S. Possidonio et Oa. El Seoud, Effects of charge and structure of surfactants on kinetics of water reactions: The pH-independent hydrolysis of bis (2,4-dinitrophenyl) carbonate, J MOL LIQ, 80(2-3), 1999, pp. 231-251
The pH-independent hydrolysis of bis (2,4-dinitrophenyl) carbonate in the p
resence of aqueous micelles of sodium dodecyl sulfate, sodium dodecylbenzen
e sulfonate, alkyltrimethylammonium chlorides, alkyldimethylbenzylammonium
chlorides (alkyl group = cetyl and dodecyl), and polyoxyethylene (9) nonylp
henyl ether has been studied spectrophotometrically. Observed rate constant
s, k(obs), decrease in the following order: alkyldimethylbenzylammonium chl
orides > bulk water = alkyltrimethyl- ammonium chlorides > nonionic micelle
s > anionic micelles. Surfactant-substrate association constants have been
determined from the dependence of k(obs) on [surfactant]. H-1 NMR study of
the solubilization of a model compound, phenyl-2,4-dinitrophenyl carbonate,
showed that all surfactant segments are affected by the solubilizate, and
that the ester penetrates deeper in micelles of alkyldimethylbenzylammonium
chlorides relative to the corresponding alkyltrimethylammonium chlorides.
Micellar effects on k(obs) are analyzed in terms of "medium" and "electrost
atic" effects. The lower microscopic polarity at the reaction site cause ra
te decrease, whereas electrostatic interactions of the dipolar (C) 1999 Els
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