基于Gouy-Chapman理论估算碱金属离子在Cu2+-蒙脱石表面Hofmeister能
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S153.3

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国家自然科学基金项目(41530855,41877026)和重庆市自然科学基金项目(cstc2019jcyj-msxmX0332)资助


Estimation of Hofmeister Energy of Alkali Metal Ions on Cu2+-Montmorillonite Surface Based on the Gouy-Chapman Theory
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National Natural Science Foundation of China (No.41530855 and 41877026) and the Natural Science Foundation of Chongqing in China (No. cstc2019jcyj-msxmX0332)

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    摘要:

    Hofmeister效应在离子交换吸附过程中具有重要的科学意义。本研究基于Gouy-Chapman理论研究三种碱金属阳离子(Na+、K+、Cs+)在Cu2+-蒙脱石饱和样表面吸附过程的Hofmeister效应,进一步计算了离子-表面Hofmeister能以及表观电荷系数。研究发现:(1)Na+、K+、Cs+在Cu2+-蒙脱石表面的吸附均表现为弱静电力作用下的一级动力学过程,平均吸附速率以及平衡吸附量均表现出明显的Hofmeister效应,呈现出Na+ < K+ < Cs+的趋势;(2)Hofmeister能随着电解质浓度的降低而增加,在Cs+-黏土矿物相互作用中,Hofmeister能为主要贡献者,在K+/Na+-黏土矿物相互作用中,经典库伦能为主要贡献者;(3)非经典极化作用显著增大了离子的表观电荷系数,Na+、K+、Cs+的表观电荷系数分别从标准的+1值增加为+1.14、+1.76和+2.78。本研究明确了Hofmeister效应主要来源于离子的非经典极化作用引起的离子与表面相互作用能的差异,为阐明土壤这一特殊体系的界面反应机制提供了新的思路。

    Abstract:

    [Objective] Hofmeister effects can be seen everywhere, and usually manifested as difference in behavior of covalent ions in solution. Hofmeister effects exist universally in physical, chemical and biological processes, playing an important role in interface interaction. Also, Hofmeister effects are of great scientific significance to ion exchange/adsorption process. The purpose of this paper is to compare Hofmeister effects on the adsorption processes of three kinds of alkali metal cations (Na+, K+, Cs+) on saturated surface of Cu2+montmorillonite and to analyze sources of the Hofmeister effects.[Method] An ion adsorption kinetics experiment was carried out using the constant current method to compare the three alkali metal cations (Na+, K+, Cs+) in adsorption on Cu2+-montmorillonite surface. The experiment was designed to have the temperature fixed at 298 K, and the binary mixed electrolyte solution composed of XNO3 + LiNO3, where X stands for Cs, Na or K. The two electrolytes in the mixed solution was equal in concentration, 0.0001, 0.001 or 0.01 mol·L-1. In the end, ion-surface Hofmeister energies and apparent charge coefficients were worked out in line with the Gouy-Chapman theory.[Result] (1) The adsorption of Na+, K+ and Cs+ on the surface of Cu2+-montmontmoillonite showed a first-order kinetic process under a weak electrostatic force, with average adsorption rate and equilibrium adsorption demonstrating obvious Hofmeister effects in an order of Na+ < K+ < Cs+. For example, when the electrolyte was 0.01 mol·L-1 in concentration, the average adsorption rate of Na+, K+ and Cs+ on the surface of Cu2+-montmorillonite reached 4.48, 8.68 and 11.74 mmol·kg-1·min-1 respectively, and the equilibrium adsorption did 129.17, 341.11 and 911.47 mmol·kg-1respectively in amount within 27 minutes. (2) Hofmeister energy increased with decreasing electrolyte concentration. On the surface of Cs+-clay mineral, Hofmeister energy was the main contributor of the interaction, while on the surface of K+/Na+-clay mineral, classical Coulomb energy was. When the electrolyte concentration was 0.0001, 0.001 and 0.01 mol·L-1, the ratio of wHi (0)/wTi (0) of Cs+ was 67.00, 65.71 and 58.00%; that of K+ 44.24, 43.36 and 42.19%; and that of Na+17.88, 9.29 and 8.82%, respectively. (3) Effective charge coefficient decreased with increasing electrolyte concentration. This is because increased electrolyte concentration compresses the electric double layer, thus enhancing its capability of shielding the electric field, and leading to decrease of the electric field in the diffusion layer in intensity, which eventually weakens polarization of the adsorbed ions and reduces effective charge coefficients. The non-classical polarization significantly amplified apparent charge coefficient of the ions. The apparent charge coefficients of Cs+, K+, Na+ worked out in this experiment under the condition of the electrolyte concentration being 0.0001, 0.001, 0.01 mol·L-1 followed the sequence of Cs+ > K+ > Na+ in Hofmeister effect. Apparent charge coefficient of Na+, K+ and Cs+ increased from the standard +1 value to +1.14, +1.76 and +2.78, respectively.[Conclusion] This study clearly demonstrates that the Hofmeister effects originate mainly from the difference in ion-surface interaction energy between the ions caused by their non-classical polarization. And all the findings in this study provides a new idea for elucidating the mechanisms of interface reactions in such a unique system as soil.

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朱晔玮,刘新敏,李睿,李航.基于Gouy-Chapman理论估算碱金属离子在Cu2+-蒙脱石表面Hofmeister能[J].土壤学报,2022,59(2):498-508. DOI:10.11766/trxb202007090378 ZHU Yewei, LIU Xinmin, LI Rui, LI Hang. Estimation of Hofmeister Energy of Alkali Metal Ions on Cu2+-Montmorillonite Surface Based on the Gouy-Chapman Theory[J]. Acta Pedologica Sinica,2022,59(2):498-508.

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  • 收稿日期:2020-07-09
  • 最后修改日期:2020-08-26
  • 录用日期:2020-10-21
  • 在线发布日期: 2020-12-22
  • 出版日期: 2022-02-11