Eyring’s rate theory and its connection to entropy scaling: viscosity and self-diffusion of hydrocarbons, alcohols, and water

Abstract Eyring’s absolute rate theory relates fluid flow with the activation energy necessary for a molecule to go from one equilibrium position to another. Developed nearly a century ago, it remains a powerful approach for understanding transport processes in liquids. This work presents a revision of Eyring’s theory by replacing the vaporization-based parts of the theory with a residual approach that conceptualizes transport as local (re)movement of molecules within the system rather than removal from it. In this new approach, the energy barrier corresponds to the difference between a molecule with and without intermolecular interactions, effectively treating it as the residual property related to an ideal gas reference state. Furthermore, we explore the physical connections between Eyring’s absolute rate theory and Rosenfeld excess entropy scaling, revealing that both approaches describe complementary aspects of the same transport phenomena. It is tempting to link both theories. The activation parameters in Eyring’s theory, particularly the energy of activation, are shown to relate to the residual entropy used in entropy scaling. This provides a pathway to establish entropy scaling on a more rigorous physical foundation while offering deeper insights into the molecular mechanisms governing viscous flow. In comparison to experimental data, the revised theory demonstrated significant predictive power for viscosity across a wide range of thermodynamic conditions and species, including associating liquids. Moreover, parameters are transferable to other properties, such as self-diffusion.