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 - F. H. Leeds; W. J. Atkinson Butterfield

which comes to the same thing. Putting the matter in another shape, it may be said that the reaction between calcium carbide and water is exothermic, evolving either 14.0 or 29.1 calories according as the byproduct is calcium oxide or solid calcium hydroxide; and therefore either reaction proceeds without external assistance in the cold. The reaction between carbide and slaked lime, however, is endothermic, absorbing 1.1 calories; and therefore it requires external assistance (presence of an elevated temperature) to start it, or continuous introduction of heat (as from the reaction between the rest of the carbide present and the water) to cause it to proceed. Of itself, and were it not for the disadvantages attending the production of a temperature remotely approaching 400° C. in an acetylene generator, which disadvantages will be explained in the following paragraphs, there is no particular reason why reaction (3) should not be permitted to occur, for it involves (theoretically) no loss of acetylene, and no waste of calcium carbide. Only one specific feature of the reaction has to be remembered, and due practical allowance made for it. The reaction represented by equation (2) proceeds almost instantaneously when the calcium carbide is of ordinarily good quality, and the acetylene resulting therefrom is wholly generated within a very few minutes. Equation (3), on the contrary, consumes much time for its completion, and the gas corresponding with it is evolved at a gradually diminishing speed which may cause the reaction to continue for hours--a circumstance that may be highly inconvenient or quite immaterial according to the design of the apparatus. When, however, it is desired to construct an automatic acetylene generator, i.e., an apparatus in which the quantity of gas liberated has to be controlled to suit the requirements of any indefinite number of burners in use on different occasions, equation (3) becomes a very important factor in the case. To determine the normal reaction (No. 2) of an acetylene generator, 64 parts by weight of calcium carbide must react with 36 parts of water to yield 26 parts by weight of acetylene, and apparently both carbide and water are entirely consumed; but if opportunity is given for the occurrence of reaction (3), another 64 parts by weight of carbide may be attacked, without the addition of any more water, producing, inevitably, another 26 parts of acetylene. If, then, water is in chemical excess in the generator, all the calcium carbide present will be decomposed according to equation (2), and the action will take place without delay; after a few minutes' interval the whole of the acetylene capable of liberation will have been evolved, and nothing further can possibly happen until another charge of carbide is inserted in the apparatus. If, on the other hand, calcium carbide is in chemical excess in the generator, all the water run in will be consumed according to equation (2), and this action will again take place without delay; but unless the temperature of the residual carbide has been kept well below 400° C., a further evolution of gas will occur which will not cease for an indeterminate period of time, and which, by strict theory, given the necessary conditions, might continue until a second volume of acetylene equal to that liberated at first had been set free. In practice this phenomenon of a secondary production of gas, which is known as "after-generation," is regularly met with in all generators where the carbide is in excess of the water added; but the amount of acetylene so evolved rarely exceeds one-quarter or one-third of the main make. The actual amount evolved and the rate of evolution depend, not merely upon the quantity of undecomposed carbide still remaining in contact with the damp lime, but also upon the rapidity with which carbide naturally decomposes in presence of liquid water, and the size of the lumps. Where "after-generation" is caused by the ascent of water vapour round lumps of carbide, the volume of gas produced in a given interval of time is largely governed by the temperature prevailing and the shape of the apparatus. It is evident that even copious "after-generation" is a matter of no consequence in any generator provided with a holder to store the gas, assuming that by some trustworthy device the addition of water is stopped by the time that the holder is two-thirds or three-quarters full. In the absence of a holder, or if the holder fitted is too small to serve its proper purpose, "aftergeneration" is extremely troublesome and sometimes dangerous, but a full discussion of this subject must be postponed to the next chapter.

EFFECT OF HEAT ON ACETYLENE.--The effect of excessive retention of heat in an acetylene generator upon the gas itself is very marked, as acetylene begins spontaneously to suffer change, and to be converted into other compounds at elevated temperatures. Being a purely chemical phenomenon, the behaviour of acetylene when exposed to heat will be fully discussed in Chapter VI. when the properties of the gas are being systematically dealt with. Here it will be sufficient to assume that the character of the changes taking place is understood, and only the practical results of those changes as affecting the various components of an acetylene installation have to be studied. According to Lewes, acetylene commences to "polymerise" at a temperature of about 600° C., when it is converted into other hydrocarbons having the same percentage composition, but containing more atoms of carbon and hydrogen in their molecules. The formula of acetylene is C_2H_2 which means that 2 atoms of carbon and 2 atoms of hydrogen unite to form 1 molecule of acetylene, a body evidently containing roughly 92.3 per cent. by weight of carbon and 7.7 per cent. by weight of hydrogen. One of the most noteworthy substances produced by the polymerisation of acetylene is benzene, the formula of which is C_6H_6, and this is formed in the manner indicated by the equation--

(4) 3C_2H_2 = C_6H_6.

