Transient response of an electrolyte to a thermal quench.

Abstract

We study the transient response of an electrolytic cell subject to a small, suddenly applied temperature increase at one of its two bounding electrode surfaces. An inhomogeneous temperature profile then develops, causing, via the Soret effect, ionic rearrangements towards a state of polarized ionic charge density q and local salt density c. For the case of equal cationic and anionic diffusivities, we derive analytical approximations to q,c, and the thermovoltage V_{T} for early (t≪τ_{T}) and late (t≫τ_{T}) times as compared to the relaxation time τ_{T} of the temperature. We challenge the conventional wisdom that the typically large Lewis number, the ratio a/D of thermal to ionic diffusivities, of most liquids implies a quickly reached steady-state temperature profile onto which ions relax slowly. Though true for the evolution of c, it turns out that q (and V_{T}) can respond much faster. Particularly when the cell is much bigger than the Debye length, a significant portion of the transient response of the cell falls in the t≪τ_{T} regime, for which our approximated q (corroborated by numerics) exhibits a density wave that has not been discussed before in this context. For electrolytes with unequal ionic diffusivities, V_{T} exhibits a two-step relaxation process, in agreement with experimental data of Bonetti et al. [J. Chem. Phys. 142, 244708 (2015)JCPSA60021-960610.1063/1.4923199].