Gaseous combustion at high pressures. Part IV.—The influence of varying initial pressures upon the rate of pressure development and the activation of nitrogen in carbon monoxide-air explosions

In the previous paper of this series it was shown :— (1) that when nitrogen is added as a diluent to a mixture of 2CO+O2 undergoing combustion in a bomb at an initial pressure of 50 atmospheres, it exerts a peculiar energy-absorbing influence upon the system, far beyond that of other diatomic gases, or of argon; (2) that by virtue of such influence, it retards the attainment of maximum pressure in a much greater degree than can be accounted for on the supposition of its acting merely as a diatomic diluent; (3) that the energy so absorbed by the nitrogen during the combustion period, which extends right up to the attainment of maximum pressure, is slowly liberated thereafter as the system cools down ; and that consequently the rate of cooling is greatly retarded for a considerable time interval after the attainment of maximum pressure; (4) that there is no such energy-absorbing effect (i. e ., other than a purely "diluent" one) when nitrogen is present in a 2H2 +O2 mixture similarly undergoing combustion ; but that, on the contrary, the presence of hydrogen in a CO-air mixture undergoing combustion at such high pressures so strongly counteracts the said " energy-absorbing " influence of the nitrogen, that it must be excluded as far as possible from the system before any large nitrogen-effect can be observed. These facts were explained on the supposition that there is some constitutional correspondence between CO and N2 molecules (whose densities are identical) whereby the vibrational energy (radiation) emitted when the one burns is of such a quality as can be readily absorbed by the other, the two thus acting in resonance. It was further supposed that, in consequence of such resonance, nitrogen becomes chemically " activated " when present during the combustion of carbon monoxide at such high pressures ; and in conformity with this supposition, it was shown that such "activated" nitrogen is able to combine with oxygen more readily than does nitrogen which has merely been raised to a correspondingly high temperature in a hydrogen-air explosion.