Mechanistic Study of the Gas-Phase Decomposition of Methyl Formate

The major products of the thermal decomposition of methyl formate in the gas phase are CH(3)OH, CH(2)O, and CO. Experimental studies have proposed that the mechanism to describe these observations involves two key steps: (1) unimolecular decomposition of methyl formate to yield CH(3)OH + CO, followed by (2) thermal decomposition of methanol to yield CH(2)O + H(2). The present study shows that there exists an alternative mechanism that is energetically more favorable. The new mechanism involves two competing parallel unimolecular decomposition pathways to yield the observed major products.