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On the derivation of a general thermodynamic expression for the reaction rate constant for cosolvent reaction systems
Author(s) -
Wiseman F. L.,
Scott D. W.,
Tamine J.,
O'Connell R.,
Smarra A.,
Mitchell N.
Publication year - 2018
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21222
Subject(s) - chemistry , isotropy , thermodynamics , solvent , reaction rate constant , constant (computer programming) , activation energy , expression (computer science) , phase (matter) , mole fraction , reaction rate , range (aeronautics) , solvent effects , computational chemistry , organic chemistry , kinetics , classical mechanics , catalysis , quantum mechanics , physics , materials science , computer science , composite material , programming language
This article presents the derivation of the thermodynamic expressions for the activation free energy and reaction rate constant for cosolvent reaction systems. These expressions account for the factors that are specific to solution‐phase reactions, which include isotropic electrostatic effects and close‐range solvent−solute interactions. This article discusses the idea that electrostatic effects can be correlated with the isotropic relative permittivity, and solvent−solute interactions can be correlated with the cosolvent mole fraction. This article also shows that this type of thermodynamic analysis is necessary for understanding certain nuances of solution‐phase reaction processes not tractable by other types of analyses.