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通过数值和半解析模型研究带电液滴在不对称和混合电解质中的扩散迁移。

Diffusiophoresis of a Charged Droplet in Asymmetric as Well as Mixed Electrolytes through Numerical and Semianalytic Models.

机构信息

Department of Mathematics, Indian Institute of Technology Kharagpur, Kharagpur 721302, India.

出版信息

Langmuir. 2023 Jun 6;39(22):7831-7845. doi: 10.1021/acs.langmuir.3c00697. Epub 2023 May 24.

DOI:10.1021/acs.langmuir.3c00697
PMID:37223877
Abstract

A numerical study on the diffusiophoresis of a droplet in an electrolyte medium is carried out by solving the full set of coupled governing equations, which are based on the conservation principle. Diffusiophoresis is considered for monovalent as well as non-z:z electrolytes and mixed electrolytes. The numerical model is supplemented with a semianalytic simplified model based on first-order perturbation analysis, which agrees with the numerical model for a low to moderate range of surface potential. The mobility for a low-viscosity fluid at a thinner Debye length is dominated by the chemiphoresis part, which creates the mobility to become an even function of the surface charge density for a monovalent electrolyte. Such a pattern in mobility does not appear in a non-z:z asymmetric electrolyte. At a thinner Debye length, diffusiophoresis becomes independent of the diffusion field, hence the mobility is independent of the composition of electrolytes in a mixed monovalent electrolyte solution. Our results show that the size-based sorting of droplets is efficient when a mixed electrolyte is considered. We have also addressed the finite ion size effects by considering a modified ion transport equation. One of the key features of the present study is the simplified semianalytical model for the diffusiophoresis of a droplet in a z:z electrolyte as well as in non-z:z and mixed electrolytes, which is shown to be valid up to a moderate range of surface potential for a finite Debye length.

摘要

通过求解基于守恒原理的全耦合控制方程组,对电解质介质中液滴的扩散迁移进行了数值研究。研究了单价和非 z:z 电解质以及混合电解质的扩散迁移。数值模型补充了基于一阶微扰分析的半解析简化模型,该模型在低到中等表面电势范围内与数值模型一致。低粘度流体在较薄德拜长度下的迁移率主要由化学迁移部分决定,这使得迁移率成为单价电解质表面电荷密度的偶函数。在非 z:z 非对称电解质中,不会出现这种迁移率模式。在较薄的德拜长度下,扩散迁移与扩散场无关,因此在混合单价电解质溶液中,迁移率与电解质的组成无关。我们的结果表明,当考虑混合电解质时,基于尺寸的液滴分类是有效的。我们还通过考虑改进的离子输运方程来解决有限离子尺寸效应。本研究的一个关键特点是简化了 z:z 电解质以及非 z:z 和混合电解质中液滴扩散迁移的半解析模型,该模型在有限德拜长度下的中等表面电势范围内是有效的。

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