Acetylene, the Principles of Its Generation and Use / A Practical Handbook on the Production, Purification, and Subsequent Treatment of Acetylene for the Development of Light, Heat, and Power

[Footnote 1: Interest and depreciation charges on generating and purifying plant = 0.15 penny. Purifying material and burner renewals = 0.05 penny.]

[Footnote 2: Mantle renewals as for coal-gas.]

[Footnote 3: Renewals of wicks and chimneys = 0.02 penny.]

[Footnote 4: Renewals and mantles (and chimneys) at contract rate of 3s. per burner per annum.]

[Footnote 5: Renewals of lamps and fuses, at price indicated per lamp per annum.]

The conventional method of making pecuniary comparisons between different sources of artificial light consists in simply calculating the cost of developing a certain number of candle-hours of light--i.e., a certain amount of standard candle-power for a given number of hours--on the assumption that as many separate sources of light are employed as may be required to bring the combined illuminating power up to the total amount wanted. In view of the facts as to dissemination and diffusion, or the difference between sheer illuminating power and useful illuminating effect, which have just been elaborated, and in view of the different intensities of the different unit sources of light (which range from the single candle to a powerful large incandescent gas-burner or a metallic filament electric lamp), such a method of calculation is wholly illusory. The plan adopted in the following table may also appear unnecessarily complicated; but it is not so to the reader if he remembers that the apparently various amount of illumination is corrected by the different numbers of illuminating units until the amount of simple candle-power developed, whatever illuminant be employed, suffices to light a room having an area of about 300 square feet (i.e., a room, 17-1/2 feet square, or one 20 feet long by 15 feet wide), so that ordinary print may be read comfortably in any part of the room, and the titles of books, engravings, &c., in any position on the walls up to a height of 8 feet from the ground may be distinguished with ease. The difference in cost, &c., of a greater or less degree of illumination, or of lighting a larger or smaller room by acetylene or any other of the illuminants named, will be almost directly proportional to the cost given for the stated conditions. Nevertheless, it should be recollected that when the conventional system is retained--useful illuminating effect being sacrificed to absolute illuminating power--acetylene is made to appear cheaper in comparison with all weaker unit sources of light, and dearer in comparison with all stronger unit sources of light than the accompanying table indicates it to be. In using the comparative figures given in the table, it should be borne in mind that they refer to more general and more brilliant illumination of a room than is commonly in vogue where the lighting is by means of electric light, candles, or oil- lamps. The standard of illumination adopted for the table is one which is only gaining general recognition where incandescent gas or acetylene lighting is available, though in exceptional cases it has doubtless been attained by means of oil-lamps or flat-flame gas-burners, but very rarely if ever by means of carbon-filament electric glow-lamps, or candles. It assumes that the occupants of a room do not wish to be troubled to bring work or book "to the light," but wish to be able to work or read wheresoever in the room they will, without consideration of the whereabouts of the light or lights.

It should, perhaps, be added that so high a price as 5s. per 1000 cubic feet for coal-gas rarely prevails in Great Britain, except in small outlying towns, whereas the price of 6d. per Board of Trade unit for electricity is not uncommonly exceeded in the few similar country places in which there is a public electricity supply.

CHAPTER II

THE PHYSICS AND CHEMISTRY OF THE REACTION BETWEEN CARBIDE AND WATER

THE NATURE OF CALCIUM CARBIDE.--The raw material from which, by interaction with water, acetylene is obtained, is a solid body called calcium carbide or carbide of calcium. Inasmuch as this substance can at present only be made on a commercial scale in the electric furnace--and so far as may be foreseen will never be made on a large scale except by means of electricity--inasmuch as an electric furnace can only be worked remuneratively in large factories supplied with cheap coal or water power; and inasmuch as there is no possibility of the ordinary consumer of acetylene ever being able to prepare his own carbide, all descriptions of this latter substance, all methods of winning it, and all its properties except those which concern the acetylene-generator builder or the gas consumer have been omitted from the present book. Hitherto calcium carbide has found but few applications beyond that of evolving acetylene on treatment with water or some aqueous liquid, hygroscopic solid, or salt containing water of crystallisation; but it has possibilities of further employment, should its price become suitable, and a few words will be devoted to this branch of the subject in Chapter XII. Setting these minor uses aside, calcium carbide has no intrinsic value except as a producer of acetylene, and therefore all its characteristics which interest the consumer of acetylene are developed incidentally throughout this volume as the necessity for dealing with them arises.

