How Might Chemical Reaction Rates in Solution Be Affected By Intense Density Fluctuations of the Solvent?

Abstract

A chance observation of the great solvation power of fluid xenon in the critical state, has led us to the suggestion that a reaction between two relatively nonpolar molecules to form a more polar product, will have a higher rate constant in the critical fluid of xenon than in the noncritical fluids at 1 K above or below T _c. the large density fluctuations in the highly compressible critical fluid enhance the solvation of the dipolar transition state, through dipole-induced-dipole attractions. This is predicted to lower the activation energy of the reaction and increase the reaction rate. an example is 1-C₄H₈ + Br₂ → C₄H₈Br₂ in the dark.

Key Words:

• Critical fluid
• density fluctuations
• reaction rate enhancement