水合作用和外加电场对(104)方解石界面水电解质结构、动力学和电导率的影响

IF 3.2 3区 化学 Q2 CHEMISTRY, PHYSICAL
Thomas R. Underwood*, Sebastien N. Kerisit and Kevin M. Rosso, 
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引用次数: 0

摘要

碳酸钙矿物方解石在各种环境、地质和工业环境中无处不在。方解石和水溶液之间的界面会产生特定的表面电荷,这是水化学的一种功能,通过这种功能,诸如成核、生长和溶解等过程都会发生。离子在矿物表面的吸附形成双电层,随后决定了界面的特性,为基于电阻率和/或阻抗的遥感技术提供信号。电场诱导离子在界面上的漂移迁移率是一个关键的未知因素,其中水化程度以及外加电场的大小和方向都会干扰离子在电双层中的平衡分布。本文报道了平衡和非平衡经典分子动力学模拟,以了解水合作用和外加电场对方解石(104)界面上1 M NaCl电解质溶液结构和动力学的影响。我们在方解石表面的等电(中性)点建立了模型,然而,我们观察到离子在界面上的强结构,导致双电层的形成。研究表明,该双电层符合Stern模型的经典描述,具有明确定义的固定Stern层、剪切面和离子浓度分布,除此之外,离子浓度分布近似遵循泊松-玻尔兹曼分布。外加电场对斯特恩层和漫射层的结构都有扰动。此外,界面的水化状态对1m NaCl溶液的输运性质有显著影响。由于方解石表面连续脱水,我们观察到离子在斯特恩层中的扩散动力学受到严重限制,而在扩散层中则没有。最后,我们建立了一个理论框架,未来基于电阻率的遥感研究可以将其电导率测量解释为水化和扭曲度的函数。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Hydration and Applied Electric Field Effects on the Structure, Dynamics, and Conductivity of Aqueous Electrolytes at the (104) Calcite Interface

Hydration and Applied Electric Field Effects on the Structure, Dynamics, and Conductivity of Aqueous Electrolytes at the (104) Calcite Interface

The calcium carbonate mineral, calcite, is ubiquitous in a wide variety of environmental, geological, and industrial settings. The interface between calcite and aqueous solutions leads to a specific surface charge as a function of aqueous chemistry through which processes such as nucleation, growth, and dissolution occur. This sorption of ions to the mineral surface forms an electric double layer that subsequently determines properties of the interface that contribute signal to remote sensing techniques based on electrical resistivity and/or impedance. The electric field induced drift mobilities of ions at the interface are a key unknown, where both hydration extent and the magnitude and direction of the applied electric field act as to perturb the equilibrium distribution of ions in the electrical double layer. Here we report equilibrium and nonequilibrium classical molecular dynamics simulations to understand the impacts of hydration and applied electric fields on the structure and dynamics of a 1 M NaCl electrolyte solution at the (104) interface of calcite. We model the calcite surface at its isoelectric (neutral) point, yet, we observe strong structuring of ions to the interface, resulting in the formation of an electric double layer. We show that this electric double layer fits the classical description of the Stern model, with a clearly defined immobilized Stern layer, a shear plane, and an ionic concentration profile that approximately follows the Poisson–Boltzmann distribution beyond this. Applied electric fields are shown to perturb the structure of both the Stern layer and the diffuse layer. Moreover, the hydration state of the interface is shown to drastically impact the transport properties of the 1 M NaCl solution. As the calcite surface is sequentially dehydrated, we observe severely restricted diffusion dynamics of ions present in the Stern layer, but not in the diffuse layer. Finally, we develop a theoretical framework from which future studies of resistivity-based remote sensing can interpret their conductivity measurements as a function of hydration and tortuosity.

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来源期刊
The Journal of Physical Chemistry C
The Journal of Physical Chemistry C 化学-材料科学:综合
CiteScore
6.50
自引率
8.10%
发文量
2047
审稿时长
1.8 months
期刊介绍: The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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