It is desirable, however, now to discuss one point connected with solid carbide about which some misconception prevails. Calcium carbide is a body which evolves an inflammable, or on occasion an explosive, gas when treated with water; and therefore its presence in a building has been said to cause a sensible increase in the fire risk because attempts to extinguish a fire in the ordinary manner with water may cause evolution of acetylene which should determine a further production of flame and heat. In the absence of water, calcium carbide is absolutely inert as regards fire; and on several occasions drums of it have been recovered uninjured from the basement of a house which has been totally destroyed by fire. With the exception of small 1-lb. tins of carbide, used only by cyclists, &c., the material is always put into drums of stout sheet-iron with riveted or folded seams. Provided the original lid has not been removed, the drums are air- and water-tight, so that the fireman's hose may be directed upon them with impunity. When a drum has once been opened, and not all of its contents have been put into the generator, ordinary caution--not merely as regards fire, but as regards the deterioration of carbide when exposed to the atmosphere--suggests either that the lid must be made air-tight again (not by soldering it), [Footnote: Carbide drums are not uncommonly fitted with self-sealing or lever-top lids, which are readily replaced hermetically tight after opening and partial removal of the contents of the drum.] or preferably that the rest of the carbide shall be transferred to some convenient receptacle which can be perfectly closed. [Footnote: It would be a refinement of caution, though hardly necessary in practice, to fit such a receptacle with a safety-valve. If then the vessel were subjected to sudden or severe heating, the expansion of the air and acetylene in it could not possibly exert a disruptive effect upon the walls of the receptacle, which, in the absence of the safety-valve, is imaginable.] Now, assuming this done, the drums are not dependent upon soft solder to keep them sound, and so they cannot open with heat. Fire and water, accordingly, cannot affect them, and only two risks remain: if stored in the basement of a tall building, falling girders, beams or brickwork may burst them; or if stored on an upper floor, they may fall into the basement and be burst with the shock--in either event water then having free access to the contents. But drums of carbide would never be stored in such positions: a single one would be kept in the generator-house; several would be stored in a separate room therein, or in some similar isolated shed. The generator-house or shed would be of one story only; the drums could neither fall nor have heavy weights fall on them during a fire; and therefore there is no reason why, if a fire should occur, the firemen should not be permitted to use their hose in the ordinary fashion. Very similar remarks apply to an active acetylene generator. Well built, such plant will stand much heat and fire without failure; if it is non-automatic, and of combustible materials contains nothing but gas in the holder, the worst that could happen in times of fire would be the unsealing of the bell or its fracture, and this would be followed, not at all by any explosion, but by a fairly quiet burning of the escaping gas, which would be over in a very short time, and would not add to the severity of the conflagration unless the generator-house were so close to the residence that the large flame of burning gas could ignite part of the main building. Even if the heat were so great near the holder that the gas dissociated, it is scarcely conceivable that a dangerous explosion should arise. But it is well to remember, that if the generator-house is properly isolated from the residence, if it is constructed of non-inflammable materials, if the attendant obeys instructions and refrains from taking a naked light into the neighbourhood of the plant, and if the plant itself is properly designed and constructed, a fire at or near an acetylene generator is extremely unlikely to occur. At the same time, before the erection of plant to supply any insured premises is undertaken, the policy or the company should be consulted to ascertain whether the adoption of acetylene lighting is possibly still regarded by the insurers as adding an extra risk or even as vitiating the whole insurance.

REGULATIONS FOR THE STORAGE OF CARBIDE: BRITISH.--There are also certain regulations imposed by many local authorities respecting the storage of carbide, and usually a licence for storage has to be obtained if more than 5 lb. is kept at a time. The idea of the rule is perfectly justifiable, and it is generally enforced in a sensible spirit. As the rules may vary in different localities, the intending consumer of acetylene must make the necessary inquiries, for failure to comply with the regulations may obviously be followed by unpleasantness.

Having regard to the fact that, in virtue of an Order in Council dated July 7, 1897, carbide may be stored without a licence only in separate substantial hermetically closed metal vessels containing not more than 1 lb. apiece and in quantities not exceeding 5 lb. in the aggregate, and having regard also to the fact that regulations are issued by local authorities, the Fire Offices' Committee of the United Kingdom has not up to the present deemed it necessary to issue special rules with reference to the storage of carbide of calcium.

The following is a copy of the rules issued by the National Board of Fire Underwriters of the UNITED STATES OF AMERICA for the storage of calcium carbide on insured premises:

RULES FOR THE STORAGE OF CALCIUM CARBIDE.

