formula:d= 144·3/(144·3 - n)
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; andceteris paribusremoval 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 formedand 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°, and on the simpler centigrade one, as 100°, water freezing at 0° 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° 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 Carré ice-making machine. The question now arises, "Why does the water freeze in the Carré 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 Carré 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° 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 temperaturein 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 withoutlosing 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° C.) with 1 kilogram of water at 79° 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° C. This simply means that 79° 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° C. with 1 kilogram of water at 79° C. there would have been no change of state, and the temperature of the mixture might be represented as a distribution of the 79° C. through the whole mass of the 2 kilograms, and so would be 39½° 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° C., or one unit of liquid water through 79°.
Let us now inquire what the latent heat of steam is. If we take 1 kilogram of water at 0° C. and blow steam from boiling water at 100° 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° C., has changed its state to that of liquid water. This liquid water, being at the boiling-point, has still the 100° C. of sensible heat, and hence the water in the gaseous steam form can have given up to the water at 0° 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° C. can heat 1 kilogram of water through100 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° F. (100° 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° F. or 100° 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 hydrocarbonoils 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° C. (212° F.) into that water, the latter will boil not at 212° 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° F. (100° C.), and at a certain stage to raise the temperature to about 327° F. (164° 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° F. (164° 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° F., a strong solution in water of the ammonium nitrate only boils at 327° 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 takesome 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 copperhas 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 intoiron 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 mightbe 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 oriron 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 anddyes 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, formedin 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 thestones, 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, followedby 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 theclear 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 blackor 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 carefullyconstructed, 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'sAlkali-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 orvice versâjust 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 andoxygen 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.
Alkali: Leblanc Process.—The manufacture of vitriol, as I have described it to you, is the first step in the Leblanc process. The next stage consists in the manufacture of sodiumsulphate (salt-cake) and hydrochloric acid from the sulphuric acid and common salt; this is called the salt-cake process. The production of salt-cake or crude sodium sulphate is carried out in two stages. A large covered iron pan, called the decomposing pan or salt-cake pot, is mounted in one part of the salt-cake furnace, and alongside it is the hearth or bed on which the second stage of the process, the drying or roasting, is effected. The mixture of common salt and vitriol is charged into the salt-cake pot, which is heated by a fire below. When from two-thirds to three-quarters of the hydrochloric acid has been expelled from the charge, the mass acquires the consistence of thick dough, and at this stage it is raked out of the pan on to the roasting hearth alongside, where the decomposition is completed by means of flames playing directly on to the top of the charge. The hydrochloric acid evolved during the process is condensed in much the same manner as in the process of Hargreaves & Robinson previously described. It is a curious fact that in the earlier years of the Leblanc process, hydrochloric acid, or "spirits of salt," as it is frequently called, was a by-product that required all the vigilance of the alkali-works inspectors to prevent it being allowed to escape from the chimneys in more than a certain small regulated amount. Now, it is the principal product; indeed, the Leblanc alkali maker may be said to subsist on that hydrochloric acid, as his chief instrument for producing chloride of lime or bleaching powder.
Mechanical furnaces are now used to a large extent for the salt-cake process. They consist broadly of a large revolving furnace-hearth or bed, on to which the mixture of salt and vitriol is charged, and on which it is continuously agitated, and gradually moved to the place of discharge, by rakes or the like, operated by suitable machinery.
The next stage of the Leblanc process is the manufacture of "black ash," or crude sodium carbonate. This is usually donein large cylindrical revolving furnaces, through, which flames from a fire-grate, or from the burning of gaseous fuel, pass; the waste heat is utilised for boiling down "black ash" liquor, obtained by lixiviating the black ash. A mixture of salt-cake, limestone or chalk (calcium carbonate), and powdered coal or coal slack is charged into the revolving cylinder; during the process the mass becomes agglomerated, and the final product is what is known as a "black-ash ball," consisting chiefly of crude sodium carbonate and calcium sulphide, but containing smaller quantities of many other substances. The soda ash or sodium carbonate is obtained from the black ash by lixiviating with water, and after various purification processes, the solution is boiled down, as previously stated, by the waste heat of the black-ash furnace. The alkali is sold in various forms as soda ash, soda crystals, washing soda, etc.
