ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 0,Vol.>> Issue()>> 0-0     doi: 10.3866/PKU.WHXB201709111         中文摘要
Accepted manuscript
Structure of Aqueous RbCl and CsCl Solutions Using X-Ray Scattering and Empirical Potential Structure Refinement Modelling
ZHOU Yongquan1, SOGA Yoshie2, YAMAGUCHI Toshio2, FANG Yan1, FANG Chunhui1
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
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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+.

Keywords: RbCl   CsCl   Solution structure   X-ray scattering   EPSR  
Received: 2017-08-07 Accepted: 2017-09-03 Publication Date (Web): 2017-09-11
Corresponding Authors: FANG Chunhui Email:

Fund: The project was supported by the Nature Science Foundation of Qinghai Province, China (2015-ZJ-945Q) and Youth Innovation Promotion Association, CAS, China (2017467).

Cite this article: 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 Phys. -Chim. Sin., 0, (): 0-0.    doi: 10.3866/PKU.WHXB201709111

(1) Xu, C.; Wang, J. C.; Chen, J. Solvent Extr. Ion Exc. 2012, 30, 623. doi: 10.1080/07366299.2012.700579
(2) Lei, H.; Li, S.; Zhai, Q.; Zhang, H.; Jiang, Y.; Hu, M. Acta Phys. -Chim. Sin. 2012, 28, 1599. [雷红, 李淑妮, 翟全国, 张晖英, 蒋育澄, 胡满成. 物理化学学报, 2012, 28, 1599.] doi: 10.3866/PKU.WHXB201204281
(3) Zhang, H.; Wang, S.; Wang, R.; Lin, C.; Zhang, X.; Wang, X. Acta Phys. -Chim. Sin. 2000, 16, 952. [张惠源, 王淑兰, 王榕树, 林灿生, 张先业, 王孝荣. 物理化学学报, 2000, 16, 952.] doi: 10.3866/PKU.WHXB20001016
(4) Izatt, R. M.; Rytting, J. H.; Nelson, D. P.; Haymore, B. L. Science 1969, 164, 443. doi: 10.1126/science.164.3878.443
(5) Maleknia, S.; Brodbelt, J. J. Am. Chem. Soc. 1993, 115, 2837. doi: 10.1021/ja00060a034
(6) Glendening, E. D.; Feller, D.; Thompson, M. A. J. Am. Chem. Soc. 1994, 116, 10657. doi: 10.1021/ja00102a035
(7) Inokuchi, Y.; Ebata, T.; Rizzo, T. R.; Boyarkin, O. V. J. Am. Chem. Soc. 2014, 136, 1815. doi: 10.1021/ja4086066
(8) Rodriguez, J. D.; Vaden, T. D.; Lisy, J. M. J. Am. Chem. Soc. 2009, 131, 17277. doi: 10.1021/ja906185t
(9) Inokuchi, Y.; Boyarkin, O. V.; Kusaka, R.; Haino, T.; Ebata, T.; Rizzo, T. R. J. Phys. Chem. A 2012, 116, 4057. doi: 10.1021/jp3011519
(10) Richens, D. T. The Chemistry of Aqua Ions: Synthesis, Structure and Reactivity: A Tour Through the Periodic Table of the Elements; Wiley: Chichester, UK, 1997; pp. 24–68.
(11) Fawcett, W. R. Liquids, Solutions, and Interfaces from Classical Macroscopic Descriptions to Modern Microscopic Details; Oxford Univesity Press: New York, USA, 2004; pp. 204–254.
(12) Hao, L.; Zhao, Y.; Zhao, J.; Jiang, X.; Yang, Z.; Zhao, D. Acta Phys. -Chim. Sin. 2016, 32, 2921. [赫兰兰, 郭宇, 赵健, 姜新蕊, 杨忠志, 赵东霞. 物理化学学报, 2016, 32, 2921.] doi: 10.3866/PKU.WHXB201609193]
(13) Galib, M.; Baer, M. D.; Skinner, L. B.; Mundy, C. J.; Huthwelker, T.; Schenter, G. K.; Benmore, C. J.; Govind, N.; Fulton, J. L. J. Chem. Phys. 2017, 146, 084504. doi: 10.1063/1.4975608
(14) Ohtaki, H.; Radnai, T. Chem. Rev. 1993, 93, 1157. doi: 10.1021/cr00019a014
(15) Cummings, S.; Enderby, J. E.; Neilson, G. W.; Newsome, J. R.; Howe, R. A.; Howells, W. S.; Soper, A. K. Nature 1980, 287, 714. doi: 10.1038/287714a0
(16) Smirnov, P. R.; Trostin, V. N. Russ. J. Gen. Chem. 2007, 77, 2101. doi: 10.1134/S1070363207120043
(17) Du, H.; Rasaiah, J. C.; Miller, J. D. J. Phys. Chem. B 2007, 111, 209. doi: 10.1021/jp064659o
(18) Mile, V.; Gereben, O.; Kohara, S.; Pusztai, L. J. Phys. Chem. B 2012, 116, 9758. doi: 10.1021/jp301595m
