Effect of alcohol addition to the aqueous phase on the thermal effects of micellization of cationic benzyldimethyldodecylammonium bromide and its adsorption onto porous and nonporous silicas

Titration calorimetry has been used to study the effect of the addition of two primary alcohols, 1-butanol and 1-heptanol, to the aqueous phase on the thermal effects of micellization of benzyldimethyldodecylammonium bromide (BDDAB) as well as its adsorption onto nonporous Spherosil XO15M and onto porous aluminosilicate SiAl32d22 possessing uniformly sized mesopores. A linear decrease of the critical micelle concentration (CMC) of the cationic surfactant with the additive content was inferred from the specific conductivity measurements. All adsorption and calorimetry experiments were carried out at 298 K and at a fixed alcohol content (0.01 mol kg(-1)) either in deionized water or in a 0.01 mol kg(-1) NaBr solution. Dilution calorimetry measurements allowed determination of the cumulative molar enthalpy changes and a new analysis of these data was proposed to calculate easily the enthalpy of micellization per mole of BDDAB, Delta(mic)h, and the CMC value. The alcohol addition was shown to render the micellization phenomenon more exothermic, the effect being larger as the chain length of alcohol increased. These effects were attributed to the location of alcohol molecules between the surfactant units, their hydroxyl groups close to the surfactant head-groups, in competition with the surfactant counterions. The individual isotherms of alcohol and surfactant adsorption onto XO15M and SiAl32d22 were determined. The plots of the pseudo-differential molar enthalpy of displacement, Delta(dpl)h, against the surface coverage by the surfactant cation, Theta(BDDA+), were derived from the titration calorimetry data. The formation of surface-bound aggregates was thought to be a prerequisite for alcohol coadsorption at the solid-solution interface. At least two different types of adsolubilization sites were postulated, one of the sites being the same as in micelles and the other related to the contact area between the hydrophobic surfactant tails and the equilibrium bulk solution. Coadsorption (adsolubilization) of alcohol molecules at such sites was found to increase the exothermic contribution to the enthalpy of displacement per mole of the BDDA+ adsorbed.