It is possible that by close attention, a rounded or elongated body, somewhat like an oil-globule, may be seen within the cell, though it is generally more obvious when the latter has been killed and stained with a weak solution of iodine. This is the nucleus, and within it is a still smaller speck called the nucleolus, which bears an important, and as yet little understood, part in the life-history of the cell. After a period, it undergoes certain somewhat complicated changes, and divides into two, the nucleus elongates, and also divides, each half carrying with it a portion of the living protoplasmic jelly, and thus forming two complete and independent cells. This is the life-history, not only of the lymph-cell, but with more or less modification, of every living cell or tissue.

These cells, like all living things, feed on the nutriment which surrounds them, and even enclose small particles of solid food, which are gradually dissolved and disappear. In this way the white blood-corpuscles are said to feed upon and destroy the still smaller organisms which gain access to the blood, and which might otherwise cause disease. The matter which cells consume is not, of course, destroyed, but simply converted into other forms, some of which are useless, or even poisonous to the cells, and which, like the secretions of higher animals, are discharged into the surrounding fluids; while others are retained, and contribute to the growth of the cell. Thus most vegetable cells secrete cellulose, or plant-tissue, which forms a wall enclosing the protoplasm, and so justifies the name of cell. If to warm water and a little sugar we add enough yeast to render it slightly milky, and examine it like the saliva, we shall have before us typical vegetable cells of the simplest form (Fig. 2). There is the same granular protoplasm, and there is the nucleus, though it cannot be seen without special preparation, the rounded spaces which look like one, being simply filled with transparent fluid, and called vacuoles. There is, however, no motion, as in the case of amœba, for the cells are enclosed in a tough skin of cellulose, which will be evident if they are crushed by putting some folds of blotting paper on the cover-glass, and pressing it with the handle of a needle or a rounded glass rod, when the protoplasm will be forced out and the skin remain like a burst bladder. This will be more obvious if the cells are previously stained with iodine or magenta, which will stain the protoplasm, but not the membrane. It is easy to observe the multiplication of the yeast-cells, which is somewhat different to that of the corpuscles. Instead of enlarging as a whole, and dividing into two equal cells, a small bud appears on the side of the parent-cell, and enlarges till it becomes itself a parent-cell with buds of its own. These do not break away at once, and hence chains and groups of attached cells are formed which are easily noticed in growing yeast if a microscope be employed. The principal nutriment of yeast is grape-sugar or glucose; and much more of this is consumed than is needed to produce the cellulose wall and the substance of new cells; just as in the animal, sugar, starch and fat are consumed to give heat and energy. In the yeast, this extra sugar is split up into carbon dioxide, which escapes as gas, and to which yeast owes its power of raising bread; and into alcohol, which in too large proportion is poisonous to the yeast itself.

In examining the saliva for lymph-cells, it is probable that some much larger objects may have been noticed of irregular polygonal outline and with a well-marked nucleus. These are cells from the lining epithelium of the mouth, and only differ from those of the epidermis of skin in their form and size (Fig. 3). Note the markings caused by the pressure of overlapping cells. In these cells the wall is formed of keratin or horny tissue, which takes the place of the cellulose of the yeast.

Other simple forms of cell are those of Saccharomyces mycoderma or torula which forms a skin on the surface of old liquors, and which much resembles a small yeast; and of the various ferments which are found in liquors, bates and drenches, which will be more fully described in the chapter following.

Many of these, such as the acetic and lactic ferments, which, like all other bacteria, multiply by division, do not separate, but remain connected in chains or chaplets, like a string of beads. From these, the step is not a long one to the hyphæ or stems of the higher moulds, which are too frequently found on leather which has been slowly dried, and which consist simply of tubular cells which elongate and divide by the formation of septa or cross-partitions, and thus build up a complicated plant-structure (Fig. 4). As we proceed higher in the scale of plant and animal life, the forms and products of the cells become more varied, and instead of one single cell, fulfilling all the functions of the plant or animal, each class of cell has its own peculiar duties and properties, while all work together for the maintenance of the complex structure of which they form a part.

