Influence of Alcohol Self-Association on Solvation Equilibria

• Applicant: Dr. Stefan Henkel
• Subject Area: Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: from 2015 to 2017
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 289176584

In order to rationalize the intermolecular interactions that govern the solution phase, Hunter and co-workers have developed empirical models that are based on molecular or functional group descriptors and allow a quantitative prediction of solvation thermodynamics. The goal of this research project will be to provide the experimental data necessary to extend these models with respect to the solvation properties of alcohols. Bulk alcohols have been shown to have higher polarity compared to their monomeric forms, which is attributed to the formation of alcohol aggregates. As this behaviour is not captured by the current model, this representation will be developed further to encompass such solutions. NMR- and UV-vis titration experiments will be used to investigate the self-association and the concomitant influence on the solvation equilibria of solute complexes for different sets of alcohols. This will allow the correlation of the overall solvation behavior to the concentration and constitution of the aggregates, thus providing a measure of the solvation properties of the self-associated alcohols. The experimental work will be complemented by calculations of molecular electrostatic potential surfaces. The results will be integrated in the current model and extend it to account for the difference between monomeric and aggregated species. The perspective of this generalization is to provide a new method that can be used to predict the solvation behavior of complex mixtures based on a simple set of molecular properties.

• DFG Programme: Research Fellowships
• International Connection: United Kingdom
• Host: Professor Christopher A. Hunter, Ph.D.