution of sulphuric acid and whatever benzene-sulphonic acid has been formed. 10. the fat or oil is transferred to the other vat. or other acid-fixing body. the requisite amount of reagent is washed into the vat by the aid of a little hot water through a glass funnel. prior to distillation. and rape oils. sodium carbonate. The second method claimed consists in the conversion of the fatty acids into their methyl esters by treatment with methyl alcohol and hydrochloric acid gas. contains the benzene-stearosulphonic acid. These compounds are stable at 100° C. lime or other impurity present. of fatty acids was only reached after fourteen and fifteen hours' steaming respectively. only 0. 0.or naphthalene-stearosulphonic acid..) for one or two hours and allowed to rest. e. of fatty acids were obtained after nine hours' steaming. preferably overnight. but in the process a considerable proportion of black pitch is obtained. the fat or oil is prepared by boiling with 1 or 2 per cent.steaming. and after another seven hours. agitated by boiling with open steam.. Pat. the better the colour of the finished product. such as benzene. thereby facilitating their dissociation into fatty acids and glycerol. and with 80 and 85 per cent. The reaction appears to proceed better with materials containing a fair quantity of free acidity. the maximum of 89. with or without the addition of an oxide. Using 98 per cent. e. The process is generally carried out in two wooden vats. from 1/2 to 3/4 per cent. the smaller the amount consistent with efficient results. and purification of the esters by steam distillation. In this way the[Pg 20] distillate is much clearer than by the ordinary process.—In Twitchell's process use is made of the important discovery that aqueous solutions of fatty aromatic sulphuric acids. the pure esters being subsequently decomposed with superheated steam. . As soon as boiling takes place. readily dissolve fatty bodies. Twitchell's Reagent. furnished with the necessary draw-off cocks. and the whole is boiled continuously for twelve or even twenty-four hours. After withdrawing the acid liquor. 12). whilst the contents of the vat settle. while the amount of unsaponifiable matter is only about 1.466. is then ready for use. The amount of reagent used varies with the grade of material. According to Lant Carpenter. In the first vat. the liberated fatty acids are washed with water and treated with an oxide.6 per cent. with good material. Further experiments have shown that dilute sulphuric acid has also scarcely any action on cotton-seed. in an autoclave.[Pg 21] When the process has proceeded sufficiently far. 93 per cent. the following reaction taking place:— C6H6 + C18H34O2 + H2SO4 = C6H4(SO3H)C18H35O + H2O. of solid fatty acids may be obtained from tallow by the sulphuric acid process. by this treatment the fat is deprived of any dirt. until the free fatty acids amount to 85-90 per cent. is sufficient. and are prepared by treating a mixture of benzene or naphthalene and oleic acid with an excess of sulphuric acid.. covered with closely fitting lids.g.9 per cent. the addition of a small quantity of this reagent to a mixture of fat (previously purified) and water. and drying at 100° C. is required. owing to the conversion of a considerable quantity of oleic acid into isoleic acid (vide p. while the upper layer. the first vat containing a lead coil and the other a brass steam coil. C. after saponification with sulphuric acid. more fatty acids were produced. which is a viscous oil. acid. and open steam applied.g. but for materials of lower grade proportionately more up to 2 per cent. effects almost complete separation of the fatty acid from glycerol.2 per cent. zinc oxide. where it is mixed with one-fifth of its bulk of water (condensed or distilled). On boiling the resultant product with water two layers separate. some 75 per cent. the boiling is stopped and free steam allowed to fill the vat to obviate any discoloration of the fatty acids by contact with the air.1 per cent. acid. and is almost odourless. after washing first with hydrochloric acid and then rapidly with petroleum ether. to facilitate their decomposition. or 60° B. 1904) two processes whereby the production of any large amount of hydrocarbons is obviated.

under a pressure of some 18 atmospheres. and. So far this process has not been adopted on the practical scale. Lime. and the ready formation of polymerisation products. can be readily calculated. but in no case was any appreciable effect produced. which should amount in bulk to 50 or 60 per cent. ignoring for the moment any catalytic influence. mercury oxide. 61. and may be stored in wooden packages. nitrobenzene and aniline being tried. and the fatty acids steam distilled. but although saponin has been tried for the purpose. (5° B. Chem. Hydrochloric Acid.05 per cent. is removed to a receptacle for subsequent neutralisation with milk of lime. probably owing to its large proportion of the glycerides of volatile fatty acids. copper sulphate. thus with stearin the reaction may be represented by the equation:— CH2OOC18H35 | 2CHOOC18H35 + 3Ca(OH)2 | CH2OOC18H35 stearin = 3Ca(OOC18H35) 2 CH2OH | + 2CHOH | CH2OH milk of calcium stearate glycerol lime In this instance. the fat being heated in contact with the reagent for about nine hours at 175°-180° C.16 has a very marked effect on most oils.—The use of these substances has been patented by Stein. of acid for twenty-four hours. its chief drawback being the length of time required for saponification. Berge and De Roubaix (Germ. cotton-seed. and have a density of 7-1/2° Tw. Sulphurous Acid or Bisulphite. It is claimed that fatty acids so treated are not affected by the air. The experiments were made on neutral lard and lard containing 5 per cent. but this is attributed to the different constitution of its fatty acids. and at the end of that period the contents of the vat are allowed to rest. after boiling 100 grams of the oil or fat with 100 c. which show that acid of a specific gravity of 1. previously mixed with a little water.The settled glycerine water. The maximum amount of hydrolysis was attained with cocoa-nut oil. 67) has carried out a number of experiments on the accelerating influence of hydrochloric acid upon the hydrolysis of oils and fats. zinc dust. 1903. tallow and lard being broken up into fatty acid and glycerol to the extent of some 82-96 per cent. Castor oil is abnormal in only undergoing about 20 per cent. The amount of lime theoretically necessary to hydrolyse a given quantity of a triglyceride. the water separated should be neutral to methyl-orange indicator. The insoluble lime soap formed is decomposed by sulphuric acid. is ready for concentration. of the fatty matter taken. mercury.. cocoa-nut.—Lewkowitsch (Journ. after the separation of sludge. but the process does not appear to be of any considerable importance.c.. it is at . Undoubtedly the hydrolysis would be greatly facilitated if the oil and acid could be made to form a satisfactory emulsion. since the molecular weight of stearin is 890 and that of milk of lime is 74. Soc. The fatty acids remaining in the vat are boiled with a small quantity (0. Pat. the boiling may be prolonged twenty or thirty minutes. or 1/10 of the Twitchell reagent requisite) of commercial barium carbonate. whale and rape oils.329). aluminium chloride. zinc. hydrolysis. Ind. of free fatty acids. in the proportion of 1 per cent.). by De Milly in 1831. Experiments were also made as to whether the addition of other catalytic agents aided the action of the hydrochloric acid.—The use of lime for the saponification of oils and fats was[Pg 22] first adopted on the technical scale for the production of candle-making material. no means of attaining this object has yet been devised.

but excess of acidity. of lime under a pressure of 10 atmospheres producing a yield of 95 per cent. The lower the pressure in the autoclave. in addition to free acid. and. were granted a patent for this process. would be required. by far.2 to 0. the lighter will be the colour of the resultant fatty acids. using 3 per cent. though doubtless. though it may be due to the decomposition of the glyceride. fresh condition. and in a sweet. CaO. of lime and 2. Other catalytic agents have been recommended from time to[Pg 23] time.780 parts of stearin.7 per cent. the treatment of fats with 3 per cent. 222 parts of milk of lime or 168 parts of quicklime. complete resolution of the fatty matter into fatty acids and glycerol could be accomplished. obtained a French patent for the saponification of oils and fats by steam under pressure in the presence of finely divided metals or metallic oxides. Fats and Oils. and it has been proposed to estimate rancidity by determining the amount of these latter produced. in 1882. but none of these is of any practical importance. and their practical use is fully described in Chapter V.—Unlike the preceding bases. It is found in practice. RAW MATERIALS USED IN SOAP-MAKING. 163). Poullain and Michaud. but comparative experiments with lime and magnesia.. the most important saponifying agents from the point of view of the present work. Chem. of a good colour and appearance. Magnesia. but that if the saponification be conducted under pressure in autoclaves the amount of lime necessary to secure almost perfect hydrolysis is reduced to 2-3 per cent. including strontianite. or phytosterol. and does not always denote rancidity. lead oxide. moreover. above the theoretical quantity of lime is necessary to complete the hydrolysis of a fat when carried on in an open vessel at 100°-105° C. [Pg 24] CHAPTER III. . the quantity of zinc oxide recommended to be added to the oil or fat being 0. It has also been proposed to use zinc oxide in conjunction with lime in the autoclave to obviate to some extent the discoloration of the fatty acids. caustic baryta. Ind. and specially mentions zinc oxide for the purpose. Zinc Oxide.—The use of zinc oxide as accelerating agent has been suggested by two or three observers. show that saponification by means of magnesia is less complete than with lime. ranges in the various oils and fats from 0.2 to 2. the soaps formed by soda and potash are soluble in water. These reagents are always used in sufficient quantity to combine with the whole of the fatty acids contained in an oil or fat. that an excess of 3-5 per cent. xii. however.. It is scarcely necessary to observe how very important it is that the sampling of fats and oils should be efficiently performed. is undesirable in soap-making material. The unsaponifiable matter naturally present as cholesterol. They are. aluminium hydrate. on the fat.—All animal and vegetable oils and fats intended for soap-making should be as free as possible from unsaponifiable matter. and constitute the soap of commerce.—It has been proposed to substitute magnesia for lime in the process of saponification under pressure. in 1903.. by the use of considerably smaller quantities. of fatty acids in seven hours.once apparent that for every 1. Rost. Soda and Potash.5 per cent. the reaction requires a higher temperature and therefore tends to darken the product. of magnesia (Journ. Rancidity of fats and oils is entirely due to oxidation.0 per cent. All oils and fats contain more or less free acidity. Soc. aldehydes and ketones being formed. under pressure. Fats and Oils—Waste Fats—Fatty Acids—Less-known Oils and Fats of Limited Use—Various New Fats and Oils Suggested for Soap-making—Rosin—Alkali (Caustic and Carbonated)—Water—Salt —Soap-stock.

The following are typical samples of tallow:[Pg 25]— Saponification Equivalent. Lard. Australian mutton Australian mutton Australian beef Australian beef Australian mixed Australian mixed South American mutton South American mutton South American beef South American beef North American mutton North American mutton North American beef.89 1. iodine. as a general rule. 45 48.81 0.75 41. Tallows.6 44 43. The following . Consequently the melted tallow for soap-making is of secondary importance to the tallow melter. 0.85 3. South American beef tallow is possessed of a deep yellow colour and rather strong odour.5 Town tallow 285.45 2.9 42. good North American ordinary North American prime city Selected English mutton Selected English beef Home-rendered or country tallow 285 284.6 285.94 1. Great Britain produces large quantities of tallow which comes into the market as town and country tallow.5 285 284. much paler in colour than those of South America.2 41.—Lard is largely imported into this country from the United States of America.2 286 283. South American mutton tallow is usually of good quality.5 42 41.07 1. we give.3 Tallow should absorb from 39 to 44 per cent. under each heading.6 Acidity (as Oleic Acid) Per Cent. rendered separately.5 47 47.1 284. Owing to the increasing demand for edible fat. °C.—Most of the imported tallow comes from America.4 284. but do not compare with them in consistence. Australia and New Zealand. but makes a bright soap of a good body and texture. and the product sold for margarine-making.52 1.5 283.6 284. Most of the Australasian tallows are of very uniform quality and much in demand.3 85 284.18 1.2 47 44 43 42.90 0.11 0.85 0. much of the rough fat is carefully selected.68 0.2 284.9 284.2 283. North American tallows are. fine North American beef.8 285.30 5.1 7.40 5.4 Titre.97 4.48 1. figures for typical samples of the qualities most suitable for soap-making.3 43.32 2. or home melt.4 45 44 44 that the sample submitted to the chemist may be a fairly representative average of the parcel.01 1.7 284 284. In the following short description of the materials used.

is a typical sample of American hog's fat offered for soap-making:— Saponification Equivalent.3 214.6 216 214.g.4535 1. Refractive Index at 25° C.60 6.8 1.6 5.65 2.4540 1. 23. iodine. Palm-nut Oil.5 Lard should absorb 59 to 63 per cent.—The best known qualities are Cochin and Ceylon oils. Cocoa-nut Oil. 37.75 23 22. and the oil expressed from it is termed English Pressed Coprah. 1.4535 1. 24 23.95 1. Refractive Index at 60° C. °C. The following are typical examples from bulk:[Pg 26]— Saponification Equivalent.9 to 9. The dried kernels of the cocoa-nut are exported to various ports in Europe. The fruit of this tree yields the oil.1 23 22.—The olive is extensively grown in Southern Europe and in portions of Asia and Africa bordering the Mediterranean Sea. Acidity (as Oleic Acid) Per Cent. French and Marseilles Coprah Oil.4540 1. which are prepared in Cochin (Malabar) or the Philippine Islands and Ceylon respectively.8 215.5 22. Coprah is also imported into England. 225 Acidity (as Oleic Acid) Per Cent.5 1.4540 1. Titre.45 Titre. °C.2 22 Refractive Index at 25° C. and this oil obtained from them.4542 286 0.4553 1.4 Titre.3 per cent. iodine.55 7.47 3.42 7.4555 Pressed 216 9. 4. 1.7 Palm-nut oil should absorb 10 to 13 per cent.5 214. Cochin oil Cochin oil Ceylon oil Ceylon oil Belgian coprah Belgian coprah French coprah French coprah Pressed coprah 215.2 215 214.41 coprah Cocoa-nut oil should absorb 8. and the oil obtained comes on the market as Continental Coprah Oil.1 23 22 22.4553 227 7. e.2 214.4541 1.4541 1. Olive Oil. Typical samples of English and Hamburg oils tested:— Saponification Equivalent.4542 1.—The kernels of the palm-tree fruit are exported from the west coast of Africa to Europe..4535 1. with the prefix of the particular country or port where it has been crushed. .8 Acidity (as Oleic Acid) Per Cent. iodine. Belgian.5 2. °C.

which abound along the west coast of Africa. 278 Acidity (as Oleic Acid) Per Cent. 10.5 Water and Impurities.8 280 31.2 Palm oil should absorb 51 to 56 per cent. more correctly termed Sulphur olive oil. [Pg 27] Olive-kernel oil. and is not applicable for soap-making. Equivalent. commercial oils may be graded according to their free acidity. its glycerol content is proportionately variable. 45 44. In its crude state cotton-seed oil is a dark fluid containing mucilaginous and colouring matter. and it entirely depends upon the desired price of the resultant soap as to what grade would be used. under 5 per cent.g.7 Titre. Titre. Per Cent. Very fine oils contain less than 1 per cent.. Per Cent. Cotton-seed Oil. e. °C. 21 1. 1.4721 1. The following is a typical sample for use in the production of highclass toilet soap:— Saponification Equivalent. The free acidity increases very rapidly. 1. due to the decomposition of the neutral oil by the action of hydrolytic ferment. In the lower qualities we have examples of the result of hydrolytic decomposition by enzymes. doubtless..4704 288 1. The following figures are representative of well-refined cotton-seed oils:— Specific Gravity at Saponification 15° C. Bonny. The amount of free fatty acids is always high and ranges from 40-70 per cent..8 Olive oil should absorb 80 to 83 per cent. and is.4666 Palm oil is produced from the fruit of palm trees. and. iodine. 298 40. °C..6 2.—The product obtained by pressing the deposit which separates on chilling .6 35 Refractive Index at 20° C.4719 0. acidity. Acidity (as Oleic Acid) Per Cent.39 Cotton-seed oil should absorb 104 to 110 per cent. [Pg 28] Cotton-seed Stearine. Refractive Index at 20° C. A representative sample of a parcel tested:— Saponification Equivalent.. whilst Camaroons. Old Calabar and New Calabar oils are in good request for bleaching purposes.924 299 0. 0. °C. of course. iodine.96 1. under 10 per cent.9229 290 Acidity (as Oleic Acid) Titre. Refractive Index at 15° C. Analysis of typical samples of crude palm oil has given:— Saponification Equivalent. iodine. Lagos is the best quality.24 33. the free acidity often amounting to 70 per cent.The free fatty acid content of olive oil varies very considerably. Acidity (as Oleic Acid) Per Cent. 0. etc.—This oil is expressed from the seeds separated from the "wool" of the various kinds of cotton tree largely cultivated in America and Egypt.

. iodine.935 292 1.9246 294 Acidity (as Oleic Acid) Per Cent.—Russia. Maize Oil.—Sesame oil is very largely pressed in Southern France from the seeds of the sesame plant which is cultivated in the Levant. Arachis oil enters largely into the composition of Marseilles White Soaps. is extensively cultivated in North America.2 Linseed oil should absorb 170 to 180 per cent. 22.. Sesame Oil.2 Refractive Index at 20° C.6 24.S. 1. .9248 294.41 Titre. Equivalent Acidity (as Oleic Acid) Titre.4766 Refined 0. °C. 15 17. 2. .) produces very large quantities of maize oil.22 Arachis oil should absorb 90 to 98 per cent. °C. This oil is used in soft soap-making. Linseed Oil.refined cotton-seed oil. Typical samples of crude and refined oil gave these figures:— Specific Gravity Saponification at 15° C. Per Cent. 20 Refractive Index at 15° C.—America (U.9227 295. 1. iodine. iodine.1 0.0 Refractive Index at 20° C. Titre.2 1.4840 0. . Commercial 0. 28. °C.40 Maize oil should absorb 120 to 128 per cent.4731 0. iodine.84 Sesame oil should absorb 108 to 110 per cent. more particularly on the Continent. It is used to a limited extent in soft-soap making. °C.4712 Refined 0.9205 285 0.—The earth-nut or ground-nut.. Representative samples of commercial and refined oils tested:— Specific Gravity at 15° C. Acidity (as Oleic Acid) Per Cent. India and Western Africa.05 38 Arachis Oil. Large quantities are exported to Marseilles where the oil is expressed. Equivalent Acidity (as Oleic Acid) Titre. 1. A good sample gave on analysis:— Specific Gravity at Saponification 15° C..8 Refractive Index at 20° C.9184 Saponification Equivalent 298 Acidity (as Oleic Acid) Per Cent.6 Titre. from which arachis oil is obtained. Per Cent. and Argentine Republic are the principal countries which extensively grow the flax plant. Hemp-seed oil is produced from the seeds of the hemp plant which grows in Russia. 1. A fairly representative sample of French expressed oil tested:[Pg 29]— Specific Gravity at Saponification 15° C. 1. Japan and Western Africa. °C. India. A typical sample tested:— Saponification Equivalent. from the seeds of which linseed oil is pressed. 285.1 0. Equivalent Crude 0. India.

79 10. We quote a few typical analyses of these oils:— Specific Saponification Gravity at 15° Equivalent.2 15.1 21. 0. but it is also cultivated in the United States (Illinois) and Egypt. 0. Iodine No. A typical commercial sample tested:— Saponification Equivalent.25 Waste Fats. 310 1.9253 Whale oil 0.—Under this classification may be included marrow fat.6 Unsaponifiable Matter Per Cent. A specimen tested:— Specific Gravity at 15° C.7 3.91 11. Iodine No.55 1.947 4. Optical Rotation αD Refractive Index at 25° C.9336 oil Japan fish 0. Pale seal oil 0.8 143 Castor Oil.5 15.4 0.5 2.8 1.7 Acidity (as Oleic Acid) Per Titre. 126.77 16. until recently.39 15.2 16.67 1.9231 oil Brown seal oil Dark whale oil 0.9271 297 5.9252 289 288 291 297 303 296 302 313 288 Acidity (as Oleic Titre.8 16.9325 oil Brown cod oil 0.1 + 4° 50' 1.9163 0. Acidity (as Oleic Acid) Per Cent. Acid) Per Cent. Cent. 0.4787 Fish and Marine Animal Oils.9353 herring oil Kipper oil 0.8 26 28 21. C. Titre.2 1.926 292. Titre. 290. °C. °C.9284 Japan fish 0. °C. 0. bone fats.43 14.9 1. Saponification Equivalent.8 21.14 22.9260 Pure 0.—The castor oil plant is really a native of India. animal .8 2.60 4.38 1.—Various oils of this class have.8 84.5 Straw seal 0.9 1.81 17 Iodine No. entered largely into the composition of soft soaps. but a demand has now arisen for soft soaps made from vegetable oils. skin greases.A typical sample gave the following figures:— Specific Gravity at 15° C.49 12. 0.9259 [Pg 30] Saponification Equivalent.6 Sunflower oil is produced largely in Russia. °C.

8 Titre.4471 (F.4 286.grease. 313 303 Acidity (as Oleic Acid) Per Cent.7 1.4 42. Marrow fat Pale skin grease Pale bone fat Brown bone fat Brown bone fat Animal grease Melted stuff [Pg 31] 283.3 Acidity (as Oleic Acid) Per Cent. 43. cocoa-nut oleine.3 286.33 Titre.3 9.. 8. . melted stuff from hotel and restaurant refuse. Fatty Acids. the distillates from e from unsaponifiable matter..8 11. This fat is somewhat tough and sticky. 53. Acids) Mowrah-seed Oil. 10 7. Samples examined by us gave the following data:— Saponification Equivalent. Under this heading should also be included stearines produced by submitting distilled fat to hydraulic pressure.7 White skin grease 287. 38.7 36.2 40.6 4. °C. °C. 3.4518 . a byeproduct from the manufacture of edible cocoa-nut butter and consisting largely of free acids.2 53 1. Refractive Index at 60° C.5 Acidity (as Oleic Acid) Per Cent.—The mowrah-seed oil now offered for soap-making is derived from the seeds of Bassia longifolia and Bassia latifolia. Shea Butter. and the amount of unsaponifiable matter present is sometimes considerable.7 40. and palm-nut oleine obtained in a similar manner from palm-nut oil.5 38. France and England.4558 1. Refractive Index at 60° C. It is largely exported from India to Belgium.0 20. °C.2 7.4 35. lime salts and other impurities.87 8.1 292 289.4566 1. and similar fatty products.4 37.—Shea butter is extracted from the kernels of the Bassia Parkii and exported from Africa and Eastern India.1 Titre.1 12. 291 291. Less-known Oils and Fats of Limited Use.3 289.7 289. These are all available for soap-making.—We have already described the various methods of liberating fatty acids by hydrolysis or saponification. The following is a fair typical selection:— Saponification Equivalent. The following are the results of some analyses made by us:— Saponification Equivalent.7 41 40.2 The materials in the above class require to be carefully examined for the presence of unsaponifiable matter.

.4° C. 116) gives the setting point of the fatty acids as 56. Deering (Imperial Institute Journ. show the oil to be similar to cotton-seed oil.. Titre. 493. Candle-nut oil obtained from the seeds of a tree flourishing in India and also the South Sea Islands.. 1901. [1] 299-304. Ind. 156. 136.7 152. This fat is moulded (by means of bamboo canes) into the form of rolls about 3 inches thick.9 43.8 . 13 . 1903. 313) gives the following figures:— Saponification Equivalent. 13.—The kernels of several species of Hopea (or Dipterocarpus).. °C.24 52. 292 11.291. 17. The following is a typical sample:— Saponification Equivalent Acidity Per Cent. Centr. A sample tested by one of us gave the following data:— Saponification Equivalent.. Chem. °C. References. Melting Point of Fatty Acids.2 5. 12. Various New Fats and Oils Suggested for Soap-making. 1898.5 . Chem. p. Kassler Farben-Zeitung. p. p. 287 [Pg 33] 12 89 Another observer (Rev. 280. Scient. 1283) and Philippe (Monit.2 9.8 Kapok oil is produced from a tree which is extensively grown in the East and West Indies. which flourish in the Malayan Archipelago. Acidity Per Cent.3-139.8 Lewkowitsch Chem.. The Dutch have placed it on the market and the figures given by Henriques (Chem. and is cultivated in Cape Verde Islands and other Portuguese Colonies. yield a fat known locally as Tangawang fat." which is similar to the castor oil plant. has been suggested as suitable for soap-making. 292 36 50. The following data have been observed:— . Titre. and exported to Europe as Borneo Tallow. °C.5 The seeds of the "tallow tree" yield an oil (stillingia oil) having drying properties. Borneo Tallow. 359..26 40. °C..5 Observers.. 730).. Carapa or Andiroba oil. 1902. Acidity (as Oleic Acid) Per Cent. Zeit. derived from the seeds of a tree (Carapa Guianensis) grown in West Indies and tropical America. Iodine No. Revue. Curcas oil is produced in Portugal from the seeds of the "purging nut tree. although varying somewhat. The following figures have been published:— Saponification Equivalent.3 De Negri 163..9 291 296 Titre. Chinese vegetable tallow is the name given to the fat which is found coating the seeds of the "tallow tree" (Stillingia sebifera)[Pg 32] which is indigenous to China and has been introduced to India where it flourishes. 1898.

29 141.[3] Acidity Per Cent. Ind. p. is extensively cultivated in Southern Russia (Saratowa) and German East[Pg 34] Africa. 1012.1 287.5 98. Cohune-nut oil is produced from the nuts of the cohune palm. obtained in the Laboratory of the Imperial Institute. C. Chem.1 0. which. 1898. The following figures have been published:— Saponification Equivalent.9 Observers.. S. angew.12 75. p. 1904. p. 106. 104. Comm. Archbut References. 1903. 1898. Zeitung. the commercial fat is obtained from other trees of the same family.2 Iodine No. This oil closely resembles cocoa-nut and palm-nut oils and is stated to saponify readily and yield a soap free from odour. Crossley and Le Sueur Shukoff Tylaikow References. 141. It resembles cocoa-nut oil and gives the following figures:— Saponification Equivalent. 211.49 Melting Point of Fatty Acids.. which flourishes in British Honduras.4 290. °C. The fat. doubtless. Revue. J. Zeits. Ind. °C. J. Ind.6° C. 867.2 Fendler Chem. 295. Research in Tropics. which flourishes in India and the East Indies. Chem. are recorded in the official Bulletin. Industry. Its use has been suggested for soft-soap making. p. 1898. 992. Klein The titre is quoted by Lewkowitsch as 28.. Ind. 78. References. Lewkowitsch Chem. Revue.6 130 Observers. Lewkowitsch J. p.. obtained from the seeds of Lophira alata. 993) during an investigation of Indian oils obtained these results:— Saponification Equivalent. Soc.1 289.7 Titre. 291. C. Revue. 42. S.3 107. as prepared by natives.[4] Average of Twelve Samples Titre.. Chem. C. 250. 25:[Pg 35]— .Saponification Equivalent.36 4. 25 Observer. Edïe. °C. Inst.[5] 217 Iodine No. Crossley and Le Sueur (Journ. p. 300 7. p. C. 99. 1907. The figures are as follows:— Saponification Equivalent. Reference. Goa butter or Kokum butter is a solid fat obtained from the seeds of Garcinia indica. but. Niam fat.3 Iodine No. 1903. S. 1898. 1902.46 0. S. p. Maripa fat is obtained from the kernels of a palm tree flourishing in the West Indies. Iodine No. 1010.. Bassière J.3 283.5 Observers. 1900. has been examined by Lewkowitsch. 293. C. although indigenous to India and the East Indies.[6] 295. The following figures. J. J. [2] °C. S. 1266. Ind.68 Iodine No. which are found extensively in the Soudan.1 34. 1898. p. p. Quart.5 287.2 Safflower oil is extracted from the seeds of the Carthamus tinctorius. 9. 1901. p. Chem.7 142. 1137. p. and more recently Edie has published the results of an analysis. Titre.

Per Cent.96 Margosa oil is obtained from the seeds of Melia azedarach.[7] Iodine No. Soc.26 Saponification Equivalent. p.[9] Iodine No.4 5.. free from rancidity. Lemarié (Bulletin Imp. He suggests that it may. of brownish yellow colour. Unsaponifiable. 1903. pp. Per Cent. Melting Point of Fatty Acids. Titre. Persimmon-seed Oil.4 0. °C. 1905. p. Inst. replace cocoa-nut oil in soap manufacture.Saponification Equivalent. a tree which is found in most parts of India and Burma. 8 Pongam oil. S. Oil extracted in laboratory 315 94 3. Bulletin Imp. C. Iodine No. 342-344) gives these figures:— Saponification Equivalent.6 27-30 Mafoureira or Mafura tallow from the nuts of the mafoureira tree. pp. 271. which flourishes in East India. Lewkowitsch (Analyst. 229. °C. 1905. Ind. p. . Per Cent.8-233.. 1903. with advantage. Titre. Pharm. and having taste and odour like pea-nut (arachis) oil.8 0.05 9. p. 27. has been suggested as available for the soap industry.. 1903.2 34. 342-44) quotes these results:— 232.22 Indian specimen 306 89. 529. 1905. °C. Lewkowitsch (Analyst.6 42 46..3 12. Chem. obtained from the beans of the pongam tree. 253.5 6.7 21. a whitish solid oil. 206) states that this fat is used in the place of cocoa-nut oil in the manufacture of soap. Ind. 1891-2. from the seeds of the baobab tree. Titre. 395) examined a large sample of dika fat obtained from seeds of Irvingia bateri (South Nigeria) and gives the following data:— Saponification Equivalent. The following are taken from Lane's figures:— Saponification Equivalent. Chem.—Lane (J.8-55.8 44-48 Acidity (as Oleic Acid) Per Cent. p. 1904. Lewkowitsch (Analyst. abstracted in Journ.[10] Iodine No.73 Baobab-seed Oil. Titre. 34) states that the natives of Madagascar extract.14 De Negri and Fabris. Unsaponifiable. 1903. References. Delle Gabelle.—Balland (Journ.[8] Iodine No. The following figures are published:— Saponification Equivalent. 390) gives constants for this oil which he describes as semi-drying. p. 253. which grows wild in Portuguese East Africa. but the unsaponifiable matter present would militate against its use. Iodine No. del Lab. and possessed of an odour similar to Tunisian olive oil.9-255. 284. by means of boiling water. °C. p. 47.9 [Pg 36] 69. Annal. Inst.9-13. Dika fat or Wild Mango oil is obtained from the seed kernels of various kinds of Irvingia by boiling with water. Acidity. Chim. °C..

1905. has been suggested as applicable for soap-making (H. 115. Per Cent..65 Iodine No. C. 209 1. 201). The following figures have been published:[Pg 37]— Saponification Equivalent. transparent substance having a smooth shining fracture and melting at about 135° C. 1906. from the seeds of a tree growing in Java and the neighbouring islands. Rosin is the residuum remaining after distillation of spirits of turpentine from the crude oleo-resin exuded by several species of the[Pg 38] pine. and also flourish in France and Spain. Rosin is a brittle. (Pale. 29.4 115. G. Oil of Inoy-kernel.[12] Acidity.75 22 Rosin.).) G. (Extra pale. nearly white. (No.. p. and is suggested as a soap-maker's material:— Saponification Equivalent. abstr. Iodine No.64 . C. S.6 20. Titre. Per Cent.67 2.7 Observers.) N. 1898. (275° F. Ind. 128) gives these values:— Saponification Equivalent. Zeit.. 1030). Frankforter & Harding References.. (Water white. and cut into 7/8 of an inch cubes. Schroeder (Arch. °C. Ind. 635-640. 1898(abstr.[11] 306 Acidity. Pinus palustris (Australis). Unsaponifiable. Chem.) . Pharm. 1899. possessing neither taste nor characteristic odour and solidifying at about 27° C. p. The gigantic forests of the United States consist principally of the long-leaved pine. in J. Per Cent.. 5. 1155). 1906.17 Titre. J. Amer. It is graded by samples taken out of the top of every barrel. (Window glass. De Negri. 1. The seeds of Poga oleosa from West Africa yield on extraction an oil which gives the figures quoted below. 297 20 115. Snyder. C. which is largely cultivated. is suitable for soap-making. 758-769 (abstr. Tangkallah fat. tasteless. Inst.. 1. S. which abound in America. which must be uniform in size—the shade of colour of the cube determines its grade and value.—(Bulletin Imp. J.. 304 89. C.) K. The grades are as follows:— W. S. p. p. (Good No.2 Wheat oil. which is lacking in those from France and Spain.) M. Soc. whilst the French and Spanish oleoresin is chiefly obtained from Pinus pinaster. particularly in North Carolina. Iodine No. extracted from the wheat germ by means of solvents..44 It is a hard fat. The American variety possesses a characteristic aromatic odour. 1. 1074). J. °C. (Low No.) H. C..) I. 1899.298.. I.) W.28 1. p. W. abstracted in J. (Low pale. 1905. S.

). Carbonate of soda or soda ash. higher than this. 330. 4 per cent. A. This is a commercially pure sodium carbonate containing about 0. Caustic potash (potassium hydrate) is offered as a liquid of 50-52° B. containing as it does more available caustic soda and less impurities.4 169. Total Acid No. Soda ash. 70°.8 120. E.) strength. The highest grade. and. together with water and impurities. 58°.6 175 179 119. also termed "light ash.7 179. B.3 320. (and even as high as 106° Tw. it is the trade custom to buy and sell on what is known as the English degree. which is about 1 per cent. Iodine No. and also in a solid form in various grades as 60°. The degrees in the latter case refer to the percentage of potassium hydrate (KHO) actually present. is much more advantageous in use.. Free Acid No. . and other degrees of dilution.—The standard for refined carbonate of potash is 90-92 per cent. of actual potassium carbonate (K2CO3) present.) (Common strain. Carbonate of Potash. C.5 American N.9 137.1 161. salt (NaCl).) (Strain. 48°. W. Caustic soda (sodium hydrate) comes into commerce in a liquid form as 90° Tw.) (Good strain. Na2O due to this amounts to about 1 per cent.F. salt (sodium chloride). but expressed as English degrees. 2." and "refined alkali".) Unsaponifiable matter is present in rosin in varying amounts. but of late years it has become more general for the soap manufacturer to buy his caustic soda or carbonated alkali from the alkali-maker. American W. Although there are some alkali-makers who invoice caustic soda and soda [Pg 39]ash in terms of actual percentage of sodium oxide (Na2O). (98-103° Tw.5 313. 77-78°.8 Alkali (Caustic and Carbonated). The 48 degrees refers to the amount of alkali present in terms of sodium oxide (Na2O). sometimes called "caustic soda ash. French Spanish 312. 2.7 129." often contains besides carbonate of soda. The English degree is a survival of the time when the atomic weight of sodium was believed to be twenty-four instead of twenty-three.4 168 160 126. (Good No. Below are a few typical figures taken from a large number of collated determinations:— Saponification Equivalent.) (Common. and 10 per cent.5 per cent. The 58° represents the English degrees and corresponds to 99 per cent.) (No. caustic soda (sodium hydrate). although it can be obtained testing 95-98 per cent. may be obtained by adding this figure to the sodium oxide really present. since the error on 76 per cent. and also in solid form as 75-80° and 88-92°. The manufacture of alkali was at one time carried on in conjunction with soap-making. sodium carbonate (Na2CO3). 76-77°. D. These degrees represent the percentage of sodium oxide (Na2O) present plus the 1 per cent.

). soda ash alone. and. and is obtainable in a very pure state.—This substance is largely imported from America. it should be treated chemically. FOOTNOTES: [1] Calculated by us from saponification value. and of course the sodium chloride content.6° Tw. is very convenient in soap-making. [4] Calculated by us from saponification value. and the density of the brine made from this salt ranges higher than 42° Tw.8° B. NaCl) is a very important material to the soap-maker. obtained from the refining of crude cotton-seed oil. [2] Calculated by us from saponification value. Brine. [8] Calculated by us from saponification value. this treatment is repeated several times until the product is free from excess of colour. If the water supply is hard. The colouring matter is removed by boiling the mucilage with water and graining well with salt.). There are many excellent plants in vogue for water softening. the colour is variable.Other Materials. (24. [5] Calculated by us from saponification value. or a saturated solution of salt. [11] Calculated by us from saponification value. when it is converted into soap and a nigre settled out from it. Soapstock.[Pg 40] The presence of sulphates alters the density. [9] Calculated by us from saponification value. Salt produced during the recovery of glycerine from the spent lyes often contains sulphates.4 per cent. [10] Calculated by us from saponification value. or caustic soda. The advantages accruing from the softening of hard water intended for steam-raising are sufficiently established and need not be detailed here. Salt (sodium chloride or common salt. Water.—Water intended for use in soap-making should be as soft as possible. termed mucilage. Mucilage consists of cotton-seed oil soap. sodium chloride and have a density of 41. [6] Calculated by us from saponification value. [12] Calculated by us from saponification value. Soapstock is sold on a fatty acid basis. will contain 26. [Pg 41] . together with the colouring and resinous principles separated during the treatment of the crude oil. the softening agents may be lime and soda ash together. [7] Calculated by us from saponification value. if the salt used is pure. which are based on similar principles and merely vary in mechanical arrangement. where it is produced from the darkcoloured residue. (25° B. [3] Calculated by us from saponification value.

