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Correspondence between Spectral-Derived and Viscosity-Derived Local Composition in Binary Liquid Mixtures Having
The Journal of Physical Chemistry. B
|November 8, 2018
Summary
A new viscosity model based on preferential solvation (PS) theory accurately estimates local molecular composition in liquid mixtures. This model, considering solvation shells, offers a simpler alternative to spectroscopy for analyzing solvent environments.
Area of Science:
- Physical Chemistry
- Solution Chemistry
- Molecular Interactions
Background:
- Local molecular interactions in solutions are typically measured using spectroscopy to determine local composition.
- Preferential solvation (PS) theory describes how solvent molecules arrange around solute molecules.
Purpose of the Study:
- To develop a viscosity model based on preferential solvation (PS) theory for estimating local composition in binary liquid mixtures.
- To assess the model's applicability to aqueous, nonaqueous, and nonpolar-polar mixtures, and its potential for estimating microviscosity.
Main Methods:
- Developed a viscosity model incorporating preferential solvation (PS) theory.
- Applied the model to aqueous and nonaqueous binary liquid mixtures containing dipolar aprotic solvents.
- Compared viscosity-derived local composition with spectral-derived composition and literature molecular simulations.
Main Results:
- The PS viscosity model accurately reflects local composition trends observed with bulk composition.
- Viscosity-derived local compositions align well with molecular simulations.
- Spectral-derived composition exhibited artifacts, while the viscosity model proved robust.
Conclusions:
- The PS viscosity model provides a reliable method for determining local composition, considering solvation shells.
- The model is versatile, applicable to various mixture types, and can estimate solvent properties like dipolarity/polarizability.
- This viscosity-based approach may enable microviscosity estimation for studying biomolecular solvent environments.
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