CHAPTER IV.
PUTREFACTION AND FERMENTATION.

The chemical changes produced by the unicellular plants, such as yeasts and bacteria, to which allusion has been made in the last chapter, are known as fermentation and putrefaction, and are of such importance to the tanner, both for good and evil, that the subject must be treated in some detail. No scientific distinction exists between fermentation and putrefaction, though it is customary to restrict the latter term to those decompositions of nitrogenous animal matter which yield products of disagreeable smell and taste.

The organisms which are the cause of both fermentation and putrefaction are known by the general term of “ferments.” This term has also been extended in recent years so as to include the so-called “unorganised ferments” (enzymes, zymases) which are active products secreted by the “organised ferments” or living organisms.

These latter are again divided into three classes:—

The members of one class are distinguished from those of another by their form, and, more especially, by the substances they produce during their life-history. All three classes are now considered to be fungi.

All ferments possess the following three properties:—

The general character of fermentation will be best understood by a closer study of the yeast cell, which has already been described (p. 12), and its life-history briefly sketched. It has been shown that it is a growing plant of a very simple type, belonging to the fungi. These are devoid of the green colouring matter which enables the higher plants to utilise the energy of sunlight to assimilate the carbonic acid of the atmosphere, exhaling its oxygen, and employing its carbon for the building up of tissue; and they must therefore, like animals, have their nutriment ready formed, and capable of supplying energy by its oxidation. For yeast, as has been stated, the appropriate nourishment is glucose, or “grape-sugar.” This is broken down, in the main, into the simpler compounds, alcohol and carbonic acid, while a small portion is utilised for the building up of the cell and the formation of secondary products. The main reaction is represented by the following equation:

Yeast cannot directly ferment ordinary cane-sugar (C₁₂H₂₂O₁₁), but secretes a substance called invertase, which so acts on the sugar as to break it up, with absorption of one molecule of water, into two molecules of fermentable glucose (dextrose and levulose) which serve as nourishment for the yeast.[4] This invertase is the type of the series of bodies which are known as “unorganised ferments,” enzymes, or zymases, differing from the organised ferments in being simply chemical products without life or power of reproduction, but capable of breaking up an unlimited quantity of the bodies on which they act, without themselves suffering change. The way in which this is done is not clearly understood, but some parallel may be found to it in the action of sulphuric acid on alcohol, of which it will convert an unlimited quantity into ether, without itself suffering any permanent change. The action of enzymes is limited to breaking down complex bodies into simpler forms, often with absorption of water, as in the case of sugar, while some of the products of living ferments are often complex, a part of their nutriment being broken down into simple products such as carbonic acid, marsh gas and ammonia, to supply the necessary energy to elaborate the remainder.

Very many different unorganised ferments are known to exist, as they are not only produced by yeasts and bacteria, but are formed by the cells of higher plants and animals; thus the digestive principles, pepsin, trypsin, ptyalin, are of this character—ptyalin, like diastase, converting starch into sugar; and such bodies fulfil many functions both in animal and vegetable economy. In fermentation, as in disease, it is often difficult to distinguish what is due to the direct action of bacteria, and what to the unorganised ferments which they produce, and the question is further complicated by the fact that in most natural fermentations more than one ferment-organism is present. Sometimes the action of the unorganised ferments may be distinguished by the fact that the addition of chloroform has little effect on their activity while it paralyses that of the living organism. By exposure to high temperature both are destroyed, the bacteria, yeasts and moulds being killed and the unorganised ferments coagulated like white of egg, and so rendered inoperative. Many antiseptics also destroy the activity of both organisms and enzymes; but others, like chloroform, have no action on the latter. In some cases, as in that of invertase, the actual zymase can be precipitated by alcohol from its aqueous solution, filtered off, and restored to activity by transference into water. Since both classes of ferments are destroyed by high temperatures, all fermentation-processes are completely and permanently arrested by exposure to sufficient heat, and subsequent preservation in vessels so closed that no new ferment-germs can gain access. A familiar instance is that of tinned meats. All fully developed bacteria are destroyed by a very short exposure to a boiling temperature, and most by 60° to 70° C., but many species produce spores which are extremely difficult to destroy. The thermophilic bacteria discovered by Globig and further investigated by Rabinowitsch,[5] thrive at a temperature of 60° C. About eight species are known, and they take part in the heating of hay and similar fermentations where high temperatures are involved, and are therefore presumably present in spent tan.