(19) Ramos, S.; Barnes, A. C.; Neilson, G. W.; Capitan, M. J. Chem. Phys. 2000, 258, 171. doi: 10.1016/S0301-0104(00)00132-4
(20) Ildikó, H.; László, P. J. Phys.: Condens. Matter 2007, 19, 335208. doi: 10.1088/0953-8984/19/33/335208
(21) Mile, V.; Pusztai, L.; Dominguez, H.; Pizio, O. J. Phys. Chem. B 2009, 113, 10760. doi:10.1021/jp900092g
(22) Buda, A.; Ali, S. M. J. Mol. Liq. 2013, 179, 34. doi: doi/abs/10.1021/ic030310t
(23) Ikeda, T.; Boero, M. J. Chem. Phys. 2012, 137, 041101. doi: 10.1063/1.4742151
(24) Mähler, J.; Persson, I. Inorg. Chem. 2011, 51, 425. doi: 10.1021/ic2018693
(25) Ling, L.; Fang, C.; Fang, Y. Salt Lake Res. 2006, 15, 45. [林联君, 房春晖, 房艳, 秦绪锋. 盐湖研究, 2006, 15, 45.]
(26) Ansell, S.; Barnes, A. C.; Mason, P. E.; Neilson, G. W.; Ramos, S. Biophys. Chem. 2006, 124, 171. doi: 10.1016/j.bpc.2006.04.018
(27) Neilson, G. W.; Mason, P. E.; Ramos, S.; Sullivan, D. Philos. Trans. R. Soc. London, Ser. A 2001, 359, 1575. doi: 10.1098/rsta.2001.0866
(28) Zhou, Y.; Fang, C.; Fang Y.; Zhu, F.; Tao, S.; Xu, S. Russ. J. Phys. Chem. A 2012, 86, 1236. doi: 10.1134/S0036024412060349
(29) Thorpe, S. J. L.; Thorpe, M. F. Local Structure from Diffraction; Kluwer Academic Publishers: New York, USA, 2002; pp. 59–85.
(30) Soper, A. K. Chem. Phys. 1996, 202, 295. doi: 10.1016/0301-0104(95)00357-6
(31) Soper, A. K. Phys. Rev. B 2005, 72, 104204. doi: 10.1103/PhysRevB.72.104204
(32) Soper, A. K. Mol. Simul. 2012, 38, 1171. doi: 10.1080/08927022.2012.732222
(33) Yamaguchi, T.; Fujimura, K.; Uchi, K.; Yoshida, K.; Katayama, Y. J. Mol. Liq. 2012, 176, 44. doi: 10.1016/j.molliq.2012.08.021.
(34) Shalaev, E.; Soper, A. K. J. Phys. Chem. B 2016, 120, 7289. doi: 10.1021/acs.jpcb.6b06157
(35) Mancinelli, R.; Botti, A.; Bruni, F.; Ricci, M. A.; Soper, A. K. J. Phys. Chem. B 2007, 111, 13570. doi: 10.1021/jp075913v
(36) Bowron, D. T.; Moreno, S. D. Coord. Chem. Rev. 2014, 277, 2. doi: 10.1021/jp202961t
(37) Krogh-Moe, J. Acta Crystallogr. 1956, 9, 951. doi: 10.1107/S0365110X56002655
(38) Norman, N. Acta Crystallogr. 1957, 10, 370. doi: 10.1107/S0365110X57001085
(39) Prince, E. International Tables for Crystallography; Kluwer Academic Publishers: London, UK, 2004; pp. 230–235, 255, 555–556, 658.
(40) Hubbell, J. H.; Veigele, W. J.; Briggs, E. A.; Brown, R. T.; Cromer, D. T.; Howerton, R. J. J. Phys. Chem. Ref. Data 1975, 4 (3), 471. doi: 10.1063/1.555523
(41) Kaplow, R.; Strong, S. L.; Averbach, B. L. Phys. Rev. 1965, 138, A1336. doi: 10.1103/PhysRev.138.A1336
(42) Johansson, G.; Sandström M. Chemica Scripta 1973, 4, 195. doi: 10.1107/S0021889875009594
(43) Zhou, Y.; Fang, C.; Fang, Y. Acta Phys. -Chim. Sin. 2010, 26, 2323. [周永全, 房春晖, 房艳. 物理化学学报, 2010, 26, 2323.] doi: 10.3866/PKU.WHXB20100903
(44) Yamaguchi, T.; Lee, K.; Yamauchi, M.; Fukuyama, N.; Yoshida, K. Bunseki Kagaku 2015, 64, 295. doi: 10.2116/bunsekikagaku.64.295
(45) Jensen, K. P.; Jorgensen, W. L. J. Chem. Theory Comput. 2006, 2, 1499. doi: 10.1021/ct600252r
(46) D'Angelo, P.; Persson, I. Inorg. Chem. 2004, 43, 3543. doi: 10.1021/ic030310t
(47) Smirnov, P. R.; Grechin, O. V. Russ. J. Coord. Chem. 2013, 39, 685. doi: 10.1134/S1070328413090078
(48) Soper, A. K. Chem. Phys. 2000, 258, 121. doi: 10.1016/S0301-0104(00)00179-8
(49) Soper, A. K. J. Chem. Phys. 1994, 101, 6888. doi: 10.1063/1.468318
(50) Marcus, Y. Chem. Rev. 2009, 109, 1346. doi: 10.1021/cr8003828.
(51) Chen, T.; Hefter, G.; Buchner, R. J. Phys. Chem. A 2003, 107, 4025. doi: 10.1021/jp026429p

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