Journal
JOURNAL OF COLLOID AND INTERFACE SCIENCE
Volume 285, Issue 2, Pages 789-794Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcis.2004.01.085
Keywords
micellar aggregation; oxidation of aminoalcohols; N-bromosuccinimide; kinetics of
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The kinetics of oxidation of some aminoalcohols (AA), viz. ethanolamine, diethanolamine, and triethanolamine, by N-bromosuccinimide (NBS) in alkaline medium has been investigated in the absence as well as in the presence of cetyltrimethylammonium bromide (CTAB), a cationic surfactant. The reaction always followed a first-order dependence of rate on NBS, while the order in each AA and alkali was found to decrease from unity to zero at higher [AA] and [OH-], respectively. The reaction is strongly catalyzed by CTAB even before the critical micelle concentration (CMC) of CTAB. However, the observed rate constants attained constancy at higher [CTAB] (> CMC of CTAB). The premicellar kinetics has been rationalized in the light of the Piszkiewicz positive cooperativity model [J. Am. Chem. Soc. 99 (1977) 1550]. The binding constants between the reactants and the surfactant have also been evaluated using the Raghvan and Srinivasan model [Proc. Ind. Acad. Sci. 98 (1987) 199], which is applicable to bimolecular micellar catalyzed reaction and predicts constancy in the observed rate constant at higher [surfactant]. The binding constants obtained by both the models are in good agreement. (c) 2004 Published by Elsevier Inc.
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