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8


Teoret. i eksperim. khimiya. 2004. Vol.40 No. 5. p. 302-306

Temperature Dependences of Kinetic Isotope Effect and Ratio of Rates
of Cyclopentane and Cyclohexane Reactions with HOCl in Water

 

E. S. Rudakov, L. K. Volkova


L. M. Litvinenko Institute of Physical-Organic and Coal Chemistry, National Academy of Sciences of Ukraine
70 R. Luxemburg Vul., 83114 Donetsk, Ukraine. E-mail: rudakov@esrud.donetsk.ua


Activation parameters ΔlgA u ΔE of Arrhenius equation for kinetic isotope effect (c-C6H12/c-C6D12) and 5/6 effect (c-C5H10/c-C6H12) in reactions of C-H bonds of cycloalkanes with HOCl in water solutions in the range 30-90 oC were found. The obtained data agree with the chlorination mechanism which in- cludes pre-activation step with formation of HO····Cl· pair, linear tearing of H-atom by OH group and corner attack of Cl-atom «from far» on carbon atom.


Key word cyclopentane, cyclohexane, cyclohexane-d12, hypochlorous acid, kinetic isotope effect of hydrogen, 5/6 ef-
fect, activation parameters, compensation effect.