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Title: Selective Se-for-S substitution in Cs-bearing uranyl compounds

Abstract

Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){submore » 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the pure sulfate and selenate compounds. The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded 4-connected site. - Highlights: • Single crystals of novel mixed sulfate-selenate uranyl oxysalts were prepared by evaporation method. • Topological analysis and information-based complexity calculations were used for structure description. • The selective Se-for-S substitution was observed. • Evolution of phase formation in the aqueous Cs{sup +}–UO{sub 2}{sup 2+}–SO{sub 4}{sup 2–}–SeO{sub 4}{sup 2–} system was analyzed.« less

Authors:
 [1]; ;  [1];  [2]
  1. Department of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia Federation (Russian Federation)
  2. Far Eastern Federal University, Suhanova st. 8, Vladivostok 690950 (Russian Federation)
Publication Date:
OSTI Identifier:
22658245
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 248; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AQUEOUS SOLUTIONS; CARBON SULFIDES; CATALYST SUPPORTS; CESIUM IONS; CRYSTALLIZATION; FOURIER TRANSFORMATION; INFRARED SPECTRA; MONOCRYSTALS; SCANNING ELECTRON MICROSCOPY; SELENATES; SOLID SOLUTIONS; SULFUR IONS; URANIUM DIOXIDE; X-RAY DIFFRACTION

Citation Formats

Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru, Tyumentseva, Olga S., Krivovichev, Sergey V., and Tananaev, Ivan G. Selective Se-for-S substitution in Cs-bearing uranyl compounds. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.02.005.
Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru, Tyumentseva, Olga S., Krivovichev, Sergey V., & Tananaev, Ivan G. Selective Se-for-S substitution in Cs-bearing uranyl compounds. United States. doi:10.1016/J.JSSC.2017.02.005.
Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru, Tyumentseva, Olga S., Krivovichev, Sergey V., and Tananaev, Ivan G. Sat . "Selective Se-for-S substitution in Cs-bearing uranyl compounds". United States. doi:10.1016/J.JSSC.2017.02.005.
@article{osti_22658245,
title = {Selective Se-for-S substitution in Cs-bearing uranyl compounds},
author = {Gurzhiy, Vladislav V., E-mail: vladgeo17@mail.ru and Tyumentseva, Olga S. and Krivovichev, Sergey V. and Tananaev, Ivan G.},
abstractNote = {Phase formation in the mixed sulfate-selenate aqueous system of uranyl nitrate and cesium nitrate has been investigated. Two types of crystalline compounds have been obtained and characterized using a number of experimental (single crystal XRD, FTIR, SEM) and theoretical (information-based complexity calculations, topological analysis) techniques. No miscibility gaps have been observed for Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se), which crystallizes in tetragonal system, P-42{sub 1}m, a =9.616(1)–9.856(2), c =8.105(1)–8.159(1) Å, V =749.6(2)–792.5(3) Å{sup 3}. Nine phases with variable amount of S and Se have been structurally characterized. The structures of the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) compounds are based upon the [(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}]{sup 2-} layers of corner-sharing uranyl pentagonal bipyramids and TO{sub 4} tetrahedra. The layers contain two types of tetrahedral sites: T1 (3-connected, i.e. having three O atoms shared by adjacent uranyl polyhedra) and T2 (4-connected). The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded T2 site. Crystallization in the pure Se system starts with the formation of Cs{sub 2}[(UO{sub 2})(SeO{sub 4}){sub 2}(H{sub 2}O)](H{sub 2}O) crystals, its subsequent dissolution and formation of Cs{sub 2}[(UO{sub 2}){sub 2}(SeO{sub 4}){sub 3}]. The information-based structural complexity calculations for these two phases support the rule that more topologically complex structures form at the latest stages of crystallization. - Graphical abstract: Nine phases representing the Cs{sub 2}[(UO{sub 2}){sub 2}(TO{sub 4}){sub 3}] (T= S, Se) solid solution series with variable amount of S and Se have been prepared by isothermal evaporation from aqueous solutions and characterized using a number of experimental and theoretical techniques. No immiscibility is observed between the pure sulfate and selenate compounds. The Se-for-S substitution in tetrahedral sites is highly selective with smaller S{sup 6+} cation showing a strong preference for the more tightly bonded 4-connected site. - Highlights: • Single crystals of novel mixed sulfate-selenate uranyl oxysalts were prepared by evaporation method. • Topological analysis and information-based complexity calculations were used for structure description. • The selective Se-for-S substitution was observed. • Evolution of phase formation in the aqueous Cs{sup +}–UO{sub 2}{sup 2+}–SO{sub 4}{sup 2–}–SeO{sub 4}{sup 2–} system was analyzed.},
doi = {10.1016/J.JSSC.2017.02.005},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 248,
place = {United States},
year = {Sat Apr 15 00:00:00 EDT 2017},
month = {Sat Apr 15 00:00:00 EDT 2017}
}