Spontaneous hydrolysis of phenyl chloroformate

Micellar Effects on the Spontaneous Hydrolysis of Phenyl Chloroformate 133... 

In contrast to reaction (5-158), addition of micelle-forming surfactants can also slow down chemical reactions. For example, the spontaneous hydrolysis of phenyl chloroformate at 25 °C according to Eq. (5-158a) is retarded by a factor of ca. 16 on addition of sodium dodecylsulfate (SDS) above the one. Below the erne, the SDS... 

Rodriguez, A., Graciani, M. del M., Munoz, M., Moya, M.L. Water-ethylene glycol alkyltrimethylammonium bromide micellar solutions as reaction media study of spontaneous hydrolysis of phenyl chloroformate. Langmuir 2003, 79(18),... 

The effects of [cationic micelles] (micelle-forming surfactants are hexade-cyltrimethylammonium bromide, CTABr, tetradecyltrimethylammonium bromide, TTABr, and dodecyltrimethylanunonium bromide, DTABr) on the rates of spontaneous hydrolysis of phenyl chloroformate in water-ethanediol (ED) solvents have been rationalized in terms of pseudophose (PP) model, i.e.. Equation 3.2 with replaced by Experimentally observed values of k M decrease... 

The rate of spontaneous hydrolysis of phenyl chloroformate decreases with increase in the concentration of micelles of various anionic, nonionic, and cationic surfactants. A comparison of the kinetic data in nonionic micellar solutions to those in anionic and zwitterionic micellar solutions makes it clear that charge effects of micelles is not the only factor responsible for the variations in the reaction rates. Depletion of water in the interfacial region and its different characteristics as compared to bulk water, the presence of high ionic concentration in the Stem layer of ionic micelles, and differences in the stabilization of the reactant state and the transition state by hydrophobic interactions with surfactant tails can also influence reactivity. 

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