Micellar Effects upon Substitutions by Nucleophilic Anions

Article abstract of DOI:10.1021/j100321a038

Micellar effects upon of OH^- with p-nitrophenyl diphenyl phosphate or 2,4-dinitro-1-chloronaphthalene have been examined with cetyltrimethylammonium surfactants, (CTAX, X=Cl, Br, (SO4)_1/2).Demethylations of methyl benzene- or naphthalene-2-sulfonate by halide ion have been examined. in micelles of CTACl, CTABr, CTA(SO4)_1/2, or cetyltrimethylammonium mesylate (CTAOMs) and for demethylation by OH^- or SO3^2- in CTA(SO4)_1/2 or CTAOMs.The rate enhancements have been treated in terms of concentrations of the substrates and the nucleophilic anion at the micellar surface.The anion concentrations depended upon nonspecific Coulombic and specific interactions that were calculated by solving the Poisson-Boltzmann equation.The same structural parameters were used in fitting data for reactions with Cl^- or Br^- as nucleophiles and for systems with Cl^- or Br^- as inert anions that were competing with OH^- or SO3^2-.The treatment is applicable to mixtures of database to mixtures of dilute mono- and dianions.