A Titration Microcalorimetric Study of the Effects of Halide Counterions on Vesicle-Forming Aggregation in Aqueous Solution of Branched-Chain Alkylpyridinium Surfactants

Titration microcalorimetry is used to study the influences of iodide, bromide, and chloride counterions on the aggregation of vesicle-forming 1-methyl-4-(2-pentylheptyl)pyridinium halide surfactants. Formation of vesicles by these surfactants was characterised using transmission electron microscopy. When the counterion is changed at 303 K through the series iodide, bromide, to chloride, the critical vesicular concentration (cvc) increases and the enthalpy of vesicle formation changes from exo- to endothermic. With increase in temperature to 333 K, vesicle formation becomes strongly exothermic. Increasing the temperature leads to a decrease in enthalpy and entropy of vesicle formation for all three surfactants. However the standard Gibbs energy for vesicle formation is, perhaps surprisingly, largely unaffected by an increase in temperature, as a consequence of a compensating change in both standard entropy and standard enthalpy of vesicle formation. Interestingly, standard isobaric heat capacities of vesicle formation are negative, large in magnitude but not strikingly dependent on the counterion. We conclude that the driving force for vesicle formation can be understood in terms of overlap of the thermally labile hydrophobic hydration shells of the alkyl chains. Copyright 2000 Academic Press.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Anomalous Doppler broadening caused by exothermic reactions: application to hydrogen Balmer lines

The three- and one-dimensional velocity distributions of a product species created by an exothermic reaction are calculated using the energy conservation, with the aim of evaluating the impact of such processes on the anomalous broadening of Doppler lines. The calculations are performed to the reaction H₂⁺ + H₂ → H₃⁺ + H, in which according to Christoffersen (1964) an amount of 1.56 eV is transferred to the product species. It is shown that the deviations relatively to Maxwell-Boltzmann distributions are significant as the internal energy defect ΔE increases, even within energies lower than 1.56 eV, and hence the profiles of excited H^∗ atoms, associated with the emission of hydrogen Balmer lines, created in the sequence of H(n = 1) produced by the above reaction are not of Gaussian-type. The profiles are markedly flatter and squarer than Gaussian distributions. The validity of the species temperature determined from the full width at half maximum (FWHM) of the lines, as well as the fit of the lines by multimodal Gaussian functions, is then analyzed.