(a) Calcium carbide in quantities not to exceed six hundred (600) pounds may be stored, when contained in approved metal packages not to exceed one hundred (100) pounds each, inside insured property, provided that the place of storage be dry, waterproof and well ventilated, and also provided that all but one of the packages in any one building shall be sealed and the seals shall not be broken so long as there is carbide in excess of one (1) pound in any other unsealed package in the building.

(b) Calcium carbide in quantities in excess of six hundred (600) pounds must be stored above ground in detached buildings, used exclusively for the storage of calcium carbide, in approved metal packages, and such buildings shall be constructed to be dry, waterproof and well ventilated.

(c) Packages to be approved must be made of metal of sufficient strength to insure handling the package without rupture, and be provided with a screwed top or its equivalent.

They must be constructed so as to be water- and air-tight without the use of solder, and conspicuously marked "CALCIUM CARBIDE--DANGEROUS IF NOT KEPT DRY."

The following is a summary of the AUSTRIAN GOVERNMENT rules relating to the storage and handling of carbide:

(1) It must be sold and stored only in closed water-tight vessels, which, if the contents exceed 10 kilos., must be marked in plain letters "CALCIUM CARBIDE--TO BE KEPT CLOSED AND DRY." They must not be of copper and if soldered must be opened by mechanical means and not by unsoldering. They must be stored out of the reach of water.

(2) Quantities not exceeding 300 kilos. may be stored in occupied houses, provided the single drums do not exceed 100 kilos. nominal capacity. The storage-place must be dry and not underground.

(3) The limits specified in Rule 2 apply also to generator-rooms, with the proviso also that in general the amount stored shall not exceed five days' consumption.

(4) Quantities ranging from 300 to 1000 kilos. must be stored in special well-ventilated uninhabited non-basement rooms in which lights and smoking are not allowed.

(5) Quantities exceeding 1000 kilos. must be stored in isolated fireproof magazines with light water-tight roofs. The floors must be at least 8 inches above ground-level.

(6) Carbide in water-tight drums may be stored in the open in a fenced enclosure at least 30 feet from buildings, adjoining property, or inflammable materials. The drums must be protected from wet by a light roof.

(7) The breaking of carbide must be done by men provided with respirators and goggles, and care taken to avoid the formation of dust.

(8) Local or other authorities will issue from time to time special regulations in regard to carbide trade premises.

The ITALIAN GOVERNMENT rules relating to the storage and transport of carbide follow in the main those of the Austrian Government, but for quantities between 300 and 2000 kilos sanction is required from the local authorities, and for larger quantities from superior authorities. The storage of quantities ranging from 300 to 2000 kilos is forbidden in dwelling-houses and above the latter quantity the storage-place must be isolated and specially selected. No special permit is required for the storage of quantities not exceeding 300 kilos. Workmen exposed to carbide dust arising from the breaking of carbide or otherwise must have their eyes and respiratory organs suitably protected.

THE PURCHASE OF CARBIDE.--Since calcium carbide is only useful as a means of preparing acetylene, it should be bought under a guarantee (1) that it contains less impurities than suffice to render the crude gas dangerous in respect of spontaneous inflammability, or objectionable in a manner to be explained later on, when consumed; and (2) that it is capable of evolving a fixed minimum quantity of acetylene when decomposed by water. Such determination, however, cannot be carried out by the ordinary consumer for himself. A generator which is perfectly satisfactory in general behaviour, and which evolves a sufficient proportion of the possible total make of gas to be economical, does not of necessity decompose the carbide quantitatively; nor is it constructed in a fashion to render an exact measurement of the gas liberated at standard temperature and pressure easy to obtain. For obvious reasons the careful consumer of acetylene will keep a record of the carbide decomposed and of the acetylene generated--the latter perhaps only in terms of burner- hours, or the like; but in the event of serious dispute as to the gas- making capacity of his raw material, he must have a proper analysis made by a qualified chemist.

Calcium carbide is crushed by the makers into several different sizes, in each of which all the lumps exceed a certain size and are smaller than another size. It is necessary to find out by experiment, or from the maker, what particular size suits the generator best, for different types of apparatus require different sizes of carbide. Carbide cannot well be crushed by the consumer of acetylene. It is a difficult operation, and fraught with the production of dust which is harmful to the eyes and throat, and if done in open vessels the carbide deteriorates in gas- making power by its exposure to the moisture of the atmosphere. True dust in carbide is objectionable, and practically useless for the generation of acetylene in any form of apparatus, but carbide exceeding 1 inch in mesh is usually sold to satisfy the suggestions of the British Acetylene Association, which prescribes 5 per cent, of dust as the maximum. Some grades of carbide are softer than others, and therefore tend to yield more dust if exposed to a long journey with frequent unloadings.