Now benzene also contains 92.3 per cent. of carbon and 7.7 per cent. by weight of hydrogen in its composition, but its molecule contains 6 atoms of each element. When the chemical formula representing a compound body indicates a substance which is, or can be obtained as, a gas or vapour, it convoys another idea over and above those mentioned on a previous page. The formula "C_2H_2," for example, means 1 molecule, or 26 parts by weight of acetylene, just as "H_2" means 1 molecule, or 2 parts by weight of hydrogen; but both formulæ also mean equal parts by volume of the respective substances, and since H_2 must mean 2 volumes, being twice H, which is manifestly 1, C_2H_2 must mean 2 volumes of acetylene as well. Thus equation (4) states that 6 volumes of acetylene, or 3 x 26 parts by weight, unite to form 2 volumes of benzene, or 78 parts by weight. If these hydrocarbons are burnt in air, both are indifferently converted into carbon dioxide (carbonic acid gas) and water vapour; and, neglecting for the sake of simplicity the nitrogen of the atmosphere, the processes may be shown thus:

(5) 2C_2H_2 + 5O_2 = 4CO_2 + 2H_2O.

(6) 2C_6H_6 + 15O_2 = 12CO_2 + 6H_2O.

Equation (5) shows that 4 volumes of acetylene combine with 10 volumes of oxygen to produce 8 volumes of carbon dioxide and 4 of water vapour; while equation (6) indicates that 4 volumes of benzene combine with 30 volumes of oxygen to yield 24 volumes of carbon dioxide and 12 of water vapour. Two parts by volume of acetylene therefore require 5 parts by volume of oxygen for perfect combustion, whereas two parts by volume of benzene need 15--i.e., exactly three times as much. In order to work satisfactorily, and to develop the maximum of illuminating power from any kind of gas consumed, a gas-burner has to be designed with considerable skill so as to attract to the base of the flame precisely that volume of air which contains the quantity of oxygen necessary to insure complete combustion, for an excess of air in a flame is only less objectionable than a deficiency thereof. If, then, an acetylene burner is properly constructed, as most modern ones are, it draws into the flame air corresponding with two and a half volumes of oxygen for every one volume of acetylene passing from the jets; whereas if it were intended for the combustion of benzene vapour it would have to attract three times that quantity. Since any flame supplied with too little air tends to emit free carbon or soot, it follows that any well-made acetylene burner delivering a gas containing benzene vapour will yield a more or lens smoky flame according to the proportion of benzene in the acetylene. Moreover, at ordinary temperatures benzene is a liquid, for it boils at 81° C., and although, as was explained above in the case of water, it is capable of remaining in the state of vapour far below its boiling-point so long as it is suspended in a sufficiency of some permanent gas like acetylene, if the proportion of vapour in the gas at any given temperature exceeds a certain amount the excess will be precipitated in the liquid form; while as the temperature falls the proportion of vapour which can be retained in a given volume of gas also diminishes to a noteworthy extent. Should any liquid, be it water or benzene, or any other substance, separate from the acetylene under the influence of cold while the gas is passing through pipes, the liquid will run downwards to the lowest points in those pipes; and unless due precautions are taken, by the insertion of draw-off cocks, collecting wells, or the like, to withdraw the deposited water or other liquid, it will accumulate in all bends, angles, and dips till the pipes are partly or completely sealed against the passage of gas, and the lights will either "jump" or be extinguished altogether. In the specific case of an acetylene generator this trouble is very likely to arise, even when the gas is not heated sufficiently during evolution for polymerisation to occur and benzene or other liquid hydrocarbons to be formed, because any excess of water present in the decomposing vessel is liable to be vaporised by the heat of the reaction--as already stated it is desirable that water shall be so vaporised--and will remain safely vaporised as long as the pipes are kept warm inside or near the generator; but directly the pipes pass away from the hot generator the cooling action of the air begins, and some liquid water will be immediately produced. Like the phenomenon of after- generation, this equally inevitable phenomenon of water condensation will be either an inconvenience or source of positive danger, or will be a matter of no consequence whatever, simply as the whole acetylene installation, including the service-pipes, is ignorantly or intelligently built.

As long as nothing but pure polymerisation happens to the acetylene, as long, that is to say, as it is merely converted into other hydrocarbons also having the general formula C_(2n)H_(2n), no harm will be done to the gas as regards illuminating power, for benzene burns with a still more luminous flame than acetylene itself; nor will any injury result to the gas if it is required for combustion in heating or cooking stoves beyond the fact that the burners, luminous or atmospheric, will be delivering a material for the consumption of which they are not properly designed. But if the temperature should rise much above the point at which benzene is the most conspicuous product of polymerisation, other far more complicated changes occur, and harmful effects may be produced in two separate ways. Some of the new hydrocarbons formed may interact to yield a mixture of one or more other hydrocarbons containing a higher proportion of carbon than that which is present in acetylene and benzene, together with a corresponding proportion of free hydrogen; the former will probably be either liquids or solids, while the latter burns with a perfectly non-luminous flame. Thus the quantity of gas evolved from the carbide and passed into the holder is less than it should be, owing to the condensation of its non-gaseous constituents. To quote an instance of this, Haber has found 15 litres of acetylene to be reduced in volume to 10 litres when the gas was heated to 638° C. By other changes, some "saturated hydrocarbons," i.e., bodies having the general formula C_nH_(2n+2), of which methane or marsh-gas, CH_4 is the best known, may be produced; and those all possess lower illuminating powers than acetylene. In two of those experiments already described, where Lewes observed maximum temperatures ranging from 703° to 807° C., samples of the gas which issued when the heat was greatest were submitted to chemical analysis, and their illuminating powers were determined. The figures he gives are as follows:

I. II.
Per Cent. Per Cent.
Acetylene 70.0 69.7
Saturated hydrocarbons 11.3 11.4
Hydrogen 18.7 18.9
_____ _____
100.0 100.0