For absolute sterilisation it is therefore necessary either to boil under pressure so as to raise the temperature to, say 110° C., or to heat repeatedly for a short time to temperatures of 80°-100° C. at successive intervals of 24 hours, in order to allow the spores to develop. This process is frequently performed for bacteriological observation in flasks or test-tubes merely stopped with a plug of sterilised cotton-wool, which has been found to efficiently filter the germs from the air which enters through it (see L.I.L.B., p. 270).

The ferment-organisms cannot thrive and multiply unless they have proper nourishment and conditions of growth, the amount of moisture and the temperature being two of the most important of the latter. Use is made of this in the preservation of many articles of food, etc., since by ensuring that at least one of the conditions necessary for growth shall be absent, these substances are prevented from decomposing. For instance, hides are preserved by drying them; the absence of sufficient moisture hindering the growth of any organisms in them so long as they are dry, but as soon as they become somewhat damp, putrefaction commences at once.

The waste products of organisms are often poisonous to themselves, and for this reason fermentations frequently come to an end before the whole of the substance is fermented. Thus neither beer nor vinegar can be obtained of more than a certain strength by direct fermentation, the alcohol or acetic acid checking the growth of their respective ferments. A solution of glucose “set” with the lactic ferment of sour milk will only produce lactic acid to the extent of about half a per cent.; but if chalk be added, the lactic acid will be neutralised as produced, and the fermentation will go on till the whole of the glucose is converted into insoluble calcium lactate.[6] When this is accomplished the lactic ferment dies from want of nutriment, and its place is taken by another organism, of which some germs are sure to be present, which ferments the calcium lactate into calcium butyrate. If the nourishment fails, or the conditions become less favourable for one ferment than for some other which exists even in small quantity in a liquid, the former is quickly overgrown and killed, and the latter takes its place. Thus the ordinary ferment of the bran drench will die out rapidly unless constantly transferred to fresh bran infusions.

Many of the products of bacteria (like those of some of the higher plants) are intensely poisonous both to animals and man. Many of the severe symptoms of disease are caused by these poisons produced in the body. Thus the tetanus-bacteria produce a poison similar in its effects to strychnine, and quite as virulent. Not only are such poisons produced by disease-bacteria in the body, but frequently also in the earlier stages of putrefactive fermentation. The latter are known as ptomaines, and when present in cheese and preserved foods are liable to cause poisoning. Such putrefactions are often unaccompanied by any disagreeable odour or flavour.

The fermentations which are most important in the tannery are, firstly, the ordinary putrefaction which attacks hides as well as other animal matter, and which is usually a complicated process carried on by many sorts of bacteria and other micro-organisms. This may be regarded as generally injurious to the tanner; but it is utilised in the “sweating” process for depilation and in the “staling” of sheepskins, in both of which advantage is taken of the fact that the soft mucous layer of the epidermis, which contains the hair-roots, putrefies more rapidly than the fibrous structure of the hide itself. In soaking also, use is made of the power of putrefactive ferments to dissolve the cementing substance of the hide, though in this case with doubtful advantage to the tanner. In the liming process putrefaction makes itself felt when the limes are allowed to become stale and charged with animal matter, softening the hide and finally rendering the leather loose, empty and inclined to “pipe.” Here the effect is in many cases useful if not carried too far.

In bating and puering, the action is almost entirely due to the enzymes and other products of bacterial activity, the original chemical constituents of the dung being apparently of minor importance. Naturally the liquid is adapted to the growth of many other organisms beside those acting most advantageously on the hide, and injury in the bates from wrong forms of putrefaction is very common, if indeed it is not always present in greater or less degree.

In drenching, the effect is, at first, entirely due to the weak acids produced by bacterial fermentation of the bran, but becomes complicated in its later stages by putrefactive and other fermentations which may be desirable or otherwise.

In the tanning liquors, fermentation is not so marked, but is of great importance owing to the production of acids by bacterial action from the sugars present in the material. The acids themselves are apt to be fermented and destroyed, principally by the oxidising action of Saccharomyces mycoderma and the higher moulds (see p. 14), which also act destructively on the tannins.

The effect of these acids on the hides is to swell them and to neutralise any lime they may contain. They also give to the liquors a characteristic sour taste, as a consequence of which, liquors containing acetic and lactic acids are usually known in the tannery as “sour liquors.”

It is doubtful whether the action of fungi is completely stayed even by the drying process. The heating of leather in the sheds is due to bacteria and the higher moulds, and Eitner considers their growth one of the causes of the “spueing” or “gumming” of curried leathers.

From what has been said, it is obvious that, with regard to fermentations, a double problem is presented to the leather manufacturer, since he desires to utilise those which make for his advantage, while controlling or destroying those which are injurious. The first step to a solution of these problems is a more complete knowledge of the organisms which serve or injure us, that we may, as it were, discriminate friends and enemies. We may then approach the question in two ways. Taking the drenching process as an example, we may on the one hand introduce a “pure cultivation” of the right ferment into a sterilised bran infusion, and so induce only the one fermentation which we require; or, on the other hand, as different ferments are affected in varying degrees by antiseptics, we may perhaps choose such as permit the growth of the organism we want, while killing or discouraging the rest. We may also arrange the nutriment, temperature, degree of acidity and other conditions, so as to favour one organism rather than another. All three methods have been applied in brewing with good results.

CHAPTER V.
ANTISEPTICS AND DISINFECTANTS.

“Antiseptics” are often defined as substances which check putrefaction without necessarily destroying bacteria and their spores, while “disinfectants” are poisonous to ferment-organisms, and actually destroy them; great differences exist in the extent of their sterilising power, and the whole distinction is one rather of degree than of kind, and has little practical value. Thus common salt is incapable of killing most bacteria, even in concentrated solution, though it holds putrefaction in check both by withdrawing water from the hide and by directly preventing the multiplication of bacteria. If the salt be washed out of the hide, putrefaction is at once resumed by the organisms present. Hides, on the other hand, which have once been sterilised by powerful disinfectants, such as phenol (“carbolic acid”) or mercuric chloride, do not again putrefy till the organisms which are killed are replaced by fresh ones from outside. The action of sodium sulphate, and many other salts, is similar to common salt in this respect, while a large proportion of the aromatic compounds are permanently disinfectant, though their efficiency varies with the species of bacteria involved.

Biernacki and others have shown that some disinfectants when extremely diluted actually stimulate alcoholic fermentation, and probably the growth of other ferments, e.g. mercuric chloride 1 in 300,000, salicylic acid 1 in 6000, and boric acid 1 in 8000, and in many cases organisms become habituated to antiseptics in doses which would at first have proved fatal.

The number of antiseptics available is now so great that it is impossible to give a detailed account of all, but the following are among those which are best known and have been practically employed.

Lime possesses some antiseptic properties, and is largely used in the preservation of fleshings before they are sent off to the glue factory. They are most conveniently stored in a large vat filled with a strong milk of lime. Dilute solutions of caustic alkalies have an effect similar to that of lime.

Common salt, sodium chloride, NaCl, acts to a certain extent by its solubility and a dehydrating effect on animal tissues common to chlorides, which removes water from hides and other materials which it is used to preserve. Probably the latter characteristic has a good deal to do with its effect in checking the development of bacteria, since many species thrive quite well in weak salt solutions, and some even in brine, and the dehydrating effect of the salt enables it to harden many animal tissues if used in sufficient quantity, the water they contain running away in the form of brine.

Ordinary rock salt frequently contains ferric chloride, and this, either originally present in the salt, or in some cases derived from the action of the latter upon the iron contained in the blood, is the cause of what is known as “salt-stains.” These show but little during the liming of the hides, unless sulphides are used, when stains appear of a greenish black, from the formation of sulphide of iron; when, however, the hides come into the tanning liquors, black or blue stains are produced by the action of the tannin, which are partially removed by the acids of the liquors during the tanning process, but generally show to some extent in the finished hide. There is another species of salt-stain, not apparently due to iron, but to the colouring matter produced by some fungoid or bacterial growth, which it is practically impossible to remove, and which is stated to be sometimes caused by the use of old salt with which hides have been previously salted. Iron stains are most readily recognised by the use of a solution of potassium ferrocyanide or thiocyanate slightly acidified by hydrochloric acid. If this be applied to the leather, the stains will be changed from a blackish to a blue, if the former, or a red colour if the latter salt has been used. A more absolutely conclusive proof is to lay a piece of filter paper soaked in dilute hydrochloric acid upon the stain, and then to test for iron upon the paper with ferrocyanide or thiocyanate. The freedom of the paper itself from iron must be ascertained before use. Iron-stains produced in the salted state are more difficult to discharge than those which are caused later in the tanning process, since iron salts have distinct tanning power, and attach themselves firmly to the untanned fibre. On the Continent, where common salt is heavily taxed, alum, carbolic acid, naphthalene and other materials are frequently added to it to “denaturise,” or render it incapable of being used as food, and these additions are often the cause of trouble to the tanner.

Sodium sulphate, Na₂SO₄, has little if any disinfectant power in dilute solution, but if used in the calcined form (anhydrous sodium sulphate) as proposed by Eitner[7] as a substitute for common salt in preserving hides, it withdraws water from the hide and crystallises with 10 Aq (about 56 per cent.). This does not run away like brine, but remains in the hide, which retains its weight, and remains plump and swells well in the limes and liquors, which chlorides have a great tendency to prevent; 10-15 per cent. on the weight of the hide is sufficient, while salt must be used in nearly double this quantity. Care must be taken that the sulphate used is free from bisulphate, NaHSO₄, which has a powerful swelling effect upon the hide-fibre, like sulphuric acid. The neutral sulphate does not redden methyl orange or litmus. Pickled skivers may be in part preserved by the sodium sulphate formed by the action of sulphuric acid upon the salt employed in the pickling bath (see p. 90).

The stronger mineral acids have considerable antiseptic power, and are of course especially fatal to such ferments as thrive best in alkaline solutions. The use of sulphuric acid in pickling skivers has already been alluded to, and a very dilute solution applied without salt to raw hides prevents putrefaction, though the principal object in using it is to plump the hides and produce a fictitious weight and substance which disappear on tanning. Such hides of course have a powerful acid reaction to litmus. Sulphuric acid in small quantities has been used with advantage in soaking E.I. kips. A very small excess of hydrochloric acid will sterilise putrid effluents, and no doubt nitric or sulphuric acid would have the same effect. The powerful effect of mineral acids on animal fibre, and their solvent action on cements and iron, preclude however, their general use as antiseptics.

More important is the use of sulphurous acid and sulphur dioxide, which, from their mild acidity and great antiseptic powers, are capable of a variety of useful applications. Considerable doubt has been raised as to the germicide power of sulphur dioxide, and it is certain that the dry gas is less effective on dry objects than when applied in solution, or to moist materials, as is almost invariably the case in the tannery. It may possibly be more efficient in its action on some moulds and putrefaction-ferments than on the pathogenic bacteria which have been most frequently used to test the power of disinfectants; but in practice it is found extremely useful in the brewery and in gelatine manufacture, and there is no reason that it should be less so in the tannery.

The gas is most conveniently produced by burning sulphur, which produces double its weight of sulphur dioxide. If used for “stoving” drying rooms and other places infested with moulds, care must be taken to avoid risk of fire. A shallow cast-iron pot set on bricks or sand is generally the most suitable vessel, and the sulphur may be ignited by a piece of red-hot iron or a rag which has been previously dipped in melted sulphur. It is corrosive to metalwork, and bleaches many colours, but does not produce any marked injurious effect on leather, though the sulphuric acid formed by oxidation may, if not removed, ultimately make it tender.

For many purposes a solution of the gas is required, and this is most easily made by burning the sulphur in a small metal or firebrick stove from which the fumes are sucked through a “scrubber,” which, on a small scale, is conveniently made of large glazed sanitary pipes, packed with coke or broken earthenware, over which water is allowed to trickle. The lowest pipe has an opening for a branch pipe, which is connected with the stove and rests on three bricks in a tub, which collects the acid solution and forms a water-seal to prevent the escape of gas. Above the inlet for the gases is fixed a wooden grating on which the coke rests. The scrubber may be 10-15 feet in height and connected at the top with a chimney or steam ejector to produce the draught. The arrangement is illustrated in Fig. 5. Another method is to burn the sulphur in a closed cylinder and to force the products through water with an air-compressor or steam-jet injector.

In place of using a scrubber, the fumes may be blown by a steam ejector direct into a tank. This is a very good arrangement for washing and bleaching hair, etc., but where large quantities of solution are required is inferior to the scrubber. Ejectors of hard lead or regulus metal should be used, and are less acted on by the dry gases than by the very dilute moist exhaust from the scrubber (see p. 335).

Bisulphites have also strong antiseptic properties. “Bisulphite of soda” (hydric sodic sulphite) solution may be made by supplying the scrubber with solution of soda-ash or washing soda; bisulphite of lime, by using milk of lime or packing the scrubber with chalk or limestone (free from much iron) in place of the coke. In either case a much stronger solution is obtained than with water alone.

Boakes’ “metabisulphite of soda”[8] is a very convenient source of sulphurous acid when the latter is wanted in small quantities. It is an anhydrosulphite, Na₂O.2(SO₂), and contains 67·4 per cent. of its weight of SO₂. One molecule of the salt (= 190) requires one molecule of H₂SO₄ (= 98) to set free the whole of the sulphurous acid. For many purposes the sulphate of soda formed may be neglected and the acidified solution used direct.

For analysis of sulphites and sulphurous acid solution, see L.I.L.B., pp. 16 and 37.

Boric acid, borax and other borates are not very powerful disinfectants. They have no injurious action upon the skin, but to be effective require to be employed in pretty strong solutions, say 1 per cent., and their comparatively high cost unfits them for general use as antiseptics in the tannery, though boric (boracic) acid is very useful as a drenching and deliming agent (see pp. 156, 229, and L.I.L.B., p. 37).

Mercuric chloride, corrosive sublimate, HgCl₂, is an extremely powerful antiseptic, preventing the growth of some species of bacteria in solutions so dilute as 1 in 300,000 (Koch). 1 in 14,000 is disinfectant (Miquel), but its power varies very much upon different organisms (Jörgensen states that 1 in 400 is required to kill Penicillium glaucum), and it is unsuited for most purposes in leather manufacture, both from its extremely poisonous character, and because it is rendered inactive by various substances present in the materials used.

Mercuric iodide dissolved in iodide of potassium solution was patented by Messrs. Collin and Benoist as an antiseptic in tanning, but it is ineffective for the same reasons as mercuric chloride; although under favourable circumstances it is even more powerful than the latter.

Copper sulphate, zinc chloride and sulphate, and many other metallic salts are powerful antiseptics, but have only a limited application in leather industries, and do not usually actually sterilise. Arsenic (arsenious acid), which has been used in curing hides, is an excellent insecticide, but not particularly effective as an antiseptic; and sulphide of arsenic (realgar) when used in limes (see p. 139) seems to have but little antiseptic effect. Arsenious acid is easily soluble in alkaline solutions.

Fluorides have been suggested as antiseptics in the tannery, but do not seem of much practical value.

The most important antiseptics at present are those derived from coal tar, and belonging to the aromatic series. Of these, the phenols (carbolic acid, cresol, etc.) are the most used.

Pure phenol, “pure crystallised carbolic acid,” is hydroxybenzene C₆H₅(OH), but the crude forms which are generally employed contain cresols and higher members of the series in which one or more of the atoms of hydrogen are substituted by CH₃ groups. These are oily bodies scarcely soluble in water, and even pure phenol is only soluble in cold water to the extent of some 7 per cent. Crude carbolic acid should not be employed in the tannery, since the insoluble oily particles stain the hide, and render it unsusceptible of tanning. Suitable carbolic acid should be of a pale yellow colour when fresh (though it will darken on exposure to air and light), and it should be wholly soluble in a sufficient quantity of water. Its specific gravity should be 1·050 to 1·065. For methods of chemical examination, see L.I.L.B., p. 40. A saturated solution of carbolic acid sterilises hide completely against most putrefactive organisms, but has a sort of tanning effect, adhering obstinately to the fibre so that it cannot be removed by washing; and hides which have been cured with it cannot be unhaired by sweating, though they may be limed in the usual manner, if somewhat more slowly. Care should be taken in mixing with water or liquor, as undissolved drops will produce the same effects as those of the crude acid. Hides are occasionally stained, as has just been described, by salt which has been denaturised with common sorts of carbolic acid. Eitner recommends the use of a solution of carbolic acid in an equal weight of crude glycerine, which readily dissolves in water, and seems to prevent any injurious effect on the hide.

An aqueous solution containing 1 per cent. of carbolic acid is sufficient for mere sterilising of hides, but if it be desired to preserve them for a long period, stronger solutions (up to 4 per cent.) may be employed.[9]

Quantities so small as 1 part per 1000 control the fermentation of liquors, and prevent the formation of moulds on the surface, economising tannin, and preserving vegetable acids already present, but at the same time lessening their production by fermentation, and therefore sometimes leading to difficulties in the early stages of tanning. Carbolic acid is not, strictly speaking, an acid, but rather of the nature of an alcohol, although it forms weak combinations with bases. It is a powerful narcotic poison, and if dropped on the skin in a concentrated form it produces severe burns; these are best treated with oil, while in cases of poisoning, oil and chalk must be administered internally, but if the quantity of carbolic acid taken has been large, are not likely to be effective. From its cheapness and efficiency, carbolic acid is likely to be increasingly used, although for special uses some of the newer antiseptics have great advantages.

Eudermin is a tar-oil manufactured by Speyer and Grund, of Frankfort-on-Main, which is intended as an antiseptic addition to stuffing greases to prevent mould and spueing. It is recommended for the purpose by Eitner[10] and can be used in proportions such as 10 per cent. of the grease. Creasotes and cresols can be dissolved in oils and stuffing greases, and act as antiseptics, though less powerfully than in aqueous solution. Rosin oils and turpentine have also antiseptic properties.

Creasote, “heavy coal oil,” or “dead oil,” is a complex mixture of hydrocarbons, phenols and cresols, obtained by distillation of coal tar, heavier than water, and almost insoluble in it. It is largely used as a preservative for timber. Carbolineum is an oil of this class, boiling at over 300° C., and intended for application to wood. One or more coats are applied to the dry wood at a temperature of 80° C. The workman’s hands must be protected by gloves, as the hot creasote raises painful blisters. Eitner[11] recommends its use for preserving pits, posts and other woodwork in tanneries. Wood-creasote is a somewhat similar product obtained from wood-tar.

The heavier cresols are so little soluble in water as to be valueless in their ordinary form as antiseptics, but several preparations are made under the names of “Creolin,” “Jeye’s fluid,” “Lysol,” “Izal,” “Soluble phenyl,” etc., in which they are treated with additions of soap or alkalies, which cause them to emulsify or dissolve in water, generally as milky liquids. These are powerful germicides and have the advantage over phenol of being non-poisonous. 0·1 to 0·5 per cent. solution of creolin will sterilise hides after bating so that no putrefaction takes place in the liquors. Mr. J. T. Wood specially recommends creolin for the general purposes of the tannery, disinfecting pits and tubs, and for checking the action of puers and drenches on goods which have gone a little too far, by throwing them into a 0·2 per cent. solution.

Salicylic acid, orthohydroxybenzoic acid, C₆H₄OH(COOH), is now artificially prepared from phenol. It is much less poisonous than the latter and has no smell, which makes it valuable for certain purposes, but is too dear for most technical applications. Many bacteria appear to become gradually habituated to its action, and the same is true of phenol to a less degree.

