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Analyses of reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems using recently developed thermodynamic rate equations
Author(s) -
Wiseman F. L.,
Scott D. W.,
Tamine J.,
O'Connell R.,
Smarra A.,
Olowoyo S.
Publication year - 2020
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.21329
Subject(s) - chemistry , acetonitrile , acetone , mole fraction , solvent , acetic anhydride , reaction rate , hydrolysis , solvent effects , thermodynamics , fraction (chemistry) , inorganic chemistry , organic chemistry , computational chemistry , catalysis , physics
Abstract This article presents reaction rate data for the simple hydrolysis of acetic anhydride in the acetonitrile/water and acetone/water cosolvent systems and regression analyses using recently developed thermodynamic rate equations that contain electrostatic and solvent‐solute terms. The isomole fraction plots for these reaction systems are linear, and previous theoretical work has shown that the electrostatic term is negligible for such systems. On the other hand, the reaction rates are dependent upon the cosolvent mole fraction, indicating that the solvent‐solute term, which is modeled empirically, is significant. The results of the analyses provide the foundation for a paradigm shift away from the emphasis on electrostatic effects to more tenable explanations of kinetic behavior in solvent systems.