LINEAR SOLVATION-ENERGY RELATIONSHIPS - SOLVOLYTIC REACTIONS OF TERT-BUTYL BROMIDE AND TERT-BUTYL IODIDE IN HYDROXYLIC SOLVENTS

Solvent effects on the solvolytic reactions of ButBr and Bu tl in water, and 12 monoalcohols and 10 dialcohols, from 1 to 5 carbon atoms, have been analysed in terms of linear solvation energy relationships. The experimentally determined rate constants, at 25°C, are well correlated through equations of the form log k = a0 + a,g(η) + a2ETN + a3C where g(η) is a function of the refractive index, ETN is the normalized Dimroth and Reichardt parameter and C is the solvent cohesive pressure. The correlation analysis revealed significant information on the solvent-solvent-solute interactions. It is also shown that results are in good agreement with previous analysis using different approaches and other sets of solvents.