The mechanism of chain development during thermal gas-phase oxidation of methane was studied experimentally and theoretically. It has been established that the limiting stage, which determines the development of the process as a whole, depends on the conditions under which it is carried out. At a temperature of 728 K, the development of the process is determined by the interaction of peroxide radicals with each other. Increasing the temperature to 873 K leads to an increase in the role of reactions of peroxide radicals with formaldehyde, and then the limiting stage of the process becomes the interaction of peroxide radicals with methane. In this case, changes in pressure and temperature have the same effect on the ratio of concentrations of hydroperoxide and methylperoxide radicals, obtained both by calculation and experimentally.
Makaryan et al. (2026) studied this question.