ON THE PRESSURE DEPENDENCE OF REACTION RATES

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Abstract
The functional dependence of the rate constant for benzyl chloride solvolysis on pressure is investigated with a view to obtaining reliable values of the activation parameters. It is concluded that a second order polynomial is the best description of this system, reproducing the experimental data with a greater degree of precision than the other published functions. A method for determining the precision of the derivatives of the logarithmic rate is presented, and the pressure dependence of the activation volume is demonstrated. Various systems from the literature are analyzed to demonstrate the general applicability of the quadratic function.