). prior to their transference to the soap-pan. the bichromate process originated by Watts is undoubtedly the best. The bright red colour of the oil gradually changes to dark brown. The reaction may be expressed by the following equation. are removed by refining with caustic soda lye. together with the mucilaginous and resinous principles. The potassium bichromate is dissolved in hot water and added to the crude palm oil. or a mixture of this and common salt. the palm oil is ready for treatment with the bleaching reagent. The chief aim of the refiner is to remove these impurities without saponifying any of the neutral oil. the green liquor is withdrawn. If the above operation is carried out carefully. and. When sufficiently bleached the oil is finally washed (without[Pg 42] further heating) with hot water (which may contain salt). potassium bichromate and 45 to 60 lb. freed from solid impurities by melting and subsidence. and the refining process carried . 6Cl + 3H2O = 6HCl + 3O. The action having proceeded for a few minutes. (8° or 10° B. Having determined the amount of free acidity. 22 to 28 lb. The bleached oil retains the characteristic violet odour of the original oil. in the place of muriatic acid in the above process. and washed with water containing a little hydrochloric acid. It has been suggested to use dilute sulphuric acid. Crude Cotton-seed Oil. however. (54° C. It is important. that the temperature should not be allowed to rise above 130° F. Having allowed it to rest. to remove the last traces of chrome liquor. though in practice it is necessary to use twice the amount of acid required by theory:— K2Cr2O7 + 14HCl = 2KCl + Cr2Cl6 + 7H2O + 6Cl. the requisite amount of muriatic acid being then run in and the whole well agitated by means of air. which consists of potassium bichromate and commercial muriatic acid. The palm oil. previously heated to 125° F. the colouring matter will be completely oxidised.—The deep colouring matter of crude cotton-seed oil. The best procedure is to act upon the colouring matter of the oil three successive times. (52° C. the quantity of caustic soda lye necessary to neutralise it is diluted with water to 12° or 15° Tw. For every ton of oil. and in the final treatment an appropriate quantity which can be easily gauged by the appearance of a cooled sample of the oil. Having described the most important and interesting oils and fats used or suggested for use in the manufacture of soap. The percentage of free fatty acids in the oil will determine the quantity of caustic lye required. otherwise the resultant oil on saponification is apt to yield a soap of a "foxy" colour. Crude Palm Oil. acid will be found sufficient to produce a good bleached oil. using in the first two treatments one-third of the average of the figures just given.) during the bleaching of palm oil. agitation is stopped.). after allowing to settle. let us now consider briefly the methods of bleaching and treating the raw materials. and soon becomes green. Palm Oil—Cotton-seed Oil—Cotton-seed "Foots"—Vegetable Oils—Animal Fats—Bone Fat— Rosin. and drawn off the liquor and sediment (chiefly sand).CHAPTER IV.—Of the various methods suggested for bleaching palm oil. which must only be sufficient to remove this acidity. is placed in the bleaching tank. BLEACHING AND TREATMENT OF RAW MATERIALS INTENDED FOR SOAP-MAKING.

a clear yellow oil separates. of salt is made and the boiling prolonged a little. by means of the steam coil. the coloured liquor rises to the surface of the resinate. This is effected by bringing the oil and a weak solution of caustic lye into intimate contact.—Tallows are often greatly improved by the above alkaline treatment at 165° F. The foots are utilised in the soap-pan. The oil is now ready for the final treatment. but if it is being refined for own use in the soap-house. it is desirable to remove a portion of the free fatty acids. A solution. a third of the necessary weak caustic soda lye added in a fine stream or by means of a sprinkler. (73° C. Animal Fats. occasionally. in some instances the constitution of the rosin is altered. of rosin. and when the treatment is complete and the waste liquor withdrawn. or decomposed by a mineral acid and made into "black grease" ready for distillation by superheated steam. The fat is agitated with a weak solution of acid in a lead-lined tank by blowing in steam. and may be siphoned off (or pumped away through a skimmer pipe) and the resinate further washed with water containing a little salt. to 120° F. and carry down the least amount of entangled oil. Cocoa-nut oil is often treated in this manner.out in three stages. to allow the impurities to precipitate well. after refining to produce a marketable article." may be converted into "soapstock" as mentioned in the preceding chapter. As the treatment proceeds. which are very objectionable substances in a soap-pan. whereas the neutral fat is not attacked. (8° B. The residue or "foots" produced during the refining of crude[Pg 43] cotton-seed oil.). The process is commenced by heating 37 cwt.—Several methods have been suggested for bleaching rosin. the oil may be brightened and filtered. and. If desired. and the whole well agitated with a mechanical agitator or by blowing a current of air through a pipe laid on the bottom of the tank. (49° C. Rosin. and further. and in others the cost is too great or the process impracticable. which treatment also causes the colouring matter to be preciptated. These impurities must be removed by a treatment with hydrochloric or sulphuric acid. the alkaline foots can be used in the production of soap. On settling. The oil is placed in a suitable tank and heated by means of a closed steam coil to 100° F. the settling should be prolonged as much as possible. it is allowed to rest and the settled coloured liquor drawn off as before. and will be found in the soap-pan to produce a reddish soap. consisting of . On resting. which are most probably the result of oxidation or polymerisation. known in the trade as "mucilage. The aim of these processes must necessarily be the elimination of the colouring matter without altering the original properties of the substance. which is performed in the same manner as the two previous ones. broken into pieces.) solution of caustic soda and allow to settle. however. this may be omitted. of 17° Tw. Prolonged agitation with air has a tendency to oxidise the oil. and continuing the boiling until all the resinate is homogeneous.) caustic soda lye. Having withdrawn these coloured "foots. when the latter is sufficiently treated. the last traces of acid are well washed out of the liquid fat with hot water. This is best carried out by converting the rosin into a resinate of soda by boiling it with a solution of either caustic soda or carbonated alkali. Bone fat often contains calcium (lime) salts. say overnight. The treatment with carbonated alkali is performed in a similar manner. (38° C. the contents of the tank are allowed to rest. It is one of the best methods and possesses advantages over acid processes—the caustic soda removes the free acid and bodies of aldehyde nature. The former acid is preferable. (11° B. the temperature may be carefully raised. which increases its specific gravity and refractive index. of its weight of a 12° Tw. when an addition of 1-1/2 cwt.). Vegetable Oils.)." the second portion of the weak caustic soda solution is agitated with the partially refined oil. The first treatment having proceeded fifteen minutes. and adding 20 cwt. as the lime salt formed is readily soluble and easily removed.—The other vegetable oils come to the soap-maker's hand in a refined condition. Sometimes it is only necessary to well agitate the oil with 1-1/2 per cent.

(C) Treatment of fat with indefinite amount of alkali and no separation of waste lye. and the condensed water and impurities withdrawn through a trap arrangement for collecting the fatty matter. (B) Treatment of fat with definite amount of alkali and no separation of waste lye. however. The whole is heated by means of the open steam coil. Many other methods have been suggested for the bleaching. after removal.—This method consists in the complete saturation of fatty acids with alkali. others saponify in a boiler connected with a trap which returns the resinate to the pan and allows the carbonic-acid gas to escape or to be collected. using the above proportions. and." the former being the soda salts. and. and the latter potash salts. According to their methods of manufacture. Classification of Soaps—Direct Combination of Fatty Acids with Alkali—Cold Process Soaps— Saponification under Increased or Diminished Pressure—Soft Soap—Marine Soap—Hydrated Soaps." and "soft. of soda ash (58°). may be added to the solution prior to the addition of rosin or sprinkled in towards the finish of the boiling. which. The salt required. refining and treatment of materials intended for saponification. is heated and 20 cwt. Soaps are generally divided into two classes and designated "hard. A large number of patents have been granted for the preparation of resinate of soda. Smooth and Marbled—Pasting or Saponification—Graining Out—Boiling on Strength— Fitting—Curd Soaps—Curd Mottled—Blue and Grey Mottled Soaps—Milling Base—Yellow Household Soaps—Resting of Pans and Settling of Soap—Utilisation of Nigres—Transparent Soaps —Saponifying Mineral Oil—Electrical Production of Soap. in about four times its weight of water. broken into small pieces. frothing takes place. SOAP-MAKING. in the example given. of the fatty acids contained in the material used. would be 1-1/2 cwt.. Owing to the liberation of CO2 gas. soaps may. there will be sufficient uncombined rosin remaining to allow the resultant product to be pumped into the soap with which it is intended to intermix it. and permits of the use of the deglycerised products mentioned . but the above practical processes are successfully employed. The molten settled fatty materials en route to the soap-pan should be passed through sieves sufficiently fine to free them from suspended matter. When the whole has been sufficiently boiled and allowed to rest. thus:— (A) Direct combination of fatty acids with alkali. be more conveniently classified. added. of rosin. With due precaution the method can be easily worked in open vessels. (D) Treatment of fat with indefinite amount of alkali and separation of waste lye. the liquor containing the colouring matter will float over the resinate. and care must be taken to avoid boiling[Pg 44] over. where it will be finally saponified thoroughly. (A) Direct Combination of Fatty Acids with Alkali. [Pg 45] CHAPTER V. All fats and oils after being melted by the aid of steam must be allowed to thoroughly settle. Some suggest mixing the rosin and soda ash (or only a portion of the soda ash) prior to dissolving in water. and many methods devised to obviate the boiling over.2-3/4 cwt. may be replaced by another washing.

Pat. (35° B. The use of the agitator. but not continuously. It is necessary to use high grade materials. with the slight alteration in temperature necessary to render the fats liquid. Sometimes tallow. and evolving sufficient heat to complete the saponification. hence the products of saponification in this way do not compare favourably in appearance with those produced from the original neutral oil or fat.—Cold-process soap is a type of this class. and when this amount of alkali has all been taken up by the fatty acids (which have been added gradually and with continuous boiling). It is imperative that the steam should not be checked but boiling[Pg 46] continued as vigorously as possible until all the alkali has been absorbed and the gas driven off. cotton-seed oil. or the cessation of the flow of fatty acids. add the molten fatty acids slowly. and the amount of caustic lye required will be less. The saponification by means of carbonated alkali may be performed in an open vat containing a steam coil. lard. In such mixtures the glycerides of the lower fatty acids commence the saponification. Combination takes place immediately with evolution of carbonic acid gas. and dissolve it in water by the aid of steam until the density of the solution is 53° Tw. to which many of the defects of cold-process soaps may be traced. It is essential that the boiling by steam should be well maintained throughout the process until all carbonic acid gas has been thoroughly expelled. palm oil and even castor oil are used in admixture with cocoa-nut oil. A better method of procedure. which alone would saponify with difficulty or only with the application of heat.e.). The process for such soap is the same as when cocoa-nut oil is employed alone. being sprinkled over each further addition of fatty acid. 333.. 1903). and frequently to boil over. and its method of production is based upon the characteristic property which the glycerides of the lower fatty acids (members of the cocoa-nut-oil class) possess of readily combining with a strong caustic soda solution at a low temperature. the steam may be lessened and the contents of the vat or pan gently boiled "on strength" with a little caustic lye until it ceases to absorb caustic alkali. which in the presence of strong caustic lye are "grained out" and difficult to remove without increasing the heat. the remaining quantity of soda ash is added in a dry state. the soap being finished in the manner described under (D). whilst boiling. The caustic lye should be made from the purest caustic soda. It is extremely difficult to prevent discoloration of fatty acids. Soaps made of these blends closely resemble. (B) Treatment of Fat with Definite Amount of Alkali and no Separation of Waste Lye. to follow suit. when that point is reached. the water used for dissolving or diluting the caustic soda should be soft (i. (30° B. free from .974. the oils and fats should be free from excess of acidity.). however. Owing to the rapidity with which free acidity is neutralised by caustic soda. This allows the process to be more easily controlled and boiling over is avoided. made from half the requisite soda ash (9-1/2 per cent.) density. and of carbonated alkalies or caustic soda or potash. then bring to the boil. in appearance. section 2. and. the soap will thus tend to become thick and gritty and sometimes discoloured.. which causes the contents of the vat or pan to swell. is to commence with a solution of 64° Tw. The use of air to replace steam in expelling the carbonic acid gas has been patented (Fr. or in a pan provided with a removable agitator. amounting to 19 per cent. Fatty acids are readily saponified with caustic soda or caustic potash of all strengths. milled toilet soaps. will sometimes tend to prevent the boiling over. of the weight of fatty acids to be saponified. granules of soap are chapter ii. and by means of the heat generated induce the other materials.[Pg 47] containing as little carbonate as possible. It is usual to take soda ash (58°).

and have now fallen considerably into disrepute. maize) are for the most part used in making this soap. It is imperative that the oils and fats and caustic lye should be intimately incorporated or emulsified. (38° to 49° C. seal. to produce neutral soaps of good appearance and firm touch by this method. rosin. must vary with the season. chemical action takes place with the generation of heat. previously placed in the saponification vessel. these materials . 1901. the soap is ready. and. when thoroughly mixed. When the quantities have been added. As the process advances the edges of the soap become more transparent. according to the grade of soap required. and for cocoa-nut oil alone may be 75° F. cotton-seed. 339. more body with a less tendency to separate is given by the introduction of oils and fats richer in stearine. after perfuming.278. have been superseded by vegetable oils.154. The materials must be varied according to the season. (38° B. Saponification under Increased or Diminished Pressure. Although it is possible. The process is generally carried out as follows:— The fluid cocoa-nut oil is stirred in a suitable vessel with half its weight of 71. but in a few hours they become a solid mass. etc. there being several machines specially constructed for the purpose. The admixture of a little caustic potash with the caustic soda greatly improves the appearance of the resultant product. and Jourdan's French Patent No. The temperature. rosin. which is provided with stirring gear. during hot weather.—Soft soap is representative of this class.—Soaps made by boiling fats and oils. Amongst the many attempts which have at various times been made to shorten the process of soap-making may be mentioned Haywood's Patent No. which is smoother and milder. 1903. it is also interesting to note that a patent has been granted (Eng. which. Pat. In one of the latest designs the caustic lye is delivered through a pipe which rotates with the stirring gear.). and when the transparency has extended to the whole mass. and the whole is driven by means of a motor.[Pg 48] (C) Treatment of Fat with Indefinite Amount of Alkali and no Separation of Waste Lye. once largely used as raw material for soft soap. Fish or marine animal oils—whale. of course. In the former. olive. the proportion ranging. with care. At first the contents of the pan are thin. saponification is carried out in a steam-jacketed vacuum chamber provided with an elaborate arrangement of stirrers. though occasionally bone fats and tallow are employed. belong also to this class. (24° C. of the fatty matter. The agitation being complete. 17. in the other process fat is allowed to fall in a thin stream into the amount of lye required for saponification.. cold-process soaps are very liable to contain both free alkali and unsaponified fat. should be as low as is consistent with fluidity. with the exact quantity of caustic soda necessary for complete combination. 759. The Soft Soap Manufacturers' Convention of Holland stipulate that the materials used in soft-soap making must not contain more than 5 per cent.4° Tw. and finally results in the saponification of the fats. but in mixtures containing tallow 100° to 120° F.) caustic soda lye at the same temperature. to be framed and crutched. The glycerine liberated during the saponification is retained in the soap. steam is admitted and saponification proceeds. and all the materials carefully freed from particles of dirt and fibre by straining. under pressure and in vacuo. The vegetable fluid oils (linseed.). 1900) for the manufacture of soft soap from material containing 50 per cent. The agitating may be done mechanically.calcium and magnesium salts). Rosin is sometimes added. from 5 to 15 per cent. the pan is covered and allowed to rest.

with potash lye to keep the soap firmer during hot weather. is usually made from cocoa-nut oil or palm-kernel oil only. for example. which often contain as much as 80 per cent. the soap is deficient in alkali. and. The process is commenced by running fatty matter and weak potash lyes into the pan or copper. (20° B. the soap requires more lye. but the desired yield or grade of soap allows of a variation in the choice of materials. and salt without separation. Having thus ascertained the condition of the pan. The potash lye must contain carbonates. a stronger lye must be afterwards employed to avoid excess of water in the soap. after which the soap is boiled.also induce "figging". and yield a smooth. i. therefore. carbonate of soda. Whilst marine soap. or silicate of soda. As soon as saponification is complete. the solution of salt is added. will produce a paste which can carry the solutions of silicate. then the carbonate of soda solution.e. firm soap. is the caustic potash lye which should average 40° Tw. carefully strained and freed from particles of dirt and fibre. Hydrated soaps. and corrected it if necessary. The soap is then carefully tasted as to its suitability for marbling by taking samples and mixing with the colouring solution (ultramarine mixed with water or silicate of soda solution). and the soap is ready for framing.. and finally the silicate of soda solution. there is an excess of water present. as a slight excess of soda gives soft soap a bad appearance and a tendency to separate. and these average 40° Tw. and be quite clear when held towards the light. without separation. the boiling is continued until the soap becomes clear. Saponification being complete.). and will retain its firmness. they may be added in the form of a solution of refined pearl ash (potassium carbonate). The glycerine liberated during saponification is contained in the soap and no doubt plays a part in the production of transparency. but are soda soaps. but it requires great care. are included in this[Pg 49] classification. For the same reason. whilst the introduction of oil and potash lye is continued. both smooth and marbled. cocoa-nut oil enters largely into the constitution of hydrated soaps. are capable of use in sea-water. and boiling together. to the extent of one-fourth. and the lye is then run in more quickly to prevent the mass thickening. if a weak solution is used to commence saponification. If the cooled sample draws out in threads. which help to give transparency to the resultant soap. and the pan allowed to rest. if the colour is precipitated. Soap made from cocoa-nut oil and palm-kernel oil will admit of the incorporation of large quantities of a solution of either salt.). the colour. (24° B. (24° B. being soluble in brine. These materials are. The fatty materials. carbonate. The right point has been reached when the marbling is distributed evenly. are boiled with weak caustic soda lye until combination has taken place. steam is shut off.). have a short texture and slightly opaque edge. of water. The saponification commences when an emulsion forms. If the lye is somewhat deficient in carbonates. the brine and carbonate of soda solution are added. the soap is too alkaline. however. particularly adapted for the manufacture of marine soaps. Having added sufficient "strength" for complete saponification. or even 2/3 tallow and 1/3 cocoa-nut oil. the soap is too alkaline and needs more oil. If the sample becomes blue throughout. mixed in water or in . The condition of the soap is judged by observing the behaviour of a small sample taken from the pan and dropped on glass or iron. The marbled hydrated soap is made from cocoa-nut oil or a mixture of palm-kernel oil and cocoanut oil with the aid of caustic soda lye 32-1/2° Tw. If the sample is turbid and somewhat white. If an opaque edge appears and vanishes. a charge of 2/3 cocoa-nut oil and 1/3 tallow. If the soap is satisfactory it will set firm. Caustic soda lye is sometimes admixed. The most important material. When thoroughly mixed.

which is ascertained by taking out samples from time to time and examining them. As the soap is gradually thrown out of solution. sufficient caustic lye (32-1/2° Tw. provided the alkali is not added in sufficient excess to retard the union. The commencement of the saponification is denoted by the formation of an emulsion. is frequently added. And in the case of milling soap base and household soaps.silicate of soda solution. Whether the fatty matters and alkali are run into the pan simultaneously or separately is immaterial. caustic soda lye of a greater density. with continued boiling. in a dry form or in solution as brine.[Pg 50] the presence of soap will often assist this by emulsifying the fat and thus bringing it into intimate contact with the caustic soda solution. When the action has started. the preparation of crude glycerine therefrom is considered in chapter ix. When a sample. (c) Boiling on strength.—The melted fats and oils are introduced into the soap-pan and boiled by means of open steam with a caustic soda lye 14° to 23. whilst the soap remains on the surface as a more or less thick mass. The object of the next operation is to separate this water (spent lye) from the soap.). There should be no greasiness in the sample. (D) Treatment of Fat with Indefinite Amount of Alkali and Separation of Waste Lye. 29° to 33° Tw. (b) Graining Out or Separation. the salt is spread uniformly over its surface. (a) Pasting or Saponification. The aim is to obtain a maximum amount of spent lye separated by the use of a minimum quantity of salt. The soap must be thoroughly boiled after each addition of salt. Boiling is continued until the faint caustic taste on applying the cooled sample to the tongue is permanent. A tallow soap is the most easily grained. consists of distinct grains of soap and a liquid portion. or brine 40° Tw. and becomes opaque and granular. The separated spent lye consists of a solution of common salt. The amount of salt required for "graining out" varies with the raw material used. the boiling is stopped and the spent lye allowed to settle out. together with water. in which is dissolved the glycerine formed by the union of the liberated glyceryl radicle from the fat with the hydroxyl radicle of the caustic soda. taken out on a wooden trowel.) is run in. is added and the soap framed. during boiling. and any slight excess of caustic soda and carbonates. Owing to the solubility in weak brine of these latter soaps. more salt is required for cotton-seed oil soap. (10° to 15° B.5° Tw.—This is the most general method of soap-making.—This is brought about by the use of common salt. it is preferable to grain them with caustic soda lye. and care taken that too large a quantity is not added at once. glycerine. whereas soaps made from cocoa-nut and palm-kernel oils require very large amounts of salt to grain out thoroughly. The degree of separation of water (spent lye) depends upon the amount of precipitant used.).) to produce the . probably containing emulsified diglycerides and monoglycerides). The various operations are:— (a) Pasting or saponification. Whilst the soap is boiling. in small quantities as long as it is being absorbed. (b) Graining out or separation. This is effected by adding. it loses its smooth transparent appearance. The pasty mass now consists of the soda salts of the fat (as imperfect soap. and the whole well boiled together. (d) Fitting. 20° B. which will easily separate. sufficient salt or brine has been added. (24° B. when it is ready for "graining out". or by caustic soda lye. but when pressed between finger and thumb it must be firm and dry. Sometimes it is difficult to start the saponification. (18° to 20° B. and alkaline salts..

is clear and bright.—This is the most important operation and is often termed "making the soap". After resting for several hours. the thin layer should drop off in two or three flakes and leave the surface of the trowel clean and dry. and is now ready for the next operation of "boiling on strength". 20° B. Thorough saponification takes place gradually. and water added until the desired degree of closing is attained. however.separation of the granules of soap. their varying alkali requirements become modified. and boiling continued by the use of the dry steam coil. but also differ in the strength of the alkali they require. and[Pg 52] the settled soap. In the case of yellow soaps or milling bases the settled lye is removed to a suitable receptacle and reserved for use in the saponification of other material. this greatly facilitating the settling of impurities. all the impurities precipitate. which would be denoted by the layer of soap not leaving the trowel. the pan covered. (c) Boiling on Strength or Clear Boiling. Samples are tested from time to time as to their behaviour in dropping off a hot trowel held sideways. The granular mass will boil steadily. half-spent lye settles to the bottom of the pan. and. is generally mixed with animal fat. As soon as the caustic soda lye is absorbed.). but cocoa-nut oil alone would not saponify unless the lye was more concentrated.—If the operations just described have been properly performed. The above is a general practical outline of the ordinary soap-boiling process. on standing. and the boiling should be prolonged. (20° to 25° B. another portion is slowly added. The object is to harden the soap and to ensure complete saponification. other materials are induced to take up alkali of a strength with which alone they would not combine. as the last traces of neutral oil are difficult to completely saturate with alkali. the fitting should present no difficulty. and once the saponification is begun with weak lye. It is considered the best procedure to commence the pasting or saponification with weak lye. Caustic soda lye (32-1/2° Tw. and too fine a fit is produced. special care has to be bestowed upon this operation to effect the complete combination of fat and alkali. A good pressure of steam is now applied to the pan. Tallow and palm oil require lye of a density of 15° to 18° Tw.). and the soap is then ready for the final operation of "fitting". a little caustic lye or brine may be very carefully added and the whole well boiled until the desired condition is obtained. containing the correct amount of water. It may be modified or slightly altered according to the fancy of the individual soap-maker or the particular material it is desired to use. According to the required soap. thin consistence. and the operation cannot be hurried.[Pg 51] The whole is allowed to rest. Cotton-seed oil requires weak lyes for saponification. (d) Fitting. After the removal of the settled lye.) is gradually added until the soap is again opened or grained. The art of fitting consists in leaving the contents of the pan in such a condition that. the grained mass is boiled with sufficient water to dissolve the grain and make it smooth ("close" it). When fats are mixed together. and this is continued until the caustic soda or "strength" remains permanent and the soapy mass. refusing to absorb more. The soap is then in a condition to allow the impurities to gravitate. 33° to 42° Tw. the fit may be "coarse" ("open") when the flakes drop off the trowel readily. and the boil allowed to rest for several days. As the water is thoroughly intermixed throughout the mass the thick paste gradually becomes reduced to a smooth. is thrown out of solution and grained.. Fats and oils not only vary in the amount of alkali they absorb during saponification. . If the dilution with water has been allowed to proceed too far. being difficult to saponify alone even with prolonged boiling. steam is then turned off. or "fine" ("close") when the flakes only leave the trowel with difficulty. the separated half-spent lye is withdrawn and may be used for the pasting of fresh materials. causing the contents to swell as high as possible. The soap is boiled with open steam. (10° to 12° B.

in some instances. of soap. but cocoa-nut oil sometimes enters into their composition. is taken advantage of. rosin.) and to dilute it as it is being added to the soap-pan by the simultaneous addition of water. Soap intended to be liquored with silicate of soda should be distinctly strong in free alkali. with the gradual addition of water to the soap. is imitated by artificial mottling. after removing the nigre. however. containing scraps of mottled soap. The first three operations above described. 33° to 37° B. and add the silicate of soda solution. use bleach liquor. After resting.5° B. sufficient water is added to the boiling soap to "close" it and then brine is run in to "grain" it. consequently. palm-kernel oil. the clear boiling by means of a closed steam coil is continued until the "head" is boiled out and the soap is free from froth. and others. Many soap-makers use 20° Tw. again. the soap is just closed by boiling with water.. in which the impurity forms the colour. Having boiled it to its correct concentration the pan is allowed to rest about two hours. soda crystals. viz. Boiling is then stopped. To every 1 cwt. Many manufacturers give all their soap a "brine wash" to remove the last traces of glycerine and free the soap from carbonates. and boiling on strength. be considered as a crystallisation of the soap. and as the soap cools it is enclosed and forms the mottling. Curd Soaps. and. fit the soap coarsely and allow a nigre to deposit. however.. get the soap into a condition for mottling. and is then ready for the silicate or other saline additions. the liquor is withdrawn. when the soap is ready for filling into frames. containing the impurities from the fats used. and. whilst boiling. insufficient boiling will cause[Pg 53] the soap to contain an excess of entangled lye. (13° B. but the clear boiling is not carried so far. The choice of a charge will naturally depend upon the cost. Some lye. therefore. pearl ash. the pan is allowed to rest for eight to ten hours. Blue and Grey Mottled Soaps. with a view to the crystallisation of the resultant soap and the development of the mottle. 28 lb.). cocoa-nut oil. kept boiling.) is added. Its preparation is substantially the same as for curd soap. This operation takes place prior to "fitting". we will now consider their application to the preparation of various kinds of hard soap. graining out. The mottling may.) (cold) silicate solution. If boiled too long the mottling will not form properly. 32-1/2° Tw. (20° B. Having described the necessary operations in general. of silicate of soda solution. the strength of the silicate solution. the property of absorbing a large amount of liquor. (59. as are also the physical properties of the various fats and oils. tallow. will depend upon the proportion of cocoa-nut oil and palm-kernel oil present in the charge. Some makers. and.In order to economise tank space. are proceeded with. whilst others prefer 140° Tw. until the product is in the correct mottling condition. After withdrawing the half-spent lye. remains in the interstices of the curd. pasting. unable to sink. A sample taken and cooled should be hard. and . and the mottled effect intensified. due to the impure materials used in the early days of soap-making. the crystalline nature of the soap is increased thereby. after which the soap is ready for framing. where it is crutched until perfectly smooth. grained and boiled on strength. The fat is saponified. entirely different to curd mottled soaps. Curd mottled is usually made from melted kitchen stuff and bone grease. then. and are. which is characteristic of soaps made from cocoa-nut oil and palm-kernel oil. bone fat. it is the general practice to store strong caustic lye (60° to 70° Tw. The art of curd mottled soap-making lies in the boiling. The materials employed in making mottled soap comprise bleached palm oil.—These are silicated or liquored soaps in which the natural mottling. after covering. on the other hand. cotton-seed oil.—Tallow is largely used in the manufacture of white curd soaps. as previously described. or transferring the settled soap to another copper. which should be done expeditiously and the frames covered up.

is mixed with a little water and added to the boiling soap—the boiling is continued until all is thoroughly amalgamated. but rosin combines with alkali to form a soft body. The resultant soap has a white ground and is firm. and when the saponification is complete. which would be ultramarine for the blue mottled and manganese dioxide for the grey mottled soap (3-4 lb. as a rosin change.—These are made from tallow with an admixture of from 15-25 per cent. so that the latter is properly distributed throughout the soap. the colouring matter. resulting in either a small mottle. and finally saponified with caustic soda lye. is readily soluble in water. especially those made from materials which give a yellowcoloured ground. when ready. and the graining is performed by the aid of caustic soda lye in preference to salt.8° B. which. Some of the English mottled soaps. The tallow is thoroughly saponified first. although not a soap in the strict sense of the term. and the surface should not be glossy.). and the soap must be carefully examined next morning to ascertain if any alkali has been absorbed. if the cooling is too rapid.salt. When this mottling condition has been obtained. (18. of bleach liquor. (a) Bar Soaps. The half-spent lyes are withdrawn. is fitted. and merely a general coloration. castor oil and lard are also employed in the production of special milling soap bases. or uniformly colour the whole mass. and in admixture with the durable tallow soap renders it more soluble in water and thereby increases its lathering properties.). olive oil. and using the clear liquid.—The materials generally used are tallows and cocoa-nut oils of the finest quality. both solutions being 30° Tw. large crystals are produced which result in a distinct bold mottle. which. The best quality is known in the South and West of England as Primrose Soap. of soda ash solution (15° Tw. The bleach liquor may be made by mixing 1 cwt. and removal of colouring matter.. or pickling in brine containing 2 per cent. A sample of the soap should test 45 per cent. It should drop off the spatula in large thick flakes. On cooling slowly. rosin. a palm oil soap being specially suitable for the production of a violet-scented toilet soap. These remarks apply equally to all soaps. take considerable time to set. but should any caustic have been absorbed. 10° B. and the amount of salt would range from 1/2 to 1 per cent. Bleached palm oil. Imperial Pale. "boiling-on-strength" is proceeded with. bleaching powder with 10 cwts. and when the steam is shut off the contents of the pan are ready for cleansing. The soap. If the caustic taste is permanent the strengthening operation is complete. Tallow alone produces a very hard soap of inferior lathering qualities. and does not either separate in coloured masses at the bottom of the frame. Yellow Household Soaps. or. ultramarine or 1-3 lb. but is designated in the North of England by such names as[Pg 55] Golden Pale. when full. as is more generally adopted. [Pg 54] manganese dioxide being sufficient for 1 ton of soap). The pan is opened with caustic soda lye and saturation of the rosin takes . The rosin may be added to the soap-pan after a previous partial saponification with soda ash. a small crystal is obtained and the mottle is not distributed. This is saponified. allowing to settle. In fact. Milling-base. the entire art of mottling soap consists in properly balancing the saline solutions and colouring matter. or no mottle at all. Gold Medal Pale. are covered over and allowed to cool very gradually. are bleached by soaking in brine. together with silicate solution. fatty acids. further addition of alkali must be made and the boiling continued. and the cocoa-nut oil added to the pan. Special care should be devoted to the "boiling-on-strength" operation—its value in good soapmaking cannot be over-rated—and perfect saponification must be ensured. Considerable skill and experience is necessary to discern when the soap acquires the correct mottling state. or by mixing 2 parts soda ash solution with 1 part of bleaching powder solution. Mottled soap is run into wooden frames. etc. The half-spent lyes are allowed to deposit during the night.

the nigre from that boil. will. The period allowed for resting is influenced.—The nigres are boiled and the liquor separated by graining with salt. (1) It may be used several times with new rapidly. and the deposited nigre . Third. Fourth. this liquor has separated from the nigre. Cheaper pale soaps may be made from lower grades of tallow and rosin and are generally silicated. In this case a system is generally adopted. termed "nigre. The colour of the nigre will determine the number of times it can be employed. according to the particular fit employed. The tallow yields firmness and durability whilst the other constituents all assist in the more ready production of a copious lather. when completely saponified it is grained with salt. the contents of the pan will have divided into the following:— First. with a little caustic. fatty acids. As to what amount of rosin can be used to yield a finished soap of sufficient body and satisfactory colour. under certain physical conditions.—A demand has arisen for soap of free lathering qualities. as the "nigre" is a weak solution of soap together with any excess of alkali (caustic or carbonate) and salt which gravitates during the settling. fatty acids. The subject of removing and treatment of this layer is fully dealt with in the next chapter. This is a fitted soap and full details of manufacture have already been given. This soap is usually made from a mixture of cotton-seed oil. On top. and also colour. which is returned to the pan after the removal of the good soap. On subsidence. Rosin imparts softness to a soap. of course. a thin crust of soap. Nigre may be utilised in various ways. but also by the composition of the soap. with a varying amount of rosin. A layer of darker weak soap. is admixed with a charge to produce a batch of third quality." which on[Pg 56] an average tests 33 per cent. The amount of the layer is very variable. Cheaper soaps are produced from lower grade materials hardened with alkaline solutions. A solution containing alkaline salts. soap of the best quality is made in a clean pan. consequently. allow a greater proportion of rosin to be incorporated with them than materials producing soaps of less body. The good settled soap. will amount to from 15-20 per cent. for example. Utilisation of Nigres. This water renders the caustic into a lye sufficiently weak to dissolve a quantity of soap. however. the quantity is increased. mostly carbonates and chlorides. (2) It may be incorporated with a soap of a lower grade than the one from which it was obtained. the soap will require a large amount of water to attain the desired fit. Resting of Pans and Settling of Soap. this naturally depends upon the grade of raw material at the soap-makers' disposal. and the season. in its turn. but is also influenced by the amount of caustic alkali remaining in the soap paste prior to fitting. The quantity of nigre may vary not only with the amount of water added during finishing. and the coloured lye allowed to deposit and finally withdrawn. which has become very popular for general household use. (b) Tablet or Washer Type. not only by the size of the boil. This particularly refers to soaps of the "Washer" type. the nigre remaining is worked up with fresh material for soap of the next quality.—The fitted soap is allowed to settle from four to six days. Those fats and oils which yield firm soaps. testing 62-63 per cent. and cocoa-nut oil. and doubtless. of the total quantity of soap in the pan. tallow. If the free caustic alkali-content is high. The four operations already detailed apply to this soap. and. for if the base has been made from firm stock it is liable to cool quicker than a soap produced from soft-bodied materials. with perhaps a little light coloured fob. Second.

boiled. of bright caustic soda solution made from high grade caustic and having a density of 72° Tw. Pat. superseded the use of alcohol and glycerine. in conjunction with castor oil. but after storage in a room at 95° F.. previously dried. (3) The nigre may be fitted and produce a soap similar to the original soap from which it was deposited.) for several months. and the alcohol distilled. Twenty-three lb. by[Pg 57] Richardson (J. from a theoretical point of view. For a small batch. (5) According to its colour. The alcoholic soap solution is then placed in a distillation apparatus. Chem. 1902) for the manufacture of transparent glycerine soap by heating in a closed vessel fatty acids together with the requisite quantity of alcoholic caustic soda solution necessary for saponification. warmed to 130° F. A patent has been granted to A. and the pan covered and allowed to rest for one hour or one and a half hours. who concludes that the function of substances inducing transparency. of this solution (previously heated) is sufficient to bleach 20 tons of nigre. the following is the procedure:— Cochin cocoa-nut oil. Cochin cocoa-nut oil and 56 lb. the alcohol. The old-fashioned transparent soap is prepared by dissolving. . or the pan containing the solution is attached by means of a still head to a condenser. (6) Nigre may be bleached by treatment with a 20 per cent. of pure glycerine and 56 lb. the difference in colour between boils from new materials alone. It is imperative that the materials should be of the highest quality and perfectly clean. and consistence. To produce a transparent glycerine soap with the aid of castor oil. and carefully strained into a small steam-jacketed pan. (4) Nigres from several boils of the same kind of soap can be collected. (38° B. becomes transparent. (54° C. The resultant mass is somewhat turbid. which would be 45 lb. or cold-water soaps.—The production of transparent soaps has recently been fully studied. is run into frames and allowed to solidify. in this example. The remaining liquid soap.293. solution of stannous chloride—1 cwt.) are crutched into the fat. sweet edible tallow may be taken.from this is again used for a fourth quality soap—the nigre obtained from this latter boil would probably be transferred into the cheapened "washer" or perhaps if it was dark in colour into the brown soap-pan. sugar solution has gradually. The formation of the transparency is sometimes assisted and hastened by the addition of glycerine or a solution of cane-sugar. a nigre may be suitable for the production of disinfectant. and those containing nigre. pp. and cooling the resultant soap. (35° C. Ruch (Fr. melted at 130° F. is to produce a jelly and retard crystallisation. 414-20). With the continual demand for cheaper production. and with or without the use of alcohol. is then added. Cheaper qualities of transparent soaps are made by the cold process with or without the aid of alcohol and castor oil. condensed and regained. The settled portion may be incorporated with a new charging to keep the resultant soap uniform in colour—unless this is done.). Saponification should ensue. sweet edible tallow. which may be coloured and perfumed. The whole must be most intimately incorporated. and with the assistance of glycerine or cane-sugar. Soc. 1908. It is also proposed to add sugar solution. The nigre settled from this fitted nigre boil would be utilised in brown soap. is very noticeable. are taken. and fitted. and castor oil. 327. of each 56 lb. 56 lb. and allowing the insoluble saline impurities to be deposited and removed. Amer. It is advisable to saponify a little fat with it. Transparent Soaps. genuine yellow soap in alcohol. which produces transparency.

