Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide

Mohammednoor Altarawneh, Ala'A H. Al-Muhtaseb, Mansour H. Almatarneh, Raymond A. Poirier, Niveen W. Assaf, Khalid K. Altarawneh

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)14092-14099
Number of pages8
JournalJournal of Physical Chemistry A
Volume115
Issue number48
DOIs
Publication statusPublished - Dec 8 2011

Fingerprint

pyrolysis
Pyrolysis
decomposition
acids
heat of formation
products
Decomposition
Potential energy surfaces
amides
Acids
amines
potential energy
Amides
specific heat
entropy
Specific heat
Amines
Entropy
acetamide
temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide. / Altarawneh, Mohammednoor; Al-Muhtaseb, Ala'A H.; Almatarneh, Mansour H.; Poirier, Raymond A.; Assaf, Niveen W.; Altarawneh, Khalid K.

In: Journal of Physical Chemistry A, Vol. 115, No. 48, 08.12.2011, p. 14092-14099.

Research output: Contribution to journalArticle

Altarawneh, Mohammednoor ; Al-Muhtaseb, Ala'A H. ; Almatarneh, Mansour H. ; Poirier, Raymond A. ; Assaf, Niveen W. ; Altarawneh, Khalid K. / Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide. In: Journal of Physical Chemistry A. 2011 ; Vol. 115, No. 48. pp. 14092-14099.
@article{5db019a9134e4ce98c908891c28edf73,
title = "Theoretical investigation into competing unimolecular reactions encountered in the pyrolysis of acetamide",
abstract = "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.",
author = "Mohammednoor Altarawneh and Al-Muhtaseb, {Ala'A H.} and Almatarneh, {Mansour H.} and Poirier, {Raymond A.} and Assaf, {Niveen W.} and Altarawneh, {Khalid K.}",
year = "2011",
month = "12",
day = "8",
doi = "10.1021/jp2067765",
language = "English",
volume = "115",
pages = "14092--14099",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "48",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=82555186816&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=82555186816&partnerID=8YFLogxK

U2 - 10.1021/jp2067765

DO - 10.1021/jp2067765

M3 - Article

VL - 115

SP - 14092

EP - 14099

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 48

ER -