There are certain varieties of ordinary carbide known as "treated carbide," the value of which is more particularly discussed in Chapter III. The treatment is of two kinds, or of a combination of both. In one process the lumps are coated with a strong solution of glucose, with the object of assisting in the removal of spent lime from their surface when the carbide is immersed in water. Lime is comparatively much more soluble in solutions of sugar (to which class of substances glucose belongs) than in plain water; so that carbide treated with glucose is not so likely to be covered with a closely adherent skin of spent lime when decomposed by the addition of water to it. In the other process, the carbide is coated with or immersed in some oil or grease to protect it from premature decomposition. The latter idea, at least, fulfils its promises, and does keep the carbide to a large extent unchanged if the lumps are exposed to damp air, while solving certain troubles otherwise met with in some generators (cf. Chapter III.); but both operations involve additional expense, and since ordinary carbide can be used satisfactorily in a good fixed generator, and can be preserved without serious deterioration by the exercise of reasonable care, treated carbide is only to be recommended for employment in holderless generators, of which table-lamps are the most conspicuous forms. A third variant of plain carbide is occasionally heard of, which is termed "scented" carbide. It is difficult to regard this material seriously. In all probability calcium carbide is odourless, but as it begins to evolve traces of gas immediately atmospheric moisture reaches it, a lump of carbide has always the unpleasant smell of crude acetylene. As the material is not to be stored in occupied rooms, and as all odour is lost to the senses directly the carbide is put into the generator, scented carbide may be said to be devoid of all utility.

THE REACTION BETWEEN CARBIDE AND WATER.--The reaction which occurs when calcium carbide and water are brought into contact belongs to the class that chemists usually term double decompositions. Calcium carbide is a chemical compound of the metal calcium with carbon, containing one chemical "part," or atomic weight, of the former united to two chemical parts, or atomic weights, of the latter; its composition expressed in symbols being CaC_2. Similarly, water is a compound of two chemical parts of hydrogen with one of oxygen, its formula being H_2O. When those two substances are mixed together the hydrogen of the water leaves its original partner, oxygen, and the carbon of the calcium carbide leaves the calcium, uniting together to form that particular compound of hydrogen and carbon, or hydrocarbon, which is known as acetylene, whose formula is C_2H_2; while the residual calcium and oxygen join together to produce calcium oxide or lime, CaO. Put into the usual form of an equation, the reaction proceeds thus--

(1) CaC_2 + H_2O = C_2H_2 + CaO.

This equation not only means that calcium carbide and water combine to yield acetylene and lime, it also means that one chemical part of carbide reacts with one chemical part of water to produce one chemical part of acetylene and one of lime. But these four chemical parts, or molecules, which are all equal chemically, are not equal in weight; although, according to a common law of chemistry, they each bear a fixed proportion to one another. Reference to the table of "Atomic Weights" contained in any text-book of chemistry will show that while the symbol Ca is used, for convenience, as a contraction or sign for the element calcium simply, it bears a more important quantitative significance, for to it will be found assigned the number 40. Against carbon will be seen the number 12; against oxygen, 16; and against hydrogen, 1. These numbers indicate that if the smallest weight of hydrogen ever found in a chemical compound is called 1 as a unit of comparison, the smallest weights of calcium, carbon, and oxygen, similarly taking part in chemical reactions are 40, 12, and 16 respectively. Thus the symbol CaC_2, comes to convoy three separate ideas: (a) that the substance referred to is a compound of calcium and carbon only, and that it is therefore a carbide of calcium; (b) that it is composed of one chemical part or atom of calcium and two atoms of carbon; and (c) that it contains 40 parts by weight of calcium combined with twice twelve, or 24, parts of carbon. It follows from (c) that the weight of one chemical part, now termed a molecule as the substance is a compound, of calcium carbide is (40 + 2 x 12) = 64. By identical methods of calculation it will be found that the weight of one molecule of water is 18; that of acetylene, 26; and that of lime, 56. The general equation (1) given above, therefore, states in chemical shorthand that 64 parts by weight of calcium carbide react with 18 parts of water to give 26 parts by weight of acetylene and 56 parts of lime; and it is very important to observe that just as there are the same number of chemical parts, viz., 2, on each side, so there are the same number of parts by weight, for 64 + 18 = 56 + 26 = 82. Put into other words equation (1) shows that if 64 grammes, lb., or cwts. of calcium carbide are treated with 18 grammes, lb., or cwts. of water, the whole mass will be converted into acetylene and lime, and the residue will not contain any unaltered calcium carbide or any water; whence it may be inferred, as is the fact, that if the weights of carbide and water originally taken do not stand to one another in the ratio 64 : 18, both substances cannot be entirely decomposed, but a certain quantity of the one which was in excess will be left unattacked, and that quantity will be in exact accordance with the amount of the said excess--indifferently whether the superabundant substance be carbide or water.

