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

被引：5

作者：

Wiseman, F. L. ^{[1
]}

Scott, D. W. ^{[2
]}

Tamine, J. ^{[3
]}

O'Connell, R. ^{[1
]}

Smarra, A. ^{[1
]}

Olowoyo, S. ^{[2
]}

机构：

[1] Davis & Elkins Coll, Dept Chem, Elkins, WV 26241 USA

[2] East Tennessee State Univ, Dept Chem, Johnson City, TN USA

[3] Chevron Sci Ctr, Chem, Pittsburgh, PA USA

来源：

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS | 2020年 / 52卷 / 01期

关键词：

acetic anhydride hydrolysis in cosolvent systems; activation free energy; cosolvent system; electrostatic term; solvent-solute term; PREFERENTIAL SOLVATION; HYDROPHOBIC INTERACTION; SOLVENT INTERACTIONS; STRUCTURAL-CHANGES; SOLVOLYSIS; KINETICS; SOLUBILITY; AZLACTONE; MIXTURES; COMPLEX;

D O I：

10.1002/kin.21329

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：52 / 60

页数：9