Effect of the filled volume and the condensed-phase cage wall rigidity on bimolecular reactions
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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
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