ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Additivity methods of the calculation of thermodynamic-kinetic parameters of HBr elimination from brominated hydrocarbons

P. Kovařík, L. Valko, and J. Oremusová

Department of Physical Chemistry, Faculty of Chemical Technology, Slovak Technical University, CS-81237 Bratislava

Abstract: In this paper, the additivity methods have been applied to calculation of the activation parameters of the HBr elimination reactions of 15 saturated and unsaturated brominated hydrocarbons. The activation energies were determined by the additivity method of the bond energies in original and activated state. The mean deviation between experimental and calculated values is + 6.25 k J mol^-1 The frequency factors were calculated on the basis of the theory of absolute reaction rates by using the values of activation entropies obtained by application of the principle of additivity of the entrop­ie contributions of bonds and structural elements to the original and to the activated state. The mean deviation between measured and calculated fre­quency factors is ±0.5 log(A/s^-1 ) units. The calculated thermodynamic-kinetic parameters were statistically evaluated for some possible mecha­nisms of HBr elimination.

Full paper in Portable Document Format: 432a167.pdf

Chemical Papers 43 (2) 167–176 (1989)