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.     

Extraction of nuclear coupling constants from data on nuclear charge form factors

A possibility of extracting nuclear coupling constants from data on nuclear charge form factors is discussed. The method exploits analytic properties of form factors in the momentum transfer plane. As an illustration the form factor of⁴He is considered in detail. In this case the value \(g_{4_{He^3 He(^3 H)} }^2 /4\pi = 16 \pm 1\) has been obtained in excellent agreement with earlier determinations by means of other methods. Similar analysis of the¹⁶O form factor yields the first estimate of the oxygen-nucleon coupling∶ \(g_{16_{O^{15} O(^{15} N)N} }^2 /4\pi = 64\) .