Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds

Abstract

Here, phase formation in the mixed sulfate–selenate Np(VI)-bearing aqueous system has been investigated. The obtained crystalline compounds, Cs2[(NpO2)2(TO4)3] (T = S, Se), crystallize in the tetragonal system, space group P$$\bar{42}$$1m, with a = 9.5737(3)–9.817(3) Å, c = 8.0824(4)–8.111(3) Å, and V = 740.79(6)–781.8(6) Å3, and have been chemically characterized. Single-crystal X-ray diffraction experiments at various temperatures were used to define the thermal behavior of the crystal structures relative to the S/Se ratio. The thermal behavior of mixed sulfate–selenate and pure selenate compounds is anisotropic, with the highest thermal expansion in the direction perpendicular to the sheets of Np-bearing polyhedra, while the structure of the pure sulfate compound experiences almost isotropic thermal expansion with slightly higher expansion within the layer, which is explained by the influence of stronger Cs–O bonding. High-temperature drop solution calorimetry was used to derive the enthalpies of formation of the Cs+-bearing neptunyl oxysalts. Lastly, within this family of isotypic structures, cesium neptunyl sulfate has a more negative enthalpy of formation in comparison to the selenate compound.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [3];  [3]; ORCiD logo [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. St. Petersburg State Univ. (Russia); Kola Science Centre, Murmansk region (Russia)
  2. St. Petersburg State Univ. (Russia)
  3. Univ. of Notre Dame, IN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566488
Grant/Contract Number:  
SC0001089
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 19; Journal Issue: 5; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear (including radiation effects); materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Kornyakov, Ilya V., Gurzhiy, Vladislav V., Szymanowski, Jennifer E. S., Zhang, Lei, Perry, Samuel N., Krivovichev, Sergey V., and Burns, Peter C. A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds. United States: N. p., 2019. Web. doi:10.1021/acs.cgd.9b00043.
Copy to clipboard
Kornyakov, Ilya V., Gurzhiy, Vladislav V., Szymanowski, Jennifer E. S., Zhang, Lei, Perry, Samuel N., Krivovichev, Sergey V., & Burns, Peter C. A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds. United States. https://doi.org/10.1021/acs.cgd.9b00043
Copy to clipboard
Kornyakov, Ilya V., Gurzhiy, Vladislav V., Szymanowski, Jennifer E. S., Zhang, Lei, Perry, Samuel N., Krivovichev, Sergey V., and Burns, Peter C. Tue . "A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds". United States. https://doi.org/10.1021/acs.cgd.9b00043. https://www.osti.gov/servlets/purl/1566488.
Copy to clipboard
@article{osti_1566488,
title = {A Novel Family of Np(VI) Oxysalts: Crystal Structures, Calorimetry, Thermal Behavior, and Comparison with U(VI) Compounds},
author = {Kornyakov, Ilya V. and Gurzhiy, Vladislav V. and Szymanowski, Jennifer E. S. and Zhang, Lei and Perry, Samuel N. and Krivovichev, Sergey V. and Burns, Peter C.},
abstractNote = {Here, phase formation in the mixed sulfate–selenate Np(VI)-bearing aqueous system has been investigated. The obtained crystalline compounds, Cs2[(NpO2)2(TO4)3] (T = S, Se), crystallize in the tetragonal system, space group P$\bar{42}$1m, with a = 9.5737(3)–9.817(3) Å, c = 8.0824(4)–8.111(3) Å, and V = 740.79(6)–781.8(6) Å3, and have been chemically characterized. Single-crystal X-ray diffraction experiments at various temperatures were used to define the thermal behavior of the crystal structures relative to the S/Se ratio. The thermal behavior of mixed sulfate–selenate and pure selenate compounds is anisotropic, with the highest thermal expansion in the direction perpendicular to the sheets of Np-bearing polyhedra, while the structure of the pure sulfate compound experiences almost isotropic thermal expansion with slightly higher expansion within the layer, which is explained by the influence of stronger Cs–O bonding. High-temperature drop solution calorimetry was used to derive the enthalpies of formation of the Cs+-bearing neptunyl oxysalts. Lastly, within this family of isotypic structures, cesium neptunyl sulfate has a more negative enthalpy of formation in comparison to the selenate compound.},
doi = {10.1021/acs.cgd.9b00043},
journal = {Crystal Growth and Design},
number = 5,
volume = 19,
place = {United States},
year = {Tue Mar 26 00:00:00 EDT 2019},
month = {Tue Mar 26 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.cgd.9b00043
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A Revised and Expanded Structure Hierarchy of Natural and Synthetic Hexavalent Uranium Compounds
journal, January 2016

  • Lussier, Aaron J.; Lopez, Rachel A. K.; Burns, Peter C.
  • The Canadian Mineralogist, Vol. 54, Issue 1
  • DOI: 10.3749/canmin.1500078

Cation–cation interaction in crystalline actinide compounds
journal, January 2004

Structures and syntheses of four Np5+ sulfate chain structures: Divergence from U6+ crystal chemistry
journal, November 2005

Neptunyl Compounds: Polyhedron Geometries, Bond-Valence Parameters, and Structural Hierarchy
journal, December 2008

Three New Sodium Neptunyl(V) Selenate Hydrates: Structures, Raman Spectroscopy, and Magnetism
journal, February 2012

  • Jin, Geng Bang; Skanthakumar, S.; Soderholm, L.
  • Inorganic Chemistry, Vol. 51, Issue 5
  • DOI: 10.1021/ic202703j

