Local volume conservation in concentrated electrolytes is governing charge transport in electric fields

TL;DR

This study reveals that local molar volume conservation, rather than momentum conservation, governs ion transport in concentrated electrolytes, impacting how transference numbers are calculated and interpreted.

Contribution

It demonstrates that local molar volume conservation, not momentum conservation, is the key constraint in ion transport within concentrated electrolytes, challenging previous assumptions.

Findings

Net volume flux is zero in experiments.

Local molar volume conservation is consistent with incompressibility.

Momentum conservation does not govern ion transport in these systems.

Abstract

While ion transport processes in concentrated electrolytes, e.g. based on ionic liquids (IL), are a subject of intense research, the role of conservation laws and reference frames is still a matter of debate. Employ-ing electrophoretic NMR, we show that momentum conservation, a typical prerequisite in molecular dynamics (MD) simulations, is not governing ion transport. Involving density measurements to deter-mine molar volumes of distinct ion species, we propose that conservation of local molar species volumes is the governing constraint for ion transport. The experimentally quantified net volume flux is found as zero, implying a non-zero local momentum flux, as tested in pure ILs and IL-based electrolytes for a broad variety of concentrations and chemical compositions. This constraint is consistent with incom-pressibility, but not with a local application of momentum conservation. The constraint affects the calcu-lation of transference numbers as well as comparisons of MD results to experimental findings.