Acid hydrolyses of hydrophobic dioxolanes in cationic micelles: A quantitative treatment based on the Poisson-Boltzmann equation

Academic Article

Abstract

  • Acid hydrolyses of hydrophobic dioxolanes, 1a and 1b, are inhibited by cationic micelles of myristyl- and cetyltrimethylammonium halides, MTAX and CTAX, respectively (X = Cl, Br), but at surfactant concentrations sufficient to bind all the substrate, first-order rate constants, kψ, at constant [HX], increase with increasing [surfactant] and on addition of NaX. In the absence of added NaX kψ increases linearly with [MTAX] and [CTACl], but at constant [surfactant] there are breaks in plots of kψ against [NaX]. These results can be explained quantitatively in terms of a pseudophase model in which hydrogen ion concentrations at micellar surfaces are calculated by solution of the Poisson-Boltzmann equation. © 1991 American Chemical Society.
  • Published In

    Digital Object Identifier (doi)

    Author List

  • Blasko A; Bunton CA; Armstrong C; Gotham W; He ZM; Nikles J; Romsted LS
  • Start Page

  • 6747
  • End Page

  • 6750
  • Volume

  • 95
  • Issue

  • 18