The water used for this solution should be as soft as possible. Ges. Chem. In this connection may be quoted the interesting work of Zelinsky (Russ. a little steam may be very cautiously admitted to the jacket of the pan. however. Having rested the necessary period. when the contents of the pan have become a homogeneous and syrupy mass. (63° C. If it is intended to use alcohol and sugar. G. the soap may appear somewhat turbid. 37). The blocks of soap should not be stripped until quite cold throughout. as hard water is liable to produce opaque streaks of lime soap. and they should be allowed to stand open for a while before slabbing. (38° B. which when decomposed by dilute sulphuric acid. the "sugar solution" is prepared by dissolving 50 lb. A greasy. and the alkaline taste not too pronounced. and carefully strained into the jacketed pan. at 168° F. with a cocoa-nut oil soap. He obtained substances. lest it should produce efflorescence. and the whole allowed to rest the specified time. by acting with carbon dioxide upon magnesia compounds of chlorinated fractions of petroleum. to which may be added 5 lb. Having examined the soap and found it to be correct.) is now stirred into the fats together with the requisite (83 lb. which . soda crystals. and possess only a faintly alkaline taste. more sugar solution is required. or having remedied its defects. the sugar solution is carefully and gradually crutched into the soap. and no alcohol. the mass well crutched until the reaction commences. cooled. cane sugar in 50 lb. or mineral[Pg 59] oil emulsified by aid of Quillaia bark. and states that he transforms the hydrocarbons into alcohols. and these. if more lye is required. Zeits. absorbing oxygen. Whilst saponification is proceeding. too much soda ash (carbonates) must be avoided.510. proposes to heat mineral oil together with spermaceti and strong alkali. an excess being specially guarded against. which are converted into soap by means of the alkali. The soap is now quickly filled into narrow frames and allowed to cool rapidly.. One of these acids on heating with glycerine formed tri-octin.(54° C. Chem. of alcohol. and any necessary colouring matter. It is absolutely necessary before proceeding further to ensure that saponification is complete. Pat. and added after the incorporation of the caustic soda lye. this should be added very carefully whilst crutching. Saponification being completed. When freshly cut into tablets. 1903. and no glycerine. but the brightness comes with the exposure it will receive prior to stamping and wrapping. 321. yielded various organic acids. If it is desired to use glycerine and cane sugar solution. great care must be exercised in its addition. and in all these instances the hydrocarbon merely exists in suspension. Saponifying Mineral Oil. Deficiency of caustic alkali should also be avoided. Reale (Fr. (77° C. 1902). but will be clear underneath and appear dark. and examined prior to framing.[Pg 58] The whole being thoroughly crutched. of uniform colour. become fatty acids.). the soap evidently contains an excess of water. the soap will have a slight froth on the surface. If the sample be soft.).). (76° C. and the pan is covered for one hour. The heat of the soap in the pan should not exceed 170° F. the latter is replaced by 47 lb. Most of the suggestions for this purpose consist of the incorporation of mineral oil. Samples may now be withdrawn. the soap in the pan is allowed to cool to 145° F. Phys.) and perfume added.) caustic soda solution 72° Tw. which may be remedied by the addition of a small quantity of soda ash.). the glycerine (25 lb. the pan is covered and saponification allowed to proceed for one hour or one and a half hours. and. the crutching is discontinued. water.—This sounds somewhat incongruous. Should the saponification for some reason be retarded. If the process has been successfully performed the soap will be firm and transparent. If the sample be firm but opaque. Angew. as mineral oil is entirely unsaponifiable. soft feel and the presence of "strength" (caustic) would denote incomplete saponification— this can only be remedied by further heating and crutching. although transparent.

1. and pipe.—Skimmer. 4. the actual soap. obtained what might be described as petroleum (for it contained almost all the hydrocarbons present in the natural mineral oil) by distilling animal fats and oils under pressure. (90°-100° C. In the former patent. Pat. a mixture of soda-lye and fat is agitated by electricity at a temperature of 194°-212° F. Pat. forming the second layer. Dr. in confirmation of the theory of the animal origin of some petroleums. this being generally termed "cleansing" the soap.had the properties of a fat. [Pg 60] CHAPTER VI. and the soap may be either ladled out and conveyed to the frames.—After completion of saponification. which is thereby saponified. Engler.). Electrical Production of Soap. attached by means of a swivel joint (Fig. or the removal may be performed by gravitation through some mechanical device from the side of the copper. 1900). 2. 2) (which allows the skimmer pipe to be raised or lowered at will by means of a winch. 22. The thin crust or layer at the top of the pan is gently removed.372. TREATMENT OF SETTLED SOAP. with flange for attachment to skimmer-pipe. Fig. Cleansing. Nodon.129. Cleansing—Crutching—Liquoring of Soaps—Filling—Neutralising. to a pipe fitted in the side of the pan as fully shown in Fig. Every precaution is taken to avoid the presence of nigre in the soap being cleansed. and also by Messrs. or withdrawn by the aid of a pump from above the nigre through a skimmer (Fig. as described in the preceding chapter. . Brettonneau and Shee (Eng. and deposited on wire-netting in the presence of fat. is now transferred to the frames. Colouring and Perfuming— Disinfectant Soaps—Framing—Slabbing—Barring—Open and Close Piling—Drying—Stamping— Cooling. while in the latter caustic alkali is electrolytically produced from brine. 1).—Attempts have been made to produce soap electrically by Messrs. Merry and Noble (Eng. and allowing the contents of the pan to settle into the various layers. Fig. 1897). 3).

(66° C.). it may be run into a power-driven crutching pan (neutralising material being added if necessary) and stirred a few times before framing. 150° F. such as milling base. in the case of firm soaps. (74°-77° C. 2. where cooling is liable to take place in the pan (and thus affect the yield). or. .—Winch.Fig. the temperature may be 165°-170° F. [Pg 61] The temperature at which soap may be cleansed depends on the particular grade—soaps requiring to be liquored should not be cleansed too hot or a separation will take place.—Swivel-joint. to save manual labour. This latter class of soap is generally run direct to the frames and crutched by hand. 3. Fig.) may be taken as a suitable temperature for this class of soap.

—Hand crutch.—Soap-boiling pan. 5. swivel and winch. [Pg 62] Fig. 4. . showing skimmer pipe.Fig.

7). will determine the most suitable type for the purpose. whether thin or stiff. the screw type is preferable.Fig. 6) or the agitator may take the form of an Archimedean screw working in a cylinder (Fig. The completion of crutching is indicated by the smoothness and stiffness of the soap when moved with a trowel. if necessary. There are various types of mechanical crutchers. 6. stationary and travelling. When well mixed the resultant product is emptied directly . the soap being forced upwards by the screw. The kind of soap to be crutched.—Mechanical crutcher.—This consists of stirring the hot soap in the frames by hand crutches (Fig. while[Pg 64] the reverse action can also be brought into play. Fig. and coloured and perfumed. in which the crutching is continued by hand. in the centre of which is rotated an agitator. Crutching may also be performed mechanically. and in that case they are merely used for mixing the liquids with the hot soap prior to its passage along wooden spouts (Fig. The former class includes "washer" soap which is generally neutralised. and descending between the cylinder and the sides of the pan. In the case of stiff soaps requiring complete incorporation of liquor. jacketed or otherwise. They may be cylindrical pans. 8) provided with outlets over the frames. consisting of a vertical or horizontal shaft carrying several blades (Fig. 5) until the temperature is sufficiently lowered and the soap begins to assume a "ropiness". and a portion taken out at this point and cooled should present a rounded appearance. [Pg 63] Crutching.—Mechanical crutcher. 7. in these crutching pans.

and the addition. It is important that the blades or worm of the agitating gear be covered with soap to avoid the occlusion of air and to prevent the soap becoming soft and spongy.). Liquoring of Soaps. to effect a reduction of 20 per cent. fatty acids content. (4° B.5° B. (16° B.) is the quality most convenient for yellow soaps. it is not so much used as formerly. This solution stiffens and hardens soap.). and is in that manner added to the hot soap. and is best performed in the crutching machines. the same quantity of silicate at different temperatures does not produce the same result. For yellow soaps. containing a low percentage of fatty acids. (39. improves the appearance of many soaps intended for household purposes. for example. 62° Tw. 4°-8° Tw.—This consists of the addition of various alkaline solutions to soap to produce different qualities. Amongst the more practical additions most frequently adopted may be mentioned carbonate of soda.9 per cent.into wheel-frames placed underneath the outlet of the pan. whereas the texture of a weak soap would be greatly improved by such addition. dissolves in its own water of crystallisation on heating. . is generally made at a temperature of 140° F. and others have gradually fallen out of use. Glauber's salt (sodium sulphate) produces a good smooth surface when added to soap. owing to its tendency to effloresce more quickly than soda carbonate.) also finds favour with some soap-makers. Mixtures of soda crystals or soda ash solution with silicate of soda solution are used for a certain grade of soap. and it will be found that the temperature should be low. Strong soda ash solution with a firm soap will result in a brittle product. 59. In some instances 140° Tw. 8. depending upon the composition and body of the soap base—neutral silicate 75° Tw. a solution of 18° Tw. (2. the density of the silicate solution should be increased. For a reduction of 3-4 per cent.4° B. (59. 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. silicate of soda. In the history of soap-making a large number and variety of substances have been suggested for the purpose of accomplishing some real or supposed desirable effect when added to soap. and pearl ash (impure carbonate of potash). and if the reduction desired is greater. or efflorescence will occur. The carbonate of soda may be used in the form of "soda crystals. (34° B. which is crutched until smooth and stiff.) silicate may be added. or of various strengths from 25° Tw. (60° C. although it is in some instances carried out in the frames. but.[Pg 65] solutions of silicate of soda of varying strengths are generally used.5° B. containing 62.) upwards. fatty acids content." which. Care should always be taken in the choice of solutions for liquoring. It is important that the soap to be "silicated" should be distinctly alkaline (i.e. have a distinct caustic taste)..) (boiling) is most suitable. this may be diluted to the desired gravity by boiling with water." but 1/10 of the quantity of soap taken is practically a limit.).—Wooden soap spout. experiment alone will demonstrate the amount which can be satisfactorily incorporated without the soap becoming "open.) (boiling) would probably be found to answer.4° B. which must not be excessive. a solution of 6° Tw. or the resultant soap is liable to become like stone with age. The alkaline silicate of soda (140° Tw. In the case of weakbodied soap. (12° B. this addition gives firmness and tends to increase the detergent qualities. of water. The soda carbonate may also be added to soap as a solution of soda ash (58° alkali) either concentrated. Fig.7-5.. Many of these have had only a very short existence. A slight addition of a weak solution of pearl ash. Various other strengths of sodium silicate are employed.

and the correct solution to be employed can only be ascertained by experiment and experience. or compounds containing carbolic acid and its homologues. cresylic acid. there is always the liability of rancidity developing. milk. and in many instances patented. Pat. often with a well in the base to allow excess of lye to accumulate—for other soaps. further. but care is necessary in employing these substances. The frames intended for mottled soaps. Pat. and egg. and further crutching may be given by hand in the frames. boric acid. Various materials have been recommended for the purpose. are constructed of wood. but the above suggestions will prove useful as a guide towards good results.357. 8. for neutralising the free caustic alkali. and. of coal-tar derivatives. Stearic and oleic acids are more suitable for the purpose..Common salt sometimes forms an ingredient in liquoring mixtures. umbers—have been superseded. The best method is the addition of an exact quantity of sodium bicarbonate (acid sodium carbonate). 9. the acid radicle of which neutralises the caustic alkali. The colouring matter used may be of either vegetable or coal-tar origin. is white and greasy to the touch. D.—The free caustic alkali in soap. the great objection being that complete saponification is difficult to ensure. 1900). when finely ground. although some soap manufacturers prefer to accomplish this during the milling operation. it is important that the appearance of the soap should not be materially altered. which converts the caustic alkali into carbonate. malt extract. bright. Potassium chloride and potassium silicate find a limited use for intermixing with soft soaps. Colouring and Perfuming. wheat glutenin "albuminoses" (albumen after acid or alkaline treatment). creosote. Morgan of Liverpool is shown in Fig. The older types of colouring matter—such as cadmium yellow. which require slow cooling.582. such as carbolic acid. as any excess is liable to decompose the soap. Neutralising. cocoa-nut oil. and borax (biborate of soda) are sometimes used. Whatever filling material is used. or vegetable albumen. is added from 3 to 4 per cent. In the production of washer household soaps. Talc is the most frequently used article of this description. ochres.—Some low-grade soaps contain filling. the use of sodium and potassium bibasic phosphate (Eng. those in most general use being sodium bicarbonate.—The object of framing is to allow the soap to solidify into blocks. a small quantity of perfume is sometimes added. It will be readily understood that hard and fast rules cannot be laid down for "liquoring" soap. vermilion. . 25. water. Filling. iron frames are in general use. The frame manufactured by H. glossy appearance is what should be aimed at.—To the soap base. firm soap of clear. Among these may be mentioned—Alder Wright's method of using an ammoniacal salt. Framing. It consists of hydrated silicate of magnesium and. which must be strong to taste. which serves no useful purpose beyond the addition of weight. A large number of other substances have been proposed. or fat). The addition of this substance to the hot soap is made by suspending it in silicate of soda solution. is usually neutralised[Pg 66] during the cleansing. and oleic acid. The reaction may be expressed by the equation:— NaOH + NaHCO3 = Na2>CO3 + H2O Caustic soda Bicarbonate of soda Carbonate of soda Water Boric acid in aqueous or glycerine solutions. and is dissolved in the most suitable medium (lye. a substance formed by treating albumen with formalin (Eng. The incorporation is made in the crutching pan. 1899). naphthalene. stearic acid. A smooth. intended for toilet or laundry purposes. The addition of cocoa-nut oil is unsatisfactory. but oleic acid has the disadvantage that oleates are very liable to go rancid. Disinfectant Soaps. ammonia being liberated.

As soon as the frame is filled, or as soon as the crutching in the frame is finished, the soap is smoothed by means of a trowel, leaving in the centre a heap which slopes towards the sides. Next day the top of the soap is straightened or flattened with a wooden mallet, this treatment assisting in the consolidation.[Pg 67]

Fig. 9.—Soap frame.

Fig. 10.—Slabbing machine. [Pg 68] The length of time the soap should remain in frames is dependent on the quality, quantity, and season or temperature, and varies usually from three to seven days. When the requisite period has elapsed, the sides and ends of the frames are removed, and there remains a solid block of soap weighing from 10 to 15 cwt. according to the size of frame used. The blocks, after scraping and trimming, are ready for cutting into slabs. Slabbing.—This may be done mechanically by pushing the block of soap through a framework containing pianoforte wires fixed at equi-distances (Fig. 10, which shows a machine designed by E. Forshaw & Son, Ltd.), or the soap may be out by hand by pulling a looped wire through the mass horizontally along lines previously scribed, or, for a standard sized slab, the wire may be a fixture in a box-like arrangement, which is passed along the top of the soap, and the distance of the wire from

the top of the box will be the thickness of the slab (Fig. 11).

Fig. 11.—Banjo slabber. All tallow soaps should be slabbed whilst still warm, cut into bars, and open-piled immediately; if this type of soap is cold when slabbed its appearance will be very much altered. Barring.—The slabs are out transversely into bars by means of the looped wire, or more usually by a machine (Fig. 12), the lower framework of which, containing wires, is drawn through the soap placed on the base-board; the framework is raised, and the bars fall upon the shelf, ready for transference into piles. It has long been the custom in England to cut bars of soap 15 inches long, and weighing 3 lb. each, or 37-1/2 bars of soap to the cwt., but in recent years a demand has arisen for bars of so many various weights that it must be sometimes a difficult matter to know what sizes to stock. In another type of barring machine, portions of the slab, previously cut to size, are pushed against a framework carrying wires, and the bars slide along a table ready for handling (Fig. 13). In cutting machines, through which "washer" household soap is being passed, the bar is pushed at right angles through another frame containing wires, which divides it into tablets; these may be received upon racks and are ready for drying and stamping. It is needless to say that the slabs and tablets are cut with a view to reducing the amount of waste to the lowest possible limit. Such a machine, made by E. Forshaw & Son, Ltd., is shown in Fig. 14.[Pg 69]

Fig. 12.—Barring machine.

Fig. 13.—Bar-cutting machine. [Pg 70]

Fig. 14.—Tablet-cutting machine. [Pg 71] Open- and Close-piling.—As remarked previously, tallow soaps should be cut whilst warm, and the bars "open-piled," or stacked across each other in such a way that air has free access to each bar for a day. The bar of soap will skin or case-harden, and next day may be "close-piled," or placed in the storage bins, where they should remain for two or three weeks, when they will be in perfect condition for packing into boxes ready for distribution.

Fig. 15.—Soap stamp. Drying.—"Oil soaps," as soaps of the washer type are termed, do not skin sufficiently by the openpiling treatment, and are generally exposed on racks to a current of hot air in a drying chamber in order to produce the skin, which prevents evaporation of water, and allows of an impression being given by the stamp without the soap adhering to the dies. It is of course understood that heavily liquored soaps are, as a rule, unsuitable for the drying treatment, as the bars become unshapely, and lose water rapidly. Stamping.—Bar soaps are usually stamped by means of a hand-stamp containing removable or fixed brass letters (Fig. 15), with a[Pg 72] certain brand or designation of quality and the name of the manufacturer or vendor, and are now ready for packing into boxes. A very large bulk of the soap trade consists of the household quality in tablet form, readily divided into two cakes. These are stamped in the ordinary box moulds with two dies—top and bottom impressions—the die-plates, being removable, allow the impressions to be changed. This type of mould (Fig. 16) can be adjusted for the compression of tablets of varying thickness, the box preventing the escape of soap. We are indebted to E. Forshaw & Son, Ltd., for this illustration.

Cardboard cartons are also used for encasing the wrapped tablets. 17) or power driven.—Soap-stamping machine.—Many attempts have been made to shorten the time required for the framing and finishing of soap.[Pg 73] Fig. Where large quantities of a particular tablet have to be stamped. Cooling. after which it is ready for wrapping. [Pg 74] . the tablets being conveyed to and from the dies by means of endless belts. Such a machine is shown in the accompanying illustration (Fig. the object being that these are more conveniently handled by tradesmen and may be advantageously used to form an attractive window display. the soap is transferred to racks and exposed to the air. 16. 17. showing box mould. although in some instances automatic wrapping machines are in use. by cooling the liquid soap as it leaves the pan. which is generally performed by manual labour. The stamping machine may be worked by hand (Fig.—Box mould. one of the many automatic mechanical stampers in existence may be employed. If necessary. 18).Fig.

The bottom of the hopper is fitted with holes corresponding with the cooling tubes. a portable tank. which terminates above in a screw spindle a. does not regain its former firmness. and when the hopper is filled with liquid soap the plugs c are raised and the air in the box C exhausted. the soap is churned by means of a worm or screw. which can be raised or lowered by means of a screw. B. and this[Pg 75] interferes with the firmness of the finished bar. containing tubes. thus causing the soap to descend into the cooling tubes. soap which has been handled too much. .—Automatic stamper. C. e.With milling base. for. 19). as soap which has been suddenly chilled lacks the appearance of that treated in the ordinary way. by means of which the frame and plugs can be raised and lowered so as to permit or stop the outflow of soap into the cooling tubes. this is successfully accomplished in the Cressonnières' plant. is carried on a truck running on rails. D. and closed by plugs c. or rotated through a cooling medium. where the resultant product must be of good appearance and have a firm texture. attached to a frame b. in passing through some of the devices for solidification after chilling. A. owing to fracture of the crystalline structure. and a detachable box. as is well known. A form of apparatus which is now giving satisfactory results is the Leimdoerfer continuous cooler (Fig. and numerous claims have been made both for mechanical appliances and for methods of removing or discharging the bars after cooling. Moreover. Several patents have been granted for various methods of moulding into bars in tubes. and its appearance is rendered unsatisfactory. In many instances these have proved unsatisfactory. Fig. by allowing the hot soap to fall upon the periphery of a revolving drum which can be cooled internally by means of water. and the box B. The charging hopper can be connected with the soap-pan by a pipe. In the case of household soaps. the difficulty is to produce a bar fit for sale after the cooling has been performed. 18. This consists of a fixed charging hopper. The tubes are closed at the bottom by slides d. in which they are mounted. where the hot soap is cooled by being either surrounded by running water in a machine of similar construction to a candle machine.

20. The soap is run into frames or moulds having open sides.Fig.—Holoubek's cooler. the soap being received from the cooling pipes on a suitable arrangement for transport to the press or store room. Pat. 20). 24. A similar idea has been made the subject of a patent by Holoubek (Eng. . and the box B moved away to make room for another.—Leimdoerfer cooler. the screw D released. which are closed by being clamped with screws and pressure plates between cooling tubes through which water circulates. 1904. 19. Fig. and the truck is run back on a side track to the machine for use over[Pg 76] again. In this way the apparatus can be worked continuously. Fig. The slides d are closed.440. At the end of the rail track is an ejecting device which pushes the cooled soap out of the tubes.

or the soap will become aerated. The second class consists of good quality settled soaps." or "little pan" soaps. is well incorporated. in a soluble form. additions of pearl ash solution are made to give it a finer and smoother texture. also. The third class is represented by soaps made by the old English method of remelting.396. (2) Settled boiled soaps. so that the perfume of this class of soap is not so delicate[Pg 78] as that of milled soaps. 1896) has been granted for the use of these substances together with wood-fibre impregnated with boric acid. and lastly the perfume. having been superseded by the other qualities. dealkalising materials. The agitation must not be too vigorous or lengthy. render it more transparent. prior to framing. much of the perfume is lost when added to hot soap. Oatmeal and bran have been recommended in combination with soap for toilet purposes. and cut into blocks. Details of the "cold process" have already been given on page 46. Perfume. Pat. the soap is slabbed. 26. TEXTILE AND MISCELLANEOUS SOAPS. suitable perfume and colouring matter.[Pg 77] CHAPTER VII.—By the term "toilet soap" is inferred a soap specially adapted for toilet use by reason not only of its good detergent and lathering qualities. Toilet soaps may be simply classified according to their method of preparation into the following four classes:— (1) Cold process soaps. The necessary colour. and increase its lathering properties. After cooling in small frames. (4) Milled soaps. it is only necessary to add the desired perfume and colouring matter to the soap. TOILET. Soaps of the first class are of comparatively trifling importance. to which have been added. if necessary. Owing to volatilisation.. Medicaments are sometimes added to these soaps. which are often termed "perfumers'. and agitated. . although it is quite possible to produce remelted soaps as free from uncombined alkali as a milled toilet soap. and a patent (Eng. (3) Remelted soaps. Toilet Soaps—Cold Process Soaps—Settled Boiled Soaps—Remelted Soaps—Milled Soaps—Drying —Milling and Incorporating Colour. borax. coal-tar. e. hence the cheaper essential oils have to be used. Toilet Soaps. and finally into portions suitable for stamping in a press (hand or steam driven) with a design or lettering on each side. or pan provided with steam coils. direct from the copper. When all the soap is molten. or Medicament—Perfume—Colouring Matter— Neutralising and Superfatting Material—Compressing—Cutting—Stamping—Medicated Soaps— Ether Soap—Floating Soaps—Shaving Soaps—Textile Soaps—Soaps for Woollen. The oldfashioned Brown Windsor soap was originally a curd soap that with age and frequent remelting had acquired a brown tint by oxidation of the fatty acids—the oftener remelted the better the resultant soap. The soap-base or mixture of various kinds of soap is remelted in a steam-jacketed pan. Cotton and Silk Industries—Patent Textile Soaps—Miscellaneous Soaps. camphor.g. Palm-oil soap often forms the basis for yellow and brown toilet soaps of this class. but also on account of its freedom from caustic alkali and any other ingredient likely to cause irritation or injury to the skin. and it is necessary to add a large quantity to get the desired odour. or carbolic.

. has been superseded by steam heat.—Practically all high-class soaps now on the market pass through the French or milling process. 21 shows a soap drying apparatus with fan made by W.. of cocoa-nut oil. is more uniform in composition. containing less water and more actual soap. Only soap made from best quality fats is usually milled. This treatment.) Drying. Cutting the soap into bars or strips and open piling greatly facilitates the drying. Fraser & Co. The advantages of milled soap over toilet soap produced by other methods are that the former. like soap-chippings. contains almost invariably from 28 to 30 per cent. Fig. possesses a better appearance. (iii.) milling and incorporating colour. is more economical in use.—Soap-drying apparatus. it is difficult to evaporate moisture without[Pg 80] constantly moving them and exposing fresh surfaces to the action of heat. of water. In the Cressonnières' system. where the shavings of chilled soap are dried by being carried through a heated chamber upon a series of endless bands (the first discharging the contents on to a lower . (ii. The air is either drawn or forced by means of quickly revolving fans through a cylinder placed in a horizontal position and containing steam coils. The first essential of a milling base is that the saponification should be thorough and complete. There are several forms of drying chambers in which the trays of chips are placed upon a series of racks one above another. was first practised by the French who introduced it to this country. (35-40° C. and consists briefly of (i. but of a firm and somewhat plastic consistency.) compressing. not exceeding 25 per cent.) cutting and stamping.—The milling-base. and essential oils and delicate perfumes may be incorporated without fear of loss or deterioration. Ltd. after solidification in the frames. which is usually effected by chipping the soap and exposing it on trays to a current of hot air at 95-105° F. J. and prepared as described in Chapter V.Milled Toilet Soaps. and Fig. perfume or medicament. The soap must not be short in texture or brittle and liable to split.) drying. does not shrink or lose its shape. a suitable base being that obtained by saponifying a blend of the finest white tallow with a proportion. as its name implies.). London.. rancidity is liable to occur and a satisfactory toilet soap cannot be produced. and (iv. if this is not ensured. 21. The older method of heating the air by allowing it to pass over[Pg 79] a pipe or flue through which the products of combustion from a coke or coal fire are proceeding under the floor of the drying chamber to a small shaft. It will be readily understood that in the case of a bad conductor of heat. and more elegant finish. and this quantity must be reduced to rather less than half before the soap can be satisfactorily milled. (i. and warm air circulated through. or passed over steam-pipes laid under the iron grating forming the floor of the chamber.

are added and the mixer closed and set in motion. and this increases the efficiency of the milling. the exact point can only be determined by judgment and experience. and ensures that the action of the rollers is one of rubbing rather than crushing. nor too little. it is apt to stick to the rollers and mill with difficulty. on the other hand. the soap is left too moist. 4. . (ii.916. is reduced to a minimum. however. is to make the addition of the perfume when the colour has been thoroughly mixed throughout the mass. care should be taken that the sheets of soap are not unnecessarily thick or the colour and odour will not be uniform. The degree of saturation of the air with moisture must be taken into consideration in regulating the temperature and flow of air through the drying chamber. the chips are frequently moved by hand to assist uniform evaporation. gives good results. one of the serrated knife edges is applied and the ribbons of the soap are delivered into the top of the hopper where the colour. etc.) Milling and Incorporation of Colour. this is performed by intercepting milling rollers in the system of belts (Eng. and the finished tablet may have a tendency to crack and contain gritty particles so objectionable in use. not too much. colouring matter. 22). The soap. of a peculiar form. and for this purpose the use of a hygrometer is advantageous. but speaking generally. from bottom to top. perfume. and so on). A better plan. where the perfumes added are necessarily more delicate and costly. the soap is reduced to a fine granular condition. and is moving in the opposite direction. When the incorporation is complete the other scraper is fixed against the top roller[Pg 81] and the soap ribbon passed into the receptacle from which it is conveyed to the compressor. and it is claimed that the formation of hardened crust is prevented. fitted with suitable gearing and working in an iron framework (Fig. Pat. and any other desired admixture is added.. after a short time. and after one passage through the mill. and also on the amount of perfume or medicament to be added. and during compression the surface assumes a blistered and sticky appearance. especially in the case of the best grade soaps. It is very important that the correct amount of moisture should be left in the soap. and to reduce it to a state in which colour. 1898) whereby the surfaces exposed to the drying are altered. If. with the colour and perfume evenly distributed throughout the whole. is introduced on to the rollers through a hopper. In the ordinary methods of drying. a range of 11 to 14 per cent. The rollers are connected in such a manner that they rotate at different speeds. in the form of chips. Perfume or Medicament. By means of suitably arranged screws the pressure of the rollers on one another can be adjusted to give the issuing soap any desired thickness. when. By the use of such machines. which during milling is quite appreciable. The perfume. which revolve in opposite directions one within the other as the mixer is rotated. fitted with internal blades. or any necessary neutralising material or other substance may be thoroughly incorporated. perfume. Another method is to mill once and transfer the mass to a rotary mixing machine. and the milling operation repeated three or four times. If the soap contains less than this amount it is liable to crumble during the milling. The milling machine consists of smooth granite rollers. the loss of perfume by evaporation. will not compress satisfactorily. and depends to a considerable extent upon the nature of the soap.—The object of milling is to render the soap perfectly homogeneous. and the delicacy of the aroma is preserved unimpaired.belt which projects at the end.

In the cheaper[Pg 82] grades of milled soaps the quantity will range from 10-30 fluid ozs. hence the advantage of giving it a slight tint.Fig. are sometimes added to the cwt. Many perfumes. Perfume. whereas in more costly soaps as much as 40-50 fluid ozs. The quantity necessary to be added varies considerably with the nature of the essential oils. and also the price at which the soap is intended to be sold. tends to produce a semi-transparent appearance. For this purpose a vegetable colouring matter is preferable. especially with a suitable soap base. tend to quickly discolour a soap. so far. and but rarely exceeds 18-20 ozs. It is obvious that a white soap guarantees the use of only the highest grade oils and fats. Colouring Matter.—During recent years an outcry has been made against highly coloured soaps. but the increased cost of production by the repeated milling is not accompanied by any real improvement in the soap. and the highest class soaps have been manufactured either colourless or at the most with only a very delicate tint. and excludes the introduction of any rosin. which is admired by some. 22. Prolonged milling. and chlorophyll is very suitable. however..—The materials used in perfuming soap will be dealt with fully in the next chapter. per cwt. the desire for a white soap is doubtless justified. ..—Milling machine. and.

The chief neutralising reagents have already been mentioned in Chapter VI. . 23. or spermaceti. per cwt: The most suitable materials are vaseline.—If desired.Fig. the final neutralisation of free alkali can be carried out during the milling process. the quantity of this should be very small. A demand still exists for brightly coloured soaps.[Pg 83] With regard to superfatting material.—Compressor. not exceeding 6-8 ozs. The quantity required is of course extremely small. any superfatting material being added at the same time. and this is usually met by the use of coal-tar dyes. lanoline. so that no harm or disagreeable result could possibly arise from their use. Neutralising and Superfatting Material.

(iii. and in which a single or twin screw is moving.[Pg 84] .) Compressing.—The next stage is the compression and binding of the soap ribbons into a solid bar suitable for stamping. 24—Hand soap-stamping press. The soap is fed through a hopper into a strong metal conical-shaped tube like a cannon. subjected to great pressure. The screws must be kept uniformly covered with shavings during compression to obviate air bubbles in the soap.Fig. and the soap is thereby forced through a perforated metallic disc. and compressed. and the plant used (Fig. 23) for this purpose is substantially the same in all factories. which tapers towards the nozzle.

however. the soap will be blistered. . and this also imparts a good gloss and finish to the ejected bar—if the nozzle is too hot.Fig. (iv. [Pg 85] The soap finally emerges through the nozzle (to which is attached a cutter of suitable shape and size according to the form it is intended the final tablet to take) as a long. solid bar. 25. and in stamping.) to allow the soap to be easily forced out. The nozzle of the plodder is heated by means of a Bunsen burner to about 120° or 130° F. is ready for cutting and stamping. (49°-55° C. the cutter should shape it somewhat similar to the required finished tablet. and if the stamping is to be done in a pin mould the shape should be a trifle larger than the exact size of the desired tablet.) Cutting and Stamping.—In cutting the soap into sections for stamping. whereas insufficient heat will result in streaky soap of a poor and dull appearance. Many manufacturers cut the soap into sections having concave ends. which is cut with a knife or wire into lengths of 2 or 3 feet. with the result that unsightly markings are produced at each end of the tablet. polished. and if of satisfactory appearance. It is preferable to have a cutter with convex ends. the corners are forced into the concavity.—Screw press.

and different impressions given by means of removable die plates. for the loan of this illustration. and the number of medicated .Fig. The band or collar prevents the soap squeezing out sideways. a 2 per cent. The edges of the mould meet very exactly. coli communis in less than six hours.—In this form (Fig. The stamping may be performed by a hand stamper (Fig. say from 2 ozs. Forehaw & Son. seek more or less successfully to still further increase the value of soap in this direction by the incorporation of various drugs and chemicals. Ltd. Many makers. There are two kinds of moulds in use for milled soaps:— (a) Pin Moulds in which tablets of one size and shape only can be produced (Fig. and even a 1 per cent. wrapping. 25).. The superfluous soap is forced out as the dies meet. to 5-1/3 ozs. solution having a marked action on germs in fifteen minutes. 26—Pin mould. solution proving fatal to B. 24). The inherent cleansing power of soap renders it invaluable in combating disease. a screw press (Fig. and boxing. Medicated Soaps. and these are received into two holes in the shoulder of the bottom plate. the upper part of the die carries two pins attached to the shoulder.[Pg 86] It is usual to moisten the soap or mould with a dilute solution of glycerine if it should have a tendency to stick to the die plates. The screw press works very satisfactorily for toilet soaps. 27) the mould may be adjusted to stamp various sized tablets. 27—Band Mould. while it also has distinct germicidal properties. however. We are indebted to R. 25). (b) Band or Collar Moulds. The soap is then ready for final trimming. Fig. or by a steam stamper.

