Diffusioosmotic flow reversals due to ion–ion electrostatic correlations

Zhang, Shengji; Chu, Henry C. W.

doi:10.1039/d3nr06152c

Title: Diffusioosmotic flow reversals due to ion–ion electrostatic correlations

Journal Article · 23 April 2024 · Nanoscale

DOI: https://doi.org/10.1039/d3nr06152c · OSTI ID:2452855

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University of Florida, Gainesville, FL (United States); University of Florida
University of Florida, Gainesville, FL (United States)

Existing theories of diffusioosmosis have neglected ion–ion electrostatic correlations, which are important in concentrated electrolytes. Here, we develop a mathematical model to numerically compute the diffusioosmotic mobilities of binary symmetric electrolytes across low to high concentrations in a charged parallel-plate channel. We use the modified Poisson equation to model the ion–ion electrostatic correlations and the Bikerman model to account for the finite size of ions. We report two key findings. First, ion–ion electrostatic correlations can cause a unique reversal in the direction of diffusioosmosis. Such a reversal is not captured by existing theories, occurs at ≈ 0.4 M for a monovalent electrolyte, and at a much lower concentration of ≈ 0.003 M for a divalent electrolyte in a channel with the same surface charge. This highlights that diffusioosmosis of a concentrated electrolyte can be qualitatively different from that of a dilute electrolyte, not just in its magnitude but also its direction. Second, we predict a separate diffusioosmotic flow reversal, which is not due to electrostatic correlations but the competition between the underlying chemiosmosis and electroosmosis. This reversal can be achieved by varying the magnitude of the channel surface charge without changing its sign. However, electrostatic correlations can radically change how this flow reversal depends on the channel surface charge and ion diffusivity between a concentrated and a dilute electrolyte. Furthermore, the mathematical model developed here can be used to design diffusioosmosis of dilute and concentrated electrolytes, which is central to applications such as species mixing and separation, enhanced oil recovery, and reverse electrodialysis.

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Research Organization:: University of Florida, Gainesville, FL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0018676

OSTI ID:: 2452855

Journal Information:: Nanoscale, Journal Name: Nanoscale Journal Issue: 19 Vol. 16; ISSN 2040-3364

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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