Promotion and inhibition of a hydrogen–oxygen flame by the addition of trimethyl phosphate

This paper gives results of numerical modeling of a laminar hydrogen–oxygen flame doped with trimethyl phosphate at various pressures and compositions of the combustible mixture. The calculations were performed using the PREMIX and CHEMKIN-II software packages. It was found that phosphorus-containing additives promoted the flame at subatmospheric pressures and inhibited it at atmospheric pressure. Kinetic analysis showed that catalytic recombination reactions were responsible for both phenomena. In the case of subatmospheric pressures, the promoting effect and its enhancement with increasing additive concentration were related to a flame temperature rise in the chemical-reaction zone due to catalysis of the recombination reactions by phosphorus-containing compounds. Increasing the additive concentration led to an increase in both the rate of the branching reaction H + O$_2$ = OH + O and the rate of the chain termination reaction, but the increase in branching reaction rate prevails, resulting in an increase in the flame velocity. In the case of atmospheric-pressure flames, where the reaction-zone temperature is close to the adiabatic equilibrium value, the additive led to an increase in the rate of decay of active flame species and, hence, to a decrease in the flame propagation velocity with increasing additive concentration.