The preparation of medicinal soaps appears to have been first taken up in a scientific manner by Unna of Hamburg in 1886. Strengths of 1/2. saponified with a mixture of two parts of soda to one part of potash. as they otherwise react with the soap and decompose it. and can be roughly divided into two classes. it is quite inadmissible for the manufacture of germicidal and disinfectant soaps. hence when it is added to soap. Compounds have been formed of metallic oxides and other salts with oleic said. however. which is soluble in alkali. and in some cases patented. such as corrosive sublimate or mercuric chloride. unsaponified. Ehrhardt (Eng. their efficiency as medicaments is very trifling or nil. and would thereby be rendered stable. causing the soap to quickly become rancid. biniodide are sold. Recent researches have shown. sufficient fat being employed to leave an excess of 3 or 4 per cent.407. to overcome this difficulty. of a dull slaty-green appearance. and 3 per cent. It is claimed that these bodies are present in an unchanged condition. as disinfectants. fatty acids are necessarily liberated. methyl salicylate. or soft soaps. β-naphthol.—At various times salts of metals other than mercury have been added to soap. Theoretically. but in practice found that[Pg 87] the best results were obtained by using a superfatted soap made from a blend of one part of olive oil with eight parts of beef tallow. the bactericidal efficiency of which is much restricted by the presence of free fat. Many of the medicaments added to soaps require special methods of incorporation therein. hard. On the contrary. however. a change which can be readily seen to occur in such a soap by the rapid development on keeping. but. should only be used under medical advice. Numerous processes have been suggested. This applies particularly to salts of mercury. This salt has also been incorporated with milled soap in a dry state in conjunction with ammonio-mercuric chloride. Pat. If simply mixed with the soap in the mill. devised and patented by J. it is an acid salt containing an excess of boric acid over the soda present. reaction very quickly takes place between the mercury salt and the soap. forming comparatively inert compounds. and (b) those impregnated with chemicals intended to act as antiseptics or germicides. 2. This process. In view of its alkaline reaction to litmus. Geissler suggested that the soap to which this reagent is to be added should contain an excess of fatty acids. (a) those which contain a specific for various definite diseases.[Pg 88] and incorporated with soap. but they have not met with much success. 1. or. with formation of the insoluble mercury compounds of the fatty acids. and. Another chemical commonly added to soap is Borax. Thomson in 1886. and are consequently frequently added to soaps. and added to the soap in an alkaline solution. he considered a soap-stock made entirely from beef tallow the most suitable for the purpose. sodium. A similar combination of bromide of mercury with potassium. has been worked since that time with extremely satisfactory results. 1898) patented a method of making antiseptic mercury soap by using mercury albuminate—a combination of mercuric chloride and casein. or ammonium bromide has recently been patented by Cooke for admixture with liquid. and biniodide of mercury. the intention being that the remedy should be absorbed by the pores of the skin and thus penetrate the system. who advocated the use of soap in preference to plasters as a vehicle for the application of certain remedies. and eucalyptol.soaps on the market is now very large. and become active when the soap is added to water as in washing. that even if a superfatted soap-base is beneficial for the preparation of toilet soaps (a point which is open to doubt). Zinc and other Metallic Salts. In the case of corrosive sublimate. turning red litmus blue. With biniodide of mercury the interaction can be readily obviated by adding to the biniodide of mercury an equal weight of potassium iodide. Such soaps may consist of either hard or soft soaps to which certain medicaments have been added. As a remedy for this it has been proposed to add sufficient alkali to . both of which have very considerable germicidal power. without action on soap. owing to their insolubility in water. as such. but owing to the readiness with which it is absorbed by the skin a soap containing more than 1/2 per cent. generally. and mixtures made with vaseline and lanoline. this salt is no doubt generally regarded as alkaline.

218. New combinations of formaldehyde with other bodies are constantly being brought forward as disinfectants.convert the borax into neutral mono-borate of soda which is then added to the soap. 1904. till it contains say only 9 or 10 per cent.—Nearly all soaps contain a small quantity of this body which is not separated in the lyes. Salicylic Acid is often recommended for certain skin diseases. and afterwards with ammonia. but the most valuable constituents from a disinfectant point of view are undoubtedly the phenols. the quantity generally used being about 5 per cent. by milling in 2-3 per cent. the resultant soap is possessed of a characteristic empyreumatic smell. 1904) consists of coating the borax with a protective layer of fat or wax before adding to the soap with the idea that reaction will not take place until required. The incorporation of borax with the addition of gum tragasol forms the subject of two patents (Eng. lavender. The odour of coal tar is considerably modified by and blends well with a perfume containing oils of cassia. To overcome this a process has recently been patented for rubbing the acid up with vaseline before addition to soap. Ichthyol or Ammonium-Ichthyol-Sulphonate is prepared by treating with sulphuric acid. An excess of naphthalene should also be avoided. 1898). the hydrocarbon oil containing sulphur obtained by the dry distillation of the fossil remains of fish and sea-animals. of pure phenol. Pats.. very dark colour. which has a characteristic pungent odour and is recommended as a remedy for eczema and psoriasis. Boric acid possesses the defects of borax in a greater degree. Pat. being now almost completely soluble in water. naphthol. Amongst the more common milled medicated toilet soaps may be mentioned. simply form sodium borate with liberation of fatty acids. containing 5 or 10 per cent. and also as an anti-rheumatic. Coal Tar.425. or tar acids. up to some 6 or 8 per cent. and stronger in odour than formerly. Formaldehyde. etc. This product has been admixed with soap for many years. which is a gas. and is recommended as an antiseptic medicament for incorporation with soap. which form a bituminous mineral deposit in Germany.169. a 40 per cent. Ichthyol has somewhat changed its character during recent years. increased detergent and lasting properties are claimed for the soap. soaps containing much of it are unpopular. Various blends of different fractions of coal tar are used. birch tar. Carbolic Soap. in addition to the above:— Birch Tar Soap. Another patented process (Eng. and 25. 1905). on account of its strong odour. In some cases. but the simplest way appears to be to add the soda salt of the acid to soap. To mill this in requires great care. a much larger quantity is desired. since. and here again the addition of the acid to soap under ordinary conditions results in the formation of sodium salicylate and free fatty acids. naphthalene and other hydrocarbons derived from coal. for with larger quantities irritation is likely to be experienced by susceptible skins. so should never be added to a neutral soap. of course. and it may be readily introduced into soap without[Pg 89] undergoing any decomposition. in addition to carbolic acid and its homologues. and would. . though in this case as with carbolic and cresylic soaps.—These soaps contain. however. 7. aqueous solution of formaldehyde. Pat. The best way is to dry the soap somewhat further than usual.—A toilet soap should not contain more than 3 per cent. White soaps containing this chemical retain their whiteness almost indefinitely. 17. 4. in a toilet soap. the amount of phenols should not exceed 3 per cent. spike. Glycerine. and is recommended for rosacea and various skin diseases. moisture and then mill in the glycerine. bases. of formalin. Among others the compound resulting from heating lanoline with formaldehyde has been patented (Eng.—This substance is one of the most powerful disinfectants known.415. and red thyme. This process is patented and the name "Kastilis" has been given to the neutral salt. otherwise the soap tends to blister during compression.

lysol. This. Sulphur. such soaps being found to rapidly become rancid and change colour. acid fluorides and soap being obviously incompatible. eczema and many other cutaneous affections.—Attempts have been made to produce tablets of soap that will float upon the .—The use of albumen—egg.—This name is applied to a soap solution of cresol.. and the use of albumen for soap-making in this country appears to be very slight. Floating Soaps. and constitutes a patented article (Fr. however. while potassium iodide should also be added to render the iodine soluble. "Lysol Soap" being simply another form of coal-tar soap. chlorine compounds. Numerous other substances have been proposed for addition to soaps. makes their use disagreeable and lessens their popular estimation. 359. and vegetable—in soap has been persistently advocated in this country during the past few years. The usual strength is 10 per cent. the mercuric iodide being dissolved in a few drops of water containing an equal weight of potassium iodide. although characteristic.—The addition of this substance to soap. however popular it may be on the Continent. and also used to some extent as food preservatives. permanganate of potash. dissolved in alcohol and mixed with ether. Lysol. very commonly sold. and intended for surgeons' use. however.—This furnishes a not unpleasant. the majority are obviously better applied in the form of ointments. and. its action when used in conjunction with soap can be but very slow and slight.—Another form of medicated soap made by a few firms is a liquid ether soap containing mercuric iodide. sodium fluoride appears to have little value as a germicide when added to soap.[Pg 90] Terebene.—These have been somewhat popular during recent years for the disinfection of breweries. Sulphur soaps are. is the strength usually advocated. recommended especially for the cleansing of ulcerated wounds and restoring the skin to a healthy state. Pat. They are said to be efficacious for acne and rosacea. Sulphur soaps. and we need not consider them further. and 10 per cent. and very useful antiseptic soap. iodine. is recommended for scabies. also a coal-tar derivative. including yeast. and some had only ephemeral existence. is a good germicide. Swedish wood tar. as a rule. milk. Of course only neutral fluorides are available for use in soap. Experiments made by the authors did not appear to justify any enthusiasm on the subject. A suitable blend is 2-1/2 per cent. when dissolved in water. Of the vast number of less known proposed additions to toilet soaps. of thymol crystals and 1-1/2 per cent. incorporated in soap to the extent of 3 per cent. and helps to bind it more closely. mention may be made in passing of:— Fluorides.—A soap containing iodine is sometimes used in scrofulous skin diseases. It should contain some 3 per cent. tar from peat (sphagnol). Ether Soap. does not materially increase the disinfectant value of the soap. The normal strength is 3 per cent. the thymene of which imparts a sweeter odour to the soap than if produced with thymol alone. Of the many drugs that it has been suggested to admix in soap for use in allaying an irritable condition of the skin.—Since sulphur is insoluble in water. of a good red thyme oil. In the authors' experience. which. that it neutralises free alkali. together with sulphur. It is preferable to replace part of the thymol with red thyme oil.061. causes the soap to yield a more copious lather. Naphthol. consists of a soap made from olive oil and potash. gradually generate sulphuretted hydrogen. etc. though imparting a very refreshing and pleasant odour. but none of these has at present come much into favour. Thymol. Albumen. 1905). and a further inducement held out is that it allows more water to be left in the soap without affecting its firmness.Iodine. The claims attributed to albumen are. though many so-called sulphur soaps actually contain very little sulphur. and this solution added to the alcohol-ether soap. perborates and percarbonates of soda and ammonia.—β-Naphthol. A suitable strength is 5 per cent.

—The scouring of wool is the most important operation—it is the first treatment raw wool is subjected to.) is carefully neutralised with bicarbonate of sodium. The more usual method is to incorporate[Pg 91] into hot soap sufficient air. unsaponified fat. (77° C. and finisher. and phosphates. and rosin. a little carbonate of soda. The object of scouring wool is to remove the wool-fat and wool perspiration (exuded from the skin of sheep). Shaving creams and pastes are of the same nature as shaving soaps. Ordinary milling soap is used as a basis for this soap. cannot be recommended as economical. and the presence of this latter in soap. gives rise to serious subsequent troubles to manufacturer. is the quick production of a profuse creamy lather which is lasting. by inserting cork. or stamped in flat cakes. is a serious drawback to its popularity as a toilet detergent. together[Pg 92] with other salts. Gum tragacanth is used in some cases to give lasting power or durability. otherwise there will be a tendency to become discoloured and develop rancidity with age. apart from its freedom from caustic alkali or any substance exerting an irritating effect upon the skin. the fatty matter is thereby emulsified and easily removed. must be free from uncombined caustic alkali. and potassium salts of fatty acids. Every precaution should be taken to ensure thorough saponification of the soaps intended for blending in shaving soap. Shaving Soaps. whilst its deficiency in lathering properties. consisting of cholesterol and isocholesterol. cloth. perfumed and aerated. and silk textile industries. the settled soap direct from the copper at 170° F. In the woollen. . is therefore liable to injure the fibres and make the resultant fabric possess a harsh "feel. Floating soap. produced by the combination of ordinary milling base with a white potash soap. or a metallic plate in such a manner that there is an air space between the metal and the soap. This is effected by washing in a warm dilute soap solution. by means of a specially designed self-contained jacketed crutcher. chlorides. Unsaponified fat denotes badly made soap—besides reducing the emulsifying power of the liberated alkali. dyer. which is usually white (some are of a cream tint). 1. this fat may be absorbed by the fibres and not only induce rancidity but also cause trouble in dyeing. oleic or stearic acids.surface of water. even in small quantities. either melted or milled together. and if it is not performed in an efficient manner. Textile Soaps.—The first essential of a shaving soap." and be devoid of lustre. as this property is readily attained by the use of a suitable proportion of potash soap. The difference in weight of a tablet of the same size before and after aerating amounts to 10 per cent. and are placed on the market either in the form of sticks which are cut from the bar of soap as it leaves the compressor. and is more satisfactorily milled in. Woollen Industry. silicates. to be suitable for the purpose. in which two shafts carrying small blades or paddles rotate in opposite directions. such as sulphates. Glycerine is sometimes added. The best shaving soaps are mixtures of various proportions of neutral soda and potash soaps. Shaving soaps are delicately perfumed. Wool can be dissolved in a moderately dilute solution of caustic soda. and the following is a brief description of the kinds of soap successfully employed in the various stages. or floats. Soap. the use of soap for detergent and emulsifying purposes is necessary in several of the processes. or boroglyceride. owing to occluded air. containing in the case of low quality wool. to reduce the density of the soap below that of water and so enable the compressed tablet to float. but is not necessary. but usually contain a larger proportion of superfatting material and considerably more water.

bleached palm oil. either soft or hard. In cotton dyeing.[Pg 93] and finds that a good soap." and in cases where lower grades of wools are handled. renders its use prohibitive for lower class goods. in the form of yarn or cloth. as they produce sticky insoluble lime and magnesia compounds which are deposited upon the fibres. lest the colours should be acted upon and tints altered. but also plays an important part in fixing and brightening the colours. is preferable. however. The fabric is thoroughly cleansed. Curd soaps or finely-fitted soaps made from tallow or bleached palm oil. may be used for fibres coloured with most delicate dyes. the user is often willing to have soap containing rosin (owing to its cheapness) and considers a little alkalinity desirable to assist in removing the oil. and in such cases no better soap can be suggested than the old-fashioned curd mottled or curd soaps (boiled very dry). after spinning and weaving. The calico-printer uses considerable quantities of soap for cleansing the printed-cloths. 3.Soaps containing silicates may have a deleterious action upon the fibres. Tallow curd soaps are sometimes used. Some manufacturers prefer a cheap curd soap. or tallow. is oiled with olive oil or oleine. as. which would be fugitive in hot soap solutions. These qualities are possessed by olive-oil soaps. The woollen dyer uses soap on the dyed pieces to assist the milling.—Silk is secured to remove the sericin or silk-glue and adhering matter from the .—Cotton fibres are unacted upon by caustic alkali. a little alkalinity is not of consequence. and this soap is employed for the most expensive work. with or without the addition of a small quantity of cocoa-nut oil. All traces of soap must be carefully removed if the fabric is to be dyed. and produces a good "feel" so essential in the best goods. and tends to preserve the lustre and pliability of the fibre. owing to its solubility in cold water. and renders them somewhat unsuitable. Soaps made from olive oil and palm oil are recommended. made from either olive oil. although they are not so soluble as the olive-oil soaps. The soap not only cleanses by helping to remove the gummy and starchy constituents of the adhering printing paste. and this alkalinity would be instantly neutralised. as free as possible from uncombined caustic alkali. as a rule. is easily washed out. it quickly penetrates the fibres. Cotton Industry. the fabric. free from objectionable odour and rosin. 2. after this cleansing operation. has to be scoured to free it from oil. with or without the addition of cocoa-nut oil. give the best results. but the difficulty with which they dissolve is a drawback. A neutral olive-oil soft soap is undoubtedly the best for the purpose of wool scouring. for which purpose the soap should be neutral and free from rosin and silicates. The same kind of soap is sometimes used for soaping the dyed cotton goods. The high price of olive-oil soap. although it is generally specified to be free from alkali. may be advantageously used for removing the natural oil. such as is generally termed "second curd. Any curd soap made from tallow. A neutral olive-oil soft soap. otherwise a harsh feeling or stickiness will be produced. acid after dyeing. Silk Industry. owing to its ready solubility in water. and in such cases the soap must be of good odour and neutral. additions of soap are often made to the bath. Soaps intended for this class of work must be quite neutral (to obviate any possible alteration in colour by the action of free alkali). is that of milling or fulling. and readily soluble in water. for the woollen goods are. Another operation in which soap is used. in fact alkalinity is a distinct advantage in order to assist the cleansing. those made from palm oil are also recommended. By general consent soaps containing rosin are unsuitable for use by woollen manufacturers. The soap in most general use for scouring woollen fabrics is neutral oleine-soda soap. Olive-oil curd (soda) soaps are in general use. prior to spinning. whereby the fabric is made to shrink and thus becomes more compact and closer in texture. The raw wool. and. so that the soap used in cleaning and preparing cotton goods for dyeing need not be neutral. causing them to become damaged and broken. and give rise to unevenness in the dyeing.

pumice and tripoli (motorists' soaps). to be used in place of Turkey-red oils in the dyeing and printing of cotton goods and finishing of textile fabrics. 1897) makes special claim for a soap. and turpentine. has for its object the obviating of the injurious effects upon wool. magnesium carbonate (tooth soaps). and it is stated that the product is not precipitated when used in the dye-bath as is ordinary soap. cassia oil. nor is it deposited upon the fibres. oleine. SOAP PERFUMES. but the action of the perfumes on the soap. both natural and artificial. and can scarcely be termed soap. Thus. but. rouge. The dyer of silk requires soap. Amongst the many other additions may be mentioned: ox-gall or derivatives therefrom (for carpetcleaning soap). It is essential.868. olive-oil and oleine hard soaps may also be used. when any liberated rosin acids would cling to the silk fibres and produce disagreeable results. has also to be taken into account. It is proposed to accomplish this by sulphonating part of the fat used in making the soap. alkali sulphides (for use of lead-workers). fractions of petroleum.382. producing thereby lustre on the softened fibre and thus preparing it for the dyer. and on each other. e. [Pg 95] CHAPTER VIII. siliceous matter. or soda crystals. 1897). whilst polishing soaps often contain from 85 to 90 per cent. The soap is prepared by heating the sulphonated oil (obtained on treatment of castor oil with sulphuric acid) with alkali. pine-needle oil. ammonium carbonate.g. 16. however. The very best soap for the purpose is an olive-oil soft soap. The number of raw materials.—Under this heading may be classed soaps intended for special purposes and consisting essentially of ordinary boiled soap to which additions of various substances have been made. whilst carbonates are permissible. 24. at the disposal of the perfumer. many essential oils and synthetic perfumes cause the soap to darken rapidly on keeping. or palm oil) are used chiefly on account of cheapness. Pat. magnesia. which is neutral and of a pleasant odour.. Pat. Another patent (Eng.raw silk. Tallow soaps are so slowly soluble that they are not applicable to the scouring of silk. of alkali liberated from a solution of soap. Essential Oils—Source and Preparation—Properties—Artificial and Synthetic Perfumes. chalk (silversmiths' soap). The soap is often used in conjunction with carbonate of soda to assist the removal of the sericin. clove oil. soda ash. precipitated chalk. With additions of naphtha. it is necessary to avoid an excess of caustic soda. powdered orris. in some instances together with lanoline (for massage soaps). Miscellaneous Soaps. Not only does the all-important question of odour come into consideration. the detergent power of the soap is increased by the action of these substances in removing grease.—Stockhausen (Eng. but hard soaps (made from olive oil. and a thorough knowledge of the products to be handled. has increased so enormously during recent years that the scenting of soaps has now become an art requiring very considerable skill. pearl-ash (for soap intended to remove oil and tar stains). aniline colours (for home-dyeing soaps). and other chemicals. Soap powders or dry soaps are powdered mixtures of soap. that the soap[Pg 94] should be free from rosin on account of its frequent use and consequent decomposition in the acid dye bath. Patent Textile Soaps. The preference is given to neutral olive-oil soft soap. termed Monopole Soap. .

in describing the chief constituents and properties of the more important oils. petitgrain. however. not only because of their complex nature. and soon decompose any soap to which they are added. or directly extracted from the flowers by means of a volatile solvent such as benzene. The last process undoubtedly furnishes products most nearly resembling the natural floral odours. eucalyptus." and among the most important of these may be mentioned musk. bay.or lævo-rotatory. and is the only one which does not destroy the delicate fragrance of the violet and jasmine. linaloe. d-pinene. the processes may be divided into three classes—(1) expression. in the effect of each being lost. ylang-ylang. the oils of Peru balsam. faintly dextro. civet. to include all normal oils. aspic. some odoriferous substances. Broadly speaking.. it is very important that these should not be added to soaps containing much free alkali. the blending of two unsuitable perfumes results. employed for otto of rose. as being simpler for reference. and otto of rose by Bulgaria. and concrete perfumes prepared in this way are therefore somewhat costly. or chloroform. 0. Anise Stell. by which the volatile oil from the flowers is either first absorbed by a neutral[Pg 96] fat such as lard.. geranium.heliotropin.555. refractive index at 20° C. cinnamon. viz. It is a matter of some difficulty to judge the purity of essential oils. lemon. and. and benzyl benzoate. Since anethol is the most valuable constituent. balsams. and resins. but owing to the very great effect upon their properties produced by growing the plants in different soils and under varying climatic conditions.553-1. vanillin. while in Europe there are the citrus oils. oils with a higher solidifying point are the best. Further. camphor. citronella. As would be expected with products of such diverse character. Such perfumes are known as "fixing agents" or "fixateurs. and consist of essential oils. we have preferred therefore to arrange them alphabetically. from Asia. from their chemical nature. the methods employed for the preparation of essential oils vary considerably. and are obtained from all parts of the world. l-phellandrene. or Star Anise. solidifying point. caraway and clove by Holland. however. and the solidifying point of the oil is roughly proportional to its anethol content. both natural and artificial. by mutual reaction. and patchouli. cedarwood. Canadian snake root. used for orange. from Africa we have geranium and clove oils. In the case of oils like bergamot oil. peppermint. lavender. . bergamot. (2) distillation. and in older oils. The following figures will be found.. petitgrain. and (3) extraction. the oxidation products of anethol. are incompatible with soap. The chief constituents of the oil are anethol. and the grass oils. optical rotation. and sassafras. cassia. including enfleurage. from the fruit of Illicium verum. civet. solubility in 90 per cent. 1 in 3 or 4. alcohol. patchouli. and ambergris being reserved principally for the preparation of "extraits". however. and still more to the highly scientific methods of adulteration adopted by unscrupulous vendors. anise by Russia. while in a few cases. sandalwood. sandalwood. star anise. from Australia. and orange. and vetivert.980-0. bois de rose. neroli.990. Specific gravity at 15° C. The essential oils used are derived from upwards of twenty different botanical families. and lime oils. sandalwood. Some perfumes possess the property of helping the soap to retain other and more delicate odours considerably longer than would otherwise be possible. the odour value of which depends chiefly on their ester content.. is extremely small. viz. The natural perfumes employed for addition to soaps are almost entirely of vegetable origin. methyl chavicol. 1. anisic aldehyde and anisic acid. lemongrass. and many other oils. from America. Attempts have been made to classify essential oils either on a botanical basis or according to their chemical composition. and rosemary by France. animal perfumes such as musk. palmarosa. and then extracted therefrom by maceration in alcohol. but neither method is very satisfactory. Thus. lemon. produced by Sicily. petroleum ether. 14°-17° C. obtained from China. The yield. as these esters are readily decomposed thereby. +0° 30' to -2°.

. rarely up to +7°. the oil is generally insoluble in 90 per cent. 1. -17° to -30°.886.. optical rotation. residue. Among the constituents of this oil are: linalyl acetate.940-0. alcohol. phenols. Canada snake root oil. 0. covered with an[Pg 98] inverted beaker. When the paper is burnt.4994-1. is saturated with the oil. caustic potash solution. distilled from the leaves of Pimenta acris. most oils are soluble in 65 per cent. esters. linalol.5 volumes of 70 per cent. 0.06.913. The chief impurity is prussic acid. obtained by expression from the fresh peel of the fruit of Citrus Bergamia. a small coil of filter paper.. calculated as linalyl acetate. and used very largely for the perfuming of toilet soaps. refractive index at 20° C.. and citral. also frequently found as an adulterant in lavender oil. filtered.880-0. 0. when a blue coloration will be produced if prussic acid is present. from the root of Asarum canadense. the inside of which is moistened with distilled water. borneol. This may be readily detected by adding to a small quantity of the oil two or three drops of caustic soda solution. dextro-rotatory up to +4°. by chemical means. Bitter Almond Oil. limonene.910-0. and obtained from St. methyl eugenol. artificial oil free from chlorine. dipentene. slightly lævo-rotatory up to -4°. 8-15 per cent. chavicol. Cananga or Kananga oil. alcohol be required for solution. +10° to +20°.. asarol alcohol. and occasionally as high as 42-43 per cent. When evaporated on the water-bath the oil should not leave more than 5-6 per cent. another alcohol.. from 45 to 60 per cent. alcohol. in no case should more than 2.5 or 85 per cent. Specific gravity at 15° C.[Pg 97] Spanish.965-0. 0. optical rotation. loosely rolled. Thomas and other West Indian Islands.904-0. it is no longer possible.. Specific gravity at 15° C. to distinguish with certainty between the natural and the artificial product. alcohol. Specific gravity at 15° C. 0. slightly lævorotatory up to -3°. refractive index at 20° C. and a few drops of ferrous sulphate solution containing ferric salt.5 volumes of 70 per cent. 1. 176-177° C. terpineol. pinene.544-1.962. from the flowers of Lavandula spica. methyl chavicol. The natural oil may frequently be differentiated from artificial benzaldehyde by the presence of chlorine in the latter. 2 to 6 per cent. esters. alcohol 1 in 4. but chiefly in the Bay Rhum toilet preparation. After thoroughly shaking.980.5 parts of 80 per cent. Specific gravity at 15° C.. 1.490. or failing that.045-1. acidulate with dilute hydrochloric acid.. and burnt in a small porcelain dish. boiling point. obtained chiefly from the Philippine Islands. optically inactive. French.. esters. and extensively employed in perfuming household and cheap toilet soaps.940.. frequently slightly lævo-rotatory to -2°. though when freshly distilled it dissolves in its own volume of alcohol of this strength. phellandrene. Bergamot oil... however. alcohol. The chief constituents of the oil are: linalol. and methyl eugenol. Specific gravity at 15° C. cineol. It is used to some extent as a perfume for shaving soaps. alcohol.Aspic oil.485-1. geraniol. The oil contains eugenol. soluble in 3 or 4 volumes of 70 per cent. the earlier distillate from the flowers of Cananga odorata. saponification number.545. estimated by absorption with 5 per cent. Specific gravity at 15° C. optical rotation. should dissolve in one volume of 82. and the filtrate tested for chloride with silver nitrate solution. calculated as linalyl benzoate. the beaker is rinsed with water. 35-40 per cent. The oil consists almost entirely of benzaldehyde which may be estimated by absorption with a hot saturated solution of sodium bisulphite. camphene and camphor.. and bergaptene.—The volatile oil obtained from the fruit of Amygdalus communis. frequently soluble in 1. As there is now on the market. To test for chlorine in a sample. Bay oil.. calculated as linalyl acetate. The oil is too expensive to be used in other than high-class toilet soaps. The principal constituents of the oil are a terpene.5024. optical rotation. optical rotation. 100-115. obtained from France and Spain. 1. soluble in 1 or 1. refractive index at 20° C. or dextro-rotatory up to +7°. . which is not always completely removed. myrcene.

Cedarwood oil.938-0. which is estimated by absorption with a saturated solution of neutral sodium sulphite. 0.485-1. The principal constituents are cedrene and cedrol. Cassia oil.. It is very largely used for perfuming cheap soaps. being probably admixed with either cassia oil or artificial cinnamic aldehyde. Besides cinnamic aldehyde the oil contains eugenol and phellandrene. potash. camphene.. soluble in 3 volumes of 70 per cent.. This is determined by absorption with a hot saturated solution of sodium bisulphite.467-1. optical rotation. and shipped to this country from China in lead receptacles. usually slightly lævo-rotatory up to -3°. but occasionally requires 1 to 2 volumes of 80 per cent. Three grades are usually offered...044-1. not exceeding 12 per cent. total acetylisable constituents. usually soluble in 2 to 3 volumes of 70 per cent.5030. total acetylisable constituents. refractive index at 20° C. The value of this oil is not determined entirely by its aldehyde content as is the case with cassia oil. soluble in 1 to 1.899.486.00-1. ..5 to 2 volumes of 95 per cent. calculated as geraniol. the former being the source of the bulk of Ceylon oil. citronellal. 0.907-0. refractive index at 20° C. aldehydes. linalol. alcohol. Cinnamon oil. Citronella Oil. the chief constituent being cinnamic aldehyde.060-1. 0. optical rotation. Specific gravity at 15° C. cadinene. Specific gravity at 15° C.471.890-0. The oils from these three localities show well-defined chemical differences. of 1.900-0. The addition of cinnamon leaf oil which has a specific gravity at 15° C. slightly dextro-rotatory up to +3° 30'.065 is detected by causing a material rise in the proportion of phenols. the second quality. distilled from the leaves of Cinnamomum cassia..960. methyl eugenol. distilled from the wood of Juniperus virginiana. refractive index at 20° C. optical rotation.6048. Specific gravity at 15° C. This oil gives the characteristic odour to Brown Windsor soap. alcohol. soluble in 1 volume of 80 per cent. Other constituents of the oil are cinnamyl acetate and cinnamic acid.. but becoming turbid on further addition. as measured by absorption with 5 per cent. esters of geraniol. but sometimes requires 1 volume of 80 per cent.. the best containing 80-85 per cent. The oil is qualitatively similar in composition to Ylang-Ylang oil. and dipentene. optical rotation. 70-75 per cent. aldehydes must be regarded with suspicion. distilled from the bark of Cinnamomum zeylanicum. and the latter being cultivated in the Straits Settlements and Java. 0.—Specific gravity at 15° C. and methyl ester of p-cresol. limonene.—This oil is distilled from two distinct Andropogon grasses. 1.915.890-0.—Specific gravity at 15° C.. alcohol as a general rule. optical rotation. distilled from the seeds of Carum carui. and any oil containing more than 75 per cent. and is useful for sweetening coal-tar medicated soaps. aldehydes.484. alcohol.5 volumes of 80 per cent. and phenols.068. The oil should contain 50-60 per cent. calculated as geraniol.soluble in 1. Java Citronella Oil. optical rotation. 80-90 per cent. Singapore Citronella Oil. soluble in 1-2 volumes of 80 per cent. 0. The chief constituents of the oil are geraniol. 1. alcohol. 1. The value of the oil depends upon its aldehyde content. refractive index at 20° C. 1. calculated as geraniol. total acetylisable constituents. -35° to -45°. 1. +77° to +79°. refractive index at 20° C. borneol. 1. alcohol for solution. Ceylon Citronella oil has the specific gravity at 15° C. by absorption with sodium bisulphite solution.6014-1..920. alcohol. Caraway oil.. 1. lævo-rotatory[Pg 99] up to -2°. soluble in 3 to 8 volumes of 80 per cent. of carvone. lævo-rotatory up to -12°.035. 75-80 per cent. alcohol... The remainder of the oil consists chiefly of limonene. 55-75 per cent. -1° to -6°. 54-70 per cent. and also serves as a source for the production of geraniol. the Lana Batu and the Maha pangiri. and the lowest grade. Specific gravity at 15° C. 75-90 per cent.480-1.5013-1. alcohol. and contains linalyl benzoate and acetate. optical rotation..901.

Clove oil. Specific gravity at 15° C. -11° 30' to -16°.874-0. usually soluble in 2-6 parts 80 per cent. slightly lævo-rotatory up to -1° 30'. d-pinene. fenchone.548. calculated as combined myristic acid. phenols are usually less satisfactory in odour. distilled from the unripe blossoms of Eugenia caryophyllata. pressing. phenols. This is particularly suitable for . the high proportion of phenols being obtained at the expense of the decomposition of some of the sesquiterpene. free acidity. soluble in 1 to 2 volumes of 70 per cent. The oil consists almost entirely of citronellic aldehyde. +1° to +10°. The greater part of the product consists of the inodorous myristic acid. butyric. potash solution.5360. cineol.. 35-45° C. 0.[Pg 101] There are three principal kinds of this oil on the market—the African." which as its name implies.) Eucalyptus citriodora. with traces of saponifiable bodies. optical rotation. together with caryophyllene and acet-eugenol. alcohol. The chief constituents of the oil are anethol. only two are of much importance to the soap-maker.4608-1. The oil consists almost entirely of linalol. While within certain limits the value of this oil is determined by its eugenol content. refractive index at 20° C. except in coloured soaps. distilled from plants of the Pelargonium species. Specific gravity at 15° C. 0.Bois de Rose Femelle oil. Besides cineol. the chief odour-bearing constituent being irone.) Eucalyptus globulus. but this oil is not much used by soap-makers. 4-10 per cent. 1. soluble in 1. alcohol. +6° to +25°. or Cayenne linaloe oil. and other parts of Europe. Oils with less than 88 per cent. alcohol. optical rotation. 1.965-0.. decomposing with hot water. The high price of the oil renders its use only possible in the very best quality soaps.. and caproic aldehydes. Melting point..905. the chief source of which is East Africa (Zanzibar and Pemba).. obtained from Algeria and the neighbourhood.061. and the Spanish. Specific gravity at 15° C. Specific gravity at 15° C. optical rotation. is supposed to be geranium oil distilled over roses. Fennel (sweet) oil. soluble in 2 to 3 parts of 70 per cent.. It is chiefly used in medicated soaps.. 1. calculated as myristic acid. oils containing more than 93 per cent.5300-1. and dipentene. alcohol.. Concrete orris oil. cineol (estimated by combination with phosphoric acid. a waxy substance obtained by steam distillation of Florentine orris root. As already mentioned.985.. soluble in 4-5 volumes of 70 per cent. and on absorption with saturated solution of sodium bisulphite should leave very little oil unabsorbed.. obtained from the fruit of Fœniculum vulgare.. ester. A specially fine article is sold by a few essential oil firms under the name of "Geranium-sur-Rose. 1. phenols will be found somewhat weak in odour. These are:— (i. the oil used in pharmacy. Roumania.870-0. the oil contains d-pinene.4630. 50-80 per cent. and measuring the liberated cineol). The principal constituent of the oil is eugenol. Specific gravity at 15° C. usually 40-45° C. and valeric. found by Barbier and Bouveault in Mexican linaloe oil. alcohol. (ii. refractive index at 20° C. This oil is distinctly finer in odour than the Mexican product. but appears to be free from methyl heptenone. and containing 50-65 per cent.—Though there are some hundred or more different oils belonging to this class. but occasionally requires 1 part of 90 per cent. it causes the soap to darken in colour somewhat rapidly. estimated by absorption[Pg 100] with 5 per cent. Eucalyptus Oil. slightly dextrorotatory up to +2°. and must not therefore be used in any quantity. 0.045-1. grown in Germany. distilled principally in the Island of Réunion.910-0..515-1. refractive index at 20° C. however. optical rotation. 86-92 per cent.5 to 2 volumes of 70 per cent. distilled from wood of trees of the Burseraceæ species.880. Geranium oils. not less than 50 per cent. alcohol. The oil is also distilled from plants grown in the South of France. optical rotation.930. 0. the Bourbon. This oil is extensively used in the cheaper toilet soaps and is an important constituent of carnation soaps.

formerly regarded as an inferior kind of palma-rosa but now stated to be from an entirely different source. 20-27 per cent.4750. . alcohol. English Oil. the Spanish oil being too costly for extensive use. esters. refractive index at 20° C. alcohol. -4° to -10°. and there is no doubt that some of the finest oils contain less than 30 per cent.—Specific gravity at 15° C. 0. Lavender oil. The French and Italian oils are the most common. 0. 68-75 per cent. . citronellal. and acetic acids. dipentene. d-limonene. but this theory has now to a very large extent become discredited. optical rotation. soluble in 3 volumes of 70 per cent.898 -8° to -11° French. optical rotation.895-.506-1.900. The chief constituents of lavender oil are linalyl acetate. calculated as linalyl acetate.900-0. calculated as linalyl acetate. optical rotation. 20-40 per cent. Spanish Oil.. and is seldom. Italy and Spain. Specific gravity at 15° C.890-. . of doubtful botanical origin.900 -8° to -11° 27-32 per cent. soluble in 3 to 5 volumes of 70 per cent. 0. 18-23 per cent. butyric.. 66-75 per cent. African.[Pg 102] French and Italian Oils..5-2 1 in 2-3 1 in 1. This oil.883-0..464.—Specific gravity at 15° C. The principal constituent of the oil is guaiac alcohol.856-0. The oil contains a large amount of geraniol.. Esters. France. esters. 65-75 per cent. Solubility in 70 per cent. Ginger-grass oil. used in soap.. 2-6 per cent. and linalyl butyrate. distilled from the flowers of Lavandula vera. The English oil is considerably the most expensive. 1. the Spanish oil being a comparatively new article. and l-carvone.967-0. 0. and more closely resembling aspic oil.. There was at one time a theory that the higher the proportion of ester the better the oil. 5-10 per cent. 1.. esters. The African and Bourbon varieties are the two most commonly used for soap-perfurmery.885-0. refractive index at 20° C.975. .—Specific gravity at 15° C. also l-menthone.889-0. and obtained almost entirely from Sicily and Southern Italy.888-. 1. which has what is generally termed a "tea-rose odour.use in high-class soaps. as geraniol. optical rotation. optical rotation.5 to 4 per cent. distilled from the wood of Bulnesia sarmienti. prepared by expressing the peel of the nearly ripe fruit of Citrus limonum. optical rotation.897. if ever. together with small quantities of pinene.459-1. The following are the general properties of these oils. 2. of esters.915. aldehydes (citral). calculated as geranyl tiglate Total alcohols. Optical rotation. refractive index at 20° C.895 -9° to -18° Spanish. while the English oil also contains a distinct amount of cineol. soluble in 1. together with di-hydrocumin alcohol. phellandrene." is occasionally used as an adulterant for otto of rose.5-2 1 in 1.. Specific gravity at 30° C. soluble in 1-2 volumes of 70 per cent. +58° to +63°.900.5-2 The oil contains geraniol and citronellol. d-phellandrene. both free. alcohol. and combined with tiglic.507.900 -6° to -10° 20-27 per cent. geraniol. -2° to +7°.4730-1. Bourbon. alcohol. 0.860. 1 in 1. occasionally higher. -4° 30' to -7°.5-3 volumes of 70 per cent. Specific gravity at 15° C. -2° to -9°.. geraniol. +15°. grown in England. linalol. valeric. and the .. The principal constituents of the oil are limonene and citral. Guaiac wood oil. Specific gravity at 15° C. 70-80 per cent.. geranyl acetate.897-. alcohol. calculated as linalyl acetate. octyl and nonyl aldehydes. 0. or gusiol. Lemon oil. It will be seen that the limits for the figures overlap to a considerable extent.

geraniol. total alcohols as linalol.. faintly lævo-gyrate.906. 10-18 per cent. 80-82 per cent.stearopten..885. calculated as linalyl acetate.854-0. 0. but occasionally dextro-rotatory up to +5° 30'. limonene.468-1. alcohol. Specific gravity at 15° C. citraptene. 65 to 78 per cent.. optical rotation.. 1-8 per cent.. distilled from Andropogon Schœnanthus. soluble in 5-8 volumes of 90 per cent. Linaloe oil. Specific gravity at 15° C.966. soluble in 2-3 volumes of 70 per cent. esters. which is grown in India and. 54-66 per cent. solubility in 70 per cent.—Specific gravity at 15° C. free. linalyl acetate.4726-1.852. alcohol. and is used as a source of geraniol. estimated by absorption with 5 per cent. Lime oil.. alcohol. geraniol.75-1. Citrus bigaradia.875-0.75 volumes of 80 per cent. Orange (sweet) oil.472-1.. the former being preferred on account of its greater solubility in alcohol. optical rotation. 1. +0° 40' to +10°. alcohol. chiefly carvacrol. -0° 30' to -6°. calculated as[Pg 103] linalyl acetate. 0. 0. more recently. optical rotation.4732. and obtained entirely from Cyprus. Expressed Oil. in the West Indies. 1. 1. by absorption with bisulphite of soda solution. and d-terpineol.895.. and obtained from Mexico..485-1. caustic potash solution.—Specific gravity at 15° C. It is largely used in cheap toilet soaps.487.882. The oil consists chiefly of geraniol. alcohol. distilled from Origanum majoranoides. optical rotation. Specific gravity at 15° C. 7-14 per cent. This oil is used in soap occasionally in place of red thyme oil. optical rotation.—This is entirely different in character to the expressed oil. expressed from the peel of Citrus aurantium. It is also a favourite adulterant for otto of rose. citronellal. Palmarosa. alcohol. Its specific gravity at 15° C. and combined with acetic and caproic acids.4855-1. refractive index at 20° C.886-0. distilled from the wood of trees of the Burseraceæ family. esters. methyl anthranilate. citral. East Indian. a herb grown in India and the . together with small quantities of methyl heptenone.876-0. This oil consists mainly of linalol. +38° to +50°. 0. The chief constituents of the oil are limonene.892. 0.. Patchouli oil. refractive index at 20° C.. soluble in 0. soluble in 1-2 volumes of 70 per cent. 1. Specific gravity at 15° C. 1.4876. +95° to +99°. d-terpineol.470. 0. Distilled Oil. optical rotation.. 0. West Indian. Neroli Bigarade oil. The oils from these two sources differ somewhat in their properties.870. refractive index at 20° C.. and also in value. +1° to -3°. soluble in 2-3 volumes of 70 per cent. and methyl anthranilate. calculated as linalyl acetate. aldehydes. refractive index at 20° C. d-linalol. +38° to +54°.. refractive index at 20° C.. obtained by expression or distillation of the peel of the fruit of Citrus medica. Its most important constituent is citral.476. together with nonyl alcohol.. linalol. soluble in 0. 0. distilled from the leaves of Pogostemon patchouli. decyl aldehyde. esters.. usually lævo-rotatory. phenols. and neroli camphor. as geraniol. and occasionally much higher.870-0. total alcohols.. particularly in rose soaps. determined by acetylation. optical rotation..893. and dipentene.888-0. a grass widely grown in India. distilled from the fresh blossoms of the bitter orange.898-0. distilled from the grass Andropogon citratus. The oil contains some 90 per cent. Lemon-grass (so-called verbena) oil.5 volume of 90 per cent.—Specific gravity at 15° C. and produced principally in the West Indies. alcohol. Specific gravity at 15° C.849-0. indol.. 75-93 per cent. 1 in 3. becoming turbid on further addition of alcohol. -3° to -13°. optical rotation. Marjoram oil. is 0. or East Indian geranium oil.