Hitherto, for the sake of simplicity, the by-product in the preparation of acetylene has been described as calcium oxide or quicklime. It is, however, one of the leading characteristics of this body to be hygroscopic, or greedy of moisture; so that if it is brought into the presence of water, either in the form of liquid or as vapour, it immediately combines therewith to yield calcium hydroxide, or slaked lime, whose chemical formula is Ca(OH)_2. Accordingly, in actual practice, when calcium carbide is mixed with an excess of water, a secondary reaction takes place over and above that indicated by equation (1), the quicklime produced combining with one chemical part or molecule of water, thus--

CaO + H_2O = Ca(OH)_2.

As these two actions occur simultaneously, it is more usual, and more in agreement with the phenomena of an acetylene generator, to represent the decomposition of calcium carbide by the combined equation--

(2) CaC_2 + 2H_2O = C_2H_2 + Ca(OH)_2.

By the aid of calculations analogous to those employed in the preceding paragraph, it will be noticed that equation (2) states that 1 molecule of calcium carbide, or 64 parts by weight, combines with 2 molecules of water, or 36 parts by weight, to yield 1 molecule, or 26 parts by weight of acetylene, and 1 molecule, or 74 parts by weight of calcium hydroxide (slaked lime). Here again, if more than 36 parts of water are taken for every 64 parts of calcium carbide, the excess of water over those 36 parts is left undecomposed; and in the same fashion, if less than 36 parts of water are taken for every 64 parts of calcium carbide, some of the latter must remain unattacked, whilst, obviously, the amount of acetylene liberated cannot exceed that which corresponds with the quantity of substance suffering complete decomposition. If, for example, the quantity of water present in a generator is more than chemically sufficient to attack all the carbide added, however largo or small that excess may be, no more, and, theoretically speaking, no less, acetylene can ever be evolved than 26 parts by weight of gas for every 64 parts by weight of calcium carbide consumed. It is, however, not correct to invert the proposition, and to say that if the carbide is in excess of the water added, no more, and, theoretically speaking, no less, acetylene can ever be evolved than 26 parts by weight of gas for every 36 parts of water consumed, as might be gathered from equation (2); because equation (1) shows that 26 parts of acetylene may, on occasion, be produced by the decomposition of 18 parts by weight of water. From the purely chemical point of view this apparent anomaly is explained by the circumstance that of the 36 parts of water present on the left-hand aide of equation (2), only one-half, i.e., 18 parts by weight, are actually decomposed into hydrogen and oxygen, the other 18 parts remaining unattacked, and merely attaching themselves as "water of hydration" to the 56 parts of calcium oxide in equation (1) so as to produce the 74 parts of calcium hydroxide appearing on the right-hand side of equation (2). The matter is perhaps rendered more intelligible by employing the old name for calcium hydroxide or slaked lime, viz., hydrated oxide of calcium, and by writing its formula in the corresponding form, when equation (2) becomes

CaC_2 + 2H_2O = C_2H_2 + CaO.H_2O.

It is, therefore, absolutely correct to state that if the amount of calcium carbide present in an acetylene generator is more than chemically sufficient to decompose all the water introduced, no more, and theoretically speaking no less, acetylene can ever be liberated than 26 parts by weight of gas for every 18 parts by weight of water attacked. This, it must be distinctly understood, is the condition of affairs obtaining in the ideal acetylene generator only; since, for reasons which will be immediately explained, when the output of gas is measured in terms of the water decomposed, in no commercial apparatus, and indeed in no generator which can be imagined fit for actual employment, does that output of gas ever approach the quantitative amount; but the volume of water used, if not actually disappearing, is always vastly in excess of the requirements of equation (2). On the contrary, when the make of gas is measured in terms of the calcium carbide consumed, the said make may, and frequently does, reach 80, 90, or even 99 per cent. of what is theoretically possible. Inasmuch as calcium carbide is the one costly ingredient in the manufacture of acetylene, so long as it is not wasted-- so long, that is to say, as nearly the theoretical yield of gas is obtained from it--an acetylene generator is satisfactory or efficient in this particular; and except for the matter of solubility discussed in the following chapter, the quantity of water consumed is of no importance whatever.

