Kinetics of octadecyltrimethylammonium bromide self-assembled monolayer growth at mica from an aqueous solution

We have studied the growth kinetics of self-assembled monolayers (SAMs) ofoctadecyltrimethylammonium bromide (C18TAB) on mica below the critical micelle concentration at 22, 30, 40, and 50 degrees C. A combination of atomic force microscopy, contact angle goniometry, and transmission infrared spectroscopy was used to follow the growth processes to determine the rates involved in the growth of a C18TAB SAM on mica. The growth of a SAM consisted of four distinct processes: deposition of adsorbate molecules, growth of a disordered 2D liquid phase, nucleation of islands of an ordered 2D solid phase, and subsequent growth of the solid phase. The rates of these various processes are determined, and the activation energies for several processes were calculated including those for the adsorption onto a bare substrate (20 kJ/mol), adsorption into the saturated liquid phase (100 kJ/mol), and nucleation of islands (0.3 kJ/mol). Despite the small activation barrier to island nucleation, the nucleation rate is qualitatively slow, suggesting that entropic effects dominate the nucleation rate.     

Étude de la cinétique de la dégradation thermique du polypropylene et du polystyrène par analyse thermogravimétrique

Kinetic studies on the thermal degradation of polypropylene and polystyrene have been carried out using the thermogravimetric technique. Experimental thermograms have been interpreted by means of a simulation model which takes into account several simultaneous or consecutive reactions. In nitrogen, polypropylene degradation involves two reactions. The activation energy calculated for the second reaction, which corresponds to the main part of the weight loss curve, agrees with values obtained by means of calculation methods based on only one overall reaction. In air, a third reaction is added. Its activation energy is also in agreement with published values. However, for the two studied materials, orders of reaction are different.     

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.