. Some twenty different constituents have been found in American peppermint oil. and contains 50-60 per cent. optical rotation. distilled from the fruit of Pimenta officinalis.. alcohol. saponification number. refractive index at 20° C.576..906 at 15° C. alcohol. The oil contains eugenol. The dementholised oil is fluid at ordinary temperatures. 0. optical rotation. -45° to -63°. soluble in 1-2 volumes of 70 per cent.. free menthol. and the bodies responsible for its persistent and characteristic odour have not yet been isolated. which is found in the West Indies and Central America. alcohol... cineol. geraniol and geranyl acetate.965-0.. Specific gravity at 15° C.. total menthol. free menthol.. 50-60 per cent. but occasionally requires 1-2 volumes of 80 per cent. Japanese.990. slightly lævorotatory up to -4°.917-0. l-limonene. The oil consists chiefly of benzyl benzoate and cinnamate. sometimes soluble in 0. Petitgrain oil. optical rotation. and caryophyllene. and isovalerianic acid. 0. 1.100-1..906-0.. The solubility of the oil in alcohol increases with age.5 volume of 90 per cent. 0. of which 65-85 per cent. though occasionally the white .—Specific gravity at 25° C. Peppermint oil. American. menthone.900. soluble as a rule in 2-3 volumes of 70 per cent. optical rotation. soluble in 3-5 volumes of 70 per cent. together with styracin. alcohol. or cinnamyl cinnamate.. 70-90 per cent. -22° to -33°. calculated as linalyl acetate. There are two varieties of the oil. -20° to -33°. 0.040-1. distilled from herbs of the Mentha family. 55-66 per cent. lævo-rotatory up to -43°. total menthol. up to 12. acetic acid. soluble in 3-5 volumes of 70 per cent. becoming turbid on further addition. of patchouliol and cadinene. 68-86 per cent. optical rotation. phellandrene. alcohol.—Specific gravity at 15° C. Specific gravity at 15° C. optical rotation. the European and American from Mentha piperita.900-0. ester. obtained by distillation of the twigs and unripe fruit of Citrus bigaradia.900. alcohol. phenols. slightly dextro-rotatory up to +2°. dimethyl sulphide. acetaldehyde. soluble in 1 volume of 90 per cent. The oil consists to the extent of 97 per cent. French. distilled from the flowers of Rosa damascena. 0. esters.Straits Settlements. for the best qualities usually above 50 per cent.. total menthol. soluble in 1 to 1. 40-55 per cent. The Michigan oil is soluble in 3-5 volumes of 70 per cent. The[Pg 104] locality in which the herb is grown has a considerable influence on the resulting oil. alcohol.. the oily portion (so-called "cinnamein") obtained from Peru balsam. and occasionally 0. Rose oil (otto of rose). has a specific gravity of 0.. menthyl isovalerianate.925. 35-45 per cent. free menthol. 1.920.5 volumes of 80 per cent. pinene.511. alcohol. refractive index at 20° C.886-0. as the following figures show:— English.5 to 1 volume of 90 per cent. 50-60 per cent. 80-87 per cent. menthyl acetate. alcohol. optical rotation. potash solution. the former being the more valuable..529-1. amyl alcohol. but the better Wayne County oil usually requires 1-2 volumes of 80 per cent.900-0. Pimento oil (allspice). and the Japanese being generally supposed to be obtained from Mentha arvensis.536.. linalyl acetate. which have little influence on its odour. including menthol. Among its constituents are limonene...060. phellandrene.4650.910.569 to 1.4604-1. -3° to +6°. -6° to -10°. 40-50 per cent. refractive index at 20° C. solidifies at 17 to 27° C. and a small quantity of free benzoic and cinnamic acids. Specific gravity at 15° C. the French and the South American. Specific gravity at 15° C. 45-55 per cent. total menthol.895-0. alcohol. cineol.. estimated[Pg 105] by absorption with 5 per cent. optical rotation. refractive index at 20° C. 0.—Specific gravity at 15° C.504-1. 1. methyl eugenol. isovalerianic aldehyde. 1.. is free.—Specific gravity at 15° C. Peru balsam oil. calculated as benzyl benzoate. 1.. 1..107.. total menthol.

roses (Rosa alba) are employed. The principal rose-growing district is in Bulgaria, but a small quantity of rose oil is prepared from roses grown in Anatolia, Asia Minor. An opinion as to the purity of otto of rose can only be arrived at after a very full chemical analysis, supplemented by critical examination of its odour by an expert. The following figures, however, will be found to include most oils which can be regarded as genuine. Specific gravity at 30° C., 0.850-0.858; optical rotation at 30° C., -1° 30' to -3°; refractive index at 20° C., 1.4600-1.4645; saponification value, 7-11; solidifying point, 19-22° C.; iodine number, 187-194; stearopten content, 14-20 per cent.; melting point of stearopten, about 32° C. A large number of constituents have been isolated from otto of rose, many of which are, however, only present in very small quantities. The most important are geraniol, citronellol, phenyl ethyl alcohol, together with nerol, linalol, citral, nonylic aldehyde, eugenol, a sesquiterpene alcohol, and the paraffin stearopten. Rosemary oil, distilled from the herb Rosemarinus officinalis, and obtained from France, Dalmatia, and Spain. The herb is also grown in England, but the oil distilled therefrom is rarely met with in commerce. The properties of the oils vary with their source, and also with the parts of the plant distilled, distillation of the stalks as well as the leaves tending to reduce the specific gravity and borneol content, and increase the proportion of the lævo-rotatory constituent (lævo-pinene). The following figures may be taken as limits for pure oils:— French and Dalmatian.—Specific gravity at 15° C., 0.900-0.916; optical rotation, usually dextrorotatory, up to +15°, but may occasionally be lævo-rotatory, especially if stalks have been distilled with the leaves; ester, calculated as bornyl acetate, 1-6 per cent.; total borneol, 12-18 per cent.; usually soluble in 1-2 volumes of 82.5 per cent. alcohol. Spanish.—The properties of the Spanish oil are similar to the others, except that it is more frequently lævo-rotatory. Rosemary oil contains pinene, camphene, cineol, borneol, and camphor. Sandalwood oil, obtained by distillation of the wood of Santalum album (East Indian), Santalum cygnorum (West Australian), and Amyris balsamifera (West Indian). The oils obtained from these three different sources differ very considerably in value, the East Indian being by far the best. East Indian.—Specific gravity at 15° C., 0.975-0.980; optical rotation, -14° to -20°; refractive index at 20° C., 1.5045-1.5060;[Pg 106] santalol, 92-97 per cent.; usually soluble in 4-6 volumes of 70 per cent. alcohol, though, an old oil occasionally is insoluble in 70 per cent. alcohol. West Australian.—Specific gravity at 15° C., 0.950-0.968; optical rotation, +5° to +7°; alcohols, calculated as santalol, 73-75 per cent.; insoluble in 70 per cent. alcohol, but readily dissolves in 1-2 volumes of 80 per cent. alcohol. West Indian.—Specific gravity at 15° C., 0.948-0.967; optical rotation, +13° 30' to +30°; insoluble in 70 per cent. alcohol. In addition to free santalol, the oil contains esters of santalol and santalal. Sassafras oil, distilled from the bark of Sassafras officinalis, and obtained chiefly from America. Specific gravity at 15° C., 1.06-1.08; optical rotation, +1° 50' to +4°; refractive index at 20° C., 1.524-1.532; soluble in, 6-10 volumes of 85 per cent. alcohol, frequently soluble in 10-15 volumes of 80 per cent. alcohol. The chief constituents are safrol, pinene, eugenol, camphor, and phellandrene. The removal of safrol, either intentionally or by accident, owing to cooling of the oil and consequent deposition of the safrol, is readily detected by the reduction of the specific gravity below 1.06. Thyme oil, red and white, distilled from the green or dried herb, Thymus vulgaris, both French and Spanish oils being met with. These oils are entirely different in character.

French.—Specific gravity at 15° C., 0.91-0.933; slightly lævo-rotatory up to -4°, but usually too dark to observe; phenols, by absorption with 10 per cent. aqueous caustic potash, 25-55 per cent.; refractive index at 20° C., 1.490-1.500; soluble in 1-1.5 volumes of 80 per cent. alcohol. Spanish.—Specific gravity at 15° C., 0.955-0.966; optical rotation, slightly lævo-gyrate; phenols, 70-80 per cent.; refractive index at 20° C.; 1.5088-1.5122; soluble in 2-3 volumes of 70 per cent. alcohol. In addition to the phenols, thymol or carvacrol, these oils contain cymene, thymene and pinene. The white thyme oil is produced by rectifying the red oil, which is generally effected at the expense of a considerable reduction in phenol content, and hence in real odour value of the oil. Verbena Oil.—The oil usually sold under this name is really lemon-grass oil (which see supra). The true verbena oil or French verveine is, however, occasionally met with. This is distilled in France from the verbena officinalis, and has the following properties: Specific gravity at 15° C., 0.891-0.898; optical rotation, slightly dextro- or lævo-rotatory; aldehydes, 70-75 per cent.; soluble in 2 volumes of 70 per cent. alcohol. The oil contains citral. Vetivert oil, distilled from the grass, Andropogon muricatus, or Cus Cus, and grown in the East Indies. Specific gravity at 15° C., 1.01-1.03; optical rotation, +20° to[Pg 107] +26°; saponification number, 15-30; refractive index at 20° C., 1.521-1.524; soluble in 2 volumes of 80 per cent. alcohol. The price of this oil makes its use prohibitive except in the highest class soaps. Wintergreen Oil.—There are two natural sources of this oil, the Gaultheria procumbens and the Betula lenta. Both oils consist almost entirely of methyl salicylate and are practically identical in properties, the chief difference being that the former has a slight lævo-rotation, while the latter is inactive. Specific gravity at 15° C., 1.180-1.187; optical rotation, Gaultheria oil, up to -1°, Betula oil, inactive; ester as methyl salicylate, at least 98 per cent.; refractive index at 20° C., 1.5354-1.5364; soluble in 2-6 volumes of 70 per cent. alcohol. Besides methyl salicylate, the oil contains triaconitane, an aldehyde or ketone, and an alcohol. Ylang-ylang oil, distilled from the flowers of Cananga odorata, the chief sources being the Philippine Islands and Java. Specific gravity at 15° C., 0.924-0.950; optical rotation, -30° to -60°, and occasionally higher; refractive index at 20° C., 1.496-1.512; ester, calculated as linalyl benzoate, 27-45 per cent., occasionally up to 50 per cent.; usually soluble in 1/2 volume of 90 per cent. alcohol. The composition of the oil is qualitatively the same as that of Cananga oil, but it is considerably more expensive and therefore can only be used in the highest grade soaps.

Artificial and Synthetic Perfumes.
During the past few years the constitution of essential oils has been studied by a considerable number of chemists, and the composition of many oils has been so fully determined that very good imitations can often be made at cheaper prices than those of the genuine oils, rendering it possible to produce cheap soaps having perfumes which were formerly only possible in the more expensive article. 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. A synthetic perfume, on the other hand, is entirely the product of the chemical laboratory, no natural oil or substance derived therefrom entering into its composition. The following are among the most important bodies of this class:— Amyl salicylate, the ester prepared from amyl alcohol and salicylic acid, sometimes known as "Orchidée" or "Trèfle". This is much used for the production of a clover-scented soap. It has the specific[Pg 108] gravity at 15° C., 1.052-1.054; optical rotation, +1° 16' to +1° 40'; refractive index at 20° C., 1.5056; and should contain not less than 97 per cent. ester, calculated as amyl salicylate. Anisic aldehyde, or aubépine, prepared by oxidation of anethol, and possessing a pleasant, hawthorn odour. This has the specific gravity at 15° C., 1.126; refractive index at 20° C., 1.5693; is optically inactive, and dissolves readily in one volume of 70 per cent. alcohol. Benzyl Acetate, the ester obtained from benzyl alcohol and acetic acid. This has a very strong and somewhat coarse, penetrating odour, distinctly resembling jasmine. Its specific gravity at 15° C. is 1.062-1.065; refractive index at 20° C., 1.5020; and it should contain at least 97-98 per cent. ester, calculated as benzyl acetate. Citral, the aldehyde occurring largely in lemon-grass and verbena oils, also to a less extent in lemon and orange oils, and possessing an intense lemon-like odour. It has a specific gravity at 15° C., 0.896-0.897, is optically inactive, and should be entirely absorbed by a hot saturated solution of sodium bisulphite. Citronellal, an aldehyde possessing the characteristic odour of citronella oil, in which it occurs to the extent of about 20 per cent., and constituting considerably over 90 per cent. of eucalyptus citriodora oil. Its specific gravity at 15° C. is 0.862; refractive index at 20° C., 1.447; optical rotation, +8° to +12°; and it should be entirely absorbed by a hot saturated solution of sodium bisulphite. Coumarin, a white crystalline product found in Tonka beans, and prepared synthetically from salicylic acid. It has an odour resembling new-mown hay, and melts at 67° C. Geraniol, a cyclic alcohol, occurring largely in geranium, palma-rosa, and citronella oils. Its specific gravity at 15° C. is 0.883-0.885; refractive index at 20° C., 1.4762-1.4770; it is optically inactive, and boils at 218°-225° C. Heliotropin, which possesses the characteristic odour of heliotrope, is prepared artificially from safrol. It crystallises in small prisms melting at 86° C. Hyacinth.—Most of the articles sold under this name are secret blends of the different makers. Styrolene has an odour very much resembling hyacinth, and probably forms the basis of most of these preparations, together with terpineol, and other artificial bodies. The properties of the oil vary considerably for different makes. Ionone, a ketone first prepared by Tiemann, and having when diluted a pronounced violet odour. It is prepared by treating a mixture of citral and acetone with barium hydrate, and distilling in vacuo. Two isomeric ketones, α-ionone and β-ionone, are produced, the article of commerce being usually a mixture of both. The two ketones have the following properties:— Alpha-ionone.—Specific gravity at 15° C., 0.9338; refractive index at 16.5 C., 1.50048 (Chuit); optically it is inactive. Beta-ionone.—Specific gravity at 15° C., 0.9488; refractive index at 16.8° C., 1.52070 (Chuit); optically it is inactive also.[Pg 109] The product is usually sold in 10 or 20 per cent. alcoholic solution ready for use. Jasmine.—This is one of the few cases in which the artificial oil is probably superior to that obtained from the natural flowers, possibly due to the extreme delicacy of the odour, and its

-18°. and having the specific gravity at 15° C.5373.. and is a very coarse. Musk (Artificial). is 0. 1. It has the specific gravity at 15° C.870-0. and found also in lavender.103-1. the alcohol forming the greater part of linaloe and bois de rose oils. and boiling point. alcohol. the alcohol or mixture of alcohols obtained from sandalwood oil. geraniol. eugenol or isoeugenol.. Among its constituents are benzyl acetate..876..464. methyl anthranilate. linalol. alcohol. Its specific gravity at 15° C. commend themselves to the soap-perfumer.5 volumes of 70 per cent. boiling point. Mirbane Oil or Nitrobenzene.094-1. and a few drops of chloroform added.consequent slight decomposition during preparation from the flowers. petitgrain. but it is doubtful whether its value is commensurate with its greatly increased price over that of ordinary bergamot oil. practically all of which are nitroderivatives of aromatic hydrocarbons. bergamot. obtained in 1889.206. methyl anthranilate. Acetanilide also increases the solubility in 95 per cent. 1. the inconvenience in cold weather of having to first melt the oil before use.—Several forms of this are to be obtained. of alcohols. Its specific gravity at 15° C. Linalyl acetate. Oeillet is a combination possessed of a sweet carnation-like odour and having as a basis. and when estimated by acetylation.. which may be detected by the characteristic isocyanide odour produced when musk containing this substance is boiled with alcoholic potash. Neroli Oil (Artificial). is the ester formed when linalol is treated with acetic anhydride. is acetanilide (antifebrin).5°-198° C. refractive index at 20° C.—Like jasmine oil. which. phenyl ethyl alcohol. is 1. though more soluble forms are also made.—Several good and fairly cheap artificial rose oils are now obtainable. and it dissolves in fifteen volumes of 80 per cent. optical rotation. consisting chiefly of citronellol. These consist chiefly of linalol. and citral. and many other oils. irritating perfume. and the solubility in 95 per cent..—This is a cheap substitute for oil of bitter almonds.463-1. 0. The original patent of Baur. or ethyl benzoate. benzyl alcohol. which should always be tested for... but as these are inodorous. The melting point of the pure article usually lies between 108° and 112° C. or benzaldehyde. Its properties vary with the source of supply. refractive index at 20° C.. Linalol. 1.[Pg 110] Niobe oil.9795. Santalol. 196. It is sold as an artificial sassafras oil. The chemical composition of the floral perfume has been very exhaustively studied. and also found in considerable quantity in camphor oil. alcohol. Its specific gravity is 1.912. and refractive index at 20° C. geraniol. Safrol. alcohol ranges from 1 in 120 to 1 in 200.205-1. refractive index at 20° C. the ester obtained from ethyl alcohol and benzoic acid. soluble in 1. and there is. . 206° C. and the artificial article now on the market may be described as a triumph of synthetical chemistry. an ether which is the chief constituent of sassafras oil. neroli. 1. and citral. -12° to -14°. 1. covered the trinitro-derivative of tertiary butyl xylene. 0. The article has the specific gravity at 15° C.106. the chemistry of neroli oil is now very fully known. to render the oil more similar in appearance to the natural article.550. It is prepared by the action of a mixture of nitric and sulphuric acids on benzene at a temperature not exceeding 40° C. and is very much used in perfuming cheap toilet or household soaps. or artificial bergamot oil. linalyl acetate. no advantage is gained in this way. An important adulterant. and it is therefore possible to prepare an artificial product which is a very good approximation to the natural oil. In some cases stearopten or other wax is added. further. and a ketone jasmone. optical rotation. It possesses a bergamot-like odour. and many such are now on the market. Rose Oil (Artificial). yields about 70 per cent.507.5167. indol.. linalyl acetate. refractive index at 20° C. 1.095. on account of their comparative cheapness. only suitable for use in the very cheapest soaps.

processes of soap-making are described in which (1) the glycerine is retained in the finished soap. which has separated during the cooling. As pointed out in Chapter II. which. and the point when enough has been added. in these days of pure caustic soda. 1.or lævo-rotatory. and elaborate plant of various forms has been devised for the purpose. Its specific gravity at 15° C. Treatment of Lyes. and (2) the glycerine is contained in the lyes. and render the liquor faintly acid. Much attention has been devoted to the purification and concentration of glycerine lyes. but also upon the materials used. Spent lyes may vary in their content of glycerol from 3 to 8 per cent. contaminated with salt and other impurities. associated with traces of benzoic acid and heliotropin. Treatment of Lyes—Evaporation to Crude Glycerine—Distillation—Distilled and Dynamite Glycerine—Chemically Pure Glycerine—Animal Charcoal for Decolorisation—Glycerine obtained by other Methods of Saponification—Yield of Glycerine from Fats and Oils. and of the latter to completely precipitate the fatty acids. in very dilute solution.. as it quickly tends to darken the colour of the soap. refractive index at 20° C. melting at 80°-82° C. and occurs.. It is optically inactive. It can only be used in small quantity in light-coloured soaps. is used chiefly in medicated soaps. in the vanilla bean.. It has a strong characteristic odour.936-0.868. the fatty acids. sufficient being added of the former to neutralise the free alkali. and the soap. especially for a lilac or lily soap. an alcohol also prepared from turpentine oil by the action of sulphuric acid. though now constituting the chief source of profit in the manufacture of cheap soaps. [Pg 111] CHAPTER IX. compounds of fatty acids with glycerol. the refractive index at 20° C.—The spent lyes withdrawn from the soap-pans are cooled. and this depends not only upon the system adopted in the working of the soap-pans. the presence of sulphides and sulphites should be carefully avoided. when a sample taken from the tank and filtered should give a . form soap. alcohol. spent lyes are more free from impurities than formerly. and as the result of saponification of a fat or oil glycerine is set free. The whole is then agitated with air. 1. Terpineol. combined with soda or potash. The lyes are transferred to a lead-lined tank of convenient size.4835.5 volumes of 70 per cent.4812-1. These lyes. a white crystalline solid. is 0. and treated with commercial hydrochloric acid and aluminium sulphate. In Chapter V..940. is indicated by blue litmus paper being slightly reddened by the lyes. were till early in last century simply run down the drains as waste liquor. a mixture of dipentene and other hydrocarbons prepared from turpentine oil by treatment with concentrated sulphuric acid. is carefully removed and returned to the soap-house for utilisation in the manufacture of brown soap. Vanillin.862-0. i.Terebene. if it is desired to produce good glycerine. terpene hydrate being formed as an intermediate substance. is 0. The acid should be run in slowly. and boiling point about 210°-212° C. and prepared by the oxidation of isoeugenol.470-1.e. Although.478. the oil is frequently slightly dextro. Its specific gravity at 15° C. and on account of its cheapness is much used in soap perfumery. and readily soluble in 1. occur in nature almost invariably in the form of glycerides. GLYCERINE MANUFACTURE AND PURIFICATION. It has a distinctly characteristic lilac odour.

The steam chamber of the first vessel is heated with direct steam. is converted into crude glycerine by concentration. being now free from fatty. The filtered liquor is now rendered slightly alkaline by the addition of caustic soda or carbonate. as this second vessel is under a greater vacuum than[Pg 113] No. which is drawn off by means of the pump employed for maintaining a vacuum of 28 inches in the vessel. may be transferred to a perforated box suspended over the tank. are conveyed into a condenser and condensed by injection water. and any deliveries of either article. hence the present standard for crude glycerine. This concentration was originally performed in open pans heated by fire or waste combustible gases. resinous. The vapours discharged from the second vessel during boiling are passed through pipes to the steam chamber of the third vessel (in a "triple effect"). Lime. suffice it to say that the multiple effects now in vogue possess distinct advantages—the greatest of these being increased efficiency combined with economy. and the liquor allowed to drain from it. which accumulates on the treatment tank. Concentration in open pans has now been superseded by evaporation in vacuo." as the plant consisting of two pans is termed.clear filtrate.). rejected. originated and successfully applied by Howard in 1813 in the sugar industry. is ready for evaporation. and the latent heat raises the temperature of the treated lyes proceeding through the tubes to supply the evaporator. Thus we get a "double effect. and copper sulphate have been suggested. which contain that impurity. with the reduced pressure. (149° C. and there being condensed. 1. is too lengthy to detail here. Special devices are attached to the plant for . and consisting practically of an aqueous solution of common salt (sodium chloride) and glycerine. than is possible by heating in open pans. and this dish was lifted out periodically by the aid of an overhead crane and the contents emptied and washed. salts (ash). the treated lyes circulating through the heated tubes is made to boil at a lower temperature. The present type of evaporator consists of one or more vessels. In the bottom of each pan was placed a dish in which the salt deposited. each fitted with a steam chamber through which are fixed vertical hollow tubes. but the latter is generally employed. barium chloride. and. the pressure being further reduced. or with exhaust steam (supplied from the exhaust steam receiver into which passes the waste steam of the factory). where its latent heat is utilised in producing evaporation. when it was allowed to rest before storing. The scum. the vapours generated from the last vessel are drawn through a device consisting of a number of tubes enclosed in a casing. and in some instances are used instead of aluminium sulphate. bog ore. The subject of the gradual development of the modern efficient evaporating plant from the vacuum pan. It will thus be observed that the object of multiple effects is to utilise all the available heat in performing the greatest possible amount of work. and[Pg 112] the contents of the tank passed through a filter press. This liquor on analysis gave 80 per cent. The acid and alum salt used in the above treatment must be carefully examined for the presence of arsenic. In the most recent designs of large evaporative installations. after filtering. The third vessel may also be heated by means of live steam. and various metallic salts. agitation is stopped. Having obtained this clear solution. Concentration was continued until the temperature of the liquor was 300° F. create a partial vacuum in the second vessel. glycerol and from 9 to 10-1/2 per cent. Evaporation to Crude Glycerine. which eliminates the water and causes most of the salt to be deposited.—The clear treated lyes. The vapours arising from the last vessel of the evaporating plant. and albuminous matter. or in the case of a "single effect" from the vessel. such as ferric chloride. The vapour given off by the boiling liquor is conveyed through large pipes into the steam chamber of the second vessel.

almost black. this precaution not only prevents loss of glycerine through carbonisation. Every care is taken that the still does not become overheated. evaporation is continued until a sample taken from the last vessel has a density of 60° Tw. When this point is reached. with a density less than 14° Tw. but with careful working the difficulty can be obviated by washing out with weak lyes after each batch of crude glycerine has been run away.) salt begins to deposit. a false bottom is supported about 1 foot from the base of the still. animal charcoal and passing through a filter press. by treating with 1 per cent. In working the plant. (19. if necessary.5° C. the liquor in each vessel is kept at a fairly constant level by judicious feeding from one to the other. Distillation. it has been suggested to rotate the contents with an agitator fixed in the still. The residue in the still. The distillate passes into a row of condensers. which consists of a coil of pipes through which high pressure steam from the boiler is superheated. sulphate. the first vessel is. and in this fire space is the superheater. The other portion of the distillate is concentrated by means of a dry steam coil in a suitable vessel under a 28 inch vacuum. As the liquor acquires a density of 42° Tw. and. is returned to the treated-lyes tank. . Difficulty is sometimes experienced with the tubes becoming choked with salt. It is claimed that by the use of the revolving heater designed by Lewkowitsch.). Crude glycerine is refined in some[Pg 114] cases by the producers themselves.automatically removing the condensed water from the steam chambers without the loss of useful heat.). thereby diminishing and retarding evaporation. and as a precaution against splashing over and subsequent loss of glycerine through conveyance to the steam chamber. The vacuum to be used will. glycerine and varying proportions of various sodium salts—e. chloride.3 B. (15. of course. washed and dried ready for use at the soap pans. often less than 1 per cent. It is needless to state that the condensing capacity should be in excess of theoretical requirements. sulphides and sulphites should be absent. to each of which is attached a receptacle or receiver. after allowing the excess of salt to deposit. It may be necessary to dissolve the encrusted salt with lyes or water. but also obviates the production of tarry and other bodies which might affect the colour. the crude glycerine is ready to be withdrawn into a tank. There are quite a large number of designs for still heads. and odour of the distilled glycerine. taste. and depends largely on the materials used for soap-making. The organic matter present in good crude glycerine is small in amount. from which it issues as "dynamite glycerine". of course. charged with treated lyes. and may be withdrawn into one of the many patented appliances. or by increasing the circulation.) at 60° F. others sell it to firms engaged more particularly in the refined glycerine trade. the salting up of tubes is prevented. The distillation is conducted at a temperature of 356°F. The salt having been precipitated and removed. (25° B. The colour of crude glycerine varies from light brown to dark brown.—Crude glycerine is distilled under vacuum with the aid of superheated steam." having for their object the prevention of loss of glycerine. To prevent the deposition and burning of salt on the still-bottom during the distillation. The still is heated directly with a coal or coke fire. (33. that portion.g. may be transferred to the storage tank. and combinations with non-volatile organic acids—is generally boiled with water and treated with acid.4° B. and "catch-alls. (180° C. With the same object in view. consisting of 50-60 per cent. acetate.. When sufficiently concentrated the glycerine may be decolorised. arsenic. dash plates and "catch-alls" or "save-alls" of various designs are fitted on each vessel. but as a general rule good results are obtained with an 18 inch vacuum. depend upon the heat of the fire and still.). in which it is freed from glycerine. The fractions are of varying strengths and quality.

dried. or sulphates. when the volatile organic acids are driven off.262 at 15° C. Animal charcoal should be freed from gypsum (sulphate of lime). Chemically pure glycerine or double distilled glycerine is produced by redistilling "once distilled" glycerine. to which the product must conform.5° C.. The distillation is very carefully performed under strict supervision. it is converted into nitroglycerine. It should yield no characteristic reaction with the tests for lead. sodium.The tar. 1. The charcoal is then separated from the liquor and treated with hydrochloric acid. and various are the views that have been propounded to explain its action.) and the colour somewhat yellow. then washed free from acid. The charcoal from the filter presses is washed free from glycerine (which is returned to the treated lyes). but it has. which is separated. lest in the burning. The specific gravity should be 1. chlorides. and a portion diluted and treated with nitrate of silver solution should give no turbidity or discoloration in ten minutes.[Pg 115] The chief stipulation for dynamite glycerine is its behaviour in the nitration test. and burned in closed vessels gives a product possessed of great decolorising power for use with glycerines. (59° F. potassium. Specifications are usually given in contracts drawn up between buyers and sellers. which separates as an oily layer on the surface of the acid. or the whole mixed with waste charcoal. and again well boiled. Distilled Glycerine.260. or it may be distilled separately. When glycerine is gradually added to a cold mixture of strong nitric and sulphuric acids. Some contend that phosphate of lime plays such an important part in decolorising that it should not be removed. The more definite and rapid the separation. and fatty acids. the concentrated liquor is finally mixed with crude glycerine which is ready for distillation.1 per cent. and no doubt this is an important factor. Animal charcoal boiled with four times its weight of a mixture consisting of equal parts of commercial hydrochloric acid (free from arsenic) and water for twelve hours. iron. Dynamite glycerine should be free from arsenic. it should be used in fine grains and not in the form of a powder. sulphur compounds be formed which would pass into the glycerine and contaminate it.. cleansed from foreign substances by the above treatment and revivified by carefully heating . Some observers base it upon the physical condition of the so-called carbon present. and may be removed by ladles. These are specified as follows: Specific gravity at 15. however. finds its chief outlet in the manufacture of explosives. which is present in all animal charcoal and extremely difficult to remove. opinions differ as to the amount of acid to be used. arsenium. lime. the inorganic matter should not amount to more than 0. copper. Others consider that the nitrogen. Every care is taken to avoid all fractions which do not withstand the nitrate of silver test. chlorides. been demonstrated that this substance after exposure to heat has very little decolorising power. and filtered. and be of a deep colour. then carbonate of soda or caustic soda added in sufficient quantity to give an alkaline reaction.[Pg 116] A good animal charcoal will have a dull appearance. The liquor is withdrawn and the charcoal washed until the washings are no longer alkaline. ammonium. calcium. the more suitable is the glycerine for dynamite-making. Animal Charcoal for Decolorisation. floats on the surface as the liquor is cooling. The filtrate is then evaporated. The "char" should be well boiled with water. coupled with the porosity. It should contain no sugars and leave no residue on burning. is essential to the action.—This class of commercial glycerine. The distillate is concentrated and after treatment with animal charcoal and filtration should conform to the requirements of the British Pharmacopœia. although of limited use in various other branches of industry.—The application of animal charcoal for decolorising purposes dates back a century.

