Page:EB1911 - Volume 10.djvu/488

Rh E. Mallard and H. L. le Chatelier and H. B. Dixon have shown that a distinction must be made between the slow initial rate of inflammation of gaseous mixtures and the rapid rate of detonation, or rate of the explosive wave, which in many cases is subsequently set up. We shall here deal only with the slow movements of flame. The development of a flame in such a gaseous mixture requires that a small portion of it should be raised to a temperature called the temperature of ignition. Here again considerable misunderstanding has prevailed. The temperature of ignition has often been regarded as the temperature at which chemical combination begins, whereas it is really the temperature at which combination has reached a certain rate. The combination of hydrogen and oxygen begins at temperatures far below that of ignition. It may indeed be supposed that the combination occurs with extreme slowness even at ordinary temperatures, and that as the temperature is raised the velocity of the reaction increases in accordance with the general expression according to which an increase of 10°C. will approximately double the rate. However that may be, it has been proved experimentally by J. H. van’t Hoff, Victor Meyer and others that the combination of hydrogen and oxygen proceeds at perceptible rates far below the temperature of ignition. The phenomenon appears to be greatly influenced by the solid surfaces which are present; thus in a plain glass vessel the combination only began to be perceptible at 448°, whilst in a silvered glass vessel it would be detected at 182°C.

The same kind of thing is true for most oxidizable substances, including ordinary combustibles. We must look upon the application of heat to a combustible mixture as resulting in an increase of the rate of combination locally. Let us suppose that we are dealing with a stratum of the mixture in small contiguous sections. If we raise the temperature of the first section a°C., an increased rate of combination is set up. The heat produced by this combination will be dissipated by conduction and radiation, and we will suppose that it does not quite suffice to raise the adjacent section of the mixture to a°C. The combination in that section, therefore, will not be as rapid as in the first one, and so evidently the impulse to combination will go on abating as we pass along the stratum. Suppose now we start again and heat the first section of the mixture to a temperature c°C., such that the rate of combination is very rapid and the heat developed by combination suffices to raise the adjacent section of the mixture to a temperature higher than c°C. The rate of combination will then be greater than in the first section, and the impulse to combination will be intensified in the same way from section to section along the stratum until a maximum temperature is reached. It is obvious that there must be a temperature of b°C. between a° and c° which will satisfy this condition, that the heat which results from the combination stimulated in the first section just suffices to raise the temperature of the second section to b°. This temperature b° is the temperature of ignition of the mixture; so soon as it is attained by a portion of the mixture the combustion becomes self-sustaining and flame spreads through the mixture. Ignition temperature may be defined briefly as the temperature at which the initial loss of heat due to conduction, &c., is equal to the heat evolved in the same time by the chemical reaction (van’t Hoff). From the above considerations we see that the temperature of ignition will vary not only when the gases are varied, but when the proportions of the same gases are varied, and also when the pressure is varied. We can see also that outside certain limiting proportions a mixture of gases will have no practicable ignition temperature, that is to say, the cooling effect of the gas which is in excess will carry off so much heat that no attainable initial heating will suffice to set up the transmission of a constant temperature. Thus in the case of hydrogen and air, mixtures containing less than 5 and more than 72% of hydrogen are not inflammable. The theory of ignition temperature enables us to understand why in an explosive mixture a very small electric spark may not suffice to induce explosion. Combination will indeed take place in the path of the spark, but the amount of it is not sufficient to meet the loss of heat by conduction, &c. It must be added that the theory of ignition temperatures given above does not explain all the observed facts. F. Emich states that the inflammability of gaseous mixtures is not necessarily greatest when the gases are mixed in the proportions theoretically required for complete combination, and the influence of foreign gases does not appear to follow any simple law. The presence of a small quantity of a gas may exercise a profound influence on the ignition temperature as in the case of the addition of ethylene to hydrogen (Sir Edward Frankland), and again when a mixture of methane and air is raised to its ignition temperature a sensible interval (about 10 seconds) elapses before inflammation occurs.

The rate at which a flame will traverse a mixture of two gases which has been ignited depends on the proportions in which the gases are mixed. Fig. 1 (Bunte) represents this relationship for several common gases.

If a ready-made gaseous mixture is to be used for the production of a steady flame, it may be forced through a tube and ignited at the end; it is obvious that the velocity of efflux must be greater than the initial rate of inflammation of the mixture, for otherwise the mixture would fire back down the tube. If the velocity of efflux be considerably greater than the rate of inflammation, the flame will be separated from the end of the tube, and only appear as a flickering crown where the velocity and inflammability of the issuing gas have been diminished by admixture with air. With much increased velocity of efflux the flame will be blown out. J. B. A. Dumas used to show the experiment of blowing out a candle with electrolytic gas. A steady flame formed by burning a ready-made gaseous mixture at the end of a tube of circular section has the form shown in fig. 2. The small internal cone marks the lower limiting surface of the flame; it is the locus of all points where the velocity of efflux is just equal to the velocity of inflammation, and its conical form is explained by the fact that the rate of efflux of gas is greatest in the vertical axis of the tube where the flow is not retarded by friction with the walls, as well as by the further fact that the gas issuing from such an orifice spreads outwards, the inflammation proceeding directly against it. The flame, it will be seen, is of considerable thickness. If the gaseous mixture be hydrogen and oxygen, or carbon monoxide and oxygen, it will have no obvious features of structure beyond those shown in the figure; that is to say, the shaded region of burning gas has the appearance of homogeneity and uniform colour which might be expected to accompany a uniform chemical condition. Some admixture of the external air will, of course, take place, especially in the upper parts of the flame, and detectable quantities of oxides of nitrogen may be found in the products of combustion, but this is an inconsiderable feature. The flame just described is essentially that of a blowpipe.

A second way of producing a flame is the more common one of allowing one gas to stream into the other. Using the same gases as before, hydrogen or carbon monoxide with oxygen, we find