Abstract
Reactions of p-nitrophenyl diphenyl phosphinate (p-NPDP) with OH− and F− are inhibited by micelles of dodecyl polyoxyethylene ethers C12E10 and C12E23. Rate constants decrease sharply in very dilute surfactant and become approximately constant as p-NPDP becomes fully micellar bound, with inhibition by approximately an order of magnitude. The first-formed fluoridate is detected by NMR spectroscopy in reaction with F− in DMSO-d6:D2O 85:15 v/v, but not in other conditions. Kinetic salt effects on the micellar reactions are ion specific. Bulky anions, ClO−4 and naphthalene-2-sulfonate ion (ONs−), inhibit reactions much more than small ions, and (C7H15)4N+ accelerates reaction of F−. Micellar incorporation of ONs− in the micelles is demonstrated by changes in 1H-NMR spectra of the surfactants. Comparison of rate constants of reaction of F− in PEG (MW 104) and in nonionic micelles shows that the micellar inhibition is due largely to lower ionic concentrations in the micelles than in water.
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