the following is an outline of the processes usually adopted in their determination. It contains 85-90 per cent. Glycerine obtained by other Methods of Saponification. The concentration may be performed in two stages—first to a density of 32° Tw. SOAP. AND GLYCERINE. " " " " " Greases (Bone 6-8 " fats) The materials vary in glycerol content with the methods of preparation. glycerol. as the oil may not only have become partially hydrolysed. glycerol and upwards. This glycerine is easily refined by treatment with charcoal. Fats and Oils.—Average figures have already been given in Chapters III. of 80 per cent. especially is this the case with tallows and greases. and the liquor evaporated to crude.). and the amount of glycerol obtainable from such a fat would be correspondingly reduced. when the calcium sulphate is allowed to deposit. testing 85 per cent. [Pg 117] CHAPTER closed vessels for twelve hours. (20° B. (28° B. . and may be readily distinguished from the soap-crude glycerine by the absence of salt (sodium chloride). Glycerol. For fuller details.240-1. also of essential oils. Fats and Oils—Alkalies and Alkali Salts—Essential Oils—Soap—Lyes—Crude Glycerine. Every care should be taken that the raw materials are fresh and they should be carefully examined to ascertain if any decomposition has taken place in the glycerides—this would be denoted by the presence of an excess of free acidity. Raw Materials.242. The glycerine water resulting from acid saponification methods requires to be rendered alkaline by the addition of lime—the sludge is separated. text-books dealing exhaustively with the respective subjects should be consulted. possesses a specific gravity of 1.—French saponification or "candle crude" glycerine is the result of concentration of "sweet water" produced in the manufacture of stearine and by the autoclave process. It is very undesirable that any of these materials should be allowed to enter the soap pan without an analysis having first been made. for the more important physical and chemical characteristics of fats and oils.—The following represent practicable results which should be obtained from the various materials:— Tallow Cotton-seed oil Cocoa-nut oil Palm-kernel oil Olive oil Palm oil 9 10 12 18 10 6 per cent. and VIII. Yield of Glycerine from Fats and Oils. and the separated liquor concentrated to 48° Tw.) glycerine. ANALYSIS OF RAW MATERIALS.

the following physical and chemical data should be determined.2 c. and warming under a reflux condenser on a steam or water-bath.c. preferably that of a boiling water bath. The value of the approximately N/2 alkali solution is ascertained by taking 50 c. Example. Example. which would have led to disaster in the soap pan. and odour of the sample.8976 grammes fat required 18. capacity). and required 5. expressed as oleic acid. free fatty acids. which is the amount of KOH in milligrammes necessary to neutralise the free acid in 1 gramme of fat or oil. The picnometer should be calibrated with distilled water at 15° C.c. N/10 alkali = 0.1 grammes of caustic potash. approximately N/2 alcoholic potash solution required 25. N/5. until saponification is complete (usually from 30-60 minutes) which is indicated by the absence of fatty globules. Specific Gravity at 15° C. neutral alcohol. or N/10.c. together with 30 c. and titrating with a standard aqueous or alcoholic solution of caustic soda or potash. noting any characteristic feature. with frequent agitation.8976 grammes were taken. and titrating with N/1 hydrochloric or sulphuric acid. The excess of alkali is titrated with N/1 hydrochloric or sulphuric acid. of N/10 KOH solution for neutralisation.61 ————— = 15. or contain albuminous matter rendering the soap liable to develop rancidity. The standard alkali may be N/2.6 c.c.c. or the Sprengel Utube. but actual sophistication may have taken place.c.8976 The free acidity is sometimes expressed as acid value. When boiling. had the bulk been used without examination. the flask is disconnected.2 × 5. or by using a picnometer of either the ordinary gravity bottle shape. 1. and express in percentage on the fat or oil. boiling for the same length of time as the fat. Fifty c. of an unsaponifiable wax.0282 gramme oleic acid). together with a few drops of phenol-phthalein solution. Free acidity is estimated by weighing out from 2 to 5 grammes of the fat or oil.8976 The saponification equivalent is determined by weighing 2-4 grammes of fat or oil into a widenecked flask (about 250 c. N/ acid. The specific gravity of solid fats may be taken at an elevated temperature. 50 c. and the boiling under a reflux condenser continued. 5. with perforated stopper. using phenol-phthalein as indicator. 1. colour. N/1 acid to neutralise the unabsorbed alkali.0282 × 100 ————————— = 7. In the above example:— 5.[Pg 118] It is usual to calculate the result in terms of oleic acid (1 c.95 c. of an approximately semi-normal alcoholic potash solution carefully added from a burette.2 × 0..72 per cent.involving a loss of glycerine. The "saponification equivalent" is the amount of fat or oil in grammes saponified by 1 equivalent or 56. . This may be taken by means of a Westphal balance.c. Thus a sample of tallow recently examined by the authors contained as much as 40 per cent.—1. The contents of the flask are well shaken after each addition of alkali.—1. adding 30 c. dissolving in neutral alcohol (purified methylated spirit) with gentle heat. neutral alcohol in a similar flask. and the reaction is complete when the slight excess of alkali causes a permanent pink coloration with the indicator.3 acid value. After observing the appearance.c.c.c.

which is attached to a condenser. In the example given.c. The result of this test is often expressed as the "Saponification Value. 50 c. N/1 KOH required by fat.) followed by neutral alcohol (previously saturated with the solvent).c. this figure giving the amount of the total fatty acids present. using phenol-phthalein as indicator. when separation immediately takes place. more ether being added to the aqueous soap solution. and the whole boiled under a reflux condenser. thus giving the amount of unsaponifiable matter. Solid alcohols occur naturally in sperm oil. In this method. of approximately N/2 alcoholic potash solution by boiling under a reflux condenser with frequent agitation for about 1 hour. it is very frequently most difficult to obtain a distinct separation of ether and aqueous soap solution—an intermediate layer of emulsion remaining even after prolonged standing. and phytosterol is a very similar substance present in vegetable fats. This may be found by dividing 56. 1. solid alcohols (cetyl and ceryl alcohols). such as addition of alcohol (when petroleum ether is used). Constitution of the Unsaponifiable Matter. by 56.3 = 181. separated. The two ethereal extracts are then washed with water to deprive them of any soap.c. or number of milligrammes of KOH required for the saponification of the neutral esters or glycerides in 1 gramme of fat. and the benzoline distilled off. and the ether distilled off upon a water-bath. the whole well shaken." which is the number of milligrammes of KOH required for the saponification of 1 gramme of fat. is represented by the difference between the saponification and acid values. water. and the resultant soap dissolved in about 200 c. is the "unsaponifiable matter. are not natural constituents of animal or vegetable oils and fats." which is calculated to per cent. When sufficiently cool. dried in the oven at 100° C. water.c. The last traces of solvent remaining in the flask are removed by gently warming in the water-oven.65 = 285. a quantity of the solvent added to take up the unsaponifiable matter.95 = 6. Cholesterol is frequently found in animal fats. and the flask cooled and weighed. Unsaponifiable Matter. The alcoholic layer is withdrawn. The presence of cholesterol and phytosterol may be detected by dissolving a small portion of the .c. and then boil for twenty or thirty minutes.3 Saponification Equivalent. preferably a light fraction of benzoline. hot water.18. boil until the fatty acids are clear. the liquid is titrated with N/2 aqueous KOH solution. transferred to a flask. and allowed to rest. After cooling. which may be generally recognised by the fluorescence or bloom they give to the oil. glycerine. Slightly cool and acidify with dilute sulphuric acid (1 to 3). and dry by filtering through a hot water funnel.100 by the saponification equivalent or by multiplying the number of c. until constant. Thus. the ester value would be 196.65 × 56. of ether added.6 Saponification Value. on the oil. of N/1 alkali absorbed.1 and dividing by the quantity of fat taken. A better plan is to proceed as in the method above described as far as dissolving the resulting soap in 200 c. The whole is then poured into a separating funnel. The solution is then evaporated to dryness in a porcelain basin over a steam or water-bath.8976 = 196. and various expedients have been recommended to overcome this.6 . wash with hot water free from mineral acid. the benzoline washed with warm water (about 32° C.8976 × 1000 / 6. or hydrocarbons (mineral oil).3. and again separated. or caustic potash solution. [Pg 119] The ester or ether value. more ether.1 / 1. but hydrocarbons.c. The residue.6 . phytosterol.15. The ethereal layer is removed to another separator.65 c.—Unsaponifiable matter[Pg 120] may consist of cholesterol. or by rotatory agitation. in the above example:— 6. Two grammes of the fatty acids are now dissolved in neutral alcohol saturated with some solvent.25. the soap solution is transferred to a separating funnel. and transferred to a tared flask.—The usual method adopted is to saponify about 5 grammes of the fat or oil with 50 c.

this method is not applicable to oils or fats liable to oxidation on heating. or it may be converted into glucose by inversion. sulphuric acid on a spot plate.. and confirmed by microscopical examination. Fibre. Another method is to convert the substance into acetate. 160). which is performed by weighing 5 grammes of fat into a separating funnel. a few milligrammes of the substance are dissolved in 2-3 c.—From 5 to 20 grammes of the fat or oil are weighed into a tared porcelain or platinum dish. which depends on the oxidation of cholesterol to oxycholesterol ester and oxycholesterol. 487) has suggested that the fat or oil should be added to a previously dried and tared coil of filter paper contained in a stoppered weighing bottle. and the proportion and nature of the ash determined. absolute alcohol. Two tests are suggested by Golodetz (1) the addition of one or two drops of a reagent consisting of five parts of concentrated sulphuric acid and three parts of formaldehyde solution. dried in the wateroven at 100° C. while the latter forms groups of needle-shaped tufts. Amer.c. and stirred with a thermometer. and Golodetz (Chem. To prevent loss by spurting. 23. and the solution boiled. (2) solution of 30 grammes mercuric chloride in 500 c. aqueous . Soc. formaldehyde solution to a solution of the substance in trichloracetic acid. and the glucose estimated by means of Fehling's solution. until constant in weight. Chem. absolute alcohol. and weighed. when with cholesterol an intense blue coloration is produced. the reagents required being as follows:— (1) Solution of 25 grammes iodine in 500 c. and its weight is constant. and the flask dried until all ether is expelled. dissolving in ether. and was devised by Hübl.3-114. Iodine Absorption. glacial acetic acid. and[Pg 121] passed through a tared filter paper..8° C. Adipose Tissue. Dregs. and allowing the whole to stand to enable the water to deposit. and take its melting point. The amount of fat in the flask gives the quantity of actual fat in the sample taken. The ether in the flask is recovered. If the amount of residue is large. Davis (J. Well wash the filter with ether..unsaponifiable matter in acetic anhydride. etc. the loss represents the water and other impurities. a little benzoyl peroxide added. 252-255). 1908.c. until bubbling or cracking has ceased. Zeit. 1908. the tube of the separator carefully dried. and these latter may be obtained from the increase of weight of the filter paper. when a characteristic blood red to violet coloration is produced. which colours cholesterol a blackish-brown. Chem. but it is more reliable to compare the crystalline forms. Starch may be detected by the blue coloration it gives with iodine solution. the green to oxycholesterol. and reweighed. It has been proposed to differentiate between cholesterol and phytosterol by their melting points. the former crystallising in laminæ.c.6°-137° C. the violet colour being due to oxycholesterol ester. and adding a drop of the solution to one drop of 50 per cent. when a violet-blue or green colour is produced. Ges. In cases of spurting a little added alcohol will carry the water off quietly. In that due to the former. after which four drops of strong sulphuric acid are added.—This determination shows the amount of iodine absorbed by a fat or oil. it may be ignited. Of course. Water. these two solutions being mixed together and allowed to stand at least twelve hours before use. Additional tests for cholesterol have been recently proposed by Lifschütz (Ber. cholesterol acetate melting at 114. and the ethereal solution filtered through a dried tared filter paper into a tared flask. Deut. After six hours' rest the water is withdrawn.. (3) a freshly prepared 10 per cent. Dirt. if cholesterol is present.—From 10 to 15 grammes of the fat are dissolved in petroleum ether with frequent stirring. and (2) the addition of one drop of 30 per cent. The amount of impurities may also be estimated by Tate's method. which is then placed in the oven and dried at 100° C. the loss in weight representing the water. The residue retained by the filter paper is washed with petroleum ether until free from fat. and carefully dry at 100° C. and phytosterol acetate at 125. whilst being heated over a gas flame at 100° C.

the stopper being then moistened with potassium iodide solution and placed firmly in the bottle. which is allowed to stand at rest in a dark place for four hours. required by the unabsorbed iodine in the other bottle.c.c. The most usual temperature of observations is 60° C. standardised just prior to use by titrating a weighed quantity of resublimed iodine dissolved in potassium iodide solution.c. Example. The Refractive index is sometimes useful for discriminating between various oils and fats.3187 Wijs showed that by the employment of a solution of iodine monochloride in glacial acetic acid reliable iodine figures are obtained in a much shorter time.c.—1 c. 0. the Abbé refractometer or the Zeiss butyro-refractometer may be recommended on account of the ease with which they are manipulated.5 .3187 gramme of fat taken. Chem. In the actual determination. and.5 c.40. and allowing to stand for the same length of time. 49) was employed by one of us for many years with very good results. thiosulphate. whilst the bromine-thermal test of Hehner and Mitchell (Analyst. The Titre or setting point of the fatty acids was devised by Dalican.0 = 8. and 30 c. of 10 per cent. of a 25 per cent.6. dividing the product by the weight of fat taken.solution of potassium iodide. Amer.c.0126 gramme iodine. of the N/10 sodium thiosulphate solution is found equal to 0. which is finished with starch paste as indicator.5 gramme of fat or fatty acids is carefully weighed into a wellfitting stoppered 250 c. The gravimetric method of Hehner (Analyst. The process is carried out in exactly the same way as with the Hübl solution except that the fat is preferably dissolved in carbon tetrachloride instead of in chloroform. and this method is now in much more general use than the Hübl. chloroform. A blank experiment is also performed.c. 0. caustic soda solution added. and 25 c. affords another means of detecting adulteration. Bottle containing oil requires 40. although there are several good methods.0126 × 100 ————————— = 33. and the excess of iodine titrated with N/10 sodium thiosulphate solution. The blank experiment is titrated in the same manner. Where a great number of samples have to be tested expeditiously. 48. solution of potassium iodide and 150 c. gives the "Iodine Number". in conjunction with other physical and chemical data.5. of redistilled methylated spirit.. More recently MacIlhiney (Jour.c. 1899. The whole is stirred down on . 0. One ounce of the fat is melted in a shallow porcelain dish. thiosulphate. bottle. After the expiration of four hours 20 c. dissolved in 10 c.c. and is generally accepted in the commercial valuation of solid fats as a gauge of firmness. water are added to the contents of the bottle. 1895.0 c. 1895. Bromine absorption has now been almost entirely superseded by the iodine absorption. 146) gives rapid and satisfactory results. 1084-1089) drew attention to bromine absorption methods and tried to rewaken interest in them.c. and the iodine absorption of the fat is— 8. of the Hübl reagent added. thirty minutes being sufficient. this figure multiplied[Pg 122] by the iodine equivalent of 1 c.5 × 0. and from the amount of thiosulphate required in the blank experiment is deducted the number of c.2 to 0. Wijs' iodine reagent is made by dissolving 13 grammes iodine in 1 litre of glacial acetic acid and passing chlorine into the solution until the iodine is all converted into iodine monochloride. Blank requires 48. using the same quantities of chloroform and Hübl reagent. Soc. together with 50 c. the whole being well agitated during the titration.c. of the thiosulphate solution and by 100. and in the case of tallow has a considerable bearing on the market value. and (4) a N/10 solution of sodium thiosulphate.c.c.

either:— (1) By adding from 3-5 c. using phenol-phthalein as indicator. and titrated with N/1 sulphuric acid.031. expressed as Na2O or K2O respectively.c. 6" × 1". or (2) After adding two drops of methyl orange solution.—These substances are valued according to the alkali present in the form of caustic (hydrate) and carbonate. . or 0. graduated into fifths of a degree Centigrade (previously standardised). and the tube introduced through a hole in the cork into a flask or wide-mouthed bottle. is immersed in the fatty acids.c. at which point the thermometer is very carefully observed. or 0. N/10 acid is run in until the solution acquires a faint pink tint.c. distilled water. The proportion of carbonate is calculated by multiplying the amount of N/10 acid required in the second titration by 2. more distilled water added to wash out any trace of mineral acid remaining. the thermometer is stirred round slowly. After this first titration. Alkalies and Alkali Salts. and stirring is continued until it ceases to fall further. N/1 acid = 0. The whole should be slightly broken in a mortar. and well boiling for five minutes to expel carbonic-acid gas. divided by 10. Care should be bestowed upon the sampling of solid caustic soda or potash as the impurities during the solidification always accumulate in the centre of the drum. This is then dissolved in distilled water. this process being repeated until the washings are no longer acid to litmus paper.0047 to give the amount of carbonate present. One c. a slight excess of dilute sulphuric acid added to liberate the fatty acids. A very accurate thermometer. About 2 grammes of the sample are dissolved in 50 c. and the whole warmed until the fatty acids form a[Pg 123] clear liquid on the surface. and when the fatty acids just begin to solidify at the bottom of the tube. and the latter placed on the water-bath. when the fatty acids are poured on to a dry filter paper. About 10-15 grammes of the pure fatty acids are now transferred to a test tube. which redissolves the soap. and then by either 0.056 gramme KOH. Caustic Soda and Caustic Potash. of acid required in the second titration.047 gramme K2O. is subtracted from that used in the first. and bright crystalline portions taken for analysis. using a stoppered weighing bottle.the water bath until a pasty soap is obtained. of N/10 acid. and this difference multiplied by 0.c. where it is left until the clear fatty acids have filtered through. and again syphoned off. after which it will again begin to drop until the temperature of the room is reached. the second half of the carbonate may be determined in one of two ways. the alkalinity so obtained representing all the caustic alkali and one-half the carbonate. and an excess of that portion must be avoided or the sample will not be sufficiently representative. and the whole again stirred down to a solid soap.0031 or 0. whence the percentage may be readily calculated. warmed until molten.c.047 gives the amount of Na2O or K2O respectively in the weight of sample taken. The water beneath the fatty acids is then syphoned off. when another 50 c. which latter is converted into bicarbonate. The mercury will descend.[Pg 124] In the calculation of the caustic alkali. so that the bulb is as near the centre as possible. of methylated spirit is added. The maximum point to which the temperature rises is known as the "titre" of the sample. The sampling should be performed expeditiously to prevent carbonating. after which the excess of acid is titrated with N/10 soda solution.040 gramme NaOH and 0. It will be found that the temperature will rise rapidly and finally remain stationary for a short time.031 gramme Na2O or 0. the number of c. and portions placed in a stoppered bottle. which is inserted in a funnel resting on a beaker.

2 grammes are dissolved in water.c. The second titration gives the amount of caustic alkali present. This is washed on to a filter-paper. dried. To another 20 c. and made up to 100 c. The filtrate is made up to 200 c. water. and in it may be determined:— Caustic soda. are acidulated with HCl. and the sulphates precipitated with barium chloride. One c. washed. Carbonate.c.—The presence of these compounds is denoted by the evolution of sulphuretted hydrogen and sulphurous acid respectively when the sample is acidulated. A more complete analysis of soda ash would comprise:— Insoluble matter. the precipitate transferred to a filter paper and well washed. About 7-8 grammes of the sample are dissolved in water. Each c. and titrate with N/1 sulphuric or hydrochloric acid.00585 gramme sodium chloride. burnt. and the difference between the two the proportion of carbonate. Reference has already been made (p. of N/1 acid required represents 1 per cent. (equal to 1 gramme) with barium chloride solution. and weighed. and the clear supernatant liquid decanted off.1 grammes of the sample..c. qualitatively. titrations must be carried out cold. Chlorides.c. When methyl orange solution is used as indicator. and the gelatinous precipitate of aluminium hydrate collected on a filter paper. ignited. the result being calculated to Na2SO4. using methyl orange as indicator. and weighed. and deduct the amount of acid required for the Caustic. and for this purpose it is convenient to weigh out 3. with lead acetate solution. ignited. Aluminates are determined gravimetrically in the usual manner. is added barium chloride solution (10 per cent. the precipitate allowed to settle. remaining after 10 grammes are dissolved in[Pg 125] warm water. the precipitate is collected on a filter paper. of course. the chief factor to be ascertained.—Twenty c.c. and weighed..c.c. qualitatively. potassium chromate being used as indicator. 39) to the manner in which the alkali percentage is expressed in English degrees in the case of caustic soda. excess of ammonia added.—The total or available alkali is.An alternative method is to determine the alkalinity before and after the elimination of carbonate by chloride of barium. with N/1 acid. and the filtrate titrated with N/1 acid. Na2O in the sample under examination. The amount of acid necessary for exact neutralisation having already been ascertained. Sulphides may be tested for.) until it ceases to give a precipitate. dissolve in 50 c. Carbonated Alkali (Soda Ash). titrated with N/10 AgNO3 solution. Sulphides and Sulphites. with N/1 acid. . by titrating with N/1 acid the filtrate resulting from the treatment of 20 c.c.—Titrate 20 c.c. dried. or test-paper of sodium nitroprusside. Sulphates. N/10 AgNO3 solution = 0.—Twenty c. are exactly neutralised with nitric acid. rendered acid with HCl. using potassium chromate as indicator.c. washed. it is recommended to use the equivalent quantity of N/10 nitric acid to produce the neutral solution. with lead acetate solution. using phenol-phthalein as indicator. using methyl orange as indicator. Chlorides are estimated by titrating the neutral solution with N/10 silver nitrate solution. Sulphides may also be tested for. and the total alkalinity determined by titrating 20 c.c.

filtering and well washing. washed. and weighed as Fe2O3. adding 250 c. Carbonate of Potash (Pearl Ash). ignited and weighed. hydrate. Sulphates. and platinic chloride in excess (the quantity may be three times the amount of the mixed chlorides) and evaporate nearly to dryness. estimated gravimetrically as silver chloride by precipitation with silver nitrate solution. chlorides of soda and potash.345 grammes of pure silver in pure nitric acid. boiling for a few minutes. This is washed. Chlorides. alcohol and allow to stand three hours covered with a watch-glass. found by deducting the K2CO3 corresponding to the actual potassium as determined above. precipitated with excess of ammonia.19254. K2CO3.0063 gramme Na2SO3.c. .c. add 15 c. using litmus as indicator. either titrated with N/10 silver nitrate solution. in the absence of Na2CO3. and finally transferred to the filter. evaporate the resultant liquor to dryness in a tared platinum basin. dried and weighed. This should be examined for the following:— Actual Chloride.—The total or available alkali may be estimated by taking 6. determined with N/10 silver nitrate solution. The ammoniacal silver nitrate solution is prepared by dissolving 13. to which ammonia has been added.c. or carbonate does not interfere with the accuracy of this method. liquor ammoniæ fortis. and calculated to KCl.005 gramme Na2S.c. and heat the residue gradually to dull redness. giving the dish a gentle rotatory movement occasionally.e. To the mixed chlorides add 10 c. estimated as barium sulphate. and weighed when cold. with an ammoniacal silver nitrate solution. and diluting to 1 litre. Insoluble matter. and carefully acidulate with hydrochloric acid. and calculated to K2SO4. N/1 acid required. the precipitate is filtered off.5 gramme in a small quantity (say 10[Pg 126] c. water. is calculated the amount of potassium oxide K2O by the use of the factor 94/488. preferably. One c.c. N/1 sulphuric acid.c.c. and titrating the excess of acid with N/1 caustic soda solution. of which corresponds to 0.—From 2-3 grammes are heated for thirty minutes in a crucible over a gas flame. to 1 per cent. and the precipitate well washed with alcohol by decantation. and express the result as "mixed chlorides. From the weight of potassium platino-chloride. Potassium may be determined by precipitation as potassium platino-chloride thus:—Dissolve 0. filtered. Sodium Carbonate. ignited. The amount of sulphides may be estimated by titrating the hot soda solution.The total quantity of these compounds may be ascertained by acidulating with acetic acid. N/10 iodine solution = 0. As the titration proceeds. using starch paste as indicator. weigh. remaining after solution in water. and filtering. the loss in weight representing the moisture. In this case each c. the precipitate transferred to a tared filter paper. Insoluble residue. and titrating with N/1 acid directly. The presence of chloride. dried and weighed. using neutral potassium chromate solution as indicator. or adding 100 c. or." i. 1 c.c. is equivalent. remaining on dissolving 5 grammes in water. Carbonate of potash may be further examined for the following:— Moisture. Cool in a desicator. and the addition of ammoniacal silver solution to the filtrate continued until a drop produces only a slight opacity.9 grammes of the sample.2 or 0. sulphate. Iron. Sodium Chloride (Common Salt).) of water. dried. The clear liquid is decanted through a tared filter. from the total alkali. K2PtCl6. and titrating with N/10 iodine solution.

and an examination of all kinds of oil is desirable. Essential Oils. in the same way as sodium chloride. moisture. extracted with hot dilute HCl. or by means of a hydrometer. known as a polarimeter. below 20° C. The potassium may be determined as potassium platino-chloride. and evaporating to complete dryness on the water-bath. above 20° C. and weighed as SiO2. In the case of otto of rose and guaiac wood oil.—This figure is occasionally useful. using methyl orange as indicator. these are very liable to adulteration. Potassium Chloride. below 20° C. which is maintained for a few minutes. ignited in a tared platinum crucible. weighing finally as Na2SO4. compared with water at 15° C. and titrating when cold..—This is found by running alcohol of the requisite strength from a burette into . this operation being repeated a third time.—5 grammes are weighed into a platinum crucible. Optical Rotation. Sulphates are estimated by precipitation as barium sulphate and calculated to Na2SO4. it may be taken either with a Westphal balance. Orange oil. which are solid at this temperature.—This may be determined by converting the salt into sodium sulphate by the action of concentrated sulphuric acid. and compared with water at the same temperature. is required. above 20° C. thoroughly washed. Specific Gravity. The temperature is gradually increased to a dull red heat. add 8' for each degree above. and weighed. dried. subtract 9' for each degree below. however. igniting to drive off hydrochloric and sulphuric acids. As already stated. it is generally observed at 30° C. Solubility in Alcohol. The specific gravity is preferably taken in a bottle or U-tube.Moisture. Sodium. details of the construction and use of which would be out of place here. Total alkali is estimated by dissolving 2 grammes in distilled water. and heat gently applied. and sulphate. Refractive Index. insoluble matter. filtered. and fusing the mass until constant in weight. add 13' for each degree above. The most important determinations for these are total alkali and silica. notably in the case of lemon and orange oils. subtract 14' for each degree below. For these Gildemeister and Hoffmann give the following corrections:— Lemon oil. This should be examined. but if sufficient of the oil is available and a high degree of accuracy is not necessary.—For this purpose a special instrument. Suffice it to mention that temperature plays an important part in the determination of the optical activity of certain essential oils. after which the residue is moistened with HCl and again evaporated. rendering the solution acid with HCl. Silica may be determined by dissolving 1 gramme in distilled water. for chloride. while in the case of the more expensive varieties it should never be omitted.. The residue is then heated to about 150° C. this is usually taken at 15° C.[Pg 127] Silicates of Soda and Potash. as described under carbonate of potash. the dish cooled in a desicator. at 20° C. with N/ 1 acid.—As with fats and oils. and is best determined with an Abbé refractometer.

154 × 100 Per cent. after saponification.1 × 0. calculated in the form of the most important ester present. Instead of expressing the result as saponification value or number. and by subtracting this from the percentage of total alcohols. and the contents of the flask heated on the water-bath for fifteen to thirty minutes. and this. The oil is now dried with anhydrous sodium sulphate. to find the percentage as linalyl acetate. Alcohols. of N/1 alkali absorbed in the saponification by the molecular weight of the ester. of the oil is placed in a flask with an equal volume of acetic anhydride. filtered. ester.[Pg 128] Acid.c.042 gramme.c. of N/1 alkali for its saponification. to liberate the combined geraniol. and 2.196 and by 100. calculated as geraniol. separated. transferred to a separating funnel. geraniol. and after neutralising the excess of alkali with acid. Ten c.196 gramme of geranyl acetate.3825 grammes of the acetylated oil required 9.2 . free alcohols. but with linalol and terpineol the figures obtained are only comparative. dried with anhydrous sodium sulphate. the number of c. Now every 196 grammes of geranyl acetate present in the acetylated oil correspond to 154 grammes of geraniol. gives 52.(9. The calculation is a little complicated. After cooling. so that for every 196 grammes of ester now present in the oil.c. this preliminary saponification is unnecessary. A geranium oil containing 26. and washed with a brine solution until the washings cease to give an acid reaction with litmus paper. which are then saponified with standard alcoholic potash. This process gives accurate results with geraniol. and observe whether any opalescence or cloudiness appears. the percentage of ester. that of the free alcohols is obtained. and is then ready for the alcohol determination. if the oil contains much ester it must first be saponified with alcoholic potash. the amount to be deducted is found by multiplying the number of c.c. calculated as geranyl tiglate. may be obtained by multiplying the number of c. the formula for the estimation of total alcohols thus becoming in the example given:— 9. absorbed by 0. and gently boiled for an hour to an hour and a half. absorbed would be multiplied by 0. was acetylated. until the oil forms a clear solution with the alcohol. and divided by the weight of oil taken. and menthol.c. 42 grammes have been added to its weight.6 per cent.c.9 per cent.1 × 0. of ester.6 per cent.1 c. thereby furnishing a measure of the amount of alcohol esterified. and saponification values are determined exactly as described under fats and oils. the oil is washed into a separating funnel with water. and 1-2 grammes weighed into a flask and saponified with alcoholic potash as in the determination of ester or saponification value. and 2 grammes of anhydrous sodium acetate. a considerable quantity of these alcohols being decomposed during the acetylation. it is well to run in a small further quantity of alcohol. Having noted the quantity of alcohol added. and since each c.—For the estimation of these. of geraniol [Pg 129] The percentage of combined alcohols can be calculated from the amount of ester found. Thus. deducted from the total alcohols. to liberate the combined alcohols. If there is only a small quantity of ester present. The aldehyde citronellal is converted by acetic anhydride into = ———————— 2. borneol. water is added. The alcohols are estimated by conversion into their acetic esters.042) = 70. of N/1 alkali absorbed corresponds to 0. the ester corresponds to 17.a measured volume of the oil with constant agitation. and it is therefore necessary to make a deduction from the weight of oil taken for the final saponification to allow for this. after which they are cooled. but an example may perhaps serve to make it clear.3825 . In the example quoted.

or 10 c. of a 5 per cent. or crystals. until. acetic-acid solution.c. measured. the unabsorbed oil rises into the neck of the flask. This is the solidifying point. adding 25 c. where.c. The flask is again placed in the water-bath. Phenols.—This is best determined by melting some of the solid oil. The innermost tube is then filled with the oil. which will fit one inside the other. and may be estimated by measuring 5 c. after cooling. For this purpose.c. similar to that described under the Titre test for fats. and the flask immersed in a boiling water bath.c. the volume of the cooled unabsorbed oil read off. and warming in the water-bath. Further quantities of the bisulphite solution are gradually added. the temperature at which this takes place being the melting point. is relatively very small. where the proportion of aldehydes. so that this is also included in the determination of graniol in citronella oil. and the residue steam distilled.c.c. Solidifying Point.) and the temperature of the bath gradually raised until the substance in the tube is sufficiently melted to rise to the surface. of different sizes. and is considered to be the point at which the last crystal disappears. graduated in tenths of a c. then adding another 25 c. The oil so obtained is separated from the condensed water. glycerine. The contents of the flask soon become red owing to the liberation of free alkali by the combination of the aldehyde with part of the sodium sulphite.—These bodies are soluble in alkalies. and the point at which the first crystal is observed is usually regarded as the congealing point. and after one hour in the water-bath filling the flask with the potash solution until the unabsorbed oil rises into the neck of the flask. or Congealing Point.. of the oil into a Hirschsohn flask (a flask of about 100 c. and the percentage of absorbed oil.).c. and this coloration is just discharged by the addition of sufficient[Pg 130] 10 per cent. In the case of lemon oil. of a hot saturated solution of sodium bisulphite added. of a saturated solution of neutral sodium sulphite added. and thoroughly shaken at frequent intervals.. In the case of otto of rose. it is necessary to first concentrate the aldehydes before determining them. after about one hour. Aldehydes.c. 100 c. The flask is then filled with the sodium sulphite solution.c. capacity with a long narrow neck holding 10 c. the shaking continued. .c. or aldehydes. dried. of the oil are placed in the Hirschsohn flask. when the stirring is interrupted. distilled off under a pressure of not more than 40 mm.. The melting point of otto of rose is usually taken in a similar tube to the setting point. and the maximum temperature to which the mercury rises noted. of the oil is measured into a Hirschsohn flask. and the percentage of aldehydes calculated as before. and 5 c. assayed for aldehydes either by the process already described. From 5-10 c.—In the estimation of these substances. and sucking a small quantity up into a capillary tube. or by the following process devised by Burgess (Analyst. etc. the volume of this oil being read off when it has cooled down to the temperature of the laboratory. suspended with its bulb completely immersed in the oil. and the flask placed in a boiling water-bath and continually agitated. together with a few drops of rosolic acid solution as indicator. the otto is continually stirred. oil. immersed in a suitable bath (water.isopulegol acetate. and any further alkali liberated neutralised by more acetic acid. A suitable apparatus may be made by obtaining three test tubes. though of great importance.c. calculated.c. With anise and fennel. and 90 c. the oil is cooled down with constant stirring until it just starts crystallising. and fixing them together in this way through corks. 1904.—This is of some importance in the examination of anise and fennel oils. Melting Point. its volume is read off. which is then attached by a rubber band to the bulb of the thermometer. aqueous caustic potash solution. use is made of their property of combining with sodium bisulphite to form compounds soluble in hot water. 78):— Five c. the process being continued in this way until no further red colour is produced.c. and a sensitive thermometer.c. of the oil is placed in a Ladenburg fractional distillation flask. about 30 c. about 20 c. and is also useful in the examination of otto of rose. From the volume of oil dissolved the percentage of phenols is readily calculated.

In the case of a household or unmilled toilet soap.9875. This is best performed in an elongated. until the weight is constant.c.c. it is a matter of considerable importance that all the determinations should be made on a uniform and average sample of the soap. However in soaps made from cocoa-nut and palmkernel oils (which contain an appreciable quantity of soluble fatty acids) the acid liquor is shaken with ether. and the whole heated until the separated fatty acids are perfectly clear. while the interior of the bar or cake may be comparatively moist. this is of some value in conjunction with other data in judging of the purity of otto of rose. after evaporation of the ethereal extract. and weigh. but the former can be estimated. dissolve the residue in water. as described later. the solution being reserved for the subsequent determination of salt. less the amount of stearic acid or beeswax added. except that only 0. and instead of 10 c. is to proceed in the manner described above as far as the decomposition with mineral acid. when they are collected on a tared filter paper. as detailed below. after subsidence. carefully read.—The best method is to incinerate 5 grammes of the soap in a platinum dish. A quicker method. the separated fatty acids may be dissolved in ether. In a complete analysis. and sulphates. 10 c. and an aliquot part taken and evaporated to dryness in a tared flask. The results of these methods are returned as fatty acids. the figure for fatty acids should be converted into terms of fatty anhydrides by multiplying by the factor 0. it is imperative that the quantities for analysis should all be weighed out as quickly after each other as possible. stoppered tube. the total volume of the ether. The weight. and the beaker heated on the water bath until the soap is dissolved. A slight excess of mineral acid is now added. remove it carefully by means of a spatula and dry on a filtering paper. or the ether method described below may be advantageously employed. otherwise very misleading and unreliable figures are obtained. distilled water added. Cool the beaker. and the best way is to carefully remove the outer edges and take the portions for analysis from the centre.—In the authors' opinion. and.—Five grammes of the soap are rapidly weighed into a small beaker. add the portions adhering to the sides of the beaker to the cake. and one which gives accurate results when care is bestowed upon it. and to then add 5 or 10 grammes of stearic acid or beeswax to the contents of the beaker and heat until a clear layer of fatty matter collects upon the acid liquor.[Pg 131] Fatty Acids. Total Alkali. In this test the resin acids contained in the soap are returned as fatty acids. and when the cake is sufficiently hard. The result multiplied by 20 gives the percentage of fatty acids in the sample. It is determined by Hübl's process as described under Fats and Oils. of pure alcohol are added.2 gramme is taken. but are in reality insoluble fatty acids.1 to 0. making the volume of filtrate up to 250 c. Care must be taken that the cake does not contain enclosed water. Where the soap under examination contains mineral matter. silicates.. multiplied by 20 gives the percentage of fatty acids. . the amount of fatty matter left is added to the result already obtained as above. the soluble fatty acids being generally disregarded. and deducted from the total. well washed with hot water and dried until constant in weight. Soap very rapidly loses its moisture on the surface. In the analysis of soap.Iodine Absorption. The rest of the process is identical. which is placed in the oven at 100° C.c. Soap. of chloroform. boil and filter. graduated.

c.00585 × 100 = per cent. Silicates. using a neutral solution of potassium chromate as indicator. of common salt. Number of c. and in soft soaps as K2O.—The difference between total alkali and free alkali (caustic and carbonate together) represents the alkali combined with fatty acids.c. in neutral pure alcohol. Number of c. as caustic. Free Carbonated Alkali. of the filtered extract from the incinerated soap.3052. The result is generally expressed in terms of Na2O. required × 0. Free Alkali. The potassium platino-chloride (K2PtCl6) is calculated to potassium chloride (KCl) by using the factor 0.c. Chlorides may also be estimated by Volhard's method. and the[Pg 133] excess titrated back with N/10 ammonium thiocyanate solution. required × 0.—The residue on the filter paper from the above determination is washed with hot water.c.52991. with N/2 acid. with gentle heat. by titrating back the excess of acid with normal soda solution. . and titrating the filtrate with N/10 acid. the aqueous extract being rendered slightly acid with nitric acid. free alkali Na2O. using lacmoid as indicator. and the aqueous filtrate titrated with N/10 acid.—These are estimated by evaporating 50 c. a measured volume of N/10 silver nitrate solution added. when the difference will equal the amount of total alkali in the quantity taken. to phenol-phthalein. Na2O. as carbonate. [Pg 132]and the result expressed in terms of Na2O. The total alkali is usually expressed in the case of hard soaps as Na2O. The potassium chloride (KCl) is converted into terms of potassium oxide (K2O) by the use of the factor 0. Number of c. well washing the filter with hot neutral spirit. The total alkali may also be estimated in the filtrate from the determination of fatty acids.031 × 100 = per cent. Free caustic alkali is estimated by dissolving 2 grammes of the soap. the alcoholic solution of soap after the free caustic estimation.c.0031 × 50 = per cent.. using iron alum as indicator. using methyl orange as indicator. and express it as free alkali (caustic. and this figure deducted from the amount of mixed chlorides found. NaCl. filtering.Fifty c. Number of c. to methyl orange. Salt may be determined in 50 c. adding hot water.0031 × 50 = per cent. required × 0.c. from which the sodium oxide (Na2O) is obtained by multiplying by 0. of the solution are titrated with N/1 acid.63087. The potash and soda in soaps may be separated by the method described for the estimation of potassium in Pearl ash (page 126). if the acid used for decomposing the soap solution has been measured and its strength known. free alkali Na2O. of the filtered aqueous extract of the incinerated soap. carbonates. or any salt having an alkaline reaction). The final reaction is more distinctly observed if a little bicarbonate of soda is added to the solution.c. by exactly neutralising with normal acid and titrating with N/10 silver nitrate solution. This figure may also be directly determined by titrating. Combined Alkali. heating to 150° C. and filtering through a tared filter paper. gives the amount of sodium chloride (NaCl). required × 0. in a platinum dish with hydrochloric acid twice to complete dryness.—Some analysts determine the alkalinity to phenol-phthalein of the alcoholic soap solution without filtering.

