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Reaction of guaiacol (o-methoxyphenol) in supercritical water at densities of 0 < pw < 0.7 g/cm3 and with added salts at pw = 0.50 g/cm3 showed its hydrolysis to catechol (o-hydroxyphenol) and methanol to be through a polar transition state. Correlation of the reaction kinetics following a modified Herbrandson analysis provided a quantitative summary of the greater polarity of the hydrolysis transition state relative to the hydrolysis reactants as Vzmhm ~^wm^wm " VGm<5Gm = 190 ± 20 (cm^cal/mol2)1/2. Salt addition at pw = 0.5 g/cm3 further shifted the transition-state equilibrium toward the transition-state species. A sodium chloride loading of 0.71 mmol/cm3 led to an "effective water density" of pWieff =1.1 g/cm3.Supercritical fluid (SCF) solvents have attracted considerable interest in separation processes because, near Tc

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