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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]
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.)
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  Data: Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase: (II) Reactions with ClOx(x= 1−4).
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. Jan2010, Vol. 114 Issue 2, p833-838. 6p.
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  Data: <searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+processes%22">Chemical processes</searchLink><br /><searchLink fieldCode="DE" term="%22Quantum+chemistry%22">Quantum chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Mathematical+optimization%22">Mathematical optimization</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+structure%22">Chemical structure</searchLink><br /><searchLink fieldCode="DE" term="%22Potential+energy+surfaces%22">Potential energy surfaces</searchLink>
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  Data: 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]
– Name: AbstractSuppliedCopyright
  Label:
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  Data: <i>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.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jp908882b
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        Text: English
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      – SubjectFull: Oxidation-reduction reaction
        Type: general
      – SubjectFull: Chemical processes
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      – SubjectFull: Quantum chemistry
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      – SubjectFull: Mathematical optimization
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      – SubjectFull: Chemical structure
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      – SubjectFull: Potential energy surfaces
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      – TitleFull: Computational Studies on Metathetical and Redox Processes of HOCl in the Gas Phase: (II) Reactions with ClOx(x= 1−4).
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              Text: Jan2010
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