Caustic soda is manufactured from solution of carbonate of soda by causticising, that is, treatment with caustic lime or quicklime.
It will have been noticed that one of the chief reagents in the Leblanc process is the sulphur used in the form of brimstone or as pyrites for making vitriol in the first stage; this sulphur goes through the entire process; from the vitriol it goes to form a constituent of the salt-cake, and afterwards of the calcium sulphide contained in the black ash. This calcium sulphide remains as an insoluble mass when the carbonate of soda is extracted from the black ash, and forms the chief constituent of the alkali waste, which until the year 1880 could be seen in large heaps around chemical works. Now, however, by means of treatment with kiln gases containing carbonic acid, the sulphur is extracted from the waste in the form of hydrogen sulphide, which is burnt to form vitriol, or is used for making pure sulphur; and so what was once waste is now a source of profit.
Ammonia-Soda Process of Alkali Manufacture.—This processdepends upon the fact that when carbonic acid is forced, under pressure, into a saturated solution of ammonia and common salt, sodium bicarbonate is precipitated, whilst ammonium chloride or "sal-ammoniac" remains dissolved in the solution. The reaction was discovered in 1836 by a Scotch chemist named John Thom, and small quantities of ammonia-soda were made at that time by the firm of McNaughton & Thom. The successful carrying out of the process on the large scale depends principally upon the complete recovery of the expensive reagent, ammonia, and this problem was only solved within comparatively recent years by Solvay. The process has been perfected and worked with great success in England by Messrs. Brunner, Mond, & Co., and has proved a successful rival to the Leblanc process.
Alkali is also produced to some extent by electrolytic processes, depending upon the splitting up of a solution of common salt into caustic soda and chlorine by the use of an electric current.
Boric Acid.—At ordinary temperatures and under ordinary conditions boric acid is a very weak acid, but like silicic and some other acids, its relative powers of affinity and combination become very much changed at high temperatures; thus, fused and strongly heated boric acid can decompose carbonates and even sulphates, and yet a current of so weak an acid as hydrogen sulphide, passed through a strong solution of borax, will decompose it and set free boric acid. Boric acid is obtained chiefly from Italy. In a tract of country called the Maremma of Tuscany, embracing an area of about forty square miles, are numerous chasms and crevices, from which hot vapour and heated gases and springs of water spurt. The steam issuing from these hot springs contains small quantities of boric acid, that acid being one of those solid substances distilling to some extent in a current of steam. The steam vapours thus bursting forth, owing to some kind of constant volcanic disturbance, are also more or less laden with sulphuretted hydrogen gas, communicating a very ill odour to the neighbourhood. These phenomena were at first looked upon by the people as the work of the devil, and priestly exorcisms were in considerable request in the hope of quelling them, very much as a great deal of the mere speech-making at the present time in England on foreign competition and its evils, and the dulness of trade, the artificial combinations to keep up prices, to reduce wages, generallamentation, etc., are essayed in the attempt to charm away bad trade. At length a kind of prophet arose of a very practical character in the form of the late Count Lardarel, who, mindful of the fact that the chemist Höffer, in the time of the Grand Duke Leopold I., had discovered boric acid in the volcanic steam jets, looked hopefully beyond the exorcisms of the priests and the superstitions of the people to a possible blessing contained in what appeared to be an unholy confusion of Nature. He constructed tanks of from 100 to 1000 ft. in diameter and 7 to 20 ft. in depth, of such a kind that the steam jets were surrounded by or contained in them, and thus the liquors formed by condensation became more and more concentrated. These tanks were arranged at different levels, so that the liquors could be run off from one to the other, and finally to settling cisterns. Subsequently the strong liquors were run to lead-lined, wooden vats, in which the boric acid was crystallised out. Had the industry depended on the use of fuel it could never have developed, but Count Lardarel ingeniously utilised the heat of the steam for all the purposes, and neither coal nor wood was required. Where would that Tuscan boric acid industry have been now had merely the lamentations of landowners, fears of the people, and exorcisms of the priests been continued? Instead of being the work of the arch-enemy of mankind, was not it rather an incitement to a somewhat high and difficult step in an upward direction towards the attainment, on a higher platform of knowledge and skill, of a blessing for the whole province of Tuscany? What was true in the history of that industry and its development is every whit as true of the much-lamented slackening of trade through foreign competition or other causes now in this country, and coming home to yourselves in the hat-manufacturing industry. The higher platform to which it was somewhat difficult to step up, but upon which the battle must be fought and the victory won, was one of a higher scientific and technologicaleducation and training. The chemist Höffer made the discovery of boric acid in the vapours, they would no doubt take note; but Höffer went no further; and it needed the man of both educated and practical mind like Count Lardarel to turn the discovery to account and extract the blessing. In like manner it was clear that in our educational schemes for the benefit of the people, there must not only be the scientific investigator of abstract truth, but also the scientific technologist to point the way to the practical realisation of tangible profit. Moreover, and a still more important truth, it is the scientific education of the proprietors and heads we want—educated capital rather than educated workmen.
