Structure-Reactivity Relationships for Predicting Environmentally Hazardous Chemicals

摘要

A method for extrapolating rate coefficients using transition-state theory was applied to reactions of hydroxyl (OH) radicals with 10 halomethanes and 18 haloethanes. The entropy of activation was calculated for each compound and together with an experimental value of the rate of reaction at 298 K was used to calculate k(T) at higher temperatures. The calculated values for all the haloalkanes differed from experimental values by no more than 25%, except that of OH + CHC13. For most haloalkanes this expression predicts rate coefficients within a factor of 3 of experimental data and provides a useful predictive tool if no reliable data are available.