HEAT EVOLVED IN THE REACTION.--The chemical reaction between calcium carbide and water is accompanied by a large evolution of heat, which, unless due precautions are taken to prevent it, raises the temperature of the substances employed, and of the apparatus containing them, to a serious and often inconvenient extent. This phenomenon is the most important of all in connexion with acetylene manufacture; for upon a proper recognition of it, and upon the character of the precautions taken to avoid its numerous evil effects, depend the actual value and capacity for smooth working of any acetylene generator. Just as, by an immutable law of chemistry, a given weight of calcium carbide yields a given weight of acetylene, and by no amount of ingenuity can be made to produce either more or less; so, by an equally immutable law of physics, the decomposition of a given weight of calcium carbide by water, or the decomposition of a given weight of water by calcium carbide, yields a perfectly definite quantity of heat--a quantity of heat which cannot be reduced or increased by any artifice whatever. The result of a production of heat is usually to raise the temperature of the material in which it is produced; but this is not always the case, and indeed there is no necessary connexion or ratio between the quantity of heat liberated in any form of chemical reaction--of which ordinary combustion is the commonest type--and the temperature attained by the substances concerned. This matter has so weighty a bearing upon acetylene generation, and appears to be so frequently misunderstood, that a couple of illustrations may with advantage be studied. If a vessel full of cold water, and containing also a thermometer, is placed over a lighted gas-burner, at first the temperature of the liquid rises steadily, and there is clearly a ratio between the size of the flame and the speed at which the mercury mounts up the scale. Finally, however, the thermometer indicates a certain point, viz., 100° C, and the water begins to boil; yet although the burner is untouched, and consequently, although heat must be passing into the vessel at the same rate as before, the mercury refuses to move as long as any liquid water is left. By the use of a gas meter it might be shown that the same volume of gas is always consumed (a) in raising the temperature of a given quantity of cold water to the boiling- point, and another equally constant volume of gas is always consumed (b) in causing the boiling water to disappear as steam. Hence, as coal-gas is assumed for the present purpose to possess invariably the same heating power, it appears that the same quantity of heat is always needed to convert a given amount of cold water at a certain temperature into steam; but inasmuch as reference to the meter would show that about 5 times the volume of gas is consumed in changing the boiling water into steam as is used in heating the cold water to the boiling-point, it will be evident that the temperature of the mass is raised as high by the heat evolved during the combustion of one part of gas as it is by that liberated on the combustion of 6 times that amount.

A further example of the difference between quantity of heat and sensible temperature may be seen in the combustion of coal, for (say) one hundredweight of that fuel might be consumed in a very few minutes in a furnace fitted with a powerful blast of air, the operation might be spread over a considerable number of hours in a domestic grate, or the coal might be allowed to oxidise by exposure to warm air for a year or more. In the last case the temperature might not attain that of boiling water, in the second it would be about that of dull redness, and in the first it would be that of dazzling whiteness; but in all three cases the total quantity of heat produced by the time the coal was entirely consumed would be absolutely identical. The former experiment with water and a gas-burner, too, might easily be modified to throw light upon another problem in acetylene generation, for it would be found that if almost any other liquid than water were taken, less gas (i.e., a smaller quantity of heat) would be required to raise a given weight of it from a certain low to a certain high temperature than in the case of water itself; while if it were possible similarly to treat the same weight of iron (of which acetylene generators are constructed), or of calcium carbide, the quantity of heat used to raise it through a given number of thermometric degrees would hardly exceed one-tenth or one- quarter of that needed by water itself. In technical language this difference is due to the different specific heats of the substances mentioned; the specific heat of a body being the relative quantity of heat consumed in raising a certain weight of it a certain number of degrees when the quantity of heat needed to produce the same effect on the same weight of water is called unity. Thus, the specific heat of water being termed 1.0, that of iron or steel is 0.1138, and that of calcium carbide 0.247, [Footnote: This is Carlson's figure. Morel has taken the value 0.103 in certain calculations.] both measured at temperatures where water is a liquid. Putting the foregoing facts in another shape, for a given rise in temperature that substance will absorb the most heat which has the highest specific heat, and therefore, in this respect, 1 part by weight of water will do the work of roughly 9 parts by weight of iron, and of about 4 parts by weight of calcium carbide.

