Visualization of magnesium and rubidium ion hydration in sulfocationite using quantum chemical calculation
https://doi.org/10.29235/1561-8323-2021-65-6-692-701
Abstract
Based on the data of ab initio calculation of the structure of (RSO3)2Mg (H2O)18 and (RSO3Rb)2(H2O)16 clusters, which simulate the structure of swollen sulfostyrene ion exchangers in the corresponding ionic forms and a water cluster of comparable size, the numbers of water molecules directly bound to cations and their coordination numbers, including the oxygen atoms of the sulfonic groups linked to the cation, were calculated. It is shown that the first molecular layer around the magnesium ion is formed from water molecules with the highest binding energy with the cluster, and around the rubidium ion – from the molecules of the nearest environment with the lowest binding energies. This is explained by the fact that the transfer of water molecules from its volume to magnesium hydrate is energetically favorable, but not to rubidium hydrate. Therefore, the magnesium ion builds its hydrate mainly from water molecules with the highest binding energy in order to obtain the greatest energy gain, and the rubidium ion – from molecules with the lowest energy, which provides the smallest energy loss.
About the Authors
V. S. Soldatov
Institute of Physical Organic Chemistry of the National Academy of Sciences of Belarus
Belarus
Belarus
Soldatov Vladimir S. - Academician, D. Sc. (Chemistry), Professor, Chief researcher
13, Surganov Str., 220072, Minsk, Republic of Belarus
T. V. Bezyazychnaya
Institute of Physical Organic Chemistry of the National Academy of Sciences of Belarus
Belarus
Belarus
Bezyazychnaya Tatiana V. - Ph. D. (Physical and Mathematics), Senior researcher
13, Surganov Str., 220072, Minsk, Republic of Belarus
E. G. Kosandrovich
Institute of Physical Organic Chemistry of the National Academy of Sciences of Belarus
Belarus
Belarus
Kosandrovich Evgenii G. – D. Sc. ( Chemistry), Associate professor, Head of the Laboratory
13, Surganov Str., 220072, Minsk, Republic of Belarus
References
1. Short chemical encyclopedia. Vol. 1A. Moscow, Sovetskaya entsiklopediya Publ., 1961. 631 p. (in Russian).
2. Samoilov O. Ya. Structure of electrolyte water solution and hydration of ions. Moscow, USSR Academy of Sciences Publishing House, 1957. 182 p. (in Russian).
3. Soldatov V. S., Kosandrovich E. G., Bezyazychnaya T. V. Hydration of ion exchangers: thermodynamics and quantum chemistry calculations. IV. The state of ions and water molecules in alkali forms of sulfostyrene resins. Reactive and Functional Polymers, 2018, vol. 131, pp. 219–229. https://doi.org/10.1016/j.reactfunctpolym.2018.07.010
4. Mendeleev D. I. Fundamentals of chemistry. 8 ed. Saint Petersburg, Tipo-litografiya M. P. Frolovoi, 1906. 560 p. (in Russian).
5. Gregor H. P., Sundheim B. R., Held K. M., Waxman M. H. Studies on ion-exchange resins. V. Water vapor sorption. Journal of Colloid Science, 1952, vol. 7, no. 5, pp. 511–534. https://doi.org/10.1016/0095-8522(52)90034-2
6. Kirgintsev A. N., Luk’yanov A. V., Vulikh A. I. Isoterms of water vapor sorption by ion exchanger KU-2 in different ionic forms. Ionity i ionnyi obmen: sbornik statei [Ion exchangers and ion exchange. Collection of articles]. Moscow, Nauka Publ., 1966, pp. 34–39 (in Russian).
7. Soldatov V. S., Kasandrovich E. G., Bezyazychnaya T. V. State of the lithium ions in the sulfostyrene cation exchanger according to ab initio quantum chemical calculations. Doklady Natsional’noi akademii nauk Belarusi = Doklady of the National Academy of Sciences of Belarus, 2020, vol. 64, no. 4, pp. 421–425 (in Russian). https://doi.org/10.29235/1561-8323-2020-64-4-421-425
8. Rowley C. N., Roux B. The solvation structure of Na+ and K+ in liquid water determined from high-level ab initio molecular dynamic simulations. Journal of Chemical Theory and Computation, 2012, vol. 8, no. 10, pp. 3526–3535. https://doi.org/10.1021/ct300091w
9. Bankura A., Carnevale V., Klein M. L. Hydration structure of salt solutions from ab initio molecular dynamics. Journal of Chemical Physics, 2013, vol. 138, no. 1, pp. 014501. https://doi.org/10.1063/1.4772761
10. Sripa P., Tongraar A., Kerdcharoen A. Characteristics of K+ and Rb+ as “structure breaking” ions in dilute aqueous solutions: Insights from ONIOM-XS MD Simulations. Journal of Chemical Physics, 2016, vol. 479, pp. 72–80. https://doi.org/10.1016/j.chemphys.2016.09.028
11. Gordon J. E. The organic chemistry of electrolyte solutions. New York, 1975. 554 p.
12. Marcus Y. Thermodynamics of solvation ions. Part 5. Gibbs free energy of hydration at 298.15 K. Journal of the Chemical Society Faraday Transactions, 1991, vol. 87, no. 18, pp. 2995–2999. https://doi.org/10.1039/ft9918702995
13. Zhang Q., Pan Zh., Zhang Lu, Zhang R., Chen Zh., Jin T., Wu T., Chen X., Zhuang W. Ion effect on the dynamics of water hydrogen bonding network: A theoretical and computational spectroscopy point of view. Wiley Interdisciplinary Reviews: Computational Molecular Science, 2018, vol. 8, no. 6, pp. 1–23. https://doi.org/10.1002/wcms.1373
14. Cappa C. D., Smith J. D., Messer B. M., Cohen R. C., Saykally R. J. Nature of the aqueous hydroxide ion probed by X-ray absorption spectroscopy. Journal of Physical Chemistry A, 2007, vol. 111, no. 22, pp. 4776–4785. https://doi.org/10.1021/jp070551c
15. Zavitsas A. A. Some opinions of an innocent bystander regarding the Hofmeister series. Current Opinion in Colloid and Interface Science, 2016, vol. 23, pp. 72–81. https://doi.org/10.1016/j.cocis.2016.06.012
Review
Views: 503
Email this article 