TY - JOUR
T1 - Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide
AU - Altarawneh, Mohammednoor
AU - Al-Muhtaseb, Ala'A H.
AU - Almatarneh, Mansour H.
AU - Poirier, Raymond A.
AU - Assaf, Niveen W.
AU - Altarawneh, Khalid K.
PY - 2011/12/8
Y1 - 2011/12/8
N2 - Motivated by the necessity to understand the pyrolysis of alkylated amines, unimolecular decomposition of acetamide is investigated herein as a model compound. Standard heats of formation, entropies, and heat capacities, are calculated for all products and transition structures using several accurate theoretical levels. The potential energy surface is mapped out for all possible channels encountered in the pyrolysis of acetamide. The formation of acetamedic acid and 1-aminoethenol and their subsequent decomposition pathways are found to afford the two most energetically favored pathways. However, RRKM analysis shows that the fate of acetamedic acid and 1-aminoethenol at all temperatures and pressures is to reisomerize to the parent acetamide. 1-Aminoethenol, in particular, is predicted to be a long-lived species enabling its participation in bimolecular reactions that lead to the formation of the major experimental products. Results presented herein reflect the importance of bimolecular reactions involving acetamide and 1-aminoethenol in building a robust model for the pyrolysis of N-alkylated amides.
AB - Motivated by the necessity to understand the pyrolysis of alkylated amines, unimolecular decomposition of acetamide is investigated herein as a model compound. Standard heats of formation, entropies, and heat capacities, are calculated for all products and transition structures using several accurate theoretical levels. The potential energy surface is mapped out for all possible channels encountered in the pyrolysis of acetamide. The formation of acetamedic acid and 1-aminoethenol and their subsequent decomposition pathways are found to afford the two most energetically favored pathways. However, RRKM analysis shows that the fate of acetamedic acid and 1-aminoethenol at all temperatures and pressures is to reisomerize to the parent acetamide. 1-Aminoethenol, in particular, is predicted to be a long-lived species enabling its participation in bimolecular reactions that lead to the formation of the major experimental products. Results presented herein reflect the importance of bimolecular reactions involving acetamide and 1-aminoethenol in building a robust model for the pyrolysis of N-alkylated amides.
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U2 - 10.1021/jp2067765
DO - 10.1021/jp2067765
M3 - Article
C2 - 22026587
AN - SCOPUS:82555186816
SN - 1089-5639
VL - 115
SP - 14092
EP - 14099
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 48
ER -