Kinetics of the reaction between cyanide ions and tris(4-methyl-1,10-phenanthroline)iron(II) cations in aqueous solutions. Analysis of kinetic data for this reaction and for solvolysis of benzyl chloride in water in terms of isothermal, isobaric and related isochoric activation parameters
Abstract
Kinetic data for the title reaction and for the solvolysis of benzyl chloride in water are analysed to obtain isobaric and isothermal activation parameters. Isochoric parameters are defined and the rate constants described as functions of temperature, pressure and molar volume of the pure solvent, V*1. A quantity Δ‡ψ(V*1) characterises the dependence of rate constant on temperature at constant V*1. We counter claims that isochoric activation parameters necessarily provide an insight into the process of activation in chemical reactions. Isobaric–isothermal functions, within the limitations of transition-state theory, have a sounder basis in terms of thermodynamic analysis of chemical reactions.
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