Micellar effects upon the reactions of complex ions in solution. Retardation of the base hydrolysis of cis-(azido)(imidazole)bis(ethylenediamine)cobalt(III) by sodium dodecyl sulphate

Dash, Anadi C. ; Nayak, Ramesh C. (1987) Micellar effects upon the reactions of complex ions in solution. Retardation of the base hydrolysis of cis-(azido)(imidazole)bis(ethylenediamine)cobalt(III) by sodium dodecyl sulphate Faraday Transactions, 4 . p. 83. ISSN 0956-5000

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Official URL: http://pubs.rsc.org/en/Content/ArticleLanding/1987...

Related URL: http://dx.doi.org/10.1039/F19878301307

Abstract

The kinetics of base hydroloysis of cis-(azido)(imidazole)bis(ethylenediamine)cobalt(III) has been studied in the presence of sodium dodecyl sulphate at 40°C. Unlike the case for univalent anions, the surfactant strongly retards the base hydrolysis of the complex. The rate data have been satisfactorily analysed by the pseudo-phase ion-exchange model: [graphic ommitted] where Cb+ denotes the imidazole (1-) conjugate base, cis-[(en)2Co(im)N3]+, and W and M stand for the aqueous and micellar pseudo-phases, respectively. The pseudo-phase ion-exchange equilibium has also been verified by measuring the equilibrium constant using a spectrophotometric method. The second-order base hydrolysis path of Cb+ is, however, absent for the fully micelle-incorporated species, Cb+M. Micellar binding of Cb+ also leads to a slowing down of its spontaneous aquation rate to a small extent (by a factor of 2), which may be ascribed to the difference in the polarity of the microenvironment of the reactant in the micellar pseudo-phase and the aqueous phase.

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