Abstract
AbstractAn attempt has been made to determine the kinetic isotope effects for the following reactions by using hydrogen atoms produced in the radiolysis of water vapor:magnified imageThe results are: kH/kD = (0.41 ± 0.05)exp(9.6 ± 0.4 kJ mol−1/RT) and kH/kD = (0.58 ± 0.06)exp(8.3 ± 0.4 kJ mol−1/RT), respectively, over the temperature range 353 K to 493 K; the errors correspond to standard deviations. The kinetic isotope effect has also been examined as a function of the ratios of c‐C6D12/c‐C6H12, total dose, total pressure and the total concentration of added cyclohexanes. Theoretical interpretation of the kinetic isotope effect has been made using the Bond‐Energy‐Bond‐Order (BEBO) method. Agreement between theoretical and experimental values is not satisfactory, even though the tunneling effect has been taken into account.
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