Theoretical study of unimolecular decomposition of catechol

Mohammednoor Altarawneh, Bogdan Z. Dlugogorski, Eric M. Kennedy, John C. Mackie

Research output: Contribution to journalArticlepeer-review

43 Citations (Scopus)

Abstract

This study develops the reaction pathway map for the unimolecular decomposition of catechol, a model compound for various structural entities present in biomass, coal, and wood. Reaction rate constants at the high-pressure limit are calculated for the various possible initiation channels. It is found that catechol decomposition is initiated dominantly via hydroxyl H migration to a neighboring ortho carbon bearing an H atom. We identify the direct formation of o-benzoquinone to be unimportant at all temperatures, consistent with the absence of this species from experimental measurements. At temperatures higher than 1000 K, water elimination through concerted expulsion of a hydroxyl OH together with an ortho H becomes the most significant channel. Rice-Ramsperger-Kassel-Marcus simulations are performed to establish the branching ratio between these two important channels as a function of temperature and pressure. All unimolecular routes to the reported major experimental products (CO, 1,3-C4H6 and cyclo-C 5H6) are shown to incur large activation barriers. The results presented herein should be instrumental in gaining a better understanding of the decomposition behavior of catechol-related compounds.

Original languageEnglish
Pages (from-to)1060-1067
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number2
DOIs
Publication statusPublished - Jan 21 2010
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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