The role of the molecular association in the change of the sign of the Soret coefficient in aqueous mixtures

TL;DR

This study uses Molecular Dynamics simulations and theoretical analysis to understand how molecular associations influence the sign change of the Soret coefficient in aqueous mixtures, aligning with experimental observations.

Contribution

It provides a quantitative analysis linking large inter-species interactions to the sign change of the Soret coefficient in associating fluids.

Findings

Simulations agree with experimental data for water-ethanol and water-methanol mixtures.

Inter-species interactions significantly influence the Soret coefficient's sign change.

Chemical contributions are not the sole factor in the sign change.

Abstract

The change of sign with composition in aqueous mixtures of associating fluids is analysed by means of Molecular Dynamics simulations. The results obtained are in quantitative agreement with the experimental data in water-ethanol and water-methanol solutions, which exhibit the mentioned change of sign. A subsequent theoretical analysis is addressed to establish a relationship between the dependence of the Soret coefficient with composition with the existence of large inter-species interactions. Although the change of sign of the Soret coefficient with composition is not only due to so-called chemical contribution analysed here, we discuss the role that these interactions play in such a change of sign