Studies on binary and ternary amphiphile combinations of tetradecyltrimethylammonium bromide (C14TAB), tetradecyltriphenylphosphonium bromide (C14TPB), and tetradecylpyridinium bromide (C14PB). A critical analysis of their interfacial and bulk behaviors.

Mixed surfactants play a promising role in surface chemical applications. In this study, interfacial and bulk behaviors of binary and ternary combinations of tetradecyltrimethylammonium bromide (C(14)TAB), tetradecyltriphenylphosphonium bromide (C(14)TPB), and tetradecylpyridinium bromide (C(14)PB) have been examined in detail using the methods of tensiometry, conductometry, fluorimetry, and microcalorimetry. The state of micellar aggregation, amphiphile composition in the micelle, extent of counterion binding by the micelle, and interaction among the surfactant monomers in the binary and ternary combinations have been quantitatively assessed in the light of the regular solution theories of Rubingh and that of Rubingh and Holland. The monomer packing in the micelles and their expected shapes have also been estimated from topological considerations. Conceptual rationalization of results has been presented together with associated energetics of the interfacial adsorption and self-aggregation in the bulk.

Self-aggregation of alkyltrimethylammonium bromides (C10-, C12-, C14-, and C16TAB) and their binary mixtures in aqueous medium: a critical and comprehensive assessment of interfacial behavior and bulk properties with reference to two types of micelle formation.

The detailed interfacial adsorption and micellization behavior of pure and mixed alkyltrimethylammonium bromides (ATABs: C10-, C12-, C14-, and C16TAB) were studied using tensiometric, conductometric, fluorimetric, viscometric, and calorimetric methods. The critical micellar concentration (CMC), thermodynamics of adsorption and micellization, counterion binding, aggregation number, and micellar polarity were determined. It was observed that the studied 1:1 molar mixtures of C10-C12TAB, C10-C14TAB, and C10-C16TAB, and the mixtures C12-C14TAB and C12-C16TAB at different mole ratios produced two CMCs that were supported by the conductometric, calorimetric and viscometric methods. Compared to the first micelle, the second micelle condensed more counterions and produced a higher aggregation number, but their interior polarity states were the same. The surface excess, area minimum of the ATABs at the CMC and Gibbs free energy of adsorption were evaluated and compared. The ideality/nonideality states of the mixed micelles formed in solution were tested in the light of Clint and Rubingh's formalisms; the mixed systems were found to undergo moderate to weak synergistic interaction. The contributions of the terminal methyl group, the intermediate methylene groups, and the hydrophilic tetramethylammonium group toward the standard Gibbs free energy, enthalpy, and entropy of the micellization processes were deciphered and discussed.

Self-aggregation of binary mixtures of alkyltriphenylphosphonium bromides: a critical assessment in favor of more than one kind of micelle formation.

The micellization behavior of binary combinations of alkyltriphenylphosphonium bromides (ATPBs) with alkyl chain carbons 10, 12, 14, and 16 has been studied by conductometry and calorimetry. The combinations C(10)-C(12), C(10)-C(14), C(10)-C(16), C(12)-C(14), C(12)-C(16), and C(14)-C(16) were found to form two cmc's by both the methods, with good agreement, except C(14)-C(16)TPB, which has evidenced only a single cmc by calorimetry for all combinations. The combinations C(10)-C(12) (for both cmc(1) and cmc(2)) and C(10)-C(14)TPB (for cmc(2)) formed ideal mixtures, whereas the rest were nonideal. In the nonideal binary mixtures, the ATPB components showed antagonistic interaction with each other. The cmc, interaction parameter (beta), mixed micellar composition, extent of counterion binding, and thermodynamic parameters for the micellization process have been reported and discussed. The enthalpy of mixed micelle formation has been found to have a fair correlation with a Clint-type relation applicable to ideal binary mixtures of surfactants.

Physicochemical Investigations on the Interaction of Surfactants and Salts with Polyvinylpyrrolidone in Aqueous Medium.

Microcalorimetric investigations have been carried out onthe interaction of the surfactants sodium cholate, sodium deoxycholate, tetradecyltrimethylammonium bromide, cetyl(hexadecyl)trimethylammonium bromide, and p-tert-octylphenoxy polyoxy-ethylene ether (Triton X-100) and the salts potassium iodide, sodium benzoate, sodium bromide, and sodium salicylate with the neutral polymer polyvinylpyrrolidone (PVP). The enthalpy of dilution of the surfactants has been measured in the absence and presence of the polymer and the results are compared to determine the effect of PVP on the micellization of the surfactants and the energetics of the process. As well, the micellization activity of the surfactants in the presence of the polymer has been studied by conductometric and fluorimetric methods. The enthalpy of dilution of the salts has been measured to provide an understanding of the nature and magnitude of their interaction with PVP. Copyright 2001 Academic Press.