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991.
Using the cyclic voltammetry (CV), the electron-transfer kinetics for the reductions of NO+ and NO2+ cations have been studied at the Pt electrode in nitromethane, sulfolane, and propylene carbonate. The heterogeneous rate constants have been determined by two independent procedures from the transfer coefficient α, the diffusion coefficient D, from a detailed examination of the CV-peak separations, and from an inspection of the values of the cathodic peak potentials at different scan rates. The results have been compared to those reported in the literature, and discussed. In the classical model, outer-sphere electron-transfer reactions are considered subject to an activation energy arising from solvent reorganization and bond reorganization processes. The solvent and molecular reorganizational barriers for these electroreductions have been assessed in aprotic media. The Marcus-Hush theory has been applied to the self-exchange reactions of the NO2+/NO2 and NO+/NO couples in an attempt to predict the rate of electron transfer. The findings indicate some improvement between theory and experiment. However, it should be noted that the experimental values of ks found for the NO2+ reduction in the solvents used are still too high in comparison with those determined theoretically. In view of the fairly strong coordination of the solvent molecule(s) as ligand(s) to NO2+ and NO+ cations, we believe that such discrepancies should stem, to some extent, from the involvement of an inner-sphere pathway by generation of an activated complex on the surface of the Pt electrode. © 1993 John Wiley & Sons, Inc. 相似文献
992.
Chemical kinetics of benzonitrile nitration with mixed acid is investigated in the temperature range 283–299 K. Pseudo-first-order rate constants are evaluated by means of rate experiments on homogeneous reacting mixtures having large stoichiometric excesses of nitric acid. The second-order kinetic constants for nitronium ion attack to the aromatic substrate are derived on the basis of the assessed nitration mechanism. An activation energy of 604 ± 37 kJ mol?1 is calculated for this reaction step. © 1993 John Wiley & Sons, Inc. 相似文献
993.
The hyperfine field andthe electric field gradient on Cd probe atoms at Ni(100) and Ni(111) surfaces are calculated self-consistently within the local density molecular/cluster approach. 相似文献
994.
An iterative method from the class of completely implicit methods (CIM) is proposed for solving the equation of the velocity
potential of elliptical-hyperbolic type. The advantage of the proposed method compared to other CIM schemes is demonstrated
in application to mixed perfect gas flows in a nozzle of a given shape. Accuracy issues, rate of convergence, and various
techniques of ensuring stability in the hyperbolic region are discussed.
Translated from Chislennye Metody v Matematicheskoi Fizike, Published by Moscow University, Moscow, 1996, pp. 39–51. 相似文献
995.
A. P. Krauklis 《Journal of Mathematical Sciences》1997,86(3):2702-2704
This paper justifies the necessity of introducing corrections for the ray curvature into the standard procedure of the tomographic
inversion in the case of using traveltime data for the creeping waves. The results of relevant numerical experiments are presented.
Bibliography: 3 titles.
Translated fromZapiski Nauchnykh Seminarov POMI, Vol. 218, 1994, pp 67–71.
This work was supported by the Russian Foundation of Fundamental Research (Grant 93-05-9961).
Translated by A. P. Krauklis. 相似文献
996.
997.
998.
999.
This research extends previous work with dynamic models to manage groundwater quality by using the consumptive nitrate use rate instead of the nitrate application rate. The analysis indicates that misspecification results in overestimation of economic benefits, and supra-optimum nitrogen fertilizer application rates and groundwater nitrate stocks at a steady state. 相似文献
1000.
We characterize orbifolds in terms of their sheaves, and show that orbifolds correspond exactly to a specific class of smooth groupoids. As an application, we construct fibered products of orbifolds and prove a change-of-base formula for sheaf cohomology. 相似文献