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

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

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

Corresponding author: FANG Chunhui, fangch@isl.ac.cn
Received Date: 7 August 2017
Revised Date: 3 September 2017
Accepted Date: 11 September 2017
Available Online: 11 May 2017
Fund Project: The project was supported by the Natural Science Foundation of Qinghai Province, China (2015-ZJ-945Q) and Youth Innovation Promotion Association, CAS, China (2017467)the Natural Science Foundation of Qinghai Province, China 2015-ZJ-945QYouth Innovation Promotion Association, CAS, China 2017467

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⁺.
- RbCl,
- CsCl,
- Solution structure,
- X-ray scattering,
- EPSR
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