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Solvation effect on kinetic rate constant of reactions in supercritical solvents
Author(s) -
Chialvo A. A.,
Cummings P. T.,
Kalyuzhnyi Yu. V.
Publication year - 1998
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690440315
Subject(s) - supercritical fluid , solvation , reaction rate constant , kinetic energy , chemistry , constant (computer programming) , thermodynamics , solvent , computational chemistry , kinetics , organic chemistry , physics , classical mechanics , computer science , programming language
A statistical mechanical analysis of the solvation effects on the kinetic rate constants of reactions in near and supercritical solvents is presented to understand the experimental findings regarding the thermodynamic pressure effects. This is an extension of the solvation formalism of Chialvo and Cummings to the analysis of the microscopic basis for the macroscopic pressure and temperature effects on the kinetic rate constants of reactions conducted in the compressible region of the solvent phase diagram. This analysis is illustrated with integral equations calculations involving Lennard–Jones infinitely dilute quaternary systems to describe the species in solution during the reaction of triplet benzophenone ( 3 BP) with a cosolvent (either O 2 or 1,4‐cyclohexadiene) in supercritical CO 2 along the supercritical isotherms T r = 1.01 and 1.06. The role of the species molecular asymmetries and consequently their solvation behavior in determining the thermodynamic pressure and temperature effects on the kinetic rate constant of reactions at near‐critical conditions are discussed.