RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟

doi:10.3866/PKU.WHXB201709111

物理化学学报 >> 2018, Vol. 34 >> Issue (5): 483-491.doi: 10.3866/PKU.WHXB201709111

RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟

周永全¹,曾我良枝²,山口敏男²,房艳¹,房春晖^1,*()

¹ 中国科学院青海盐湖研究所，青海西宁810008
² 福冈大学理学院化学系，福冈814-0180，日本

收稿日期:2017-08-07 发布日期:2018-01-24
通讯作者: 房春晖 E-mail:fangch@isl.ac.cn
基金资助:
青海省自然科学基金(2015-ZJ-945Q);中国科学院青年创新促进会(2017467)

Structure of Aqueous RbCl and CsCl Solutions Using X-Ray Scattering and Empirical Potential Structure Refinement Modelling

Yongquan ZHOU¹,Yoshie SOGA²,Toshio YAMAGUCHI²,Yan FANG¹,Chunhui FANG^1,*()

¹ Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, Qinghai Province, P. R. China
² Department of Chemistry, Faculty of Science, Fukuoka University, 8-19-1 Nanakuma, Jonan, Fukuoka 814-0180, Japan

Received:2017-08-07 Published:2018-01-24
Contact: Chunhui FANG E-mail:fangch@isl.ac.cn
Supported by:
the Natural Science Foundation of Qinghai Province, China(2015-ZJ-945Q);Youth Innovation Promotion Association, CAS, China(2017467)

摘要/Abstract

摘要：

采用X射线散射法研究了RbCl和CsCl水溶液的结构，利用基于经验势的结构精修(EPSR)方法获得了溶液中的水合Cl^-、Rb⁺、Cs⁺、离子缔合及本体水的对径向分布函数、配位数分布及空间密度分布(3D结构)等结构信息。在水溶液中，Cl^-具有相对稳定的6水合结构，其水合距离为0.321 nm，外加阳离子对其水合作用的影响不明显。7.3 ± 1.4个水分子与Rb⁺水合，其特征水合距离为0.297 nm，8.4 ± 1.6个水分子与Cs⁺水合其水合距离为0.312 nm。Cs⁺不具有第二水合层，而Rb⁺表现出了更强的水合能力，具有较明显的第二水合层。Cl^-、Rb⁺及Cs⁺常被认为是“结构破坏”型离子。从微观角度来看这种所谓的“结构破坏”主要体现在破坏了本体水分子的第二水合层保持四面体构型的趋势。RbCl和CsCl水溶液中部分存在着Rb-Cl和Cs-Cl直接接触离子对，在1.0 mol·dm^-3的溶液中Rb-Cl及Cs-Cl的特征距离分别为0.324和0.336 nm，溶剂分割离子对的距离则都在0.6 nm左右。相对于Cs⁺，Rb⁺与Cl^-离子之间表现出了更强的缔合能力。

关键词: RbCl, CsCl, 溶液结构, X射线散射, EPSR

Abstract:

X-ray scattering measurements were performed on 1.0 mol·dm^-3 RbCl and CsCl aqueous solutions. The X-ray structure factors were subjected to empirical potential structure refinement to extract detailed structural information on hydrated Cl^-, Rb⁺, Cs⁺, and ion association, as well as bulk water, in terms of the individual site-site pair correlation functions, coordination number distributions, and spatial density functions (three-dimensional structure). Cl^- is found to have a relatively stable six-fold coordination of water molecules with a Cl^--H₂O distance of 0.321 nm, and without a significant cation effect on its local structure. Rb⁺ is surrounded on an average by 7.3 ± 1.4 water molecules with a Rb⁺-H₂O distance of 0.297 nm, whereas 8.4 ± 1.6 water molecules hydrate Cs⁺ at a Cs⁺-H₂O distance of 0.312 nm. It is likely that Rb⁺ has a stronger hydration shell than Cs⁺, as evidenced by the presence of the second hydration shell of the former. Contact ion-pairs are partially formed in both solutions and characterized by the Rb⁺-Cl^- and Cs⁺-Cl^- distances of 0.324 nm and 0.336 nm. The solvent-separated ion pairs for both ions are discernible at around 0.6 nm. Rb⁺ has a stronger electrostatic interaction and hence a relatively stronger ion association with Cl^- than Cs⁺.

Key words: RbCl, CsCl, Solution structure, X-ray scattering, EPSR

周永全,曾我良枝,山口敏男,房艳,房春晖. RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟[J]. 物理化学学报, 2018, 34(5), 483-491. doi: 10.3866/PKU.WHXB201709111

Yongquan ZHOU,Yoshie SOGA,Toshio YAMAGUCHI,Yan FANG,Chunhui FANG. Structure of Aqueous RbCl and CsCl Solutions Using X-Ray Scattering and Empirical Potential Structure Refinement Modelling[J]. Acta Phys. -Chim. Sin. 2018, 34(5), 483-491. doi: 10.3866/PKU.WHXB201709111

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201709111

https://www.whxb.pku.edu.cn/CN/Y2018/V34/I5/483

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RbCl和CsCl水溶液结构的X射线散射及经验势结构精修模拟

Structure of Aqueous RbCl and CsCl Solutions Using X-Ray Scattering and Empirical Potential Structure Refinement Modelling

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