Borax.—A good deal of the Tuscan boric acid is used in France for the manufacture of borax, which is a sodium salt of boric acid. Borax is also manufactured from boronitrocalcite, a calcium salt of boric acid, which is found in Chili and other parts of South America. The crude boronitrocalcite or "tiza" is boiled with sodium carbonate solution, and, after settling, the borax is obtained by crystallisation. Borax itself is found in California and Nevada, U.S.A., and also in Peru, Ceylon, China, Persia, and Thibet. The commercial product is obtained from the native borax (known as "tincal") by dissolving in water and allowing the solution to crystallise. The Peruvian borax sometimes contains nitre. For testing the purity of refined borax the following simple tests will usually suffice. A solution of the borax is made containing 1 part of borax to 50 parts of water, and small portions of the solution are tested as follows:Heavy metals(lead,copper, etc.).—On passing sulphuretted hydrogen into the solution, no coloration or precipitate should be produced.Calcium Salts.—The solution should not give a precipitate with ammonium oxalate solution.Carbonates.—The solution should not effervesce on addition of nitric or hydrochloric acid.Chlorides.—No appreciableprecipitate should be produced on addition of silver nitrate solution and nitric acid.Sulphates.—No appreciable precipitate should be produced on adding hydrochloric acid and barium chloride.Iron.—50 c.c. of the solution should not immediately be coloured blue by 0·5 c.c. of potassium ferrocyanide solution.
Soap.—Soap is a salt in the chemical sense, and this leads to a wider definition of the term "salt" or "saline" compound. Fats and oils, from which soaps are manufactured, are a kind ofquasisalts, composed of a fatty acid and a chemical constant, if I may use the term, in the shape of base, namely, glycerin. When these fats and oils, often called glycerides, are heated with alkali, soda, a true salt of the fatty acid and soda is formed, and this is the soap, whilst the glycerin remains behind in the "spent soap lye." Now glycerin is soluble in water containing dissolved salt (brine), whilst soap is insoluble, though soluble in pure water. The mixture of soap and glycerin produced from the fat and soda is therefore treated with brine, a process called "cutting the soap." The soap separates out in the solid form as a curdy mass, which can be easily separated. Certain soaps are able to absorb a large quantity of water, and yet appear quite solid, and in purchasing large quantities of soap it is necessary, therefore, to determine the amount of water present. This can be easily done by weighing out ten or twenty grams of the soap, cut in small pieces, into a porcelain dish and heating over a gas flame, whilst keeping the soap continually stirred, until a glass held over the dish no longer becomes blurred by escaping steam. After cooling, the dry soap is weighed, and the loss of weight represents the amount of moisture. I have known cases where soap containing about 83 per cent. of water has been sold at the full market price. Some soaps also contain more alkali than is actually combined with the fatty acids of the soap, and that excess alkali is injurious in washing silks and scouringwool, and is also not good for the skin. The presence of this free or excess alkali can be at once detected by rubbing a little phenolphthalein solution on to the freshly-cut surface of a piece of soap; if free alkali be present, a red colour will be produced.