From the practical aspect what has been said amounts to this: During the operation of an acetylene generator a large amount of heat is produced, the quantity of which is beyond human control. It is desirable, for various reasons, that the temperature shall be kept as low as possible. There are three substances present to which the heat may be compelled to transfer itself until it has opportunity to pass into the surrounding atmosphere: the material of which the apparatus is constructed, the gas which is in process of evolution, and whichever of the two bodies-- calcium carbide or water--is in excess in the generator. Of these, the specific heat at constant pressure of acetylene has unfortunately not yet been determined, but its relative capacity for absorbing heat is undoubtedly small; moreover the gas could not be permitted to become sufficiently hot to carry off the heat without grave disadvantages. The specific heat of calcium carbide is also comparatively small, and there are similar disadvantages in allowing it to become hot; moreover it is deficient in heat-conducting power, so that heat communicated to one portion of the mass does not extend rapidly throughout, but remains concentrated in one spot, causing the temperature to rise objectionably. Steel has a sufficient amount of heat-conducting power to prevent undue concentration in one place; but, as has been stated, its specific heat is only one-ninth that of water. Water is clearly, therefore, the proper substance to employ for the dissipation of the heat generated, although it is strictly speaking almost devoid of heat-conducting power; for not only is the specific heat of water much greater than that of any other material present, but it possesses in a high degree the faculty of absorbing heat throughout its mass, by virtue of the action known as convection, provided that heat is communicated to it at or near the bottom, and not too near its upper surface. Moreover, water is a much more valuable substance for dissipating heat than appears from the foregoing explanation; for reference to the experiment with the gas- burner will show that six and a quarter times as much heat can be absorbed by a given weight of water if it is permitted to change into steam, as if it is merely raised to the boiling-point; and since by no urging of the gas-burner can the temperature be raised above 100° C. as long as any liquid water remains unevaporated, if an excess of water is employed in an acetylene generator, the temperature inside can never-- except quite locally--exceed 100° C., however fast the carbide be decomposed. An indefinitely large consumption of water by evaporation in a generator matters nothing, for the liquid may be considered of no pecuniary value, and it can all be recovered by condensation in a subsequent portion of the plant.

It has been said that the quantity of heat liberated when a certain amount of carbide suffers decomposition is fixed; it remains now to consider what that quantity is. Quantities of heat are always measured in terms of the amount needed to raise a certain weight of water a certain number of degrees on the thermometric scale. There are several units in use, but the one which will be employed throughout this book is the "Large Calorie"; a large calorie being the amount of heat absorbed in raising 1 kilogramme of water 1° C. Referring for a moment to what has been said about specific heats, it will be apparent that if 1 large calorie is sufficient to heat 1 kilo, of water through 1° C. the same quantity will heat 1 kilo. of steel, whose specific heat is roughly 0.11, through (10/011) = 9° C., or, which comes to the same thing, will heat 9 kilos, of steel through 1° C.; and similarly, 1 large calorie will raise 4 kilos. of calcium carbide 1° C. in temperature, or 1 kilo. 4° C. The fact that a definite quantity of heat is manifested when a known weight of calcium carbide is decomposed by water is only typical; for in every chemical process some disturbance of heat, though not necessarily of sensible (or thermometric) character, occurs, heat being either absorbed or set free. Moreover, if when given weights of two or more substances unite to form a given weight of another substance, a certain quantity of heat is set free, precisely the same amount of heat is absorbed, or disappears, when the latter substance is decomposed to form the same quantities of the original substances; and, per contra, if the combination is attended by a disappearance of heat, exactly the same amount is liberated when the compound is broken up into its first constituents. Compounds are therefore of two kinds: those which absorb heat during their preparation, and consequently liberate heat when they are decomposed--such being termed endothermic; and those which evolve heat during their preparation, and consequently absorb heat when they are decomposed--such being called exothermic. If a substance absorbs heat during its formation, it cannot be produced unless that heat is supplied to it; and since heat, being a form of motion, is equally a form of energy, energy must be supplied, or work must be done, before that substance can be obtained. Conversely, if a substance evolves heat during its formation, its component parts evolve energy when the said substance is being produced; and therefore the mere act of combination is accompanied by a facility for doing work, which work may be applied in assisting some other reaction that requires heat, or may be usefully employed in any other fashion, or wasted if necessary. Seeing that there is a tendency in nature for the steady dissipation of energy, it follows that an exothermic substance is stable, for it tends to remain as it is unless heat is supplied to it, or work is done upon it; whereas, according to its degree of endothermicity, an endothermic substance is more or less unstable, for it is always ready to emit heat, or to do work, as soon as an opportunity is given to it to decompose. The theoretical and practical results of this circumstance will be elaborated in Chapter VI., when the endothermic nature of acetylene is more fully discussed.

