Kinetics of hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in binary water-cosolvent mixtures; the role of solvent activity and solute-solute interactions.

Rate constants are reported for the pH-independent hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in aqueous solution as a function of the concentration of added cyanomethane (acetonitrile), polyethylene glycol (PEG 400) and tetrahydrofuran (THF). The concentration of water was varied between ca. 25 and 55.5 M. It was found that the variation in water activity yields only a minor contribution to the observed variation in rate constants. Interestingly, for both cyanomethane and PEG 400 log(k) varies approximately linearly with the molar concentration of water. Medium effects in highly aqueous solutions ([H(2)O] > 50 M) of ethanol, 1-propanol, 2-propanol, 1-butanol and 2-methyl-2-propanol have also been determined. Unexpectedly, in this concentration range the alcohols induce significantly smaller effects per unit volume than cyanomethane. The present results are discussed in terms of pairwise interaction parameters. Isobaric activation parameters have been determined and reveal remarkable differences in the nature of the induced medium effects.