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DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system

Theoretical and Experimental Chemistry volume 48, pages 227–232 (2012)Cite this article

The DFT method was used to study gas-phase chlorination reactions CH4 + HOCl (1) and CH4 + HOCl + H2O (2). These reactions entail singlet–triplet (s→t) preactivation of HOCl and terminate in a reverse t→s transition. At 298 K, the barrier ∆G ≠ t for reaction (2) is higher than for reaction (1) by 1.5 kcal/mol, while the singlet transition state TS s -2 lies higher than TS t-2 by MG= 21.4 kcal/mol.

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Authors and Affiliations

  1. L. M. Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, Vul. R. Luxemburg, 70, Donets’k, 83114, Ukraine

    S. L. Litvinenko & E. S. Rudakov

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  1. S. L. Litvinenko
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  2. E. S. Rudakov
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Correspondence to E. S. Rudakov.

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Translated from Teoreticheskaya i Éksperimental’naya Khimiya, Vol. 48, No. 4, pp. 212-216, July-August, 2012.

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Litvinenko, S.L., Rudakov, E.S. DFT analysis of the mechanism for the gas-phase chlorination of methane in the HOCL–H2O system. Theor Exp Chem 48, 227–232 (2012). https://doi.org/10.1007/s11237-012-9265-7

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  • DOI: https://doi.org/10.1007/s11237-012-9265-7

Key words

  • methane
  • molecular chlorination
  • hypochlorous acid
  • singlet–triplet transition
  • reagent preactivation
  • mechanism
  • DFT method