Synthesis and spectra of Np(V) γ-Octamolybdates of the composition M6[(NpO2)2(Mo8O28)]·2H2O (M = NH4, K, Rb, Cs, Tl)
journal, May 2015

  • Budantseva, N. A.; Grigor’ev, M. S.; Fedoseev, A. M.
  • Radiochemistry, Vol. 57, Issue 3
  • DOI: 10.1134/S1066362215030017

THE CRYSTAL STRUCTURES OF X(NpO2)(PO4)(H2O)3 (X = K+, Na+, Rb+, NH4+) AND THEIR RELATIONSHIP TO THE AUTUNITE GROUP
journal, June 2007

Synthesis and single crystal X-ray diffraction study of U(VI), Np(VI), and Pu(VI) perchlorate hydrates
journal, August 2010

Role of Anions and Reaction Conditions in the Preparation of Uranium(VI), Neptunium(VI), and Plutonium(VI) Borates
journal, March 2011

  • Wang, Shuao; Villa, Eric M.; Diwu, Juan
  • Inorganic Chemistry, Vol. 50, Issue 6
  • DOI: 10.1021/ic102356d

Unexpected Actinyl Cation-Directed Structural Variation in Neptunyl(VI) A-Type Tri-lacunary Heteropolyoxotungstate Complexes
journal, April 2015

  • Berg, John M.; Gaunt, Andrew J.; May, Iain
  • Inorganic Chemistry, Vol. 54, Issue 9
  • DOI: 10.1021/ic5024345

Unexpected Behavior of Np in Oxo-selenate/Oxo-selenite Systems
journal, January 2018

Selective Se-for-S substitution in Cs-bearing uranyl compounds
journal, April 2017

  • Gurzhiy, Vladislav V.; Tyumentseva, Olga S.; Krivovichev, Sergey V.
  • Journal of Solid State Chemistry, Vol. 248
  • DOI: 10.1016/j.jssc.2017.02.005

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Progress and new directions in high temperature calorimetry
journal, January 1977

  • Navrotsky, Alexandra
  • Physics and Chemistry of Minerals, Vol. 2, Issue 1-2
  • DOI: 10.1007/BF00307526

Progress and new directions in high temperature calorimetry revisited
journal, April 1997

Progress and New Directions in Calorimetry: A 2014 Perspective
journal, October 2014

  • Navrotsky, Alexandra
  • Journal of the American Ceramic Society, Vol. 97, Issue 11
  • DOI: 10.1111/jace.13278

Experimental thermochemistry of neptunium oxides: Np2O5 and NpO2
journal, April 2018

The crystal structure of cesium biuranyl trisulphate, Cs2(UO2)2(SO4)3
journal, October 1960

Syntheses and Crystal Structures of Two Topologically Related Modifications of Cs 2 [(UO 2 ) 2 (MoO 4 ) 3 ]
journal, January 2002

  • Krivovichev, S. V.; Cahill, C. L.; Burns, P. C.
  • Inorganic Chemistry, Vol. 41, Issue 1
  • DOI: 10.1021/ic010345y

Cr VI →Cr V Transition in Uranyl Chromium Compounds: Synthesis and High-temperature X-ray Diffraction Study of Cs 2 [(UO 2 ) 2 (CrO 4 ) 3 ]: Cr VI →Cr V Transition in Uranyl Chromium Compounds
journal, July 2013

  • Siidra, Oleg I.; Nazarchuk, Evgeny V.; Kayukov, Roman A.
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 12-13
  • DOI: 10.1002/zaac.201300219

Sulfate Compounds of Hexavalent Neptunium and Plutonium
journal, July 1999

Revaluation of the correlation of isomer shift with Np-O bond length in various neptunyl(V and VI) compounds
journal, November 2006

  • Saeki, M.; Nakada, M.; Kawasaki, T.
  • Journal of Radioanalytical and Nuclear Chemistry, Vol. 270, Issue 2
  • DOI: 10.1007/s10967-006-0360-x

Neptunium Diverges Sharply from Uranium and Plutonium in Crystalline Borate Matrixes: Insights into the Complex Behavior of the Early Actinides Relevant to Nuclear Waste Storage
journal, January 2010

  • Wang, Shuao; Alekseev, Evgeny V.; Ling, Jie
  • Angewandte Chemie International Edition, Vol. 49, Issue 7
  • DOI: 10.1002/anie.200906127

Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f -block contraction
journal, January 2018

  • Gagné, Olivier Charles
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 74, Issue 1
  • DOI: 10.1107/S2052520617017425

Mixed Uranyl Sulfate–Selenates: Evolution of Structural Topology and Complexity vs Chemical Composition
journal, June 2016

  • Gurzhiy, Vladislav V.; Tyumentseva, Olga S.; Krivovichev, Sergey V.
  • Crystal Growth & Design, Vol. 16, Issue 8
  • DOI: 10.1021/acs.cgd.6b00611

Topologically and geometrically flexible structural units in seven new organically templated uranyl selenates and selenite–selenates
journal, September 2015

  • Gurzhiy, Vladislav V.; Kovrugin, Vadim M.; Tyumentseva, Olga S.
  • Journal of Solid State Chemistry, Vol. 229
  • DOI: 10.1016/j.jssc.2015.04.040

General concept of increasing crystal symmetry with an increase in temperature
journal, November 2011

Thermochemistry of a Few Neptunium and Neodymium Oxides and Hydroxides
journal, December 1994

Charge Density Influence on Enthalpy of Formation of Uranyl Peroxide Cage Cluster Salts
journal, August 2018

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections:

    Other research related to this record: