The Chemistry of Hat Manufacturing - Lectures Delivered Before the Hat Manufacturers' Association
by Watson Smith
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Transcriber's Note: Underscores around words indicates italics while an underscore and curly brackets in an equation indicates a subscript.


The subject-matter in this little book is the substance of a series of Lectures delivered before the Hat Manufacturers' Association in the years 1887 and 1888.

About this period, owing to the increasing difficulties of competition with the products of the German Hat Manufacturers, a deputation of Hat Manufacturers in and around Manchester consulted Sir Henry E. Roscoe, F.R.S., then the Professor of Chemistry in the Owens College, Manchester, and he advised the formation of an Association, and the appointment of a Lecturer, who was to make a practical investigation of the art of Hat Manufacturing, and then to deliver a series of lectures on the applications of science to this industry. Sir Henry Roscoe recommended the writer, then the Lecturer on Chemical Technology in the Owens College, as lecturer, and he was accordingly appointed.

The lectures were delivered with copious experimental illustrations through two sessions, and during the course a patent by one of the younger members became due, which proved to contain the solution of the chief difficulty of the British felt-hat manufacturer (see pages 66-68). This remarkable coincidence served to give especial stress to the wisdom of the counsel of Sir Henry Roscoe, whose response to the appeal of the members of the deputation of 1887 was at once to point them to scientific light and training as their only resource. In a letter recently received from Sir Henry (1906), he writes: "I agree with you that this is a good instance of the direct money value of scientific training, and in these days of 'protection' and similar subterfuges, it is not amiss to emphasise the fact."

It is thus gratifying to the writer to think that the lectures have had some influence on the remarkable progress which the British Hat Industry has made in the twenty years that have elapsed since their delivery.

These lectures were in part printed and published in the Hatters' Gazette, and in part in newspapers of Manchester and Stockport, and they have here been compiled and edited, and the necessary illustrations added, etc., by Mr. Albert Shonk, to whom I would express my best thanks.


LONDON, April 1906.


















_Vegetable Fibres._—Textile fibres may be broadly distinguished as vegetable and animal fibres. It is absolutely necessary, in order to obtain a useful knowledge of the peculiarities and properties of animal fibres generally, or even specially, that we should be, at least to some extent, familiar with those of the vegetable fibres. I shall therefore have, in the first place, something to tell you of certain principal vegetable fibres before we commence the more special study of the animal fibres most interesting to you as hat manufacturers, namely, wool, fur, and hair. What cotton is as a vegetable product I shall not in detail describe, but I will refer you to the interesting and complete work of Dr. Bowman, _On the Structure of the Cotton Fibre_. Suffice it to say that in certain plants and trees the seeds or fruit are surrounded, in the pods in which they develop, with a downy substance, and that the cotton shrub belongs to this class of plants. A fibre picked out from the mass of the downy substance referred to, and examined under the microscope, is found to be a spirally twisted band; or better, an irregular, more or less flattened and twisted tube (see Fig. 1). We know it is a tube, because on taking a thin, narrow slice across a fibre and examining the slice under the microscope, we can see the hole or perforation up the centre, forming the axis of the tube (see Fig. 2). Mr. H. de Mosenthal, in an extremely interesting and valuable paper (see _J.S.C.I._,[1] 1904, vol. xxiii. p. 292), has recently shown that the cuticle of the cotton fibre is extremely porous, having, in addition to pores, what appear to be minute stomata, the latter being frequently arranged in oblique rows, as if they led into oblique lateral channels. A cotton fibre varies from 2.5 to 6 centimetres in length, and in breadth from 0.017 to 0.05 millimetre. The characteristics mentioned make it very easy to distinguish cotton from other vegetable or animal fibres. For example, another vegetable fibre is flax, or linen, and this has a very different appearance under the microscope (_see_ Fig. 3). It has a bamboo-like, or jointed appearance; its tubes are not flattened, nor are they twisted. Flax belongs to a class called the bast fibres, a name given to certain fibres obtained from the inner bark of different plants. Jute also is a bast fibre. The finer qualities of it look like flax, but, as we shall see, it is not chemically identical with cotton, as linen or flax is. Another vegetable fibre, termed "cotton-silk," from its beautiful, lustrous, silky appearance, has excited some attention, because it grows freely in the German colony called the Camaroons, and also on the Gold Coast. This fibre, under the microscope, differs entirely in appearance from both cotton and flax fibres. Its fibres resemble straight and thin, smooth, transparent, almost glassy tubes, with large axial bores; in fact, if wetted in water you can see the water and air bubbles in the tubes under the microscope. A more detailed account of "cotton-silk" appears in a paper read by me before the Society of Chemical Industry in 1886 (see _J.S.C.I._, 1886, vol. v. p. 642). Now the substance of the cotton, linen or flax, as well as that of the cotton-silk fibres, is termed, chemically, cellulose. Raw cotton consists of cellulose with about 5 per cent. of impurities. This cellulose is a chemical compound of carbon, hydrogen, and oxygen, and, according to the relative proportions of these constituents, it has had the chemical formula C_{6}H_{10}O_{5} assigned to it. Each letter stands for an atom of each constituent named, and the numerals tell us the number of the constituent atoms in the whole compound atom of cellulose. This cellulose is closely allied in composition to starch, dextrin, and a form of sugar called glucose. It is possible to convert cotton rags into this form of sugar—glucose—by treating first with strong vitriol or sulphuric acid, and then boiling with dilute acid for a long time. Before we leave these vegetable or cellulose fibres, I will give you a means of testing them, so as to enable you to distinguish them broadly from the animal fibres, amongst which are silk, wool, fur, and hair. A good general test to distinguish a vegetable and an animal fibre is the following, which is known as Molisch's test: To a very small quantity, about 0.01 gram, of the well-washed cotton fibre, 1 c.c. of water is added, then two to three drops of a 15 to 20 per cent. solution of alpha-naphthol in alcohol, and finally an excess of concentrated sulphuric acid; on agitating, a deep violet colour is developed. By using thymol in place of the alpha-naphthol, a red or scarlet colour is produced. If the fibre were one of an animal nature, merely a yellow or greenish-yellow coloured solution would result. I told you, however, that jute is not chemically identical with cotton and linen. The substance of its fibre has been termed "bastose" by Cross and Bevan, who have investigated it. It is not identical with ordinary cellulose, for if we take a little of the jute, soak it in dilute acid, then in chloride of lime or hypochlorite of soda, and finally pass it through a bath of sulphite of soda, a beautiful crimson colour develops upon it, not developed in the case of cellulose (cotton, linen, etc.). It is certain that it is a kind of cellulose, but still not identical with true cellulose. All animal fibres, when burnt, emit a peculiar empyreumatic odour resembling that from burnt feathers, an odour which no vegetable fibre under like circumstances emits. Hence a good test is to burn a piece of the fibre in a lamp flame, and notice the odour. All vegetable fibres are easily tendered, or rendered rotten, by the action of even dilute mineral acids; with the additional action of steam, the effect is much more rapid, as also if the fibre is allowed to dry with the acid upon or in it. Animal fibres are not nearly so sensitive under these conditions. But whereas caustic alkalis have not much effect on vegetable fibres, if kept out of contact with the air, the animal fibres are very quickly attacked. Superheated steam alone has but little effect on cotton or vegetable fibres, but it would fuse or melt wool. Based on these differences, methods have been devised and patented for treating mixed woollen and cotton tissues—(1) with hydrochloric acid gas, or moistening with dilute hydrochloric acid and steaming, to remove all the cotton fibre; or (2) with a jet of superheated steam, under a pressure of 5 atmospheres (75 lb. per square inch), when the woollen fibre is simply melted out of the tissue, and sinks to the bottom of the vessel, a vegetable tissue remaining (Heddebault). If we write on paper with dilute sulphuric acid, and dry and then heat the place written upon, the cellulose is destroyed and charred, and we get black writing produced. The principle involved is the same as in the separation of cotton from mixed woollen and cotton goods by means of sulphuric acid or vitriol. The fabric containing cotton, or let us say cellulose particles, is treated with dilute vitriol, pressed or squeezed, and then roughly dried. That cellulose then becomes mere dust, and is simply beaten out of the intact woollen texture. The cellulose is, in a pure state, a white powder, of specific gravity 1.5, _i.e._ one and a half times as heavy as water, and is quite insoluble in such solvents as water, alcohol, ether; but it does dissolve in a solution of hydrated oxide of copper in ammonia. On adding acids to the cupric-ammonium solution, the cellulose is reprecipitated in the form of a gelatinous mass. Cotton and linen are scarcely dissolved at all by a solution of basic zinc chloride.

[Footnote 1: J.S.C.I. = Journal of the Society of Chemical Industry.]

Silk.—We now pass on to the animal fibres, and of these we must first consider silk. This is one of the most perfect substances for use in the textile arts. A silk fibre may be considered as a kind of rod of solidified flexible gum, secreted in and exuded from glands placed on the side of the body of the silk-worm. In Fig. 4 are shown the forms of the silk fibre, in which there are no central cavities or axial bores as in cotton and flax, and no signs of any cellular structure or external markings, but a comparatively smooth, glassy surface. There is, however, a longitudinal groove of more or less depth. The fibre is semi-transparent, the beautiful pearly lustre being due to the smoothness of the outer layer and its reflection of the light. In the silk fibre there are two distinct parts: first, the central portion, or, as we may regard it, the true fibre, chemically termed fibroin; and secondly, an envelope composed of a substance or substances, chemically termed sericin, and often "silk-glue" or "silk-gum." Both the latter and fibroin are composed of carbon, hydrogen, nitrogen, and oxygen. Here there is thus one element more than in the vegetable fibres previously referred to, namely, nitrogen; and this nitrogen is contained in all the animal fibres. The outer envelope of silk-glue or sericin can be dissolved off the inner fibroin fibre by means of hot water, or warm water with a little soap. Warm dilute (that is, weak) acids, such as sulphuric acid, etc., also dissolve this silk-glue, and can be used like soap solutions for ungumming silk. Dilute nitric acid only slightly attacks silk, and colours it yellow; it would not so colour vegetable fibres, and this forms a good test to distinguish silk from a vegetable fibre. Cold strong acetic acid, so-called glacial acetic acid, removes the yellowish colouring matter from raw silk without dissolving the sericin or silk-gum. By heating under pressure with acetic acid, however, silk is completely dissolved. Silk is also dissolved by strong sulphuric acid, forming a brown thick liquid. If we add water to this thick liquid, a clear solution is obtained, and then on adding tannic acid the fibroin is precipitated. Strong caustic potash or soda dissolves silk; more easily if warm. Dilute caustic alkalis, if sufficiently dilute, will dissolve off the sericin and leave the inner fibre of fibroin; but they are not so good for ungumming silk as soap solutions are, as the fibre after treatment with them is deficient in whiteness and brilliancy. Silk dissolves completely in hot basic zinc chloride solution, and also in an alkaline solution of copper and glycerin, which solutions do not dissolve vegetable fibres or wool. Chlorine and bleaching-powder solutions soon attack and destroy silk, and so another and milder agent, namely, sulphurous acid, is used to bleach this fibre. Silk is easily dyed by the aniline and coal-tar colours, and with beautiful effect, but it has little attraction for the mineral colours.

Wool.—Next to silk as an animal fibre we come to wool and different varieties of fur and hair covering certain classes of animals, such as sheep, goats, rabbits, and hares. Generally, and without going at all deeply into the subject, we may say that wool differs from fur and hair, of which we may regard it as a variety, by being usually more elastic, flexible, and curly, and because it possesses certain features of surface structure which confer upon it the property of being more easily matted together than fur and hair are. We must first shortly consider the manner of growth of hair without spending too much time on this part of the subject. The accompanying figure (see Fig. 5) shows a section of the skin with a hair or wool fibre rooted in it. Here we may see that the ground work, if we may so term it, is four-fold in structure. Proceeding downwards, we have—(first) the outer skin, scarf-skin or cuticle; (second) a second layer or skin called the rete mucosum, forming the epidermis; (third) papillary layer; (fourth) the corium layer, forming the dermis. The peculiar, globular, cellular masses below in the corium are called adipose cells, and these throw off perspiration or moisture, which is carried away to the surface by the glands shown (called sudoriparous glands), which, as is seen, pass independently off to the surface. Other glands terminate under the skin in the hair follicles, which follicles or hair sockets contain or enclose the hair roots. These glands terminating in the hair follicles secrete an oily substance, which bathes and lubricates as well as nourishes the hair. With respect to the origin of the hair or wool fibre, this is formed inside the follicle by the exuding therefrom of a plastic liquid or lymph; this latter gradually becomes granular, and is then formed into cells, which, as the growth proceeds, are elongated into fibres, which form the central portion of the hair. Just as with the trunk of a tree, we have an outer dense portion, the bark, an inner less dense and more cellular layer, and an inmost portion which is most cellular and porous; so with a hair, the central portion is loose and porous, the outer more and more dense. On glancing at the figure (Fig. 6) of the longitudinal section of a human hair, we see first the outer portion, like the bark of a tree, consisting of a dense sheath of flattened scales, then comes an inner lining of closely-packed fibrous cells, and frequently an inner well-marked central bundle of larger and rounder cells, forming a medullary axis. The transverse section (Fig. 7) shows this exceedingly well. The end of a hair is generally pointed, sometimes filamentous. The lower extremity is larger than the shaft, and terminates in a conical bulb, or mass of cells, which forms the root of the hair. In the next figure (Fig. 8) we are supposed to have separated these cells, and above, (a), we see some of the cells from the central pith or medulla, and fat globules; between, (b), some of the intermediate elongated or angular cells; and below, (c), two flattened, compressed, structureless, and horny scales from the outer portion of the hair. Now these latter flattened scales are of great importance. Their character and mode of connection with the stratum, or cortical substance, below, not only make all the difference between wool and hair, but also determine the extent and degree of that peculiar property of interlocking of the hairs known as felting. Let us now again look at a human hair. The light was reflected from this hair as it lay under the microscope, and now we see the reason of the saw-like edge in the longitudinal section, for just as the tiles lie on the roof of a house, or the scales on the back of a fish, so the whole surface of the hair is externally coated with a firmly adhering layer of flat overlying scales, with not very even upper edges, as you see. The upper or free edges of these scales are all directed towards the end of the hair, and away from the root. But when you look at a hair in its natural state you cannot see these scales, so flat do they lie on the hair-shaft. What you see are only irregular transverse lines across it. Now I come to a matter of great importance, as will later on appear in connection with means for promoting felting properties. If a hair such as described, with the scales lying flat on the shaft, be treated with certain substances or reagents which act upon and dissolve, or decompose or disintegrate its parts, then the free edges of these scales rise up, they "set their backs up," so to say. They, in fact, stand off like the scales of a fir-cone, and at length act like the fir-cone in ripening, at last becoming entirely loose. As regards wool and fur, these scales are of the utmost importance, for very marked differences exist even in the wool of a single sheep, or the fur of a single hare. It is the duty of the wool-sorter to distinguish and separate the various qualities in each fleece, and of the furrier to do the same in the case of each fur. In short, upon the nature and arrangement and conformation of the scales on the hair-shafts, especially as regards those free upper edges, depends the distinction of the value of many classes of wool and fur. These scales vary both as to nature and arrangement in the case of the hairs of different animals, so that by the aid of the microscope we have often a means of determining from what kind of animal the hair has been derived. It is on the nature of this outside scaly covering of the shaft, and in the manner of attachment of these scaly plates, that the true distinction between wool and hair rests. The principal epidermal characteristic of a true wool is the capacity of its fibres to felt or mat together. This arises from the greater looseness of the scaly covering of the hair, so that when opposing hairs come into contact, the scales interlock (see Fig. 9), and thus the fibres are held together. Just as with hair, the scales of which have their free edges pointing upwards away from the root, and towards the extremity of the hair, so with wool. When the wool is on the back of the sheep, the scales of the woolly hair all point in the same direction, so that while maintained in that attitude the individual hairs slide over one another, and do not tend to felt or mat; if they did, woe betide the animal. The fact of the peculiar serrated, scaly structure of hair and wool is easily proved by working a hair between the fingers. If, for instance, a human hair be placed between finger and thumb, and gently rubbed by the alternate motion of finger and thumb together, it will then invariably move in the direction of the root, quite independently of the will of the person performing the test. A glance at the form of the typical wool fibres shown (see Fig. 10), will show the considerable difference between a wool and a hair fibre. You will observe that the scales of the wool fibre are rather pointed than rounded at their free edges, and that at intervals we have a kind of composite and jagged-edged funnels, fitting into each other, and thus making up the covering of the cylindrical portion of the fibre. The sharpened, jagged edges enable these scales more easily to get under the opposing scales, and to penetrate inwards and downwards according to the pressure exerted. The free edges of the scales of wool are much longer and deeper than in the case of hair. In hair the overlapping scales are attached to the under layer up to the edges of those scales, and at this extremity can only be detached by the use of certain reagents. But this is not so with wool, for here the ends of the scales are, for nearly two-thirds of their length, free, and are, moreover, partially turned outwards. One of the fibres shown in Fig. 10 is that of the merino sheep, and is one of the most valuable and beautiful wools grown. There you have the type of a fibre best suited for textile purposes, and the more closely different hairs approach this, the more suitable and valuable they become for those purposes, and vice versa. With regard to the curly structure of wool, which increases the matting tendency, though the true cause of this curl is not known, there appears to be a close relationship between the tendency to curl, the fineness of the fibre, and the number of scales per linear inch upon the surface. With regard to hair and fur, I have already shown that serrated fibres are not specially peculiar to sheep, but are much more widely diffused. Most of the higher members of the mammalia family possess a hairy covering of some sort, and in by far the larger number is found a tendency to produce an undergrowth of fine woolly fibre, especially in the winter time. The differences of human hair and hairs generally, from the higher to the lower forms of mammalia, consist only in variations of size and arrangement as regards the cells composing the different parts of the fibre, as well as in a greater or less development of the scales on the covering or external hair surface. Thus, under the microscope, the wool and hairs of various animals, as also even hairs from different parts of the same animal, show a great variety of structure, development, and appearance.

We have already observed that hair, if needed for felting, is all the better—provided, of course, no injury is done to the fibre itself—for some treatment, by which the scales otherwise lying flatter on the hair-shafts than in the case of the hairs of wool, are made to stand up somewhat, extending outwards their free edges. This brings me to the consideration of a practice pursued by furriers for this purpose, and known as the secretage or "carrotting" process; it consists in a treatment with a solution of mercuric nitrate in nitric acid, in order to improve the felting qualities of the fur. This acid mixture is brushed on to the fur, which is cut from the skin by a suitable sharp cutting or shearing machine. A Manchester furrier, who gave me specimens of some fur untreated by the process, and also some of the same fur that had been treated, informed me that others of his line of business use more mercury than he does, i.e. leave less free nitric acid in their mixture; but he prefers his own method, and thinks it answers best for the promotion of felting. The treated fur he gave me was turned yellow with the nitric acid, in parts brown, and here and there the hairs were slightly matted with the acid. In my opinion the fur must suffer from such unequal treatment with such strong acid, and in the final process of finishing I should not be surprised if difficulty were found in getting a high degree of lustre and finish upon hairs thus roughened or partially disintegrated. Figs. 11 and 12 respectively illustrate fur fibres from different parts of the same hare before and after the treatment. In examining one of these fibres from the side of a hare, you see what the cause of this roughness is, and what is also the cause of the difficulty in giving a polish or finish. The free edges are partially disintegrated, etched as it were, besides being caused to stand out. A weaker acid ought to be used, or more mercury and less acid. As we shall afterwards see, another dangerous agent, if not carefully used, is bichrome (bichromate of potassium), which is also liable to roughen and injure the fibre, and thus interfere with the final production of a good finish.



With regard to the preparation of fur by acid mixtures for felting, mentioned in the last lecture, I will tell you what I think I should recommend. In all wool and fur there is a certain amount of grease, and this may vary in different parts of the material. Where there is most, however, the acid, nitric acid, or nitric acid solution of nitrate of mercury, will wet, and so act on the fur, least. But the action ought to be uniform, and I feel sure it cannot be until the grease is removed. I should therefore first wash the felts on the fur side with a weak alkaline solution, one of carbonate of soda, free from any caustic, to remove all grease, then with water to remove alkali; and my belief is that a weaker and less acid solution of nitric acid and nitrate of mercury, and a smaller quantity of it, would then do the work required, and do it more uniformly.

A question frequently asked is: "Why will dead wool not felt?" Answer: If the animal become weak and diseased, the wool suffers degradation; also, with improvement in health follows pari passu, improvement in the wool structure, which means increase both in number and vigour of the scales on the wool fibres, increase of the serrated ends of these, and of their regularity. In weakness and disease the number of scales in a given hair-shaft diminishes, and these become finer and less pronounced. The fibres themselves also become attenuated. Hence when disease becomes death, we have considerably degraded fibres. This is seen clearly in the subjoined figures (see Fig. 13), which are of wool fibres from animals that have died of disease. The fibres are attenuated and irregular, the scale markings and edges have almost disappeared in some places, and are generally scanty and meagre in development. It is no wonder that such "dead wool" will be badly adapted for felting. "Dead wool" is nearly as bad as "kempy" wool, in which malformation of fibre has occurred. In such "kemps," as Dr. Bowman has shown, scales have disappeared, and the fibre has become, in part or whole, a dense, non-cellular structure, resisting dye-penetration and felting (see Fig. 14).

One of the physical properties of wool is its hygroscopicity or power of absorbing moisture. As the very structure of wool and fur fibre would lead us to suppose, these substances are able to absorb a very considerable amount of water without appearing damp. If exposed freely to the air in warm and dry weather, wool retains from 8 to 10 per cent., and if in a damp place for some time, it may absorb as much as from 30 to 50 per cent. of water: Wool, fur, or hair that has been washed, absorbs the most moisture; indeed, the amount of water taken up varies inversely with the fatty or oily matter present. Hence the less fat the more moisture. In the washed wool, those fibres in which the cells are more loosely arranged have the greatest absorbing power for water. No doubt the moisture finds its way in between the cells of the wool fibre from which the oil or fat has been removed. But I need hardly remind you that if wool and fur are capable, according to the circumstances under which they are placed, of absorbing so much moisture as that indicated, it becomes (especially in times of pressure and competition) very important to inquire if it be not worth while to cease paying wool and fur prices for mere water. This question was answered long ago in the negative by our Continental neighbours, and in Germany, France, and Switzerland official conditioning establishments have been founded by the Governments of those countries for the purpose of testing lots of purchased wool and silk, etc., for moisture, in order that this moisture may be deducted from the invoices, and cash paid for real dry wool, etc. I would point out that if you, as hat manufacturers, desire to enter the lists with Germany, you must not let her have any advantage you have not, and it is an advantage to pay for what you know exactly the composition of, rather than for an article that may contain 7 per cent. or, for aught you know, 17 per cent. or 30 per cent. of water. There is, so far as I know, no testing for water in wools and furs in this country, and certainly no "conditioning establishments" (1887), and, I suppose, if a German or French wool merchant or furrier could be imagined as selling wool, etc., in part to a German or French firm, and in part to an English one, the latter would take the material without a murmur, though it might contain 10 per cent., or, peradventure, 30 per cent. of water, and no doubt the foreign, just as the English merchant or dealer, would get the best price he could, and regard the possible 10 per cent. or 30 per cent. of water present with certainly the more equanimity the more of that very cheap element there were present. But look at the other side. The German or French firm samples its lot as delivered, takes the sample to be tested, and that 10 or 30 per cent. of water is deducted, and only the dry wool is paid for. A few little mistakes of this kind, I need hardly say, will altogether form a kind of vade mecum for the foreign competitor.

We will now see what the effect of water is in the felting operation. Especially hot water assists that operation, and the effect is a curious one. When acid is added as well, the felting is still further increased, and shrinking also takes place. As already shown you, the free ends of the scales, themselves softened by the warm dilute acid, are extended and project more, and stand out from the shafts of the hairs. On the whole, were I a hat manufacturer, I should prefer to buy my fur untreated by that nitric acid and mercury process previously referred to, and promote its felting properties myself by the less severe and more rational course of proceeding, such, for example, as treatment with warm dilute acid. We have referred to two enemies standing in the way to the obtainment of a final lustre and finish on felted wool or fur, now let us expose a third. In the black dyeing of the hat-forms a boiling process is used. Let us hear what Dr. Bowman, in his work on the wool fibre, says with regard to boiling with water. "Wool which looked quite bright when well washed with tepid water, was decidedly duller when kept for some time in water at a temperature of 160 deg. F., and the same wool, when subjected to boiling water at 212 deg. F., became quite dull and lustreless. When tested for strength, the same fibres which carried on the average 500 grains without breaking before boiling, after boiling would not bear more than 480 grains." Hence this third enemy is a boiling process, especially a long-continued one if only with water itself. If we could use coal-tar colours and dye in only a warm weak acid bath, not boil, we could get better lustre and finish.

We will now turn our attention to the chemical composition of wool and fur fibres. On chemical analysis still another element is found over and above those mentioned as the constituents of silk fibre. In silk, you will recollect, we observed the presence of carbon, hydrogen, oxygen, and nitrogen. In wool, fur, etc., we must add a fifth constituent, namely, sulphur. Here is an analysis of pure German wool—Carbon, 49.25 per cent.; hydrogen, 7.57; oxygen, 23.66; nitrogen, 15.86; sulphur, 3.66—total, 100.00. If you heat either wool, fur, or hair to 130 deg. C., it begins to decompose, and to give off ammonia; if still further heated to from 140 deg. to 150 deg. C., vapours containing sulphur are evolved. If some wool be placed in a dry glass tube, and heated strongly so as to cause destructive distillation, products containing much carbonate of ammonium are given off. The ammonia is easily detected by its smell of hartshorn and the blue colour produced on a piece of reddened litmus paper, the latter being a general test to distinguish alkalis, like ammonia, soda, and potash, from acids. No vegetable fibres will, under any circumstances, give off ammonia. It may be asked, "But what does the production of ammonia prove?" I reply, the "backbone," chemically speaking, of ammonia is nitrogen. Ammonia is a compound of nitrogen and hydrogen, and is formulated NH_{3}, and hence to discover ammonia in the products as mentioned is to prove the prior existence of its nitrogen in the wool, fur, and hair fibres.

Action of Acids on Wool, etc.—Dilute solutions of vitriol (sulphuric acid) or hydrochloric acid (muriatic acid, spirits of salt) have little effect on wool, whether warm or cold, except to open out the scales and confer roughness on the fibre. Used in the concentrated state, however, the wool or fur would soon be disintegrated and ruined. But under all circumstances the action is far less than on cotton, which is destroyed at once and completely. Nitric acid acts like sulphuric and hydrochloric acids, but it gives a yellow colour to the fibre. You see this clearly enough in the fur that comes from your furriers after the treatment they subject it to with nitric acid and nitrate of mercury. There is a process known called the stripping of wool, and it consists in destroying the colour of wool and woollen goods already dyed, in order that they may be re-dyed. Listen, however, to the important precautions followed: A nitric acid not stronger than from 3 deg. to 4 deg. Twaddell is used, and care is taken not to prolong the action more than three or four minutes.

Action of Alkalis.—Alkalis have a very considerable action on fur and wool, but the effects vary a good deal according to the kind of alkali used, the strength and the temperature of the solution, as also, of course, the length of period of contact. The caustic alkalis, potash and soda, under all conditions affect wool and fur injuriously. In fact, we have a method of recovering indigo from indigo-dyed woollen rags, based on the solubility of the wool in hot caustic soda. The wool dissolves, and the indigo, being insoluble, remains, and can be recovered. Alkaline carbonates and soap in solution have little or no injurious action if not too strong, and if the temperature be not over 50 deg. C. (106 deg. F.). Soap and carbonate of ammonium have the least injurious action. Every washer or scourer of wool, when he uses soaps, should first ascertain if they are free from excess of alkali, i.e. that they contain no free alkali; and when he uses soda ash (sodium carbonate), that it contains no caustic alkali. Lime, in water or otherwise, acts injuriously, rendering the fibre brittle.

Reactions and tests proving chemical differences and illustrating modes of discriminating and separating vegetable fibres, silk and wool, fur, etc.—You will remember I stated that the vegetable fibre differs chemically from those of silk, and silk from wool, fur, and hair, in that with the first we have as constituents only carbon, hydrogen, and oxygen; in silk we have carbon, hydrogen, oxygen, and nitrogen; whilst in wool, fur, and hair we have carbon, hydrogen, oxygen, nitrogen, and sulphur. I have already shown you that if we can liberate by any means ammonia from a substance, we have practically proved the presence of nitrogen in that substance, for ammonia is a nitrogen compound. As regards sulphur and its compounds, that ill-smelling gas, sulphuretted hydrogen, which occurs in rotten eggs, in organic effluvia from cesspools and the like, and which in the case of bad eggs, and to some extent with good eggs, turns the silver spoons black, and in the case of white lead paints turns these brown or black, I can show you some still more convincing proofs that sulphur is contained in wool, fur, and hair, and not in silk nor in vegetable fibres. First, I will heat strongly some cotton with a little soda-lime in a tube, and hold a piece of moistened red litmus paper over the mouth of the tube. If nitrogen is present it will take up hydrogen in the decomposition ensuing, and escape as ammonia, which will turn the red litmus paper blue. With the cotton, however, no ammonia escapes, no turning of the piece of red litmus paper blue is observed, and so no nitrogen can be present in the cotton fibre. Secondly, I will similarly treat some silk. Ammonia escapes, turns the red litmus paper blue, possesses the smell like hartshorn, and produces, with hydrochloric acid on the stopper of a bottle, dense white fumes of sal-ammoniac (ammonium chloride). Hence silk contains nitrogen. Thirdly, I will heat some fur with soda-lime. Ammonia escapes, giving all the reactions described under silk. Hence fur, wool, etc., contain nitrogen. As regards proofs of all three of these classes of fibres containing carbon, hydrogen, and oxygen, the char they all leave behind on heating in a closed vessel is the carbon itself present. For the hydrogen and oxygen, a perfectly dry sample of any of these fabrics is taken, of course in quantity, and heated strongly in a closed vessel furnished with a condensing worm like a still. You will find all give you water as a condensate—the vegetable fibre, acid water; the animal fibres, alkaline water from the ammonia. The presence of water proves both hydrogen and oxygen, since water is a compound of these elements. If you put a piece of potassium in contact with the water, the latter will at once decompose, the potassium absorbing the oxygen, and setting free the hydrogen as gas, which you could collect and ignite with a match, when you would find it would burn. That hydrogen was the hydrogen forming part of your cotton, silk, or wool, as the case might be. We must now attack the question of sulphur. First, we prepare a little alkaline lead solution (sodium plumbate) by adding caustic soda to a solution of lead acetate or sugar of lead, until the white precipitate first formed is just dissolved. That is one of our reagents; the other is a solution of a red-coloured salt called nitroprusside of sodium, made by the action of nitric acid on sodium ferrocyanide (yellow prussiate). The first-named is very sensitive to sulphur, and turns black directly. To show this, we take a quantity of flowers of sulphur, dissolve in caustic soda, and add to the lead solution. It turns black at once, because the sulphur unites with the lead to form black sulphide of lead. The nitroprusside, however, gives a beautiful crimson-purple coloration. Now on taking a little cotton and heating with the caustic alkaline lead solution, if sulphur were present in that cotton, the fibre would turn black or brown, for the lead would at once absorb such sulphur, and form in the fibre soaked with it, black sulphide of lead. No such coloration is formed, so cotton does not contain sulphur. Secondly, we must test silk. Silk contains nitrogen, like wool, but does it contain sulphur? The answer furnished by our tests is—no! since the fibre is not coloured brown or black on heating with the alkaline lead solution. Thirdly, we try some white Berlin wool, so that we can easily see the change of colour if it takes place. In the hot lead solution the wool turns black, lead sulphide being formed. On adding the nitroprusside solution to a fresh portion of wool boiled with caustic soda, to dissolve out the sulphur, a splendid purple coloration is produced. Fur and hair would, of course, do the same thing. Lead solutions have been used for dyeing the hair black; not caustic alkaline solutions like this, however. They would do something more than turn the hair black—probably give rise to some vigorous exercise of muscular power! Still it has been found that even the lead solutions employed have, through gradual absorption into the system, whilst dyeing the hair black, also caused colics and contractions of the limbs.

Having now found means for proving the presence of the various elements composing cotton, silk, and wool, fur or hair, we come to methods that have been proposed for distinguishing these fibres more generally, and for quantitatively determining them in mixtures. One of the best of the reagents for this purpose is the basic zinc chloride already referred to. This is made as follows: 100 parts of fused zinc chloride, 85 parts of water, and 4 parts of zinc oxide are boiled together until a clear solution is obtained. This solution dissolves silk slowly in the cold, quickly if hot, and forms a thick gummy liquid. Wool, fur, and vegetable fibres are not affected by it. Hence if we had a mixture, and treated with this solution, we could strain off the liquid containing the dissolved silk, and would get cotton and wool left. On weighing before and after such treatment, the difference in weights would give us the silk present. The residue boiled with caustic soda would lose all its wool, which is soluble in hot strong caustic alkali. Again straining off, we should get only the cotton or other vegetable fibre left, and thus our problem would be solved. Of course there are certain additional niceties and modifications still needed, and I must refer you for the method in full to the Journal of the Society of Chemical Industry, 1882, page 64; also 1884, page 517. I will now conclude with some tests with alkaline and acid reagents, taken in order, and first the acids. These will also impress upon our minds the effects of acids and alkalis on the different kinds of fibres.

I. In three flasks three similar portions of cotton lamp-wick, woollen yarn, and silk are placed, after previously moistening them in water and wringing them out. To each is now added similar quantities of concentrated sulphuric acid. The cotton is quickly broken up and dissolved, especially if assisted by gentle warming, and at last a brown, probably a black-brown, solution is obtained. The woollen is a little broken up, but not much to the naked eye, and the vitriol is not coloured. The silk is at once dissolved, even in the cold acid. We now add excess of water to the contents of each flask. A brownish, though clear, solution is produced in the case of cotton; the woollen floats not much injured in the acid, whilst a clear limpid solution is obtained with the silk. On adding tannic acid solution to all three, only the silk yields a precipitate, a rather curdy one consisting of fibroin.

II. Three specimens of cotton, wool, and silk, respectively, are touched with nitric acid. Cotton is not coloured, but wool and silk are stained yellow; they are practically dyed.

III. Three specimens, of cotton, wool, and silk, respectively, are placed in three flasks, and caustic soda solution of specific gravity 1.05 (10 deg. Twaddell) is added. On boiling, the wool and silk dissolve, whilst the cellulose fibre, cotton, remains undestroyed.

IV. If, instead of caustic soda as in III., a solution of oxide of copper in ammonia be used, cotton and silk are dissolved, but wool remains unchanged, i.e. undissolved. If sugar or gum solutions be added to the solutions of cotton and silk, the cotton cellulose is precipitated, whilst the silk is not, but remains in solution.

V. Another alkaline solvent for silk, which, however, leaves undissolved cotton and wool, is prepared as follows: 16 grains of copper sulphate ("blue vitriol," "bluestone") are dissolved in 150 c.c. of water, and then 16 grains of glycerin are added. To this mixture a solution of caustic soda is added until the precipitate first formed is just re-dissolved, so as not to leave an excess of caustic soda present.



I have already had occasion to refer, in my last Lecture, to water as a chemical substance, as a compound containing and consisting of hydrogen and oxygen. What are these water constituents, hydrogen and oxygen? Each of them is a gas, but each a gas having totally different properties. On decomposing water and collecting the one of these two gases, the hydrogen gas, in one vessel, and the other, the oxygen gas, in another vessel, twice as large a volume of hydrogen gas is given off by the decomposing water as of oxygen. You may now notice a certain meaning in the formula assigned to water, H{2}O: two volumes of hydrogen combined with one of oxygen; and it may be added that when such combination takes place, not three volumes of resulting water vapour (steam), but two volumes are produced. This combination of the two gases, when mixed together, is determined by heating to a high temperature, or by passing an electric spark; it then takes place with the consequent sudden condensation of three volumes of mixture to two of compound, so as to cause an explosion. I may also mention that as regards the weights of these bodies, oxygen and hydrogen, the first is sixteen times as heavy as the second; and since we adopt hydrogen as the unit, we may consider H to stand for hydrogen, and also to signify 1—the unit; whilst O means oxygen, and also 16. Hence the compound atom or molecule of water, H{2}O, weighs 18. I must now show you that these two gases are possessed of totally different properties. Some gases will extinguish a flame; some will cause the flame to burn brilliantly, but will not burn themselves; and some will take fire and burn themselves, though extinguishing the flame which has ignited them. We say the first are non-combustible, and will not support combustion; the second are supporters of combustion, the third are combustible gases. Of course these are, as the lawyers say, only ex parte statements of the truth; still they are usually accepted. Oxygen gas will ignite a red-hot match, but hydrogen will extinguish an inflamed one, though it will itself burn. You generally think of water as the great antithesis of, the universal antidote for, fire. The truth is here again only of an ex parte character, as I will show you. If I can, by means of a substance having a more intense affinity for oxygen than hydrogen has, rob water of its oxygen, I necessarily set the hydrogen that was combined with that oxygen free. If the heat caused by the chemical struggle, so to say, is great, that hydrogen will be inflamed and burn. Thus we are destroying that antithesis, we are causing the water to yield us fire. I will do this by putting potassium on water, and even in the cold this potassium will seize upon the oxygen of the water, and the hydrogen will take fire.

Specific Gravity.—We must now hasten to other considerations of importance. Water is generally taken as the unit in specific gravities assigned to liquids and solids. This simply means that when we desire to express how heavy a thing is, we are compelled to say it is so many times heavier or lighter than something. That something is generally water, which is regarded, consequently, as unit or figure 1. A body of specific gravity 1.5, or 1-1/2, means that that body is 1-1/2 or 1.5 times as heavy as water. As hat manufacturers, you will have mostly to do with the specific gravities of liquids, aqueous solutions, and you will hear more of Twaddell degrees. The Twaddell hydrometer, or instrument for measuring the specific gravities of liquids, is so constructed that when it stands in water, the water is just level with its zero or 0 deg. mark. Well, since in your reading of methods and new processes, you will often meet with specific gravity numbers and desire to convert these into Twaddell degrees, I will give you a simple means of doing this. Add cyphers so as to make into a number of four figures, then strike out the unit and decimal point farthest to the left, and divide the residue by 5, and you get the corresponding Twaddell degrees. If you have Twaddell degrees, simply multiply by 5, and add 1000 to the result, and you get the specific gravity as usually taken, with water as the unit, or in this case as 1000. An instrument much used on the Continent is the Beaume hydrometer. The degrees (n) indicated by this instrument can be converted into specific gravity (d) by the

formula: d = 144.3/(144.3 - n)

Ebullition or Boiling of Water, Steam.—The atmosphere around us is composed of a mixture of nitrogen and oxygen gases; not a compound of these gases, as water is of hydrogen and oxygen, but a mixture more like sand and water or smoke and air. This mass of gases has weight, and presses upon objects at the surface of the earth to the extent of 15 lb. on the square inch. Now some liquids, such as water, were it not for this atmospheric pressure, would not remain liquids at all, but would become gases. The pressure thus tends to squeeze gases together and convert them into liquids. Any force that causes gases to contract will do the same thing, of course—for example, cold; and ceteris paribus removal of pressure and expansion by heat will act so as to gasify liquids. When in the expansion of liquids a certain stage or degree is reached, different for different liquids, gas begins to escape so quickly from the liquid that bubbles of vapour are continually formed and escape. This is called ebullition or boiling. A certain removal of pressure, or expansion by heat, is necessary to produce this, i.e. to reach the boiling-point of the liquid. As regards the heat necessary for the boiling of water at the surface of the earth, i.e. under the atmospheric pressure of 15 lb. on the square inch, this is shown on the thermometer of Fahrenheit as 212 deg., and on the simpler centigrade one, as 100 deg., water freezing at 0 deg. C. But if what I have said is true, when we remove some of the atmospheric pressure, the water should boil with a less heat than will cause the mercury in the thermometer to rise to 100 deg. C., and if we take off all the pressure, the water ought to boil and freeze at the same time. This actually happens in the Carre ice-making machine. The question now arises, "Why does the water freeze in the Carre machine?" All substances require certain amounts of heat to enable them to take and to maintain the liquid state if they are ordinarily solid, and the gaseous state if ordinarily liquid or solid, and the greater the change of state the greater the heat needed. Moreover, this heat does not make them warm, it is simply absorbed or swallowed up, and becomes latent, and is merely necessary to maintain the new condition assumed. In the case of the Carre machine, liquid water is, by removal of the atmospheric pressure, coerced, as it were, to take the gaseous form. But to do so it needs to absorb the requisite amount of heat to aid it in taking that form, and this heat it must take up from all surrounding warm objects. It absorbs quickly all it can get out of itself as liquid water, out of the glass vessel containing it, and from the surrounding air. But the process of gasification with ebullition goes on so quickly that the temperature of the water thus robbed of heat quickly falls to 0 deg. C., and the remaining water freezes. Thus, then, by pumping out the air from a vessel, i.e. working in a vacuum, we can boil a liquid in such exhausted vessel far below its ordinary boiling temperature in the open air. This fact is of the utmost industrial importance. But touching this question of latent heat, you may ask me for my proof that there is latent heat, and a large amount of it, in a substance that feels perfectly cold. I have told you that a gasified liquid, or a liquefied solid, or most of all a gasified solid, contains such heat, and if reconverted into liquid and solid forms respectively, that heat is evolved, or becomes sensible heat, and then it can be decidedly felt and indicated by the thermometer. Take the case of a liquid suddenly solidifying. The heat latent in that liquid, and necessary to keep it a liquid, is no longer necessary and comes out, and the substance appears to become hot. Quicklime is a cold, white, solid substance, but there is a compound of water and lime—slaked lime—which is also a solid powdery substance, called by the chemist, hydrate of lime. The water used to slake the quicklime is a liquid, and it may be ice-cold water, but to form hydrate of lime it must assume a solid form, and hence can and does dispense with its heat of liquefaction in the change of state. You all know how hot lime becomes on slaking with water. Of course we have heat of chemical combination here as well as evolution of latent heat. As another example, we may take a solution of acetate of soda, so strong that it is just on the point of crystallising. If it crystallises it solidifies, and the liquid consequently gives up its latent heat of liquefaction. We will make it crystallise, first connecting the tube containing it to another one containing a coloured liquid and closed by a cork carrying a narrow tube dipping into the coloured liquid. On crystallising, the solution gives off heat, as is shown by the expansion of the air in the corked tube, and the consequent forcing of the coloured liquid up the narrow tube. Consequently in your works you never dissolve a salt or crystal in water or other liquid without rendering heat latent, or consuming heat; you never allow steam to condense in the steam pipes about the premises without losing vastly more heat than possibly many are aware of. Let us inquire as to the latent heat of water and of steam.

Latent Heats of Water and Steam.—If we mix 1 kilogram (about 2 lb.) of ice (of course at zero or 0 deg. C.) with 1 kilogram of water at 79 deg. C., and stir well till the ice is melted, i.e. has changed its state from solid to liquid, we find, on putting a thermometer in, the temperature is only 0 deg. C. This simply means that 79 deg. of heat (centigrade degrees) have become latent, and represent the heat of liquefaction of 1 kilogram of ice. Had we mixed 1 kilogram of water at 0 deg. C. with 1 kilogram of water at 79 deg. C. there would have been no change of state, and the temperature of the mixture might be represented as a distribution of the 79 deg. C. through the whole mass of the 2 kilograms, and so would be 39-1/2 deg. C. We say, therefore, the latent heat of water is the heat which is absorbed or rendered latent when a unit of weight, say 1 kilogram of water as ice, melts and liquefies to a unit of water at zero, or it is 79 heat units. These 79 units of heat would raise 79 units of weight of liquid water through 1 deg. C., or one unit of liquid water through 79 deg..

Let us now inquire what the latent heat of steam is. If we take 1 kilogram of water at 0 deg. C. and blow steam from boiling water at 100 deg. C. into it until the water just boils, and then stop and weigh the resulting water, we shall find it amounts to 1.187 kilograms, so that 0.187 kilogram of water which was in the gaseous steam form, and had besides a sensible heat of 100 deg. C., has changed its state to that of liquid water. This liquid water, being at the boiling-point, has still the 100 deg. C. of sensible heat, and hence the water in the gaseous steam form can have given up to the water at 0 deg. C. into which it was blown, only the latent heat of gasification which was not sensible, but by virtue of which it was enabled to assume the gaseous form. But if 0.187 kilogram of steam at 100 deg. C. can heat 1 kilogram of water through 100 degrees, then 1 kilogram of steam can raise 5.36 kilograms of ice-cold water through 100 degrees, or 536 kilograms through 1 degree, and thus the latent heat of steam is 536 heat units.

Effect of Increase of Pressure on the Boiling of Water.—Now we have referred to diminution of pressure and its effect on the boiling-point of water, and I may point out that by increasing the pressure, such, e.g., as boiling water under a high pressure of steam, you raise the boiling-point. There are some industrial operations in which the action of certain boiling solutions is unavailing to effect certain decompositions or other ends when the boiling is carried on under the ordinary atmospheric pressure, and boiling in closed and strong vessels under pressure must be resorted to. Take as an example the wood-pulp process for making paper from wood shavings. Boiling in open pans with caustic soda lye is insufficient to reduce the wood to pulp, and so boiling in strong vessels under pressure is adopted. The temperature of the solution rises far above 212 deg. F. (100 deg. C.). Let us see what may result chemically from the attainment of such high temperatures of water in our steam boilers working under high pressures. If you blow ordinary steam at 212 deg. F. or 100 deg. C., into fats or oils, the fats and oils remain undecomposed; but suppose you let fatty and oily matters of animal or vegetable origin, such as lubricants, get into your boiler feed-water and so into your boiler, what will happen? I have only to tell you that a process is patented for decomposing fats with superheated steam, to drive or distil over the admixed fatty acids and glycerin, in order to show you that in your boilers such greasy matters will be more or less decomposed. Fats are neutral as fats, and will not injure the iron of the boilers; but once decompose them and they are split up into an acid called a fat acid, and glycerin. That fat acid at the high temperature soon attacks your boilers and pipes, and eats away the iron. That is one of the curious results that may follow at such high temperatures. Mineral or hydrocarbon oils do not contain these fat acids, and so cannot possibly, even with high-pressure steam, corrode the boiler metal.

Effect of Dissolved Salts on the Boiling of Water.—Let us inquire what this effect is? Suppose we dissolve a quantity of a salt in water, and then blow steam at 100 deg. C. (212 deg. F.) into that water, the latter will boil not at 212 deg. F., but at a higher temperature. There is a certain industrial process I know of, in course of which it is necessary first to maintain a vessel containing water, by means of a heated closed steam coil, at 212 deg. F. (100 deg. C.), and at a certain stage to raise the temperature to about 327 deg. F. (164 deg. C.). The pressure on the boiler connected with the steam coil is raised to nearly seven atmospheres, and thus the heat of the high-pressure steam rises to 327 deg. F. (164 deg. C.), and then a considerable quantity of nitrate of ammonium, a crystallised salt, is thrown into the water, in which it dissolves. Strange to say, although the water alone would boil at 212 deg. F., a strong solution in water of the ammonium nitrate only boils at 327 deg. F., so that the effect of dissolving that salt in the water is the same as if the pressure were raised to seven atmospheres. Now let us, as hat manufacturers, learn a practical lesson from this fact. We have observed that wool and fur fibres are injured by boiling in pure water, and the heat has much to do with this damage; but if the boiling take place in bichrome liquors or similar solutions, that boiling will, according to the strength of the solution in dissolved matters, take place at a temperature more or less elevated above the boiling-point of water, and so the damage done will be the more serious the more concentrated the liquors are, quite independently of the nature of the substances dissolved in those liquors.

Solution.—We have already seen that when a salt of any kind dissolves in water, heat is absorbed, and becomes latent; in other words, cold is produced. I will describe a remarkable example or experiment, well illustrating this fact. If you take some Glauber's salt, crystallised sulphate of soda, and mix it with some hydrochloric acid (or spirits of salt), then so rapidly will the solution proceed, and consequently so great will be the demand for heat, that if a vessel containing water be put in amongst the dissolving salt, the heat residing in that vessel and its water will be rapidly extracted, and the water will freeze. As regards solubility, some salts and substances are much more quickly and easily dissolved than others. We are generally accustomed to think that to dissolve a substance quickly we cannot do better than build a fire under the containing vessel, and heat the liquid. This is often the correct method of proceeding, but not always. Thus it would mean simply loss of fuel, and so waste of heat, to do this in dissolving ordinary table salt or rock salt in water, for salt is as soluble in cold water as in hot. Some salts are, incredible though it may appear, less soluble in boiling water than in cold. Water just above the freezing-point dissolves nearly twice as much lime as it does when boiling. You see, then, that a knowledge of certain important facts like these may be so used as to considerably mitigate your coal bills, under given circumstances and conditions.



In the last lecture, under the head of "Solution," I mentioned that some salts, some chemical substances, are more soluble in water than others, and that their solubilities under different circumstances of temperature vary in different ways. However, some salts and compounds are practically insoluble in water under any circumstances. We now arrive at the important result known to chemists as the precipitation of insoluble compounds from solutions. In order to define this result, however, we must, of course, first consider the circumstances of causation of the result. Let us take a simple case of chemical decomposition resulting in the deposition or precipitation of a substance from solution in the insoluble state. We will take a salt you are probably acquainted with—sulphate of copper, or bluestone, and dissolve it in water, and we have then the sulphate of copper in solution in water. Now suppose it is our desire to obtain from that solution all the copper by depositing it in some insoluble form. We may accomplish this in several different ways, relying on certain methods of decomposing that sulphate of copper. One of the simplest and most economical is that adopted in a certain so-called wet method of extracting copper. It is based on the fact that metallic iron has a greater tendency to combine in water solutions, with the acids of copper salts, than the copper has in those salts. We simply need to place some scraps of iron in the copper sulphate solution to induce a change which may be represented as follows: Copper sulphate, consisting of a combination of copper oxide with sulphuric acid, yields with iron, iron sulphate, a combination of iron oxide with sulphuric acid, and metallic copper. The metallic copper produced separates in the form of a red coating on the iron scraps. But we may also, relying on the fact that oxide of copper is insoluble in water, arrange for the deposition of the copper in that form. This we can do by adding caustic soda to a hot solution of copper sulphate, when we get the following change: Copper sulphate, consisting of a combination of copper oxide with sulphuric acid, yields with caustic soda, sulphate of soda, a combination of soda with sulphuric acid and oxide of copper. Oxide of copper is black, and so in this decomposition what is called a "black precipitate" of that oxide is produced on adding the caustic soda. But it might not suit us thus to deposit the copper from our solution; we might desire to remove the sulphuric acid from the copper sulphate, and leave the copper dissolved, say in the form of a chloride. We select, then, a compound which is a chloride, and a chloride of a metal which forms an insoluble combination with sulphuric acid—chloride of barium, say. On adding this chloride of barium to sulphate of copper solution, we get then a change which we might represent thus: Copper sulphate, consisting of a combination of copper oxide with sulphuric acid, yields with barium chloride, which is a combination of barium and chlorine, insoluble barium sulphate, a combination of barium oxide with sulphuric acid, and soluble copper chloride, a combination of copper and chlorine. This is called a double interchange. Now these are a few illustrations to show you what is meant by chemical decompositions. One practical lesson, of course, we may draw is this: We must have a care in dissolving bluestone or copper sulphate, not to attempt it in iron pans, and not to store or put verdigris into iron vessels, or the iron will be acted upon, and to some extent the copper salt will become contaminated with iron. It will now be clear to you that, as a solvent for bodies usually soluble in water, water that is perfectly pure will be most suitable and not likely to cause any deposition or precipitation through chemical decompositions, for there are no salts or other compounds in pure water to cause such changes. Such pure water is called soft water. But the term is only a comparative one, and water that is not quite, but nearly pure—pure enough for most practical purposes—is also called soft water. Now rain is the purest form of natural water, for it is a kind of distilled water. Water rises in vapour from the ocean as from a still, and the salt and other dissolved matters remain behind. Meeting cold currents of air, the vapours condense in rain, and fall upon the earth. After coming in contact with the earth, the subsequent condition of that water entirely depends upon the character, as regards solubility or insolubility, of the substances composing the strata or layers of earth upon which it falls, and through which it sinks. If it meets with insoluble rocks—for all rocks are not insoluble—it remains, of course, pure and soft, and in proportion as the constituents of rock and soil are soluble, in that proportion does the water become hard. We all know how dangerous acid is in water, causing that water to act on many substances, the iron of iron vessels, the lime in soil or rock, etc., bringing iron and lime respectively into solution. Now the atmosphere contains carbonic acid, and carbonic acid occurs in the earth, being evolved by decomposing vegetation, etc. Carbonic acid is also soluble to a certain, though not large extent, in water. As we shall see, water charged with carbonic acid attacks certain substances insoluble in pure water, and brings them into solution, and thus the water soon becomes hard. About the close of the last lecture, I said that lime is, to a certain extent, soluble in cold water. The solution is called lime-water; it might be called a solution of caustic lime. When carbonic acid gas first comes in contact with such a solution, chalk or carbonate of lime, which is insoluble in water, is formed, and the lime is thus precipitated as carbonate. Supposing, however, we continued to pass carbonic acid gas into that water, rendered milky with chalk powder, very soon the liquid would clear, and we should get once more a solution of lime, but not caustic lime as it was at first, simply now a solution of carbonate of lime in carbonic acid, or a solution of bicarbonate of lime. I will take some lime-water, and I will blow through; my breath contains carbonic acid, and you will see the clear liquid become milky owing to separation of insoluble carbonate of lime, or chalk. I now continue blowing, and at length that chalk dissolves with the excess of carbonic acid, forming bicarbonate of lime. This experiment explains how it is that water percolating through or running over limestone strata dissolves out the insoluble chalk. Such water, hard from dissolved carbonate of lime, can be softened by merely boiling the water, for the excess of carbonic acid is then expelled, and the chalk is precipitated again. This would be too costly for the softening of large quantities of water, the boiling process consuming too much coal, and so another process is adopted. Quicklime, or milk of lime, is added to the water in the proper quantity. This lime unites with the excess of carbonic acid holding chalk in solution, and forms with it insoluble chalk, and so all deposits together as chalk. By this liming process, also, the iron of the water dissolved likewise in ferruginous streams, etc., by carbonic acid, would be precipitated. To show this deposition I will now add some clear lime-water to the solution I made of chalk with the carbonic acid of my breath, and a precipitate is at once formed, all the lime and carbonic acid together depositing as insoluble chalk. Hence clear lime-water forms a good test for the presence of bicarbonates of lime or iron in a water. But water may be hard from the presence of other salts, other lime salts. For example, certain parts of the earth contain a great deal of gypsum, or natural sulphate of lime, and this is soluble to some extent in water. Water thus hardened is not affected by boiling, or the addition of lime, and is therefore termed permanently hard water, the water hardened with dissolved chalk being termed temporarily hard water. I have said nothing of solid or undissolved impurities in water, which are said to be in suspension, for the separation of these is a merely mechanical matter of settling, or filtration and settling combined. As a general rule, the water of rivers contains the most suspended and vegetable matter and the least amount of dissolved constituents, whereas spring and well waters contain the most dissolved matters and the least suspended. Serious damage may be done to the dyer by either of these classes of impurities, and I may tell you that the dissolved calcareous and magnesian impurities are the most frequent in occurrence and the most injurious. I told you that on boiling, the excess of carbonic acid holding chalk or carbonate of lime in solution as bicarbonate, is decomposed and carbonate of lime precipitated. You can at once imagine, then, what takes place in your steam boilers when such water is used, and how incrustations are formed. Let us now inquire as to the precise nature of the waste and injury caused by hard and impure waters. Let us also take, as an example, those most commonly occurring injurious constituents, the magnesian and calcareous impurities. Hard water only produces a lather with soap when that soap has effected the softening of the water, and not till then. In that process the soap is entirely wasted, and the fatty acids in it form, with the lime and magnesia, insoluble compounds called lime and magnesia soaps, which are sticky, greasy, adhesive bodies, that precipitate and fix some colouring matters like a mordant. We have in such cases, then, a kind of double mischief—(i) waste of soap, (ii) injury to colours and dyes on the fabrics. But this is not all, for colours are precipitated as lakes, and mordants also are precipitated, and thus wasted, in much the same sense as the soaps are. Now by taking a soap solution, formed by dissolving a known weight of soap in a known volume of water, and adding this gradually to hard water until a permanent lather is just produced, we can directly determine the consumption of soap by such a water, and ascertain the hardness. Such a method is called Clark's process of determination or testing, or Clark's soap test. We hear a great deal just now of soaps that will wash well in hard water, and do wonders under any conditions; but mark this fact, none of them will begin to perform effective duty until such hard water has been rendered soft at the expense of the soap. Soaps made of some oils, such as cocoa-nut oil, for example, are more soluble in water than when made of tallow, etc., and so they more quickly soften a hard water and yield lather, but they are wasted, as far as consumption is concerned, to just the same extent as any other soaps. They do not, however, waste so much time and trouble in effecting the end in view, and, as you know, "Time is money" in these days of work and competition. After making a soap test as described above, and knowing the quantity of water used, it is, of course, easy to calculate the annual loss of soap caused by the hardness of the water. The monthly consumption of soap in London is 1,000,000 kilograms (about 1000 tons), and it is estimated that the hardness of the Thames water means the use of 230,000 kilograms (nearly 230 tons) more soap per month than would be necessary if soft water were used. Of course the soap manufacturers around London would not state that fact on their advertising placards, but rather dwell on the victorious onslaught their particular brand will make on the dirt in articles to be washed, in the teeth of circumstances that would be hopeless for any other brand of soap! I have referred to the sticky and adhesive character of the compounds called lime soaps, formed in hard waters. Now in washing and scouring wool and other fibres, these sticky lime soaps adhere so pertinaciously that the fibres, be they of wool, silk, or any other article, remain in part untouched, impermeable to mordant or colouring matter, and hence irregular development of colour must be the consequence. Also an unnatural lustre or peculiar bloom may in parts arise, ruining the appearance of the goods. In some cases the lime soaps act like mordants, attracting colouring matter unequally, and producing patchy effects. In the dye-baths in which catechu and tannin are used, there is a waste of these matters, for insoluble compounds are formed with the lime, and the catechu and tannin are, to a certain extent, precipitated and lost. Some colours are best developed in an acid bath, such as Cochineal Scarlet, but the presence of the bicarbonate of lime tends to cause neutralisation of the acidity, and so the dyeing is either retarded or prevented. Such mordants as "red liquor" and "iron liquor," which are acetates of alumina and iron respectively, are also wasted, a portion of them being precipitated by the lime, thus weakening the mordant baths.

Ferruginous Impurities in Water.—Iron in solution in water is very objectionable in dyeing operations. When the iron is present as bicarbonate, it acts on soap solutions like the analogous lime and magnesia compounds, producing even worse results. In wool scouring, cotton bleaching, and other processes requiring the use of alkaline carbonates, ferric oxide is precipitated on the fibre. A yellowish tinge is communicated to bleached fabrics, and to dye bright and light colours is rendered almost out of the question. You may always suspect iron to be present in water flowing from or obtained directly out of old coal pits, iron mines, or from places abounding in iron and aluminous shales. Moreover, you sometimes, or rather generally, find that surface water draining off moorland districts, and passing over ochre beds, contains iron, and on its way deposits on the beds of the streamlets conveying it, and on the stones, red or brown oxide of iron. All water of this kind ought to be avoided in dyeing and similar operations. The iron in water from old coal pits and shale deposits is usually present as sulphate due to the oxidation of pyrites, a sulphuret or sulphide of iron. Water from heaths and moorlands is often acid from certain vegetable acids termed "peaty acids." This acidity places the water in the condition of a direct solvent for iron, and that dissolved iron may cause great injury. If such water cannot be dispensed with, the best way is to carefully neutralise it with carbonate of soda; the iron is then precipitated as carbonate of iron, and can be removed.

Contamination of Water by Factories.—You may have neighbours higher up the stream than yourselves, and these firms may cast forth as waste products substances which will cause immense waste and loss. Amongst these waste products the worst are those coming from chemical works, paper works, bleach works, etc. If the paper works be those working up wood pulp, the pollutions of effluent water will be about as noxious as they well can be. You will have gums and resins from the wood, calcium chloride from the bleach vats, acids from the "sours"; resin, and resin-soaps; there may also be alumina salts present. Now alumina, lime, resin, and resin-soaps, etc., precipitate dyestuffs, and also soap; if the water is alkaline, some of the mordants used may be precipitated and wasted, and very considerable damage done.

Permanent hardness in water, due to the presence of gypsum or sulphate of lime in solution, may be remedied by addition of caustic soda. Of course, if an alkaline water is objectionable in any process, the alkali would have to be neutralised by the addition of some acid. For use in boilers, water might thus be treated, but it would become costly if large quantities required such treatment. Water rendered impure by contaminations from dyehouses and some chemical works can be best purified, and most cheaply, by simple liming, followed by a settling process. If space is limited and much water is required, instead of the settling reservoirs, filtering beds of coke, sand, etc., may be used. The lime used neutralises acids in the contaminated and impure water, precipitates colouring matters, mordants, soap, albuminous matters, etc.

Tests of Purity.—I will now describe a few tests that may be of value to you in deciding as to what substances are contaminating any impure waters that may be at hand.

Iron.—If to a water you suspect to be hard from presence of carbonate of lime or carbonate of iron in solution in carbonic acid, i.e. as bicarbonates, you add some clear lime-water, and a white precipitate is produced, you have a proof of carbonate of lime—hardness. If the precipitate is brownish, you may have, also, carbonate of iron. I will now mention a very delicate test for iron. Such a test would be useful in confirmation. If a very dilute solution of such iron water be treated with a drop or two of pure hydrochloric acid, and a drop or so of permanganate of potash solution or of Condy's fluid, and after that a few drops of yellow prussiate of potash solution be added, then a blue colour (Prussian blue), either at once or after standing a few hours, proves the presence of iron.

Copper.—Sometimes, as in the neighbourhood of copper mines or of some copper pyrites deposits, a water may be contaminated with small quantities of copper. The yellow prussiate once more forms a good test, but to ensure the absence of free mineral acids, it is first well to add a little acetate of soda solution. A drop or two of the prussiate solution then gives a brown colour, even if but traces of copper are present.

Magnesia.—Suppose lime and magnesia are present. You may first evaporate to a small bulk, adding a drop of hydrochloric acid if the liquid becomes muddy. Then add ammonia and ammonium oxalate, when lime alone is precipitated as the oxalate of lime. Filter through blotting paper, and to the clear filtrate add some phosphate of soda solution. A second precipitation proves the presence of magnesia.

Sulphates.—A solution of barium chloride and dilute hydrochloric acid gives a white turbidity.

Chlorides.—A solution of silver nitrate and nitric acid gives a white curdy precipitate.

Test for Lead in Drinking Water.—I will, lastly, give you a test that will be useful in your own homes to detect minute quantities of lead in water running through lead pipes. Place a large quantity of the water in a glass on a piece of white paper, and add a solution of sulphuretted hydrogen and let stand for some time. A brown colour denotes lead. Of course copper would also yield a brown coloration, but I am supposing that the circumstances preclude the presence of copper.

