of water becomes greater and greater, until at about 500° the gradual formation of water is observed, while at still higher temperatures the reaction-velocity becomes enormous. We are now in a position to understand what is the result of a strong local heating of the knallgas, as, for example, by an electric spark. The strongly heated parts of the knallgas combine to form water-vapour with great velocity and the evolution of large amounts of heat, whereby the adjacent parts are brought to a high temperature and into a state of rapid reaction, i.e. we observe an ignition of the whole mixture. If we suppose the knallgas to be at a very high temperature, then its combustion will be no longer complete owing to the dissociation of water-vapour, whilst at extremely high temperatures it would practically disappear. Hence it is clear that knallgas appears to be stable at low temperatures only because the reaction-velocity is very small, but that at very high temperatures it is really stable, since no chemical forces are then active, or, in other words, the chemical affinity is very small.
The determination of the question whether the failure of some reaction is due to an inappreciable reaction-velocity or to absence of chemical affinity, is of fundamental importance, and only in the first case can the reaction be hastened by catalysts.
Many chemical compounds behave like knallgas. Acetylene is stable at ordinary temperatures, inasmuch as it only decomposes slowly; but at the same time it is explosive, for the decomposition when once started is rapidly propagated, on account of the heat evolved by the splitting up of the gas into carbon and hydrogen. At very high temperatures, however, acetylene acquires real stability, since carbon and hydrogen then react to form acetylene.
Many researches have shown that the combustion of an inflammable gas-mixture which is started at a point, e.g. by an electric spark, may be propagated in two essentially Explosion-waves.different ways. The characteristic of the slower combustion consists in this, viz. that the high temperature of the previously ignited layer spreads by conduction, thereby bringing the adjacent layers to the ignition-temperature; the velocity of the propagation is therefore conditioned in the first place by the magnitude of the conductivity for heat, and more particularly, in the second place, by the velocity with which a moderately heated layer begins to react chemically, and so to rise gradually in temperature, i.e. essentially by the change of reaction-velocity with temperature. A second entirely independent mode of propagation of the combustion lies at the basis of the phenomenon that an explosive gas-mixture can be ignited by strong compression or—more correctly—by the rise of temperature thereby produced. The increase of the concentrations of the reacting substances consequent upon this increase of pressure raises the reaction-velocity in accordance with the law of chemical mass-action, and so enormously favours the rapid evolution of the heat of combustion.
It is therefore clear that such a powerful compression-wave can not only initiate the combustion, but also propagate it with extremely high velocity. Indeed a compression-wave of this kind passes through the gas-mixture, heated by the combustion to a very high temperature. It must, however, be propagated considerably faster than an ordinary compression-wave, for the result of ignition in the compressed (still unburnt) layer is the production of a very high pressure, which must in accordance with the principles of wave-motion increase the velocity of propagation. The absolute velocity of the explosion-wave would seem, in the light of these considerations, to be susceptible of accurate calculation. It is at least clear that it must be considerably higher than the velocity of sound in the mass of gas strongly heated by the explosion, and this is confirmed by actual measurements (see below) which show that the velocity of the explosion-wave is from one and a half times to double that of sound-waves at the combustion temperature.
We are now in a position to form the following picture of the processes which follow upon the ignition of a combustible gas-mixture contained in a long tube. First we have the condition of slow combustion; the heat is conveyed by conduction to the adjacent layers, and there follows a velocity of propagation of a few metres per second. But since the combustion is accompanied by a high increase of pressure, the adjacent, still unburnt layers are simultaneously compressed, whereby the reaction-velocity increases, and the ignition proceeds faster. This involves still greater compression of the next layers, and so if the mixture be capable of sufficiently rapid combustion, the velocity of propagation of the ignition must continually increase. As soon as the compression in the still unburnt layers becomes so great that spontaneous ignition results, the now much more pronounced compression-waves excited with simultaneous combustion must be propagated with very great velocity, i.e. we have spontaneous development of an “explosion-wave.” M. P. E. Berthelot, who discovered the presence of such explosion-waves, proved their velocity of propagation to be independent of the pressure, the cross-section of the tubes in which the explosive gas-mixture is contained, as well as of the material of which these are made, and concluded that this velocity is a constant, characteristic of the particular mixture. The determination of this velocity is naturally of the highest interest.
In the following table Berthelot’s results are given along with the later (1891) concordant ones of H. B. Dixon, the velocities of propagation of explosions being given in metres per second.
|Reacting Mixture.||Velocity of Wave in
Metres per second.
|Hydrogen and oxygen,||H2+O||2810||2821|
|Hydrogen and nitrous oxide,||H2+N2O||2284||2305|
|Methane and oxygen,||CH4+4O||2287||2322|
|Ethylene and oxygen,||C2H4+6O||2210||2364|
|Acetylene and oxygen,||C2H2+5O||2482||2391|
|Cyanogen and oxygen,||C2N2+4O||2195||2321|
|Hydrogen and chlorine,||H2+Cl2||..||1730|
|Hydrogen and chlorine,||2H2+Cl2||..||1849|
The maximum pressure of the explosion-wave possesses very high values; it appears that a compression of from 1 to 30-40 atmospheres is necessary to produce spontaneous ignition of mixtures of oxygen and hydrogen. But since the heat evolved in the path of the explosion causes a rise of temperature of 2000°-3000°, i.e. a rise of absolute temperature about four times that directly following upon the initial compression, we are here concerned with pressures amounting to considerably more than 100 atmospheres. Both the magnitude of this pressure and the circumstance that it so suddenly arises are peculiar to the very powerful forces which distinguish the explosion-wave from the slow combustion-wave.
Nascent State.—The great reactive power of freshly formed or nascent substances (status nascens)may be very simply referred to the principles of mass-action. As is well known, this phenomenon is specially striking in the case of hydrogen, which may therefore be taken as a typical example. The law of mass-action affirms the action of a substance to be the greater the higher its concentration, or, for a gas, the higher its partial-pressure. Now experience teaches that those metals which liberate hydrogen from acids are able to supply the latter under extremely high pressure, and we may therefore assume that the hydrogen which results, for example, from the action of zinc upon sulphuric acid is initially under very high pressures which are then afterwards relieved. Hence the hydrogen during liberation exhibits much more active powers of reduction than the ordinary gas.
A deeper insight into the relations prevailing here is offered from the atomistic point of view. From this we are bound to conclude that the hydrogen is in the first instance evolved in the form of free atoms, and since the velocity of the reaction H + H = H2 at ordinary temperatures, though doubtless very great, is not practically instantaneous, the freshly generated hydrogen will contain a remnant of free atoms, which are able to react both more actively and more rapidly. Similar considerations are of course applicable to other cases.
Ion-reactions.—The application of the law of chemical mass