Soc.c. The difference between this latter figure and the amount required for a blank test with 10 c. The flask. The acid liquor is run off. neutralise with alcoholic KOH solution and add exactly 10 c. is allowed to stand one hour to ensure complete combination. until it ceases to lose weight. Fifty c. and the petroleum ether layer washed first with water and then with a solution of 1/2 gramme KOH and 5 c. acidified. alcohol in 50 c. Free or Uncombined Fat. Ind. Halphen's Reaction. Examination of the fatty acids as a guide to the probable composition of the soap:— From the data obtained by estimating the "titre. The rosin is thus saponified and separated.The residue is well washed. and the ethereal layer washed with water until free from acid. water.c. when it is poured into a separator. a fragment of granulated zinc being added to prevent bumping.c. The titre.—This is usually determined by repeated extraction of an aqueous solution of the soap with petroleum ether. is to dissolve 10 grammes of soap in 50 c. and boiled until the acid solution is clear. 804) which is carried out thus:— Two grammes of the mixed fatty and rosin acids are dissolved in 20 c.c. and the rosin content. and from this silica is calculated the sodium silicate. Chem. and saponification equivalent are determined in exactly the same manner as described under Fats and Oils. A good method. the flask being kept cool by means of cold[Pg 134] water to prevent the rosin acids being acted upon. the percentage of rosin being calculated from its combining weight. and burning. and weighed as SiO2. From the loss thus found is calculated the moisture percentage. after washing with water to remove traces of soap. and adding to a few drops of this solution 1 drop of 50 per cent. iodine number. The heat is removed. expressing the result in terms of Na2SO4 by the use of the factor 0. Moisture. boil for fifteen minutes under a reflux condenser and titrate with N/1 acid. A violet coloration is produced with rosin acids." iodine number. Add 3-5 drops HCl and boil to expel carbonic acid. after disconnecting. is evaporated to dryness and the residue weighed. neutral alcohol and titrate to phenolphthalein with N/1 acid. the ethereal solution. is used for washing out the beaker into the separator. and dry hydrochloric acid gas passed through until no more is absorbed. and agitated. and the solution titrated with N/1 KOH or NaOH solution. dried and weighed. well washed out with water so that the volume is increased about five times.—This is a special test to determine the presence or absence of cotton-seed oil . After shaking.c. absolute alcohol. alcoholic KOH. neutral alcohol are added. Sulphates may be determined in the filtrate from the silica estimation by precipitation with barium chloride solution. when its contents are transferred to a Philips' beaker. and drying in the oven at 105° C. The amount of rosin may be estimated by the method devised by Twitchell (Journ. The presence of rosin may be detected by the Liebermann-Storch reaction. and saponification equivalent of the mixed fatty and rosin acids. after filtering. a fairly good idea of the constitution of the soap may be deduced. The resinate solution is withdrawn. boiling at 74° C.c. in excess. which consists in dissolving a small quantity of the fatty acids in acetic anhydride. the acid liquor is withdrawn. sulphuric acid. but 330 is a closer approximation. and the liquid allowed to cool. and the resin acids collected.. Twitchell suggests 346 as the combining weight of rosin. 1891. denotes the amount of alkali absorbed by the uncombined fat.—This is simply estimated by taking a weighed portion in small shavings in a tared dish.6094. The method may be also carried out gravimetrically. in which case petroleum ether. and the beaker thoroughly rinsed out with ether. which can be recommended for employment where many determinations have to be performed. ignited.c. and weighing the barium sulphate.

fatty acids in mixtures. Equal parts of the fatty acids, amyl alcohol, and a 1 per cent. solution of sulphur in carbon bisulphide, are heated in a test-tube placed in a water-bath until effervescence ceases, then in boiling brine for one hour or longer when only small quantities are present. The presence of cotton-seed oil is denoted by a pink coloration. The reaction is rendered much more rapid, according to Rupp (Z. Untersuch. Nahr. Genussm., 1907, 13, 74), by heating in a stoppered flask. Other bodies which it is occasionally necessary to test for or determine in soap include:— Carbolic acid.—Fifty grammes of the soap are dissolved in water and 20 c.c. of 10 per cent. caustic potash added. The solution is treated with an excess of brine, the supernatant liquor separated, and the precipitate washed with brine, the washings being added to the liquor withdrawn. This is then evaporated to a small bulk, placed in a Muter's graduated tube, and acidified with mineral acid. The volume of separated phenols is observed and stated in percentage on the soap taken. Or the alkaline layer may be rendered acid and steam distilled; the distillate is made up to a known volume, and a portion titrated by the Koppeschaar method with standard bromine water. Glycerine.—Five grammes of soap are dissolved in water, decomposed with dilute sulphuric acid, and the clear fatty acids filtered and washed. The filtrate is neutralised with barium carbonate, evaporated[Pg 135] to 50 c.c., and the glycerol estimated by the bichromate method detailed under Crude Glycerine. Starch or gum may be detected by dissolving the soap in alcohol, filtering, and examining the residue on the filter paper. Starch is readily recognised by the blue coloration it gives with a solution of iodine in potassium iodide. Sugars are tested for by means of Fehlings' solution, in the liquor separated from the fatty acids, after first boiling with dilute acid to invert any cane sugar. Mercury will be revealed by a black precipitate produced when sulphuretted hydrogen is added to the liquor separated from the fatty acids, and may be estimated by filtering off this precipitate on a tared Gooch's crucible, which is then dried and weighed. Borax or borates are tested for in the residue insoluble in alcohol. This is dissolved in water, rendered faintly acid with dilute hydrochloric acid, and a strip of turmeric paper immersed for a few minutes in the liquid. This is then dried in the water-oven, when if any boric acid compound is present, a bright reddish-pink stain is produced on the paper, which is turned blue on moistening with dilute alkali. The amount of the boric acid radicle may be determined by incinerating 5-10 grammes of soap, extracting with hot dilute acid, filtering, neutralising this solution to methyl orange, and boiling to expel carbon dioxide. After cooling, sufficient pure neutralised glycerine is added to form one-third of the total volume, and the liquid titrated with N/2 caustic soda solution, using phenol-phthalein as indicator. Each c.c. of N/2 NaOH solution corresponds to 0.031 gramme crystallised boric acid, H3BO3 or 0.0477 gramme crystallised borax, Na2B4O7·10H2O.

The amounts of caustic alkali (if any), carbonated alkali, and salt present are determined in the manner already described under Alkali and Alkali Salts. The glycerol content is ascertained by taking 2.5 grammes, adding lead subacetate solution, and filtering without increasing the bulk more than is absolutely necessary; the solution is concentrated to about 25 c.c., and the oxidation with bichromate and sulphuric acid conducted as described in the examination of Crude Glycerine. The solution, after oxidation, is made up to 250 c.c., and titrated against standard ferrous ammonium sulphate solution, the formula for the calculation being:—

Per cent. of (0.25 - (2.5/n)) × = glycerol 40 where n equals the number of c.c. of oxidised lyes required to oxidise the ferrous ammonium sulphate solution.[Pg 136] The estimation of actual glycerol in this is necessarily a matter of considerable importance, and a very large number of processes, which are constantly being added to, have been suggested for the purpose. Hitherto, however, only two methods have been generally adopted, viz. the acetin and the bichromate processes. Unfortunately the results obtained by these do not invariably agree, the latter, which includes all oxidisable matter as glycerol, giving sometimes considerably higher results, and it has been suggested that a determination should be made by both methods, and the average of the two results considered the true value. This involves a considerable amount of time and trouble, and it will generally be found sufficient in a works laboratory to determine the glycerol by one method only in the ordinary course, reserving the other process for use as a check in case of dispute or doubt. Acetin Method.—This consists in converting the glycerol into its ester with acetic acid, the acetic triglyceride, or triacetin being formed. This is then saponified with a known volume of standard alkali, the excess of which is titrated with acid, and the percentage of glycerol calculated from the amount of alkali absorbed. From 1 to 1.5 grammes of the glycerine is weighed into a conical flask of about 150 c.c. capacity, 7 or 8 c.c. of acetic anhydride added, together with about 3 grammes of anhydrous sodium acetate, and the whole boiled on a sand-bath under a reflux condenser for one to one and a half hours, after which it is allowed to cool, 50 c.c. water added, and the ester dissolved by shaking, and gently warming, the reflux condenser still being attached as the acetin is very volatile. The solution is then filtered from a white flocculent precipitate, which contains most of the impurities, into a larger conical flask, of some 500-600 c.c. capacity, and after cooling, rendered just neutral to phenolphthalein by means of N/2 caustic soda solution, the exact point being reached when the solution acquires a reddish-yellow tint; 25 c.c. of a strong caustic soda solution is then added, and the liquid boiled for about fifteen minutes, the excess of alkali being titrated after cooling, with N/1 or N/2 hydrochloric acid. A blank experiment is carried out simultaneously, with another 25 c.c. of the soda solution, and the difference in the amounts of acid required by the two, furnishes a measure of the alkali required to saponify the acetin formed, and hence the amount of glycerol in the crude glycerine may be calculated. Example.—1.4367 grammes crude glycerine, after treatment with acetic anhydride, and neutralising, was saponified with 25 c.c. of a 10 per cent. caustic soda solution. The blank experiment required 111.05 c.c. N/1 hydrochloric acid. Flask containing acetin " 75.3 c.c. —— 35.75 c.c. " " Hence, the acetin formed from the glycerol present in 1.4367[Pg 137] grammes of the crude glycerine required 35.75 c.c. N/1 caustic alkali for its saponification, so that the percentage of glycerol may be calculated from the following formula:— 35.75 × 0.03067 × 100 Per cent. glycerol = ——————— = 76.3. 1.4367 Bichromate Method.—This process was originally devised by Hehner (Journ. Soc. Chem. Ind., " "

1889, 4-9), but the modification suggested by Richardson and Jaffe (ibid., 1898, 330) is preferred by the authors, and has been practised by them for several years with perfectly satisfactory results. Twenty-five grammes of the crude glycerine are weighed out in a beaker, washed into a 250 c.c. stoppered flask, and made up to the graduation mark with water. Twenty-five c.c. of this solution are then measured from a burette into a small beaker, a slight excess of basic lead acetate solution added to precipitate organic matter, the precipitate allowed to settle, and the supernatant liquid poured through a filter paper into another 250 c.c. flask. The precipitate is washed by decantation until the flask is nearly full, then transferred to the filter, and allowed to drain, a few drops of dilute sulphuric acid being added to precipitate the slight excess of basic lead acetate solution, and the contents of the flask made up with water to 250 c.c. This solution is filtered, 20 c.c. measured from a burette into a conical flask of about 150 c.c. capacity, 25 c.c. of a standard potassium bichromate solution containing 74.86 grammes bichromate per litre added, together with 50 c.c. of 50 per cent. sulphuric acid, and the whole placed in a boiling water-bath for one hour, after which it is allowed to cool, diluted with water to 250 c.c., and this solution run in to 20 c.c. of a 3 per cent. ferrous ammonium sulphate solution until the latter is completely oxidised, as shown by no blue coloration being produced when one drop is brought into contact with one drop of a freshly prepared solution of potassium ferricyanide on a spot-plate. The ferrous ammonium sulphate solution is previously standardised by titration with a potassium bichromate solution of one-tenth the above strength, made by diluting 10 c.c. of the strong solution to 100 c.c. with water. The reaction taking place in the oxidation may be represented by the equation:— 3C3H5(OH)3 + 7K2Cr2O7 + 28H2SO4 = 9CO2 + 40H2O + 7K2SO4 + 7Cr2(SO4)3. Now the strong potassium bichromate solution above mentioned is of such a strength that 1 c.c. will oxidise 0.01 gramme glycerine, and 20 c.c. of the ferrous ammonium sulphate solution should require about 10 c.c. of the one-tenth strength bichromate in the blank experiment. If it requires more or less than this, then the amount of ferrous ammonium sulphate solution which would require exactly 10 c.c. (corresponding[Pg 138] to 0.01 gramme glycerine) is calculated, and the oxidised glycerine solution run into this until oxidation is complete. The formula for the calculation of the percentage of glycerol then becomes:— Per cent. of (0.25 -((250 × = × 500, glycerol 0.01)/n)) where n equals the number of c.c. of oxidised glycerine solution required to oxidise the ferrous ammonium sulphate solution. Example:— In the blank experiment 20 c.c. ferrous ammonium sulphate solution required 9.8 c.c. one-tenth strength bichromate solution, so that 20.4 c.c. ferrous solution would equal 10 c.c. bichromate. 20.4 c.c. ferrous solution required 27.8 c.c. of oxidised glycerine solution before it ceased to give a blue coloration with potassium ferricyanide. Therefore, per cent. of glycerol = (0.25 -((250 × 0.01)/27.8)) × 500,

= 80.04 per cent. Other methods have been suggested for the preliminary purification, e.g., silver oxide, silver carbonate and lead subacetate, and copper sulphate and caustic potash, but the lead subacetate alone with care gives satisfactory results. Other determinations include those of specific gravity, alkalinity, proportion of salts and chloride, and tests for metals, arsenic, sulphur compounds, sugar, and fatty acids.

a few fragments of granulated zinc free from arsenic. Alkalinity.c. or with a Westphal balance or hydrometer It usually ranges from 1. STATISTICS OF THE SOAP INDUSTRY. Sugars may be tested for both before and after inversion. by boiling with Fehlings' solution. About 5 c. The dried residue represents the salts in the weight taken.Specific gravity is determined at 15° C. adding potassium chromate. when in the presence of a mere trace of thiosulphate. is determined after dilution with water by titrating with N/2 acid. lead. and the following figures. Chloride of sodium (common salt) may be estimated by dissolving the total salts in water. is placed in a test-tube. by ordinary reactions. show the steady development of the industry during that period:— Year. the presence of sulphites is proved by the gradual disappearance of the blue starch-iodine compound first formed. and evaporating the filtrate on the water bath. and a few drops of iodine solution together with starch paste added. acidifying. Duty per Ton.—These may be precipitated with barium chloride in acid solution. iron.c. dried. and titrating with N/10 silver nitrate solution. which is usually sodium carbonate. and may be somewhat considerable if the soap has been grained with caustic alkali. Any sulphide causes a blackening of the lead acetate paper. when a yellow stain will be observed if arsenic is present. filtering. magnesium. Sulphides. [Pg 140] CHAPTER XI. ignited.. and the mouth of the tube covered with a small filter paper.3 to 1. Consumed. Copper. and adding a few drops of potassium permanganate solution. and weighed. filtering.31. Exported. Fatty acids are detected by the turbidity they produce when the diluted glycerine is acidified. and may be taken in specific gravity bottle. and 10 c. Thiosulphates are detected by precipitating any sulphite and sulphate with barium chloride. the solution becomes cloudy. Sulphites give with barium chloride a precipitate soluble in hydrochloric acid. Salts. Arsenic is best tested for by the Gutzeit method. taken at intervals of ten years for the half century prior to that date. Until the year 1853 the amount of soap produced annually in this country was readily obtainable from the official returns collected for the purpose of levying the duty. dilute hydrochloric acid added. If the precipitate is well washed with hot water. and calcium may also be tested for in the salts. moistened three successive times with an alcoholic solution of mercury bichloride and dried.[Pg 139] After thirty minutes the filter paper is examined. when no reduction should take place.—Lewkowitsch recommends testing for these by replacing the mercury bichloride with lead acetate paper in the Gutzeit arsenic test. using methyl orange as indicator. Sulphates. extracting the carbonaceous mass with distilled water. in the usual way. . Manufactured. if pure.—These may be determined by gently incinerating 5-6 grammes of the glycerine.

966 500.710 545.385 Household and toilet soaps were not given separately prior to 1903. per annum. Value.035 263. 482.570 1821 875.790 26...368 24.860 Cwts.070 196. the returns for the last eight years being:— Imports.620 17.. The number of soap manufacturers in the United Kingdom is nearly 300.430 468.345 315..032 81.044 19. 191. 1801 509. no accurate means of gauging the production exists.244 99... Official figures are still available for the amount and value of soap annually imported and exported to and from the United Kingdom.098.000 or 8.430 14 Since the repeal of the soap duty.741.114 18.937. . £ From Netherlands France 4.500 1.339 1905.000. Cwts.. 26. £ 3.959 383.Cwts.026 429.542 1904 254.555 361.243 399. but it is estimated that it has nearly quadrupled during the last fifty-five years.140 651.000.. ..300 499.070 1907 228.000 per annum. . being now some 7.517.067 £ 244.. . 1901 . ..790 Cwts. . 1902 .783 1906.507 Total..162 98.408 17.238 1906 309... .631 311.780 839. Toilet. Quantity. Household. Year. £ 3. [Pg 141] The imports during the last three years for which complete figures are obtainable.000 1831 1... and the amount of capital invested in the industry is roughly estimated to approach £20. 1900 .000.000 sterling.407 438. 98..360 1. came from the following sources:— Household Soap..000.376 25.747 .000 cwt.749 268.962 279. Cwts....122 473. £ .425 1905 274.315 14. Value.975 £ .[13] Quantity. 1904..980 1811 678. the revenue from which had reached about £1.790 35. 1903 273.776.930 £ 21 21 28 28 14 1851 1..710 142.554 101. Quantity..850 258.086 284.210 1841 1.965 18.432 504.290 955.851 462. Value Cwts.233 302.

108.174 1. 38.406 £ . £ 3.186 1.114.823 4..829 20 27 285 268.294 1. £ From Germany Netherlands Belgium France Italy United States Other Foreign Countries Total from British Possessions Total Exports.425 1.805 1.240.114 1904. ..448 218.774 1905 1. Value...670 1. .049.126.895 The exports from the United Kingdom during the past eight years have been as follows:— Household.524 1.[14] Quantity. .459.120 1.176 166 1905...485 £ 939.022 955. 1901 .995 £ .186 1.574 1. .208. 874...095. 900..013.017 310. Cwts. 1903 998.794 1.928 1.937 1.972 7.612 242.113 1904 1.657 217..129 3...408 279.131.233 196 59.633 255 147 1906.294 Total from Foreign Countries 268. Cwts.509 5.009.230. Value. Year. Total.339 93.655 . £ 3.164 1.661 228.210..556 280.516 78.814 Toilet.284.001 5.364 1907 1.727 261.919 3.598 1.863 74. 3.225 81..653 46.701 97.976 1.861 7.773 1.837 1906 1.568 7.624 1. Quantity. Cwts.712 248.310 1. 1902 .143.209 6... 1900 . 24.372 40..388 279. Quantity.740 235. ..Italy United States Other Foreign Countries Total from British Possessions Total Toilet Soap. ...145 5....214 947.112 100.051..167.510 999.162 98. Value.624 1.785 18.170 50.309. .411 3.837 43.516 5.873 32.382 Total from Foreign Countries 79.057.044 311.

746 7.951 136.865 28.987 24.942 18.328 13.586 73.750 . 1904.677 6.075 5.096 4.726 13.842 6.293 51.972 35.981 27.198 8.921 41.598 7.478 27.763 2.513 8.601 3. £ 3.911 3.156 1.420 8.222 42.802 40.661 365.058 5.364 6.974 12.996 11.924 1.187 7.687 419.518 20.954 53.235 3.110 49.583 12.084 77.143 158.423 9.751 14.299 23.868 1906.272 1905.027 4.032 15.729 22.203 31. £ 2.467 114.962 5.897 12.858 9.741 28.035 89.861 9. £ To Sweden Norway Netherlands Dutch Possessions in the Indian Seas Belgium France Portuguese East Africa Canary Islands Italy Turkey Egypt China (exclusive of Hong-Kong and Macao) United States Columbia Ecuador Chili Brazil Argentine Republic Other Foreign Countries Total to Foreign Countries To Channel Islands Gibraltar British West Africa— Gold Coast Lagos Nigerian Protectorate Cape of Good Hope 22.968 12.517 143.885 3.Household and toilet soaps were not given separately prior to 1903.634 7.197 7.907 40.444 429.301 13.005 48.914 8.173 39.579 3.864 3.388 3.975 501 3.169 3.197 10. [Pg 142] The exports for the last three years for which complete figures are available.601 7. consisted of the following:— Household Soap.

214 15.013.653 1904.333 14.300 50.Natal British India— Bombay (including Kurachi) Madras Bengal.668 2.303 46.103 39.153 58.094 8.649 50.215 2.406 6.879 22. 74.774 1.389 26.867 10.988 3.087 35.652 118.557 50.280 28. Burmah Straits Settlements and Dependencies Hong-Kong British West India Islands British Guiana Other British Possessions Total to British Possessions Total [Pg 143] Toilet Soap.322 3.730 7.331 11.364 26.685 67.697 23.665 4.355 22.624 15. Eastern Bengal and Assam.051 3.648 37.525 3.969 101.355 9.096 3.516 14. £ 6.945 6.848 59.771 77.316 6.913 24.851 16.645 3.115 4.043 71. £ To Germany Belgium France Portuguese East Africa Egypt China (exclusive of Hong-Kong and Macao) Japan (including Formosa) United States Brazil Other Foreign Countries Total to Foreign Countries To Cape of Good Hope Natal British India— Bombay (including Kurachi) Madras Bengal.292 29.023 52.521 112.382 52.069 12.815 11.043 1.661 47.727 32.988 7.081 14.021 1906.837 1. Eastern Bengal and Assam 24. £ 6.265 8.119 74.124 2.694 955.302 3.534 26.672 5.324 4.620 3.330 584.881 12.009.350 3.973 3.658 3.214 14.903 2.044 590.129 5.002 14.019 590.139 .874 68.897 1905.749 15.241 26.

118 made in establishments engaged primarily in the manufacture of other products.498 6.—According to the Oil.108 547 5.092 11.855 4.486 1. produces annually some 3.989 3.850 130.521 127.358..225.196 10.610.624.Burmah Straits Settlements and Dependencies Ceylon and Dependencies Australia— Western Australia South Australia. which.312 846.210 1.394 644 13..590 12.363.773 143.097 315 4..425 261.854 1.437.139 1.. and other special soaps Powdered soaps. reached a value of $68. including medicated. 29. shaving. Paint and Drug Report the total production of soap in the United States during 1905. etc. 554.097.607.920 957 482 5.000.574 248. .636 3.878.069 3.137 637 12.667 4.390.000 cwts. $ 56.047 Total 228.276 120. sold as such All other soaps Soft soap .416 667.000.798 12.957 6. Hard soaps Tallow soap Olein soap Foots soap Toilet soaps.278 1.549 895 11. with about fifty soap factories.400 5.613.798 32.000.700.118 1.093 6.881 France. United States.376 85.000 more than in 1905.133 Value.417 9.053 135.064 Special soap articles .363. exclusive of soap products to the value of $1..774 4.968 4.—This country exported common soap during 1906 to the value of £556.614 4. made up in the following manner:[Pg 144]— Quantity.299 3.503 8. (including Northern Territory) Victoria New South Wales Queensland Tasmania New Zealand Canada Other British Possessions Total to British Possessions 3.382 11.090.682 143. show the extent of the soap industry in other parts of the world.753. Lbs.274.185 13.186 The following statistics extracted from official consular reports. or £8.670 33. The chief centre of the soap industry is Marseilles.

568 hands.000 lb... 1.800 kilos. . 1906 Lourenço. .324. .. in which 142 hands were employed.. Toilet...—According to a Board of Trade report. Fiji Islands. Quantity..—There are fifty large soap factories in Russia.—In this country there are some 200 small soap factories.... Denmark..... .. .638 lb...983 £6.. per annum £9. .. Marques. the annual output from which is about 2. .. employing 1.000 lb. ... ..263. £23..000 tablets monthly... . ..—In 1905 this country contained twenty-one soap and candle works. Japan. 1905 Iceland. Queensland...293 4.870 lb.423 .000 lb...036 cwt. most of which produce only common soap.. that exported amounting to £15. Australia. 1906 Turkey Africa— Algeria.032. 1..800.987 . . .... Hong-Kong.—This country possesses about 230 small and eighteen large soap and candle factories.000 cwt. £4.. daily. producing about 15. . Russia. £23. ...748 lb.600 £145.. . Place and Date. 1906 Gold Coast. . .. . Roumania.000. 15.. . . Value. £2. . 357. shows the quantity and value of soap imported into different countries and places during the years 1905-7:[Pg 145]— Household. . compiled from various consular and other official returns..—There are about twenty-four soap factories on this island.Germany imported in 1905 soap and perfumery to the value of £3.. ..—These possess only one soap factory. . 1906 Cape Colony.. of soap.. Value.. lb...800 427.... .. .—A Swiss consular report states that in Japan there are now some fifty soap works... . Europe— Cyprus.. Total.000 ... . .. About 1. . . 1906 Natal. The following table... 1906 Switzerland. there were ninety-eight soap and candle factories in Australia in 1905.000 9.702... .897.000 lb....609 tons £228. the output from which is 9 cwt. 2... . 36..195 ...364.640 . In Saxony there are eighty soap factories. Quantity. and having an output valued at £86.. .. and producing 495.250. . Quantity.. there being only one firm—in Bucharest—which makes milled soaps...... ..382. Value. 1906 Orange River 13..

.... . . £29. . 1906 Tripoli.. .. . $14.... 1905 Rhodesia... £3. .. .. 759...... .. 754... . 1904 Granada...... .. . ... £11..... .. .967 Costa Rica. 1. ... .... . 1906 — Cartagena Barranquilla lb.. 1906 America— Bahia.999 257.. 1906 .. ..... . ... 1. . ... . .....671 lb. .. . . ..... . .. 65.. .. . ... 1906 Brazil.. 1906 British Guiana.. ...269 from U.. £81.... . . .782 tons from U..407.. ...... .. 1906 .. 1906 St......000 .587 lb.909 lb...080 £23...... ...554 . 1906-7 Columbia. .269 kilos..... 693..046 milreis .. 1906 Zanzibar... .... .. 202.031 tons 1. .. 1906 Mexico. .... . 1905-6 Surinam.. 1905-6 San Domingo..... .. .. Ecuador... ... .. ....733 $600. 1..142 tons . .. .... 1905 Tunis. .K. £3... .102 606. . ... ..982 ...... . . ... ... ... . 1906-7 ... ....... . 1906-7 Canada..200 lb.... .. .. .... .539 tons .. . 1905 Tangier Transvaal...... . .000 lb... £1.727 £6. . . 1906 Southern Nigeria... . ... . . Vincent.... £1.712 £1. ..... .092 . .... .. .. £13. Guatemala.. £6. 2. ..991 tons 814... . .K.... . 1905 ...867 . 1906 Trinidad.. £900 £6.. . 4..905 .375 .034 kilos....955 £5... . . . Martinique.. ...600 lb...Colony... . . .. .......990 £4.... .. 1906 Pemba.. .

. ..521 tons. . .700 rupees £216.. Total Quantity...... $1..800 kilos.... £93. 77... . .. .. ... Quantity. . Value..... .. 4.. £95... ...200 tons... 1906 New Zealand. 3..888 Hangchow.992..... .... . .... 1906 . .256 . £34. .... . 1906 .... . .. . . ..998 cwts.042 £5.. 1905 [Pg 146] Exports.. . 423..065 . .. 2.840 . About 500.000 .. £65. . $1.750.446 . 1906-7 Kiungchow. . .. . ... ..300 kilos... Value. . . 1906 Africa-Cape Colony...... .....210 . 1906 Fiji... .. £98. . . 1905 Philippine Islands... ..843 £9.... . Place and Date Europe-Candia. 891..000 Fr. 1905 Smyrna...... . .. . 1906 India..471... . .... . .. .. Quantity.137 Household. Crete....797 .. 1906 China............ £1. £215...071... . 1905 Switzerland...United States... .. .. ... . £575 . 183.. .. ....... 1905 Shanghai.. Value .... .... . ....243 ... ...996 kilos. .760 £36.. 1905 Asia-Ceylon..... ... £37. . . . . .. . Toilet........ ... . . 1..840 . 1906 Greece Italy.. ... .. 1907 .. .840 . 1906 Australasia-Australia. per annum. .... ... Spain. Leghorn. 200 lb. 261 tons .....117 lb. $399.

.7 1. 0 1 2 3 4 5 6 7 8 9 0 0..2 1. 419. B. Tw.582 tons.690 139 59. . 1. .042. 3. . 1906 America-New Orleans. Tw.685 138 58..700 .250 29...005 1.. ..329 kilos. B.260 30. . ..1 1.4 1. 1906 Perambuco. . $1. £83. .1 1.. .590 Rs...040 1. 1906 .470 46..680 137 58.797. Density..150 rei.2 1. [14] Including soap powder and soap stock... .4 1. . . FOOTNOTES: [13] Including soap powder and soap stock.7 3... Tw. 1906 Seychelles.... [Pg 147] APPENDIX A...2 1.9 1. .4 6... .. 1905 Asia-Japan. 129.7 1.225 lb. 88 89 90 91 92 93 94 95 96 97 Density.465 46.485 131 57..675 136 58.3 1.1 1.4 1.480 47. .. B.220 26.. Tw..665 134 57..460 45. COMPARISON OF DEGREES.020 1.655 132 57.. ..475 46.670 135 58.110.235 27.8 1. .949 lb.225 26.0 1.245 28. . TWADDELL AND BAUMÉ.1906 Natal... B.1 1..4 1.695 140 59..534 75.4 1. WITH ACTUAL DENSITIES.035 1..... .. ...4 1.000 1.. 1906 Smyrna..7 5.265 44.4 4.025 1.1 2.240 28..4 1...9 1. ..450 45...0 Density.255 29. . ..1 4.4 2.7 1.440 44. . ....010 1..1 1.045 44 45 46 47 48 49 50 51 52 53 Density.8 1.087. .015 1. .660 133 57.5 1. £55.9 1. 322 tons.8 1.877 .455 45.9 1..030 1.7 1.230 27...4 1. .185 .. 44.8 1. .445 44.. 1906 United States.... 26. 1.

6 1.9 1.495 141 59.1 1.525 106 50.4 1.5 1.7 1.6 1.4 1.375 39.855 172 66.9 1.395 41.520 105 49.4 1.7 9.1 1.540 109 50.720 145 60.350 37.2 1.1 1.6 1.7 7.4 1.170 21.300 33.7 1.2 1.590 119 53.2 1.650 10.0 1.140 18.0 1.2 1.745 150 61.1 1.0 1.335 36.145 18.3 1.1 1.365 39.0 1.8 1.370 39.130 17.7 1.0 1.)[Pg 148] .5 1.800 161 64.835 168 65.605 122 54.3 1.4 1.290 32.0 1.0 1.125 16.7 1.190 23.785 158 63.550 111 51.8 1.270 31.6 1.8 1.5 1.845 170 66.385 40.0 1.075 10.645 130 56.6 1.7 1.080 11.360 38.065 1.420 43.390 40.735 148 61.2 1.345 37.0 1.1 1.9 1.545 110 51.1 1.575 116 53.5 1.535 108 50.615 124 55.4 1.710 143 60.865 100 48.6 1.7 1.8 1.755 152 62.4 1.3 1.8 1.175 22.5 1.185 23.105 14.8 1.0 1.110 14.9 1.120 16.6 1.2 1.505 102 48.4 1.3 1.725 146 60.2 1.565 114 52.7 1.5 1.8 1.090 12.9 1.435 (From The Oil and Colour Trades Journal Diary.570 115 52.0 1.9 1.180 22.805 162 64.315 35.6 1.9 1.320 35.4 1.0 1.5 1.510 103 49.0 1.850 171 66.9 1.410 42.7 1.340 37.8 1.795 160 64.555 112 51.600 121 54.275 31.765 154 62.415 42.7 1.1 1.500 101 48.055 1.4 8.560 113 52.160 20.810 163 64.305 34.295 33.4 1.8 1.740 149 61.0 1.4 1.380 40.215 87 48.760 153 62.3 1.2 1.155 19.0 1.5 1.280 32.860 173 67.430 98 99 47.620 125 55.0 1.0 1.640 129 56.050 1.580 117 53.3 1.3 1.790 159 64.210 43 25.630 127 56.1 1.2 1.330 36.100 13.7 1.815 164 65.770 155 63.070 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 30.085 11.625 126 55.825 166 65.0 1.7 1.490 47.135 17.8 1.2 1.780 157 63.0 1.820 165 65.5 1.8 1.285 32.515 104 49.8 1.195 24.310 34.2 1.840 169 66.4 1.6 1.3 1.6 1.730 147 61.165 20.115 15.775 156 63.0 1.6 1.355 38.705 142 60.6 1.4 1.4 1.10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 6.425 43.205 25.5 1.8 1.1 1.530 107 50.200 24.405 42.4 1.635 128 56.4 1.060 1.325 35.3 1.3 1.585 118 53.150 19.0 1.8 1.610 123 55.095 13.595 120 54.750 151 62.0 1.0 8.2 1.5 1.400 41.830 167 65.6 1.5 1.715 144 60.5 1.4 1.

4 120.6 82.6 32.8 8.8 197.8 224.4 3.2 5 6.2 212 213. Fahr.4 138.4 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 35.2 50 51.6 23. Cent.6 73.4 +68 +154.2 68 69.6 226.2 140 143.8 152.6 46.6 190.8 215.2 27.4 66.2 41 42.6 10.8 44.2 18.8 71.6 5.2 231. Fahr. 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 104 105 106 107 108 109 111 112 113 114 186.2 158 159.6 199.8 80.6 136.4 75.8 +103 +217.6 Cent. -40 39 38 37 36 35 34 33 32 31 30 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 -40 38.6 235.8 125.8 4 2.6 156.8 188.8 13 11.4 228. Fahr.4 192. Fahr.APPENDIX B.6 145.4 +1.2 131 132.6 55.6 118.4 39.2 122 123.4 34. Cent.8 62.4 84.8 206.4 237.4 48.2 9.4 147.4 129.2 36.2 141.4 7.8 134.6 64.4 210.2 149 150.8 116.2 86 Cent.8 31 29.4 57.4 16.2 221 222.4 201.2 203 204.6 219.6 87. 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 69 70 71 72 111.8 283.2 0.8 58.2 77 78.2 194 195.2 59 60.4 25.4 +110 +230 .2 113 114.8 22 20. COMPARISON OF DIFFERENT THERMOMETRIC SCALES.6 208.8 161.6 14.6 127.

