A shock tube study of the reaction of methyl radicals with hydroxyl radicals

The reaction of CH₃ with OH has been studied near 1200 K and 1 atmosphere pressure in shock tube experiments in which UV absorption was used to monitor [OH]. A rate coefficient of (1.1 ± 0.3) × 10¹³ cm³/mol-s was measured for removal of OH by CH₃. This measured value is compared with previous experimental data and calculations. Several possible reaction channels are discussed, and although products were not monitored, it seems probable, on the basis of other work and theoretical estimates, that the primary mechanism (?75%) for the removal of OH by CH₃ at these conditions is their combination to form CH₃OH. Rate coefficients of (5.3 ± 0.8) × 10¹² and (9.0 ± 1.4) × 10¹² cm³/mol-s were measured for the reactions of OH with acetone and ethane, respectively, at the same temperature and pressure.     

Analyse de couches minces de verres chalcogenures par diffusion elastique de protons et mesure de gammas prompts

Résumé Une méthode d'étude de la composition stoéchiométrique de couches minces (10 à 500 μg/cm²) de verres chalcogénures est développée. L'étude des réactions nucléaire; induites par bombardement de protons de basse énergie (<4 MeV) sur les éléments constitutifs Ge, As, Te et S, conduit à choisir la diffusion élastique et la détection de gammas prompts pour le dosage simulatené. La précision et la sensibilité de la méthode sont discutées à partir des résultats obtenus. L'utilisation de la résonance fine sur le soufre (p, p'γ) est appliquée à l'étude de l'homogénéité des cibles.     

The use of transition-state theory to extrapolate rate coefficients for reactions of H atoms with alkanes

The thermochemical kinetics formulation of conventional transition state theory has been applied to metathesis reactions of H atoms with a series of alkanes in order to provide a sound framework for the intercomparison of experimental data, and also to extrapolate rate coefficients to temperature regimes that may lie beyond the range of experiments. The calculations require a value for the rate coefficient at some temperature, necessitating a discussion of the extant experimental data and their reliability. The procedures are described, the results of the calculations are presented, and their agreement with experimental data (for methane, ethane, propane, butane, pentane, isobutane, cyclopropane, cyclohexane, neopentane, neooctane, and 2,2,3-trimethylbutane) is discussed. A general expression for reactions of H with large (more than 4 carbons) alkanes is proposed: where n_p, n_s, and n_t are the numbers of primary, secondary, and tertiary H atoms available for abstraction.     

Adsorption of charged macromolecules at a gold electrode

Using an optical reflectometer with impinging-jet system, the adsorption from aqueous solution onto gold of three charged macromolecules has been studied: the strong linear-chain polyelectrolyte polyvinyl pyridine (PVP(+)), the fifth-generation poly(propylene imine) dendrimer DAB-64, which has a pH-dependent charge and a relatively fixed shape, and the protein lysozyme, of which both the charge and the structure-stability are dependent on solution composition. Experimental conditions that have been varied include the adsorbate concentration, electrolyte concentration, pH, and externally applied potential across the gold/solution interface. Making use of the earlier established dependency of the double layer potential of the gold substrate on solution conditions and externally applied potential, the results of measurements as a function of pH and as a function of external potential control are compared. The total set of results enables us to draw conclusions with respect to the relative importance of electrostatic interactions for the adsorption process. PVP(+) adsorption follows the electric potential of the gold/solution interface and is further determined by a rather strong nonelectrostatic affinity between segments and surface. The adsorption behavior of DAB-64 is not quite understood, but electrostatic interactions with the gold surface seem to play a minor role. For lysozyme, surface-induced conformational changes dominate the adsorption process. The extent of spreading of the molecules decreases with increasing polarity of the surface, resulting in a minimum in adsorbed amount around the point of zero potential of the gold.