Abstract
1. An equation describing the influence of the pressure on the rate constant of liquid-phase homolytic bond-cleavage reactions has been obtained. 2. A difference in the values of (∂ΔV≠/∂p)p=0/ΔV0≠ in addition and homolytic bond cleavage reactions and in diffusional processes has been found which is explained by the different contribution of the free volume to the volume effect of activation (ΔV0≠). In addition reactions and reactions involving the radical detachment of a hydrogen atom the values of (∂ΔV≠/∂p)p=0/ΔV0≠ are close to one another, and the contributions of the free volume to ΔV0≠ are approximately the same. 3. An equation has been proposed for describing the influence of the pressure on the viscosity of liquids. It has been shown that a linear relationship of free energies with a change in the pressure is inapplicable for this process.
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