Abstract
AbstractThe entropy of activation for the hydrolysis of pentaphenoxyphosphorane in 25% aqueous dioxane is −188 J/mol deg. The enthalpy of activation is 22.5 kJ/mol, which is small for the relatively slow reaction. This suggests that the reaction is a multistep process having a preliminary equilibrium with a negative heat of reaction. This conclusion is supported by the results obtained for the hydrolysis of C6H5 equation image [OCH(CF3)2]2. A kinetic isotope effect kH2O/kD2O of 3.46 was found for the latter reaction. Orders in water were obtained, and a mechanism of hydrolysis is proposed.
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