A theoretical study on the bimolecular reactions encountered in the pyrolysis of acetamide

Bimolecular reactions of acetamide with acetamide itself, acetimidic acid and acetic acid are investigated to account for the formation of the three major experimental products from the pyrolysis of acetamide, namely ammonia, acetic acid and acetonitrile. This mechanism involves bimolecular deammonation reactions to form acetamide anhydride, acetic anhydride and N‐acetyl acetamide, and the subsequent fragmentation of these intermediates into acetic acid and acetonitrile. It is found that the overall reaction barrier for the formation of the three major experimental products from the bimolecular reaction of acetamide with its enol form (acetimidic acid) amount to a 36.1 kcal/mol barrier. This barrier is in excellent agreement with the corresponding experimental data from the self‐condensation of acetamide. This finding stresses on the role of acetimidic acid as a major intermediate in the pyrolysis of acetamide. The calculated activation barriers for the two available pathways in the bimolecular reaction of acetamide and acetic acid into imide and N‐acetyl acetamide (36.3 kcal/mol and 24.0 kcal/mol) is in accord with the corresponding experimental activation energy of 30.1 kcal/mol for the autocatalytic reaction of acetamide with the acetic acid. Reaction rate constants are obtained for all plausible reactions. Kinetic data presented herein should be instrumental in building a robust model for the decomposition of N‐alkylated amides, that is, a major structural entity in biomass. Copyright © 2011 John Wiley & Sons, Ltd.