Relative permittivity measurements of aqueous co-solvent systems including tetrahydrofuran

Scott, Dane W.; Wiseman, Floyd L.; Cooper, William C.; Alseiha, Yahya Sami

doi:10.1016/j.cdc.2017.08.001

Cited by 4 publications

(6 citation statements)

References 7 publications

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Section: Discussionmentioning

confidence: 99%

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A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions

Wiseman,

Scott

2024

Phys. Chem. Chem. Phys.

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Section: Discussionmentioning

confidence: 99%

“…Fortunately, such data is available for some systems. 39 Secondly, for analyzing both electrostatic and mole fraction effects, we must study the reaction under a variety of conditions, which is data intensive. Another drawback concerns the need for high quality data, particularly when analyzing electrostatic effects.…”

Section: Discussionmentioning

confidence: 99%

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions

Wiseman,

Scott

2024

Phys. Chem. Chem. Phys.

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“…As relative permittivity data are needed for the analysis, it is fortunate that literature data are available for a number of common aqueous systems. Among these include acetonitrile/water, acetone/water, tetrahydrofuran/water, methanol/water, ethanol/water, n ‐propanol/water, isopropanol/water, dimethylformamide/water, and 1,4‐dioxane/water . However, on a different note, the application of this method requires not only a thorough and perhaps lengthy experimental protocol but also a variety of molecular data not readily available in the literature.…”

Section: Discussionmentioning

confidence: 99%

On the derivation of a general thermodynamic expression for the reaction rate constant for cosolvent reaction systems

Wiseman

Scott

Tamine

et al. 2018

Int J of Chemical Kinetics

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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. K E Y W O R D Sactivation free energy terms, electrostatic effects, Eyring plots, kinetics, solvent-solute interactions Int J Chem Kinet. 2018;50:873-879.

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“…References and provided the relative permittivity data for the acetonitrile/water and acetone/water cosolvent systems.…”

Section: Methodsmentioning

confidence: 99%

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

Wiseman

Scott

Tamine

et al. 2019

Int J of Chemical Kinetics

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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.

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Relative permittivity measurements of aqueous co-solvent systems including tetrahydrofuran

Cited by 4 publications

References 7 publications

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions

On the derivation of a general thermodynamic expression for the reaction rate constant for cosolvent reaction systems

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

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Relative permittivity measurements of aqueous co-solvent systems including tetrahydrofuran

Cited by 4 publications

References 7 publications

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to SN1 reactions

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to SN1 reactions

On the derivation of a general thermodynamic expression for the reaction rate constant for cosolvent reaction systems

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

Contact Info

Product

Resources

About

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions

A thermodynamic approach to analyzing relative permittivity and solvent mole fraction models, and application to S_N1 reactions