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.