A very simple experiment will show that a notable quantity of heat is set free when calcium carbide is brought into contact with water, and by arranging the details of the apparatus in a suitable manner, the quantity of heat manifested may be measured with considerable accuracy. A lengthy description of the method of performing this operation, however, scarcely comes within the province of the present book, and it must be sufficient to say that the heat is estimated by decomposing a known weight of carbide by means of water in a small vessel surrounded on all sides by a carefully jacketed receptacle full of water and provided with a sensitive thermometer. The quantity of water contained in the outer vessel being known, and its temperature having been noted before the reaction commences, an observation of the thermometer after the decomposition is finished, and when the mercury has reached its highest point, gives data which show that the reaction between water and a known weight of calcium carbide produces heat sufficient in amount to raise a known weight of water through a known thermometric distance; and from these figures the corresponding number of large calories may easily be calculated. A determination of this quantity of heat has been made experimentally by several investigators, including Lewes, who has found that the heat evolved on decomposing 1 gramme of ordinary commercial carbide with water is 0.406 large calorie. [Footnote: Lewes returns his result as 406 calories, because he employs the "small calorie." The small calorie is the quantity of heat needed to raise 1 gramme of water 1° C.; but as there are 1000 grammes in 1 kilogramme, the large calorie is equal to 1000 small calories. In many respects the former unit is to be preferred.] As the material operated upon contained only 91.3 per cent. of true calcium carbide, he estimates the heat corresponding with the decomposition of 1 gramme of pure carbide to be 0.4446 large calorie. As, however, it is better, and more in accordance with modern practice, to quote such data in terms of the atomic or molecular weight of the substance concerned, and as the molecular weight of calcium carbide is 64, it is preferable to multiply these figures by 64, stating that, according to Lewes' researches, the heat of decomposition of "1 gramme- molecule" (i.e., 64 grammes) of a calcium carbide having a purity of 91.3 per cent. is just under 26 calories, or that of 1 gramme-molecule of pure carbide 28.454 calories. It is customary now to omit the phrase "one gramme-molecule" in giving similar figures, physicists saying simply that the heat of decomposition of calcium carbide by water when calcium hydroxide is the by-product, is 28.454 large calories.

Assuming all the necessary data known, as happens to be the case in the present instance, it is also possible to calculate theoretically the heat which should be evolved on decomposing calcium carbide by means of water. Equation (2), given on page 24, shows that of the substances taking part in the reaction 1 molecular weight of calcium carbide is decomposed, and 1 molecular weight of acetylene is formed. Of the two molecules of water, only one is decomposed, the other passing to the calcium hydroxide unchanged; and the 1 molecule of calcium hydroxide is formed by the combination of 1 atom of free calcium, 1 atom of free oxygen, and 1 molecule of water already existing as such. Calcium hydroxide and water are both exothermic substances, absorbing heat when they are decomposed, liberating it when they are formed. Acetylene is endothermic, liberating heat when it is decomposed, absorbing it when it is produced. Unfortunately there is still some doubt about the heat of formation of calcium carbide, De Forcrand returning it as -0.65 calorie, and Gin as +3.9 calories. De Forcrand's figure means, as before explained, that 64 grammes of carbide should absorb 0.65 large calorie when they are produced by the combination of 40 grammes of calcium with 24 grammes of carbon; the minus sign calling attention to the belief that calcium carbide is endothermic, heat being liberated when it suffers decomposition. On the contrary, Gin's figure expresses the idea that calcium carbide is exothermic, liberating 3.9 calories when it is produced, and absorbing them when it is decomposed. In the absence of corroborative evidence one way or the other, Gin's determination will be accepted for the ensuing calculation. In equation (2), therefore, calcium carbide is decomposed and absorbs heat; water is decomposed and absorbs heat; acetylene is produced and absorbs heat; and calcium hydroxide is produced liberating heat. On consulting the tables of thermo-chemical data given in the various text-books on physical chemistry, all the other constants needed for the present purpose will be found; and it will appear that the heat of formation of water is +69 calories, that of acetylene -58.1 calories, and that of calcium hydroxide, when 1 atom of calcium, 1 atom of oxygen, and 1 molecule of water unite together, is +160.1 calories. [Footnote: When 1 atom of calcium, 2 atoms of oxygen, and 2 atoms of hydrogen unite to form solid calcium hydroxide, the heat of formation of the latter is 229.1 (cf. infra). This value is simply 160.1 + 69.0 = 229.1; 69.0 being the heat of formation of water.] Collecting the results into the form of a balance-sheet, the effect of decomposing calcium carbide with water is this: