Micellar effect on the electron transfer reaction of chromium(V) ion with organic sulfides

The rate of electron transfer from organic sulfides to [CrV(ehba)2]− (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge–charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO4−, HSO5− and HCO4− oxidation of organic sulfides.