Solvent Effect under High Pressure. II

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Abstract
The activation volume of the reaction of triethylamine with ethyl iodide has been measured in four solvents. A linear relationship has been observed between the values of ΔV0\eweq for the Menschutkin reaction in various solvents and the products of the compressibility and the molar volume of the pure solvent, as has been suggested in a previous paper. From the slope of the plots of (−ΔV0\eweq) vs. KV°, the product of the solvation number and the average pressure within the solvation shell of an activated complex has been calculated to be 2.6×103 (kg·cm−2) according to a model proposed by the authors. An abnormal acceleration due to pressure has been observed for the reaction of triethylamine with ethyl iodide in p-xylene and dioxane at 30°C. This acceleration effects has been attributed to the partial freezing of the solvent under high pressure.