View in EDS

Ab Initio Kinetics for the Unimolecular Reaction C6H5OH → CO + C5H6.

Saved in:
Bibliographic Details
Title: Ab Initio Kinetics for the Unimolecular Reaction C6H5OH → CO + C5H6.
Authors: Z. F. Xu1, M. C. Lin1
Source: Journal of Physical Chemistry A. Feb2006, Vol. 110 Issue 4, p1672-1677. 6p.
Subjects: Chemical reactions, Asynchronous transfer mode, Isomerization, Quantum chemistry
Abstract: The unimolecular decomposition of C6H5OH on its singlet-state potential energy surface has been studied at the G2M//B3LYP/6-311G(d,p) level of theory. The result shows that the most favorable reaction channel involves the isomerization and decomposition of phenol via 2,4-cyclohexadienone and other low-lying isomers prior to the fragmentation process, producing cyclo. 5H6 + CO as major products, supporting the earlier assumption of the important role of the 2,4-cyclohexadienone intermediate. The rate constant predicted by the microcanonical RRKM theory in the temperature range 800−2000 K at 1 Torr − 100 atm of Ar pressure for CO production agrees very well with available experimental data in the temperature range studied. The rate constants for the production of CO and the H atom by O−H dissociation at atmospheric Ar pressure can be represented by kCO = 8.62 × 1015T-0.61 exp(−37 300/T) s-1 and kH = 1.01 × 1071T-15.92 exp(−62 800/T) s-1. The latter process is strongly P-dependent above 1000 K; its high- and low-pressure limits are given. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
Description
Abstract:The unimolecular decomposition of C6H5OH on its singlet-state potential energy surface has been studied at the G2M//B3LYP/6-311G(d,p) level of theory. The result shows that the most favorable reaction channel involves the isomerization and decomposition of phenol via 2,4-cyclohexadienone and other low-lying isomers prior to the fragmentation process, producing cyclo. 5H6 + CO as major products, supporting the earlier assumption of the important role of the 2,4-cyclohexadienone intermediate. The rate constant predicted by the microcanonical RRKM theory in the temperature range 800−2000 K at 1 Torr − 100 atm of Ar pressure for CO production agrees very well with available experimental data in the temperature range studied. The rate constants for the production of CO and the H atom by O−H dissociation at atmospheric Ar pressure can be represented by kCO = 8.62 × 1015T-0.61 exp(−37 300/T) s-1 and kH = 1.01 × 1071T-15.92 exp(−62 800/T) s-1. The latter process is strongly P-dependent above 1000 K; its high- and low-pressure limits are given. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/jp055241d