Theoretical study on the thermodynamic properties and self-decomposition of methylbenzenediol isomers

Mohammednoor Altarawneh, Ala'A H. Al-Muhtaseb, Bogdan Z. Dlugogorski, Eric M. Kennedy, John C. MacKie

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Alkylated hydroxylated aromatics are major constituents of various types of fuels, including biomass and low-rank coal. In this study, thermochemical parameters are obtained for the various isomeric forms of methylbenzenediol isomers in terms of their enthalpies of formation, entropies, and heat capacities. Isodesmic work reactions are used in quantum chemical computations of the reaction enthalpies for O-H and H 2C-H bond fissions and the formation of phenoxy- and benzyl-type radicals. A reaction potential energy on the singlet-state surface surface is mapped out for the unimolecular decomposition of the 3-methylbenzene-1,2-diol isomer. According to the calculated high pressure-limit reaction rate constants, concerted hydrogen molecule elimination from the methyl group and the hydroxyl group, in addition to intermolecular H migration from the hydroxyl group, dominates the unimolecular decomposition at low to intermediate temperatures (T ≤ 1200 K). At higher temperatures, O-H bond fission and concerted water elimination are expected to become the sole decomposition pathways.

Original languageEnglish
Pages (from-to)11751-11760
Number of pages10
JournalJournal of Physical Chemistry A
Volume114
Issue number43
DOIs
Publication statusPublished - Nov 4 2010

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Isomers
Thermodynamic properties
isomers
thermodynamic properties
Decomposition
decomposition
Hydroxyl Radical
fission
elimination
Enthalpy
enthalpy
Coal
Surface states
biomass
Potential energy
coal
Reaction rates
Specific heat
Hydrogen
Rate constants

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical study on the thermodynamic properties and self-decomposition of methylbenzenediol isomers. / Altarawneh, Mohammednoor; Al-Muhtaseb, Ala'A H.; Dlugogorski, Bogdan Z.; Kennedy, Eric M.; MacKie, John C.

In: Journal of Physical Chemistry A, Vol. 114, No. 43, 04.11.2010, p. 11751-11760.

Research output: Contribution to journalArticle

Altarawneh, Mohammednoor ; Al-Muhtaseb, Ala'A H. ; Dlugogorski, Bogdan Z. ; Kennedy, Eric M. ; MacKie, John C. / Theoretical study on the thermodynamic properties and self-decomposition of methylbenzenediol isomers. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 43. pp. 11751-11760.
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