Physicochemical Properties of Deuterated Compounds. 8th Communication. The kinetic isotope effect for the reaction of hydrogen atoms with methylcyclohexane and perdeuteromethylcyclohexane in the gas phase

Using H-atoms produced in the radiolysis of water vapour, we determined the kinetic isotope effect for the reaction where RH and R′D are methylcyclohexane and perdeuterated methylcyclohexane, respectively. The result obtained from the isotope competitive method can be expressed with the Arrhenius-type equation k_H/k_D = (0.51 ± 0.04) exp(8.58 ± 0.25) kJ mol^?1/RT] over the temperature range from 363 to 483 K. The occurrence of H abstraction from primary, secondary, and tertiary C? H bonds in methylcyclohexane is taken into consideration in the interpretation of the Arrhenius-type expression obtained. Theoretical interpretation of the kinetic isotope effect has been achieved on the basis of the transition-state theory and a semiempirical London-Eyring-Polanyi-Sato potential-energy surface. The tunnel effect is found to play a role in the H-abstraction. Several methods for estimating the tunnel correction factors have been discussed.