I have already said that rain water is the purest of natural waters; it is so soft, and free from dissolved mineral matters because it is a distilled water. In distilling water to purify it, we must be very careful what material we use for condensing the steam in, since it is a fact probably not sufficiently well known, that the softer and purer a water is, the more liable it is to attack lead pipes. Hence a coil of lead pipe to serve as condensing worm would be inadmissible. Such water as Manchester water, and Glasgow water from Loch Katrine still more so, are more liable to attack lead pipes than the hard London waters. To illustrate this fact, we will distil some water and condense in a leaden worm, then, on testing the water with our reagent, the sulphuretted hydrogen water, a brown colour is produced, showing the presence of lead. On condensing in a block tin worm, however, no tin is dissolved, so tin is safer and better as the material for such a purpose than lead.

Filtration.—We hear a great deal about filtration or filters as universal means of purifying water. Filtration, we must remember, will, as a rule, only remove solid or suspended impurities in water. For example, if we take some ivory black or bone black, and mix it with water and afterwards filter the black liquid through blotting-paper, the bone black remains on the paper, and clear, pure water comes through. Filtering is effective here. If we take some indigo solution, however, and pour it on to the filter, the liquid runs through as blue as it was when poured upon the filter. Filtering is ineffective here, and is so generally with liquids containing matters dissolved in them. But I said "generally," and so the question is suggested—Will filtration of any kind remove matters in solution? This question I will, in conclusion, try to answer. Bone charcoal, or bone black, has a wonderful attraction for many organic matters such as colours, dyes, and coloured impurities like those in peat water, raw sugar solutions, etc. For example, if we place on a paper filter some bone black, and filter through it some indigo solution, after first warming the latter with some more of the bone black, the liquid comes through clear, all the indigo being absorbed in some peculiar way, difficult to explain, by the bone black, and remaining on the filter. This power of charcoal also extends to gases, and to certain noxious dissolved organic impurities, but it is never safe to rely too much on such filters, since the charcoal can at length become charged with impurities, and gradually cease to act. These filters need cleaning and renewing from time to time.



Properties of Acids and Alkalis.—The name acids is given to a class of substances, mostly soluble in water, having an acid or sour taste, and capable of turning blue litmus solution red. All acids contain one or more atoms of hydrogen capable of being replaced by metals, and when such hydrogen atoms are completely replaced by metals, there result so-called neutral or normal salts, that is, neutral substances having no action on litmus solution. These salts can also be produced by the union of acids with equivalent quantities of certain metallic oxides or hydroxides, called bases, of which those soluble in water are termed alkalis. Alkalis have a caustic taste, and turn red litmus solution blue.

In order to explain what is called the law of equivalence, I will remind you of the experiment of the previous lecture, when a piece of bright iron, being placed in a solution of copper sulphate, became coated with metallic copper, an equivalent weight of iron meanwhile suffering solution as sulphate of iron. According to the same law, a certain weight of soda would always require a certain specific equivalent weight of an acid, say hydrochloric acid, to neutralise its alkaline or basic properties, producing a salt.

The specific gravities of acids and alkalis in solution are made use of in works, etc., as a means of ascertaining their strengths and commercial values. Tables have been carefully constructed, such that for every degree of specific gravity a corresponding percentage strength of acidity and alkalinity may be looked up. The best tables for this purpose are given in Lunge and Hurter's Alkali-Makers' Pocket-Book, but for ordinary purposes of calculation in the works or factory, a convenient relationship exists in the case of hydrochloric acid between specific gravity and percentage of real acid, such that specific gravity as indicated by Twaddell's hydrometer directly represents percentage of real acid in any sample of hydrochloric acid.

The point at which neutralisation of an acid by alkali or vice versa just takes place is ascertained very accurately by the use of certain sensitive colours. At first litmus and cochineal tinctures were used, but in testing crude alkalis containing alumina and iron, it was found that lakes were formed with these colours, and they become precipitated in the solution, and so no longer sensitive. The chemist was then obliged to resort to certain sensitive coal-tar colours, which did not, as the dyer and printer knew, form lakes with alumina and iron, such as methyl orange, fluorescein, Congo red, phenolphthalein, and so forth. For determining the alkalimetric strength of commercial sodas, a known weight of the sample is dissolved in water, and a few drops of a solution of methyl orange are added, which colour the solution yellow or orange. Into this solution is then run, from a burette or graduated tube, a standard solution of an acid, that is, a solution prepared by dissolving a known weight of an acid, say hydrochloric acid, in a known volume of water. The acid is run in gradually until the yellow colour changes to pink, at which point the volume of acid used is noted. Knowing the weight of acid contained in this volume of standard acid, and having regard to the law of equivalence mentioned above, it is an easy matter to calculate the amount of alkali equivalent to the acid used, and from this the alkali contained in the sample.

Sulphuric Acid.—The first process for manufacturing sulphuric acid or vitriol was by placing some burning sulphur in a closed vessel containing some water. The water absorbed the acid formed by the burning sulphur. It was next discovered that by mixing with the sulphur some nitre, much more sulphuric acid could be produced per given quantity of brimstone. At first large glass carboys were used, but in 1746 the carboys were replaced by chambers of lead containing water at the bottom, and in these lead chambers the mixture of sulphur and nitre was burnt on iron trays. Next, although gradually, the plant was divided into two portions—a furnace for burning the sulphur, and a chamber for receiving the vapours. The system was thus developed into the one followed at the present time. The sulphur, or, in most cases, cupreous iron pyrites (a combination of iron and copper with sulphur), is burned in specially constructed kilns or furnaces, and the hot gases, consisting essentially of sulphur dioxide with the excess of air, pass through flues in which are placed cast-iron "nitre pots" containing a mixture of nitre (sodium nitrate) and vitriol. The gases thus become mixed with nitrous fumes or gaseous oxides of nitrogen, and, after cooling, are ready for mixing with steam or water spray in the lead chambers in which the vitriol is produced. These oxides of nitrogen enable the formation of sulphuric acid to take place more quickly by playing the part of oxygen-carriers. Sulphuric acid is formed by the union of oxygen with sulphur dioxide and water; the oxides of nitrogen combine with the oxygen of the air present in the chambers, then give up this oxygen to the sulphur dioxide and water or steam to form sulphuric acid, again combine with more oxygen, and so on. The exact processes or reactions are of course much more complicated, but the above represents what is practically the ultimate result. It is evident that the gases leaving the last lead chamber in which the formation of vitriol is effected, must still contain nitrous fumes, and it becomes a matter of importance to recover them, so that they can be used over again. To effect this object, use is made of the solubility of nitrous fumes in strong vitriol. The gases from the last lead chamber of the series are passed through what is called a Gay-Lussac tower (the process was invented by the eminent French chemist Gay-Lussac), which is a tower made of lead, supported by a wooden framework, and filled with coke or special stoneware packing, over which strong vitriol is caused to flow. The vitriol dissolves the nitrogen oxides, and so-called "nitrous vitriol" flows out at the base of the tower. The recovery of the nitrogen compounds from the nitrous vitriol is effected in Glover towers (the invention of John Glover of Newcastle), which also serve to concentrate to some extent the weak acid produced in the lead chambers, and to cool the hot gases from the sulphur burners or pyrites kilns. The weak chamber acid is mixed with the nitrous vitriol from the Gay-Lussac tower, and the mixture is pumped to the top of the Glover tower, which is of similar construction to the Gay-Lussac tower, but is generally packed with flints. This Glover tower is placed between the sulphur burners or pyrites kilns and the first lead chamber. The nitrous vitriol passing down the tower meets the hot gases from the kilns, and a threefold object is effected: (1) The nitrous fumes are expelled from the nitrous vitriol, and are carried into the chambers, to again play the part of oxygen-carriers; (2) the weak chamber acid which was mixed with the nitrous vitriol is concentrated by the hot kiln gases; and (3) the hot gases themselves are cooled. The acid from the Glover tower is purified by special treatment—for example, the arsenic may be removed, after precipitation with sulphuretted hydrogen, in the form of insoluble arsenic sulphide,—and the purified acid is concentrated by heating in glass or platinum vessels.

A considerable amount of sulphuric acid is now made by the so-called "contact process," in which sulphur dioxide and oxygen unite to form sulphuric acid in presence of a heated "contact" substance, usually some form of finely-divided platinum.

Nitric Acid.—This acid is usually prepared by distilling a mixture of sodium nitrate and vitriol in cast-iron retorts or pots, the nitric acid being collected in stoneware vessels connected one with another, or, as is more generally the case at the present time, in condensing apparatus consisting of stoneware pipes or coils cooled by water. The effluent gases are passed through a scrubber in order to free them from the last traces of acid before discharging them into the atmosphere.

Hydrochloric Acid.—The greater part of the hydrochloric acid manufactured in Great Britain is obtained as an intermediate product in the Leblanc alkali process, which will presently be described, being produced by heating common salt with vitriol. A large quantity is, however, also produced by the so-called direct process of Hargreaves & Robinson, which is, in principle, the same method as that employed in the Leblanc process, except that the intermediate product, vitriol, is not separated. It consists essentially in passing the hot gases from pyrites kilns, as used in the manufacture of vitriol, through large cast-iron vessels containing common salt heated to a high temperature. Various physical conditions must be complied with in order to make the process a success. For example, the salt is used in the form of moulded hard porous cakes made from a damp mixture of common salt and rock salt. The cast-iron vessels must be heated uniformly, and the hot pyrites kiln gases must be passed downwards through the salt in order to ensure uniform distribution. The hydrochloric acid is condensed in stoneware pipes connected with towers packed with coke or stoneware.

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