Decomposition of CH3NH2${\rm CH}_3{\rm NH}_2$: Implications for CHx/NHy${\rm CH}_{\rm {\it x}}/{\rm NH}_{\rm {\it y}}$ radical–radical reactions

Abstract

Experiments on methylamine () decomposition in shock tubes, flow reactors, and batch reactors have been re‐examined to improve the understanding of hydrocarbon/amine interactions and constrain rate constants for + reactions. In high‐temperature shock tube experiments, the rapid thermal dissociation of provides a fairly clean source of and radicals, allowing an assessment of reactions of with and NH. At the lower temperatures in batch and flow reactors, is mostly consumed by reaction with H to form + ; these results are useful in determining the fate of the radical. Interpretation of these data, along with flow reactor data for the /H system at lower temperature, indicates that at temperatures up to about 1400 K at atmospheric pressure and above 2000 K at 100 atm, the + reaction forms mainly methylamine. At sufficiently high temperature, H‐abstraction to form + NH and addition–elimination to form + H become competitive. The + NH reaction, with a rate constant close to collision frequency, forms + H, also leading into the hydrocarbon amine pool. Thus, methylamine can be expected to be an important intermediate in co‐combustion of natural gas and ammonia, and more work on the chemistry of is desirable.