528 .830 3.536 0.6 91.2 248 249.194 2.060 Na2O.2 95 96.510 0.015 1.474 0.8 107.2 176 177.436 1. Hurst.252 3.) [Pg 149] APPENDIX C.262 0.045 1.184 4.2 14 15.005 1.393 0.6 244.8 26.4 255.6 19.097 0. 1 2 3 4 5 6 7 8 9 10 11 12 Specific gravity.4 30.4 93. TABLE OF THE SPECIFIC GRAVITIES OF SOLUTIONS OF CAUSTIC SODA.055 1.129 0.2 23 24.040 1. of actual NaOH contained in 1 gallon of lye made from commercial caustic of 77 per cent.6 73 74 75 76 77 78 79 80 81 82 83 84 163.087 0.631 5.486 0.438 0.6 (From Soaps.909 2.020 1.536 Lb.389 0.8 98.320 0.243 0. by weight of Degrees Twaddell.092 0. Greenwood & Son.417 0. 0.590 3.6 +1 33. 0.086 5.131 0. published by Scott.742 1.8 170.303 0.114 1.6 172.050 1.368 0.048 0.043 0.6 181.8 165.4 21.2 115 117 118 119 120 121 123 124 125 126 239 242.2 32 31 +32 33 34 35 36 37 49 39 40 41 42 87.4 102. Per cent. by G.2 104 105.350 0.8 179.010 1.335 0.185 0.8 43 109.244 3. 0.292 NaOH.180 0.194 0.957 1. H.278 0.461 0.146 0.4 183.291 0.4 167 168.2 +116 +240.480 1.943 4.438 0.483 0.8 253.8 +89.030 1.046 0.4 85 185 127 260.746 4.2 257 258. 0.834 2. 0.6 100.231 0.11 10 9 8 7 6 5 4 3 2 1 0 12.8 +122 +251.4 246.521 2.371 0. 1.8 17.035 1.219 0.964 3.025 1.4 174.558 70 per cent.586 74 per cent.365 2.6 28.

185 2.653 0.804 1.381 1.354 1.413 1.646 1.627 1.026 2.055 2.916 1.981 6.190 1.856 1.223 8.230 4.025 12.140 8.413 6.981 1.311 6.180 1.786 0.120 1.794 17.444 2.372 16.008 11.311 5.997 20.970 9.460 1.471 11.637 15.593 1.181 1.613 19.749 0.110 1.541 1.933 12.539 1.817 1.456 1.277 1.844 13.982 6.386 9.097 2.160 1.600 1.904 1.692 13.037 1.175 1.823 15.356 12.337 1.237 1.638 4.684 1.502 15.313 10.187 1.095 1.822 1.130 1.125 1.859 14.115 1.680 0.645 1.639 6.121 19.887 1.080 1.016 13.251 9.122 1.122 2.280 2.350 1.893 9.296 1.392 2.607 0.705 1.470 1.087 1.090 1.037 1.937 0.973 2.564 8.339 13.033 2.238 1.221 2.075 1.562 0.323 2.573 0.965 10.954 7.161 2.742 0.185 1.140 1.124 15.085 1.417 0.648 5.583 8.836 0.170 1.764 1.942 1.438 14.707 0.800 0.292 1.203 10.617 0.962 2.998 2.715 8.911 7.205 1.133 18.989 1.139 16.137 1.796 10.401 12.798 0.959 5.303 13.200 1.986 1.972 5.886 0.512 16.636 0.210 1.594 7.147 2.070 1.709 0.155 1.614 9.629 18.413 1.123 1.170 1.081 15.135 1.853 1.100 1.215 1.071 1.739 1.252 2.195 1.894 0.065 1.347 11.890 0.618 19.203 17.586 0.910 8.107 11.145 1.285 7.846 0.666 11.150 1.220 1.755 0.528 1.938 0.338 2.660 14.190 14.105 1.668 0.691 12.058 14.845 0.445 1.117 1.285 .175 1.206 2.026 1.941 0.276 7.753 1.13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 1.719 1.085 2.165 1.607 11.529 1.225 1.

932 2.318 20.237 3.478 4.810 74 per cent.669 2.265 1.919 3.595 29.250 1.105 28.514 3.476 22.240 16.275 1. 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 Specific gravity.117 3.609 19.881 2.961 20.760 3.539 3.681 2.433 23.354 4.970 4.424 17. 1.312 4.645 4.046 24.171 3.670 24.891 3.603 3.446 32.452 3.415 33.524 3.556 22.593 3.376 24.863 2.410 24.674 3.785 22.335 1.894 3.300 1.310 23.008 22.532 2.255 1.355 1.280 1.341 2. 2.535 31.295 25.967 4.816 3.474 2.548 2.325 1.152 25. 2.405 21.299 16.330 1.396 4.020 3.308 3.345 1.161 29.166 18.380 Na2O.095 3.513 4.962 23.156 21.290 1.274 4.529 18.897 19.224 3.269 4.018 31.655 21.305 1.253 3.739 2.742 3.109 4.395 3.750 26.809 2.475 3.988 3.754 3.610 3.058 30.47 48 [Pg 150] 1.375 1.060 17.952 3.072 4.948 32.930 33. of actual NaOH contained in 1 gallon of lye made from commercial caustic of 77 per cent.370 1.592 70 per cent.561 4.750 2.260 1.158 3.394 3.730 2.255 19.795 2.536 2.849 3.382 34.381 3.615 2.360 1.245 1.156 4.340 1.285 26.027 3.295 1.194 4.196 4.053 3. 17.410 Per cent.886 2.996 21.526 25.593 2.574 30.818 2.285 1.090 3.611 28.270 1.210 26.602 2.692 20.765 25.232 4.439 3.855 Lb.320 1. 2.182 3.666 2.901 26.116 4.315 1.042 4.997 4.800 18.344 . by weight of Degrees Twaddell.926 23.168 22.227 3.901 24.235 1.475 2.490 31.110 27.955 3.728 4.434 4.650 27.681 3. 22.364 3.658 27.021 NaOH.310 1.365 1.905 34.682 3.824 3.043 4.350 1.858 25.

141 5.493 4.193 6.490 1.640 5.460 32.784 6.980 44.495 27.093 6.674 38.816 5.110 28.586 6.836 29.982 6.041 4.004 6.950 5.700 32.081 46.475 1.035 6.670 4.) [Pg 151] APPENDIX D.283 33.720 4.435 1.110 1.558 5.25 1.415 1.381 6. Lb. Degrees Twaddell.420 1.181 5.875 42.907 4.435 40.482 5.440 1. by G.823 5.385 1.59 1.191 6.400 42.027 5.314 5.467 5.233 5.290 6.608 5.410 1.505 45.908 5.695 34.567 4.795 36.31 15.203 37.450 1.418 4.828 4.303 100 1. H.390 1.500 36.797 4.126 6.480 1.745 28.396 5.530 46.48 0. KOH.59 11.043 32.610 39.425 1.873 4.476 6.385 27.571 4.135 5.679 5.071 39. of KOH per gal.465 28.909 6.923 6.445 1.882 41.412 5.856 5.335 41.721 5.395 1.948 6.467 43.258 36.691 35.460 1.455 1.485 1.104 5.146 38.77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 1.397 5.092 34.245 35.930 30.899 35. Specific gravity.530 39.203 29.349 31.893 4.567 5.653 5.738 5.430 1.769 5.216 6.986 40. Per cent. published by Scott.545 6.405 1.665 (From Soaps.720 37. Hurst.312 5.328 35.502 5.642 4.287 6.500 34.645 30.060 1.258 5.071 5. TABLE OF STRENGTH OF CAUSTIC POTASH SOLUTIONS AT 60° F.470 1.884 4.058 5.989 5.975 5.870 33.995 31.935 43.400 1.570 29.150 12 22 30 5.685 6.794 4.013 45.227 5.487 6.389 6.335 5.77 .009 6.465 1. 1.285 30. Greenwood & Son.

Caproic.29 23.22 17. 10 ---.22 27.24 12. Greenwood & Son.Caprylic.21 2.440 1.32 35. Hurst.84 3. 10 .23 2.Butyric.83 47.330 1.360 1.780 1.) THE END.600 1. 10 ---.04 14.390 1.89 10. 10 ---. Acetic.Behenic.Carnaubic.01 38.Arachidic. A.98 67. Acetic Acid.81 6.520 1.56 4.93 7. 10 ---.16 4.76 8.24 (From Soaps. 10 ---.59 40.62 60. [Pg 153] INDEX.190 1.36 5.87 31.74 2.230 1. H.09 55. published by Scott. 10 Acid.680 1.Capric. 10 ---.65 75.16 51.880 38 46 56 66 72 78 84 88 94 104 112 136 156 176 19.76 5.000 200 86.97 43.31 6.280 1.420 1.1.470 1. 10 ---. by G.

Moringic. 10 .---. 10 ---. 10 ---.Elæostearic.Lauric.Physetoleic. 11 ---. 10 ---.Linolenic. 10 ---.Margaric.Ficocerylic.Pisangcerylic.Erucic. 10 ---. 12 ---.Palmitic. 10 ---. 12 ---.Daturic. 11 ---.Oleic.Myristic. 12 ---.Medullic.Melissic. 10 ---.Linolic.Hypogæic.Psyllostearylic.Elæomargaric.Lignoceric.Doeglic. 10 ---.Isovaleric. 11 ---.Jecoric.Isolinolenic. 10 ---. 12 ---.Hyænic. 10 ---. 10 ---. 10 ---. 11 ---. 10 ---. 11 ---. 12 ---.Cerotic. 11 ---. 12 ---.

16 ---. 45. 20 ---.---. 118.Saturated fatty. 9-13 ---. 107 Andiroba oil. 11 ---. 129 Alkali. 19-21 ---. Caustic and carbonated. Determination of.---. Estimation of.Combination with Alkali.Saponification.---. 32 Animal charcoal.Unsaturated fatty. 13 Twitchell's process. Classification of fatty.fats. 12 ---.value. 128 Aldehydes. 43 . 131. 11 ---. 10 ---. 11 ---.Rapic. 132 Amyl salicylate. 10 ---. 46 Acids. 11 Albumen in soap.Telfairic. 10 ---. ferment process. Treatment of.---.---. 123-126 Alkali in soap. 39. 115 ---. Preparation by acid process. 19-21 ---. 38. Estimation of. 90 Alcohols. 128 Acids.---.Ricinoleic.Tariric.Fatty.Tiglic.Theobromic. 12 ---.

43 Boiling-on-strength. 55 Barring soap. 68 Bay oil. 107-110 Ash. 36 Bar soap. 18 Baobab-seed oil. 41 ---. 10 Benzyl acetate. Decomposition of fats by. 39. 108 Arachidic acid. Bacteria. 54. 14 Aubépine. 108 Bergamot oil.(artificial). Soda. 87 Birch-tar soap. 99 . 10 Arachis oil. 97 ---. 96 Aqueous saponification. 88 Bitter almond oil. 125 Aspic oil. 109 Biniodide soaps. 124.---. 28 Artificial perfumes. 108 B.rosin.Anise (star) oil. 96 Anisic aldehyde. 51 Bois de Rose Femelle oil. 97 Bleaching palm oil. 97 Behenic acid.

31 Butyric acid. 10 Caprylin. 33 Capric acid. 10 Caproin. 32 . 32 Brine. 33 ---. 122 Brown Windsor soap. 39 Bromine absorption of oils and fats. 8 C.kokum. 98 Candle-nut oil. Calico-printer's soap. 30 ---. 33 ---. 98 Butter goa.treatment of. 93 Cananga oil. 8 Carapa oil.---. 43 Borax in soap. 10 Butyrin. 88 Boric acid in soap. 78. 88 [Pg 154]Boric acid in soap. 10 Caprin. 8 Caprylic acid. 8 Caproic acid.Bone-fat. Determination of. 135 Borneo tallow.shea.

39. 26 Cohune-nut oil. 126 ---. 10 Charcoal. 108 Cleansing soap. 34 . 30 Caustic potash. 124. Determination of. Animal. 115 Chinese vegetable tallow. 134 Carbolic soap. 98 Citral. 61 Close-piling soap. 39.soda. 10 Cassia oil. 98 Cerotic acid. 39. 123 ---. 125 Carnaubic acid. 125. 108 Citronella oil. 71 Clove oil. 123 Cayenne linaloe oil.Caraway oil. 88 Carbonate potash. 120 Cinnamon oil. 25. 88 Cocoa-nut oil. 39. 31 Cholesterol in unsaponified matter. 99 Cedarwood oil. 99 Coal tar soaps.soda. 98 Carbolic acid in soap. 98 Castor oil. 99 Citronellal. 60.

53 Curd soaps. 108 Crude glycerine.Refining. Glycerine. 80. 42 ---. 74. 18 Detergent action of soap.stearine. 42 ---. 26 Cotton-seed oil. 4. 12 Cooling soap. 76 Coprah oil.---. 136-139 Crutching soap. 6. 85 D. 52. 7 Dika fat.Cold process soap-making. 10 Decolorisation. 52 Cutting and stamping toilet soap. 46.soapstock. 5 Diglycerides. 66. 113. 11. 25. 7 Conversion of oleic acid into solid acids. 82 Compressing soap. 83. 115 Decomposition of fats by bacteria. 33 Curd mottled soap. 27. 47 Colouring soap. 28 Coumarin. 63 Curcas oil. 40 ---. 85 Concrete orris oil. 36 . Daturic acid. 100 Constitution of oils and fats.

112. 12 Electrical production of soap. 71. 114 Distilled glycerine. 128 Ether soap. 30 ---. 113 F. 12 Elæostearic acid.Examination of. Bone. 127-130 Ester value. 90 Eucalyptus oil.---. 36 . glycerine. 66 Distearine. 120. 115 E. 11 Double distilled glycerine.Disinfectant soaps. 7 Distillation. 114 Doeglic acid. 119. 12 Enzymes. Fat. Determination of. 78-80 Dynamite glycerine. 115 Dregs in fats and oils. 121 Drying soap. 100 Evaporation to crude glycerine. Elaidin reaction.Dika. 11 Essential oils. 15-18 Erucic acid. Action of. 59 Elæomargaric acid. 96-107 ---.

Direct combination with alkali of.of iodine absorption of. 123 ---.of saponification ---.of specific gravity of.---.of bromine absorption of. 122 ---. Decomposition by bacteria of.---.---. 45.. 34 ---. 19-21 . 116 Fatty acids. 34 ---. Determination of acid value of. Determination of.Classification of. 118 ---. 118 ---.---.Treatment of bone.---. 133. 134 ---.---.Niam.---.---.---. 121. 122.of free acidity of. 10 ---. 119 ---.of dregs.equivalents of.Marrow. 43 Fats.Examination of.---.---. 46 ---. 31 ---.---. 43 ---. 30 ---.Treatment of animal.---. in. 18 ---. 117 [Pg 155]---.Tangkallah. 120.---. etc. 120 ---. 121 ---.---.---.Preparation by acid process.---.Maripa. 117 of titre of. soap.---.of saponification value.---.---.---.---.---. 131 ---.---.Waste. 122 ---. 37 ---. 118 ---.---.of unsaponifiable matter in.Yield of glycerine from. 30 Fats and oils.of water in.---.---.---.---.

11 ---. 66 Free alkali in soap. 88 Framing soap. 8 . Determination of.---." 51 Floating soap. 30 "Fitting. action of. 132 ---. 108 Geranium oils.fat in soap. 101 Glycerides. Geraniol. 11 Fennel oil.---. 88 Formaldehyde ferment process.---. 10 Filling soap. 117 G. 133 ---. Neutralising. 101 Ginger-grass oil. Estimation of.---. 91 Fluorides in soap.---. 16 Ferments. 65 Fish oils.caustic in soap. 15-18 Ficocerylic acid. 90. 20 ---.---.---. 66 ---.fatty acids. Determination of.Unsaturated. 100 Ferment process for preparation of fatty Twitchell's process. 16 ---. 7. 101 Geranium-sur-rose oil.

from fats and oils. 114 ---. 136-139 ---. 136 ---. 29 Hyacinth. 30 ---. 30 Guaiac wood oil. Halphen's reaction." 50 Grease. 138 ---. 30 ---.Glycerine. Estimation of.Skin. Animal. 108 Hemp-seed oil. 134 Heliotropin. Determination of. 101 H. Chemically pure.Yield of. 111-114 ---. 115 soap. 135 ---.bichromate lyes. 33 "Graining-out.Distilled.saponification. 113. 114 ---. 108 .Crude.---.soaps.distillation. 135 Goa-butter.Kitchen. 89 ---. 137. 30 ---. 116 Glycerol determination. 115 ---. 116 ---. 115 ---.manufacture. 134.Bone.dynamite. acetin method.decolorisation.

10 Isovalerin. 89 Inoy-kernel oil. 121. 8 J.122: ---.Hyænic acid.absorption of oils and fats. 89 Ionone. 48.Enzymic. 3 Hypogæic acid. 108 Isolinolenic acid. 98 . 12 K. 12 Isovaleric acid. 130 ---. 21 ---. 49 Hydrolysis accelerated by heat and electricity. 109 Jecoric acid. 10 Hydrated soaps. 14. 15 ---. Ichthyol soap. 19. 11 I. 15-18 ---.soap.accelerated by use of chemical reagents. Kananga oil. 13-23 ---.of soap. Jasmine. 19-23 ---.of oils and fats. 37 Iodine absorption of rose oil.accelerated with acid.

Evaporation of. 12 Linolic acid. 18 Liquoring of soaps. 111. 112 ---.saponification. 102 Lignoceric acid.Kapok oil. 22 Linaloe oil. 101 Lemon-grass oil.Treatment of. 32 "Kastilis. 33 L. 10 Lime oil. 109 Linolenic acid. 12 Linseed oil.Determination of glycerol in. analysis of. 102 ---. 102 [Pg 156]Linalol. 64 Lyes. 25 Lauric acid. 10 Laurin. 135 ---. 135 ---. 29 Lipase. 102 Lemon oil. 112 Lysol soap. 89 . 109 Linalyl acetate." 88 Kokum butter. Lard. 8 Lavender oils.

7 Monostearin. 35 Marine animal oils. 78 Milling soap. 11 Mottled soaps. 35 Magnesia. 10 Margosa oil.soap.soap-base. 22 Maize oil. 53 . 34 Marjoram oil. 130 Mercury soaps. 54. 58. 10 Melissic acid. 81 ---. 8 Monoglycerides. Mafura tallow. 52. 87 Milled toilet soaps. 109 Mixed glycerides. 30 ---. 49 Maripa fat. 59 Mirbane oil or nitrobenzene. 78 Mineral oil. 28 Margaric acid.M. saponifying. 80. 7 Moringic acid. Hydrolysis by. 103 Medicated soaps. 86-90 Medullic acid. 10 Melting point.

80 Niam fat.---. 8 Myristin. 97 ---. 66. 32 ---. 54 Moulds. 109 Neutralising free caustic in soap. 110 Nitrobenzene. 56 Niobe oil or ethyl benzoate.oil (artificial). 97 . 8 N.Pickling.Bay. 31 Musk (artificial). 36 ---. 96 ---.---.Bergamot. Soap.Bitter almond. 72. 109 Myristic acid. 103 ---.Baobab-seed. 89 Neroli Bigarade oil. 56 Nigres. 97 ---. 10 Oil. 34 Nigre.Arachis. Naphthol soap. 109 O. Oeillet. 86 Mowrah-seed oil.Aspic (lavender spike). 85. Utilisation of. Andiroba. 28 ---.

29 ---. 30 ---. 99 ---. 27. 37 .Cassia.Cayenne linaloe.Concrete orris.Cohune-nut. 101 ---.Guaiac-wood.Bleaching palm.Inoy-kernel.Carapa.Eucalyptus. 34. 33 ---. 26 ---. 99 ---.Cedarwood. 100 ---. 100 ---. 32 ---.Citronella. 25. 41 ---. 99 ---. 101 ---. 101 ---. 35 ---.---.Cananga.Fennel.Curcas.Caraway. 98 ---. 98 ---.Clove.Cotton-seed. 99 ---.Castor. 42 ---. 25.Candle-nut.Hemp-seed.Coprah. 100 ---.Ginger-grass. 33 ---.Geranium.Cocoa-nut. 98 ---.Bois de Rose Femelle.Cinnamon. 26 ---. 98 ---. 98 ---.

102 ---. 31 ---. 35 ---. 41 ---. 98 ---. 103 ---.---. 26 ---. 28 ---.Marjoram. 104 ---. 163 ---.Neroli Bigarade. 27. 29 ---.Linseed.Olive-kernel.Patchouli. 103. 32 ---. 35 ---. 26 ---.Persimmon-seed.Peppermint.Refining cotton-seed.Mowrah-seed. 105 . 102 ---. 102 ---.Linaloe.Palm-nut.Pongam.Orange.Rose. 103 ---.Maize. 103 ---.Lime.Lemon-grass.Peru-balsam.Margosa.Palm.Kapok.Olive. 104 ---.Palmarosa. 102 ---.Kananga.Lemon.Petit-grain. 42 ---. 104 ---. 103 ---. 27 ---. 36 ---.

106-107 ---.Wild mango. Conversion of. 9. 59 ---. 6.Vetivert. 105. 36 ---. 96 [Pg 157]---.Fish and marine animal.into solid acids. 33. 106 ---.---.Thyme.Lavender.Sesame. 28.---. 43 Oleic acid.treatment of vegetable.Sunflower.Ylang-ylang.Cocoa-nut.Wintergreen. 13-22 ---. Constitution of.Refractive Index of. 58. 106 ---. 106 ---. 11 ---. 8. 29 ---. 7 ---. 105 ---.Saponifying mineral.Star-anise. 117-123 ---.Verbena. 107 ---. 34 ---. 36 ---.Hydrolysis of. 31 .Rosemary. 30 ---.Safflower.Sassafras. 11. 29 ---.---. 31 ---.---. 107 Oils and fats. 106 ---.Examination of. 12 Olein. 101 ---.Sandalwood.Wheat. 122 ---.

concrete. 27. 107 Orris oil. Palm oil. 104 Perfumer's soaps. 41 Palmarosa oil.Bleaching. 26 Open-piling soap. 127 Orange oil. 10 Palmitin. 103. Analysis of. 31 Oleodidaturin. 8 Oleodipalmitin. 41 ---.---. 8 Palm-nut oil. 71 Optical rotation. 103 Palmitic acid.Palm-nut. 8 Palmitodistearin. 125. 103 Patent textile soaps. 8 Olive-kernel oil. 103 Orchidée. 94 Pearl-ash. 27 Olive oil. 77.---. 78 . 8 Oleopaimitostearin. 8 Oleodistearin. 26 Pasting or saponification. 126 Peppermint oil. 100 P. 49 Patchouli oil.

126 ---. 104 Petit-grain oil. Rancidity. 89.Caustic. 10 Polishing soaps. 77. Artificial and synthetic. 39. 36 Peru-balsam oil. Soap. 132 Powders. 78 . 125. 94 Psyllostearylic acid.Soap. 95-110 Perfuming soaps. 129 Physetoleic acid. 104 Phenols. 54 Pisangcerylic acid. 11 Phytosterol in unsaponifiable matter. 126.Perfumes. 24 Rapic acid. 11 Refining cotton-seed oil. 107-110 ---. 35 Potash. 94 Persimmon seed oil. 120 Pickling mottled soap. 10 R. 94 Pongam oil.Determination of. 42 Refractive index of oils and fats. Determination of. 122 Remelted soaps. Carbonate. 126 ---. 18. 123 Potassium chloride.

Resinate of soda, 43, 44 Ricinoleic acid, 13 Ricinolein, 8 Rose oil, 105 ---- ---- (artificial), 110 Rosemary oil, 105 Rosin, 37, 38, 43, 44, 55 ---- Bleaching, 43 ---- Determination of, 133, 134 ---- treatment, 43, 44 S. Safflower oil, 33, 34 Safrol, 110 Salt, 39, 126 ---- Determination of, 124, 125, 126, 132 Sandalwood oil, 105, 106 Santalol, 110 Saponification, 13-22, 49 ---- accelerated by heat and electricity, 14, 15 ---- accelerated by use of chemical reagents, 19, 23 ---- accelerated with Twitchell's reagent, 20 ---- Acid, 19, 21 ---- Aqueous, 14 ---- by ferment process, 20 ---- equivalent, 118 ---- Glycerine, 116

---- Lime, 22 ---- under pressure, 47 ---- value, 118, 128 Saponifying mineral oil, 58, 59 Sassafras oil, 106 Saturated acids, 11 Scouring soaps, 92, 93 Sesame oil, 28, 29 Settled soap, Treatment of, 60-76 Shaving soaps, 91 Shea butter, 31 Silicate of soda in soap, 65 Silicates of soda and potash, 127, 138 Silk scouring soaps, 93 ---- dyer's soap, 93, 94 Slabbing soap, 68 Soap, Albumen in, 90 [Pg 158]---- Analysis of, 130-35 ---- Bar, 54, 55 ---- Barring, 68 ---- -base, Milling, 54, 78 ---- Biniodide, 87 ---- Birch-tar, 88 ---- Borax, 88 ---- Boric acid in, 88 ---- ---- ---- ---- Determination, 135

---- Carbolic, 88 ---- Classification of, 45 ---- Cleansing, 60, 61 ---- Coal-tar, 88 ---- Cold process, 46, 47 ---- Compressing, 83, 85 ---- Cooling, 74-76 ---- Crutching, 63 ---- Curd, 52 ---- Curd mottled, 53 ---- Definition of, 1, 2 ---- Detergent action of, 4, 5 ---- Determination of carbolic acid in, 134 ---- ---- of fatty acids in, 131 ---- ---- of free alkali in, 132 ---- ---- of free fat in, 133 ---- ---- of glycerine in, 134, 135 ---- ---- of total alkali in, 131 ---- ---- of water in, 133 ---- Drying, 71, 78-80 ---- Electrical production of, 59 ---- Ether, 90 ---- Examination of fatty acids 133, 134 ---- Filling, 65 ---- Fluorides in, 90 ---- formaldehyde, 88

powders.Stamping.Naphthol. 41 ---. 71 ---. 66 ---. 80.Milling.perfumes.Lysol. 49 ---.Mottled. 54 ---. 89 ---. 94 ---. 85.moulds. 95-110 ---. 86 . 86 ---.Properties of. 66. 72.framing. 72.Settling of. 94 ---.Open and close piling. 2 ---.from fatty acids. 80.Marine.---.Neutralising. 89 ---. 52.Slabbing. 89 ---.Salicylic acid. 88 ---.Hydrolysis of.Soft. 3 ---. 68 ---. 71. colouring and perfuming.Glycerine. 45. 89 ---. 53 ---. 81 ---. 55 ---. 89 ---. 48. 66 ---.frame.Pickling mottled. 49 ---. 82 ---. 46 ---. 85.Monopole.Iodine.Ichthyol.Hydrated.

65 ---." 51 ---.Disinfectant. 53 ---. 58 ---.Transparent. 58 ---.Transparent.---."Pasting" or saponification. 49 ---.---. 91 ---. 47 ---. 47 Soaps.Sulphur. Calico-printer's.Cold process. 93 ---.Thymol.---. Mottled. 90 ---. 46 ---."Graining-out" or separation. 45-59 ---. 49 ---. 60-76 ---.under pressure. 46. 55 Soap-making.Milled toilet. 90 ---. 50 ---.Combination of fatty acids with alkali. 86-90 ---. 48 ---. 89 ---."Fitting. 57. 66 ---.Medicated. 64.Curd. 78 .---.Floating.Hydrated.---.---." 51 ---. 52 ---.---."Boiling-on-strength. 54. 90.---.---. 45.---.Liquoring of.---.Soft. 53 ---.---.Treatment of settled.---.Terebene.---.Blue and grey mottled.Curd.Yellow household. 57.

18 Stearic acid. 135 Steapsin. 39. 85. 125 ---. 65 ---. 44 Soft soap-making. 124.Remelted. 125 ---.Silicating.Toilet. 48 Solidifying-point.Scouring. Determination of.Carbonate. 77. 8. 78 ---. 91 ---. 94 ---.---.Shaving.Caustic. 77. 71.Caustic. 94 ---. 43. 39. 72.Resinate.Polishing. 117. 39. 125 ---. Detection of. Cotton-seed. 39. 77. 10 Stearin.Silk dyer's. 92 Soap-stock. 130 Specific gravity. 9 Stearine. 127 Stamping soap.Woollen dyer's. 40 Soda ash. 121. 92 ---. 93. 123 ---. 86 Starch. 28 . 124. 78 ---.Textile.---.Miscellaneous. 91-94 ---. 78 ---. 94 ---.Perfumer's.

24 ---. 110 ---. 12 Telfairic acid. 125 Sulphur soap. 29 Superfatting material. 35 Tangkallah fat. 149. 83 [Pg 159]Synthetic perfumes. 12 Terebene. 147 ---.of comparative densities.of caustic soda solutions. Determination of. 91-94 ---. 37 Tariric acid. 89 Sunflower oil.of thermometric equivalents.soap. 8 Sulphides and sulphites. 150 ---. Table of caustic potash solutions.Chinese vegetable. 90 Terpineol. 31 ---.Borneo. 94 . 151 ---. 65 Tallow.---. 148 Tablet soap.Stearodipalmitin. 107-110 T.Patent. 32 ---. 55 Talc. 110 Textile soaps.Mafura.

78 ---. 122.lyes. 8 Trilaurin. 112 ---. 9 Tripalmitin. 9 Twitchell's process. 86 Transparent soaps. 107 Triglycerides.Compressing. 78 ---.Milled. 120 . 119.---. 9 Triolein.---.---.Theobromic acid. Constitution of. 22 U.Milling. 58 Treatment of animal fats.Stamping.bone fat.Vegetable oils.---. 85 ---. 57.settled soap. 43 ---. 43 ---.---. 90 Tiglic acid. 10 Thyme oil.---. 60-76 ---. 7.---. 43 ---. 11 Titre test. 80. 123 Toilet soaps. Unsaponifiable matter. 77.rosin.---. 9 Tristearin. 43 Trèfle. 83. 106 Thymol soap.---. 7. 85. 81 ---. 111.

36 Wild mango soap. 43 ---. Determination of. 110 Vegetable fats. 30 Water. Determination of. 106 Violet soap. 132 W. Ylang-ylang oil. 119 Unsaturated acids. Treatment of. 106 Vetivert oil. 36 Wintergreen oil. Waste fats.Determination of. 133 Wheat oil. 56 V. Vanillin.---.---. Chinese. 39 ---. . 107 Wool scouring soaps. 92 Y. 120 ---. 54 Volhard's method for chloride determination.---. 11 Utilisation of nigres. 107 Z.tallow. 31 Verbena oil.---. 92 Woollen dyer's soap.

S. Hyacinth. Heliotrope. Cinnamon. Sweet. Terpineol. Almonds. Bay Leaves.Zinc oxide. Neroli. &c. Camomile. Cassia. LONDON. Frangipanni. 22 ---. Crategine.soap. Otto of Rose. Rose Pink. Cologne. Palmarosa. Fennel. LemonGrass. Sassafras. Sage. Eucalyptus Globulus. Kuromoji. Spanish & Turkish. Cananga. Vanillin. Musk. . Walnut Leaf. Lily of Valley. Bourbon. Toilet Soap Perfumes FINEST QUALITY Almond. Caraway. &c. Parisian. Brown Windsor. Lilac. HOPE ST. Cuir de Russiè. Oriental. Indian Brown. Nerolin. Speciality:—RELIABLE CHLORPHYL. Orange Sweet & Bitter. Petit-Grain. &c. Thyme. 87 THE ABERDEEN UNIVERSITY PRESS LIMITED [Pg 161] Stevenson & Howell's SPECIALITIES FOR Soapmakers & Wholesale Perfumers. Heliotropine. Cedar Wood. Manchester Yellow. Artificial Perfumes. Rosemary. Spearmint. Wintergreen Ylang-Ylang. Cascarilla. &c. Patchouli. Essential Oils OF GUARANTEED PURITY. Yara-Yara. Pimento. French.. Lemon. Florida. Geranium — Algerian. Dark Blue. E. Bergamot. Cloves. Glasgow Office 128. Hydrolysis by. STANDARD WORKS Southwark St. East Indian. Citronella. Lavender. Carbolic Pink & Red. &c. Bay Rum. Coumarin. Myrbane. Lilac. Coriander. Limes. Sandal Wood. Wood Violet. Aubepine. Soap Colours.

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-gr.. 1908. Artificial Lilac. 6d. and Rotn. b.p. Extraction. (II. (I. Limonene. opt.. Sulphur Compounds. Artificial Rose Oil. Fenchene. Tables of sp.. GREENWOOD & SON. etc.) The Geraniol and Citronellol Group—Coriandrol. Specification of Patents for Preparation of Ionone. etc. Optical Properties. Quantitative Estimations of Constituents. Ketones. F.. Juniper Wood Oil.-gr. Absorption Processes.—Thuja Oil. Russian. Caryophellene. Aubepine or Hawthorn. (III. Table of Pine Oils (after Schimmel).) The Camphor Series—Borneol.) Wood Oils. Terpeneless Oil of Orange.) 1. (I. Specification of Patent of Musk Substitute. Vanillin. Table of Specific Gravities. Terpeneless Oil of Lemon. Oils of the Gymnosperms. Home. Niobe Oil. Geraniol. Isoborneol. Artificial Cognac Oil. (II. (IV... Aldehydes. The Preparation of Essential Oils. Phenols and their Derivatives. Oils of Turpentine. Fenchyl Alcohol. b. Patchoulene. sp.—III. . etc. Fenchone. 13s. Thujyl Alcohol.-gr. PUBLISHED BY SCOTT. (Lond. Artificial Neroli.—V. Table of Percentages. French Oil of Turpentine. Expression. Melting and Solidifying Points.C. The Chemistry of Artificial Perfumes. Acids. Terpineol. Chapters I.) Monocotyledons.. Heliotropin.—Appendix. Linalol. etc. Table. the Determination of Free Alcohols. American Turpentine. Abroad). Sylvestrene. net (Post Free. Phellandrene. Citrenellol. Ledene. Terpenes—Pinene. Sesquiterpenes—Cadinene. B. Cypress Leaf Oil. Price 12s. Carvestrene. and Swedish ditto. 552 Pages. Bergamiol.—Juniper Berry Oil.-gr. Clovene. (II. of same. (III.) Benzene Compounds—Cymene. Artificial Jasmin Oil. Dipentene. of Commercial Samples of Oils. Coumarin. Compounds occurring in Essential Oils. Aldehydes..Sc.I. PARRY. Fir Cone Oils. Oil of Savin. F.THE CHEMISTRY OF Essential Oils AND Artificial Perfumes. Sprengel Tube Method. Second Edition. 6d. Revised and Enlarged. The General Properties of Essential Oils. Physical Properties. Cedar Leaf Oil. Artificial Hyacinth. and Sesquiterpene from Oils of Cannabis Indica. 13s. Distillation.) Fruit Oils. sp. Phenols with Nine Carbon Atoms. etc. Index. Cineol.. Table of sp. Camphene. Ionone. Table.—II. etc. Demy 8vo. Rot. Optical Methods.p. Nerolol. BY ERNEST J. Oils of the Angiosperms—(I.—VII. Ditto of Caraway. Humulene. Terpinene and Thujene.).) Leaf Oils. Phenols with Ten Carbon Atoms. Specific Gravity.C. Artificial Musk.) Dicotyledons: (a) Monochlamydeæ—(b) Gamopetalæ— (c) Polypetalæ—VI.—Cedar Oils. German.—IV. for Artificial Violet Oil. of Lavender. Terpinolene. Artificial Lemon Oil. Rhodinol.) Aliphatic Compounds—Alcohols. Table on Constants of the more Important Essential Oils. Acids. The Analysis of Essential Oils. Terpeneless Oils. Cedrene. etc. and Rotn. of several Terpeneless Oils.S. CONTENTS. Table of Activities of same. Thujone. Boiling Point and Distillation. Ref. 2. Refractive Indices and Rotation. Pine Needle Oil. Systematic Study of the Essential Oils. Tabulated Angiosperms. Alcohols. Camphor. (V.—Index.

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