Computational study of the unimolecular and bimolecular decomposition mechanisms of propylamine

A detailed computational study of the dehydrogenation reaction of trans-propylamine (trans-PA) in the gas phase has been performed using density functional method (DFT) and CBS-QB3 calculations. Different mechanistic pathways were studied for the reaction of n-propylamine. Both thermodynamic functions and activation parameters were calculated for all investigated pathways. Most of the dehydrogenation reaction mechanisms occur in a concerted step transition state as an exothermic process. The mechanisms for pathways A and B comprise two key-steps: H(2) eliminated from PA leading to the formation of allylamine that undergoes an unimolecular dissociation in the second step of the mechanism. Among these pathways, the formation of ethyl cyanide and H(2) is the most significant one (pathway B), both kinetically and thermodynamically, with an energy barrier of 416 kJ mol(−1). The individual mechanisms for the pathways from C to N involve the dehydrogenation reaction of PA via hydrogen ion, ammonia ion and methyl cation. The formation of α-propylamine cation and NH(3) (pathway E) is the most favorable reaction with an activation barrier of 1 kJ mol(−1). This pathway has the lowest activation energy calculated of all proposed pathways.