Comment on: Describing temperature-dependent self-diffusion coefficients and fluidity in alcohols using the compensated Arrhenius formalism

TL;DR

This paper critiques the use of the compensated Arrhenius formalism for analyzing temperature-dependent properties of alcohols, arguing it lacks physical adequacy and proposing more appropriate Arrhenius-based methods for understanding molecular fluid dynamics.

Contribution

It provides a critical assessment of CAF's physical validity and suggests alternative Arrhenius approaches for better molecular-level understanding.

Findings

CAF analysis is physically inadequate for polyhydric alcohols.

Alternative Arrhenius approximations yield more meaningful correlations.

The critique emphasizes the importance of physically valid models in fluid dynamics studies.

Abstract

In Supplemental Information (SI) to the article [A. M. Fleshman, G. E. Forsythe, M. Petrowsky, R. Frech, J. Phys. Chem. B 2016, 120, 37, 9959-68] the temperature dependences (TDs) of the dielectric and dynamic properties of polyhydric alcohols, as well as the activation energy (Ea) obtained using the compensated Arrhenius formalism (CAF) are given. The authors present CAF as an approach provides physical significance into the molecular level nature of the transport process. However, the CAF logic is physically inadequate and analysis of TDS polyhydric alcohols using CAF cannot provide physically significant correlations useful for understanding the molecular mechanisms of fluid dynamics. However, such correlations from SI can be obtained by applying physically adequate Arrhenius approximations of TDs properties of liquids [A. Kholmanskiy, N. Zaytseva, J. Mol. Liq. 275 (2019) 741-8].