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Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase: (II) Reactions with ClOx(x= 1−4).

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Title: Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase: (II) Reactions with ClOx(x= 1−4).
Authors: Z. F. Xu1, M. C. Lin1
Source: Journal of Physical Chemistry A. Jan2010, Vol. 114 Issue 2, p833-838. 6p.
Subjects: Oxidation-reduction reaction, Chemical processes, Quantum chemistry, Mathematical optimization, Chemical structure, Potential energy surfaces
Abstract: The reactions of HOCl + ClOx(x= 1−4) have been studied theoretically by ab initio quantum chemical and statistical mechanical methods. The structures of reactants, intermediates, products, and transition states were optimized at the MPW1PW91/6-311+G(3df,2p) level of theory, and the potential energy surface of each reaction was refined at the G2M and CCSD(T)/6-311+G(3df,2p) levels of theory. The most favorable reaction channels are predicted to be Cl-abstraction in HOCl + ClO with a barrier of 18.5 kcal/mol and H abstraction in HOCl + OClO with a barrier of 23.9 kcal/mol. In the HOCl + ClO3reaction both processes can occur; the barriers of Cl and H abstraction are 16.4 and 17.1 kcal/mol, respectively. In the HOCl + ClO4reaction, the H abstraction transition state lies below that of the reactants by 1.4 kcal/mol. The rate constants for all low barrier channels have been calculated in the temperature range 200−3000 K by statistical theory. In addition, the rate constant for the reverse of the HOCl + ClO reaction, Cl2O + OH → HOCl + ClO, has been predicted; the result is in good agreement with the bulk of available experimental data. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
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Abstract:The reactions of HOCl + ClOx(x= 1−4) have been studied theoretically by ab initio quantum chemical and statistical mechanical methods. The structures of reactants, intermediates, products, and transition states were optimized at the MPW1PW91/6-311+G(3df,2p) level of theory, and the potential energy surface of each reaction was refined at the G2M and CCSD(T)/6-311+G(3df,2p) levels of theory. The most favorable reaction channels are predicted to be Cl-abstraction in HOCl + ClO with a barrier of 18.5 kcal/mol and H abstraction in HOCl + OClO with a barrier of 23.9 kcal/mol. In the HOCl + ClO3reaction both processes can occur; the barriers of Cl and H abstraction are 16.4 and 17.1 kcal/mol, respectively. In the HOCl + ClO4reaction, the H abstraction transition state lies below that of the reactants by 1.4 kcal/mol. The rate constants for all low barrier channels have been calculated in the temperature range 200−3000 K by statistical theory. In addition, the rate constant for the reverse of the HOCl + ClO reaction, Cl2O + OH → HOCl + ClO, has been predicted; the result is in good agreement with the bulk of available experimental data. [ABSTRACT FROM AUTHOR]
ISSN:10895639
DOI:10.1021/jp908882b