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Temperature Dependences of the Kinetic Isotope Effect and the Ratio of the Reaction Rates for Reaction of Cyclopentane and Cyclohexane with HOCl in Water

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Abstract

We have determined the activation parameters ΔlogA and ΔE for the Arrhenius equations for the kinetic isotope effect (c-C6H12/c-C6D12) and the 5/6 effect (c-C5H10/c-C6H12) in reactions of the C—H bonds of cycloalkanes with HOCl in aqueous solutions in the interval 30-90 °C. The data obtained are consistent with a chlorination mechanism including a pre-activation step with formation of an HO· ... Cl· pair, linear abstraction of the H atom by the OH group and angular attack by the Cl atom "at a distance" on the carbon atom.

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Authors and Affiliations

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

    E. S. Rudakov & L. K. Volkova

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  1. E. S. Rudakov
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  2. L. K. Volkova
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Rudakov, E.S., Volkova, L.K. Temperature Dependences of the Kinetic Isotope Effect and the Ratio of the Reaction Rates for Reaction of Cyclopentane and Cyclohexane with HOCl in Water. Theoretical and Experimental Chemistry 40, 314–319 (2004). https://doi.org/10.1023/B:THEC.0000049078.03336.f5

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  • DOI: https://doi.org/10.1023/B:THEC.0000049078.03336.f5

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