Effect of the filled volume and the condensed-phase cage wall rigidity on bimolecular reactions
In a condensed phase, particle movement and collison occur in a free volume which is much less than the total volume occupied by the medium, the result being that the bimolecular collison frequency factor is higher in the condensed phase than in the gaseous.
The interaction of nonspherical particles increases the cage wall rigidity in the condensed phase, i.e., an increase in the viscosity of the medium reduces the rate constant for the bimolecular reaction by increasing the effect of the neighboring molecules on transition-state particle orientation.
KeywordsViscosity Cage Free Volume Particle Movement Condensed Phase
Unable to display preview. Download preview PDF.
- 1.S. Glasstone, K. J. Laidler, and H. Éyring, Theory of Absolute Reaction Rates (Russian translation], IL (1948).Google Scholar
- 2.É. S. Amis, Solvent Effects on Reaction Rates and Mechanisms, Academic Press (1966).Google Scholar
- 3.N. M. Émanuel', G. E. Zaikov, and Z. K. Malzus, Role of the Medium in Radical-Chain Oxidations of Organic Compounds [in Russian], Nauka (1973).Google Scholar
- 4.S. G. Éntelis and R. P. Tiger, Kinetics of Reactions in the Liquid Phase [in Russian], Khimiya (1973).Google Scholar
- 5.A. P. Griva and E. T. Denisov, Dokl. Akad. Nauk SSSR,219, 640 (1974).Google Scholar
- 6.V. N. Kondrat'ev, Rate Constants for Gas-Phase Reactions [in Russian], Nauka (1970).Google Scholar
- 7.E. T. Denisov, Rate Constants for Homolytic Liquid-Phase Reactions [in-Russian], Nauka (1971),Google Scholar
- 8.A. F. Trotman-Dickenson and G. S. Milne, Tables of Bimolecular Gas Reactions, NBS, Washington 1967).Google Scholar
- 9.J. A. Kerr and E. Ratzjczak, Second Supplementary Table of Bimolecular Gas Reactions, University of Birmingham (1973).Google Scholar
- 10.S. W. Benson and H. E. O'Neal, Kinetic Data on Unimolecular Gas Phase Reactions, NBS, Washington (1970).Google Scholar
- 11.É. A. Moelwyn-Hughes, Chemical Statics and Kinetics of Solutions, Academic Press (1972).Google Scholar
- 12.K. J. Laidler, Chemical Kinetics, McGraw-Hill, New York (1965).Google Scholar
- 13.E. N. Eremin, Principles of Chemical Kinetics in Gases and Solutions [in Russian], Izd-vo Mosk. Un-ta (1971).Google Scholar
- 14.A. M. North, Collision Theory of Chemical Reactions in Liquids, Methuen, London (1964).Google Scholar
- 15.É. A. Moelwyn-Hughes, Physical Chemistry, Vols.1 and 2, Pergamon (1969).Google Scholar
- 16.N. V. Zolotova and E. T. Denisov, Zh. Fiz. Khim.,46, 008 (1972).Google Scholar