A delicate balance-of-forces governs the interactions responsible for surfactant self-assembly and chemical reactivity within them. Chemical reactions in micellar media generally occur in the interfacial region of micelles that is a complex mixture of: water, headgroups, counterions, co-ions, acids or bases, organic solvents, and the reactants themselves. We have carried out a detailed study of a complex chemical reaction in mixed CTAB/C12E6 micelles by using the chemical kinetic (CK) and chemical trapping (CT) methods. The results provide a detailed quantitative treatment of the reaction of the anion of the antioxidant t-butylhydroquinone, TBHQ-, with 4-hexadecylbenzenediazonium, 16-ArN2+, within the interfacial region of the mixed micelles in the C12E6 mole fraction range of 0 to 1 at three different total surfactant concentrations. CK experiments showed that this reaction is monophasic in C12E6 micelles, but biphasic in mixed micelles. The results were fully consistent with a complex mechanism in which TBHQ- reacts with 16-ArN2+ to give a transient diazoether intermediate that competitively breaks down into products and or reverts to starting materials. The kinetics are the same in mixed micelles of CTAB/C12E6 (grow) and CTAB/C12E8 (don't grow) showing that the rates only depend on micelle composition, not shape. CT results provided estimates of interfacial molarities of H2O are approximately constant at ca. 39 and Br- decreases from ca. 2.75 to 0.05 moles per liter of interfacial volume as C12E6 mole fraction increases from 0 to 1. Combined CK/CT results provided values for interfacial pH, ranging from ca. 4.25 in cationic micelles to 1.5 in nonionic micelles despite a constant bulk pH of 1.5 and the TBHQ interfacial pKa = 3.8 at all C12E6 molar fractions. In totality, these results yielded an extraordinary amount of quantitative information about the relationships between the chemical reactivity and interfacial compositions of the mixed micelles.
Bibliographical noteFunding Information:
AAD is greatly thankful to Vice Chancellor and Head, Department of Chemistry of the University of Kashmir for providing leave for pursuing postdoctoral research in Rutgers University in 2016– 2017 for a period of one year. NN thanks University Grants Commission, New Delhi, for providing Raman Postdoctoral Fellowship under file no. 5-101/2016(IC) for one year from Nov. 2016 to Nov. 2017. All the authors thank NSF International Collaboration in Chemistry for funding this project, NSF-ICC 1124776, for NSF support for Grant No. CHE 0411990, and the Agriculture and Food Research Initiative Competitive Grant No. 2009-02403 from the USDA National Institute of Food and Agriculture.