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Theoretical study of unimolecular decomposition of catechol

Altarawneh, M.ORCID: 0000-0002-2832-3886, Dlugogorski, B.Z., Kennedy, E.M. and Mackie, J.C. (2010) Theoretical study of unimolecular decomposition of catechol. The Journal of Physical Chemistry A, 114 (2). pp. 1060-1067.

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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.

Item Type: Journal Article
Publisher: American Chemical Society
Copyright: © 2010 American Chemical Society.
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