Shellac.—The resin tribe, of which shellac is a member, comprises vegetable products of a certain degree of similarity. They are mostly solid, glassy-looking substances insoluble in water, but soluble in alcohol and wood spirit. In many cases the alcoholic solutions show an acid reaction. The resins are partly soluble in alkalis, with formation of a kind of alkali salts which we may call resin-soaps.
Shellac is obtained from the resinous incrustation produced on the bark of the twigs and branches of various tropical trees by the puncture of the female "lac insect" (Taccardia lacca). The lac is removed from the twigs by "beating" in water; the woody matter floats to the surface, and the resin sinks to the bottom, and when removed forms what is known as "seed-lac." Formerly, the solution, which contains the colouring matter dissolved from the crude "stick-lac," was evaporated for recovery of the so-called "lac-dye," but the latter is no longer used technically. The seed-lac is bleached by boiling with sodium or potassium carbonate, alum, or borax, and then, if it is not pale enough, is further bleached by exposure to sunlight. It is now dried, melted, and mixed with a certain proportion of rosin or of orpiment (a sulphide of arsenic) according to the purpose for which it is desired. After further operations of melting and straining, the lac is melted and spreadinto thin sheets to form ordinary shellac, or is melted and dropped on to a smooth surface to form "button-lac." Ordinary shellac almost invariably contains some rosin, but good button-lac is free from this substance. The presence of 5 per cent. of rosin in shellac can be detected by dissolving in a little alcohol, pouring the solution into water, and drying the fine impalpable powder which separates. This powder is extracted with petroleum spirit, and the solution shaken with water containing a trace of copper acetate. If rosin be present, the petroleum spirit will be coloured emerald-green.
Borax, soda crystals, and ammonia are all used to dissolve shellac, and it may be asked: Which of these is least injurious to wool? and why? How is their action modified by the presence of dilute sulphuric acid in the wool? I would say that soda crystals and ammonia are alkalis, and if used strong, are sure to do a certain amount of injury to the fibre of wool, and more if used hot than cold. Of the two, the ammonia will have the least effect, especially if dilute, but borax is better than either. The influence of a little sulphuric acid in the wool would be in the direction of neutralising some of the ammonia or soda, and shellac, if dissolved in the alkalis, would be to some extent precipitated on the fibre, unless the alkali, soda or ammonia, were present in sufficient excess to neutralise that sulphuric acid and to leave a sufficient balance to keep the shellac in solution. Borax, which is a borate of soda, would be so acted on by the sulphuric acid that some boric acid would be set free, the sulphuric acid robbing some of that borax of its soda. This boric acid would not be nearly so injurious to wool as carbonate of soda or ammonia would.
The best solvent for shellac, however, in the preparation of the stiffening and proofing mixture for hats, is probably wood spirit or methylated spirit. A solution of shellac in wood spirit is indeed used for the spirit-proofing of silk hats, and to someextent of felt hats, and on the whole the best work, I believe, is done with it. Moreover, borax is not a cheap agent, and being non-volatile it is all left behind in the proofed material, whereas wood spirit or methylated spirit is a volatile liquid,i.e.a liquid easily driven off in vapour, and after application to the felt it may be almost all recovered again for re-use. In this way I conceive the use of wood spirit would be both more effective and also cheaper than that of borax, besides being most suitable in the case of any kind of dyes and colours to be subsequently applied to the hats.
Wood Spirit.—Wood spirit, the pure form of which is methyl alcohol, is one of the products of the destructive distillation of wood. The wood is distilled in large iron retorts connected to apparatus for condensing the distillation products. The heating is conducted slowly at first, so that the maximum yield of the valuable products—wood acid (acetic acid) and wood spirit—which distil at a low temperature, is obtained. When the condensed products are allowed to settle, they separate into two distinct layers, the lower one consisting of a thick, very dark tar, whilst the upper one, much larger in quantity, is the crude wood acid (containing also the wood spirit), and is reddish-yellow or reddish-brown in colour. This crude wood acid is distilled, and the wood spirit which distils off first is collected separately from the acetic acid which afterwards comes over. The acid is used for the preparation of alumina and iron mordants (see next lecture), or is neutralised with lime, forming grey acetate of lime, from which, subsequently, pure acetic acid or acetone is prepared. The crude wood spirit is mixed with milk of lime, and after standing for several hours is distilled in a rectifying still. The distillate is diluted with water, run off from any oily impurities which are separated, and re-distilled once or twice after treatment with quicklime.
Stiffening and Proofing Process.—Before proceeding todiscuss the stiffening and proofing of hat forms or "bodies," it will be well to point out that it was in thoroughly grasping the importance of a rational and scientific method of carrying out this process that Continental hat manufacturers had been able to steal a march upon their English rivals in competition as to a special kind of hat which sold well on the Continent. There are, or ought to be, three aims in the process of proofing and stiffening, all the three being of equal importance. These are: first, to waterproof the hat-forms; second, to stiffen them at the same time and by the same process; and the third, the one the importance of which I think English hat manufacturers have frequently overlooked, at least in the past, is to so proof and stiffen the hat-forms as to leave them in a suitable condition for the subsequent dyeing process. In proofing the felt, the fibres become varnished over with a kind of glaze which is insoluble in water, and this varnish or proof is but imperfectly removed from the ends of the fibres on the upper surface of the felt. The consequence is a too slight penetration of the dyestuff into the inner pores of the fibres; indeed, in the logwood black dyeing of such proofed felt a great deal of the colour becomes precipitated on the outside of the fibres—a kind of process of "smudging-on" of a black pigment taking place. The subsequent "greening" of the black hats after a short period of wear is simply due to the ease with which such badly fixed dye rubs off, washes off, or wears off, the brownish or yellowish substratum which gradually comes to light, causing a greenish shade to at length appear. If we examine under the microscope a pure unproofed fur fibre, its characteristic structure is quite visible. Examination of an unproofed fibre dyed with logwood black shows again the same characteristic structure with the dye inside the fibre, colouring it a beautiful bluish-grey tint, the inner cellular markings being black. A proofed fur fibre, on the other hand, when examined under the microscope, is seen to be covered with akind of translucent glaze, which completely envelops it, and prevents the beautiful markings showing the scaly structure of the fibre from being seen. Finally, if we examine microscopically a proofed fibre which has been dyed, or which we have attempted to dye, with logwood black, we find that the fibre presents an appearance similar to that of rope which has been drawn through some black pigment or black mud, and then dried. It is quite plain that no lustrous appearance or good "finish" can be expected from such material. Now how did the Continental hat manufacturers achieve their success, both as regards dyeing either with logwood black or with coal-tar colours, and also getting a high degree of "finish"? They attained their object by rubbing the proofing varnish on the inside of the hat bodies, in some cases first protecting the outside with a gum-varnish soluble in water but resisting the lac-varnish rubbed inside. Thus the proofing could never reach the outside. On throwing the hat bodies, thus proofed by a logical and scientific process, into the dye-bath, the gums on the outer surface are dissolved and removed, and the dye strikes into a pure, clean fibre, capable of a high degree of finish. This process, however, whilst very good for the softer hats used on the Continent, is not so satisfactory for the harder, stiffer headgear demanded in Great Britain. What was needed was a process which would allow of a through-and-through proofing and stiffening, and also of satisfactory dyeing of the stiffened and proofed felt. This was accomplished by a process patented in 1887 by Mr. F.W. Cheetham, and called the "veneering" process. The hat bodies, proofed as hard as usual, are thrown into a "bumping machine" containing hot water rendered faintly acid with sulphuric acid, and mixed with short-staple fur or wool, usually of a finer quality than that of which the hat bodies are composed. The hot acid water promotes in a high degree the felting powers of the short-staple wool or fur, and, to a lesser extent, the thinlyproofed ends of the fibres projecting from the surfaces of the proofed hat-forms. Thus the short-staple wool or fur felts itself on to the fibres already forming part of the hat bodies, and a new layer of pure, unproofed wool or fur is gradually wrought on to the proofed surface. The hat-forms are then taken out and washed, and can be dyed with the greatest ease and with excellent results, as will be seen from the accompanying illustration (see Fig. 15). This successful invention emphasisesthe value of the microscope in the study of processes connected with textile fibres. I would strongly advise everyone interested in hat manufacturing or similar industries to make a collection of wool and fur fibres, and mount them on microscope slides so as to form a kind of index collection for reference.