Salicylic acid is closely related to protocatechuic and gallic acids, and, like these, gives a blackish colour with iron salts. It is freely soluble in hot water, but very sparingly in cold. The addition of 1-2¹⁄₂ parts of sodium phosphate, sulphate, or potassium nitrate to each part of salicylic acid greatly increases its solubility. It seems much more powerful in preventing the development of bacteria than carbolic acid; a solution of 1 part of salicylic acid in 666 of water is said to be equal in this respect to 1 part of carbolic in 200.

Benzoic acid, C₆H₅COOH, though not much employed, except in medicine, is a still more powerful disinfectant, and has the advantage of being non-poisonous to human beings.

“Cresotinic acid,” which is derived from the cresols as salicylic acid is derived from phenol, is more soluble than salicylic acid. It is not very poisonous, and a powerful disinfectant. In a crude form it has been introduced by Hauff, of Feuerbach, for bating or removing lime from hides. This it does very well, though without the softening action of a true bate. It has a tendency to produce a pinkish stain, and in some degree a sort of tanning of the fibre. Its price, moreover, is rather high for extensive technical use. (See also p. 162.)

“Anticalcium” is a more recent preparation introduced as a bate by the same firm.[12] It is a solution of mixed sulphonic acids derived from cresols, and has considerable disinfectant powers. It removes lime very effectively, but from its acid character somewhat swells the skin. It is used very successfully as a drench for thin skins (p. 163).

“C.T.” (coal-tar) bate is a grey crystalline pasty mass, with a tarry smell, and is chemically very similar to anticalcium if not identical with it.

Naphthalene sulphonic acid has strong antiseptic properties. Its use in bating has been patented by Burns and Cross. (See p. 163.)

Naphthols, C₁₀H₇(OH).—These bodies, which have the same relation to naphthalene as the phenols to benzene, are powerful antiseptics; and naphthalene itself appears to have antiseptic power, and is occasionally used for denaturising salt. There are two naphthols, varying in the position of the OH group in the molecule, and denominated α and β, of which α naphthol is the more powerful antiseptic and the less poisonous, though β, being cheaper, is the common commercial article. It is said that quantities so small as 0·1-0·4 grams of α naphthol per liter are sufficient to prevent the development of microbes, while of β naphthol about ten times that quantity is required.

Naphthols are not very expensive, but their value is diminished by the fact that they are insoluble in water. They are soluble in alkaline solutions, but their compounds with bases are of much lower antiseptic value, and the same is true of their alcoholic solutions; when an alcoholic solution is added to water the naphthol is precipitated, but if an addition of soap or camphor be made to the alcoholic solution, the naphthol remains in a very finely divided condition, if not dissolved.

Adopting Eitner’s suggestion with regard to oxynaphthoic acid (see below), hides may no doubt be sterilised by treatment first with an alkaline naphthol solution, and then with a very dilute acid to set the naphthol free.

“Hydronaphthol,” β tetra-hydro-naphthol, C₁₀H₁₂O, is obtained by the reduction of β naphthol by sodium (Rideal). It seems to be an excellent disinfectant.

Oxynaphthoic acid, α hydroxynaphthoic acid, C₁₀H₆(OH)COOH, which bears the same relation to naphthol as salicylic acid does to phenol, is cheaper than salicylic acid, and said to be a more powerful antiseptic. Its salts have no antiseptic power. In its commercial form it is a reddish crystalline powder, inodorous, but with a burning taste, and its dust causes violent sneezing. It is scarcely soluble in water, and is said to undergo some change on keeping which lessens its germicide power; it is readily soluble in alcohol, and the solution produces a milky fluid on mixture with water. Such a solution containing 15 grams of the acid in 4 liters of water, will sterilise a hide. Eitner recommends[13] that it should be dissolved in dilute soda solution, and the hides, after soaking in it, passed through water slightly acidified with hydrochloric acid, as has been suggested in the case of naphthol; the method is also applicable to creosotinic acid, the hides being permanently sterilised so that they cannot be unhaired by sweating, though they will lime in the usual manner.