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Title: Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems

Abstract

Here, the dissolution rate and solubility of NaBiO 3 have been investigated in nitric acid systems ranging from 4–6 M HNO 3, and were found to be 58–76 µg/cm 2·d and 490–830 mM, respectively. The presence of 50 mM U(VI) drastically increased the solubility to 540–1200 mM, while rates of dissolu-tion were relatively unchanged. The solubility of NaBiO 3 increased with an increase in U(VI) con-centrations at 4 M HNO 3, with log-log analysis indicating a one-to-one complex between Bi and U and IR spectroscopic evidence monitoring uranyl stretching suggesting complex formation. Absorb-ance spectra were obtained experimentally and computationally with an absorbance band in the range of 450–600 nm that has been attributed to Bi(V). The ingrowth and decay of Bi(V) in solution was also studied as a function of mass of solid NaBiO 3 present, acidity, and temperature. The ac-tivation energies of dissolution and decomposition were calculated to be 39 ± 4 and 61 ± 6 kJ/mol, re-spectively. Furthermore, these results indicate that dissolution of NaBiO 3 into the respective Na + and BiO 3 is occur-ring prior to undergoing reduction, a process which conventionally has been believed to occur in the reverse order.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
Publication Date:
Research Org.:
Texas A & M Univ., College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1489278
Grant/Contract Number:  
NE0008653
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 24; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Citation Formats

Einkauf, Jeffrey D., Wilcox, Andrew J., and Burns, Jonathan D. Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.8b02672.
Einkauf, Jeffrey D., Wilcox, Andrew J., & Burns, Jonathan D. Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems. United States. doi:10.1021/acs.inorgchem.8b02672.
Einkauf, Jeffrey D., Wilcox, Andrew J., and Burns, Jonathan D. Mon . "Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems". United States. doi:10.1021/acs.inorgchem.8b02672.
@article{osti_1489278,
title = {Solubility and Complexation of the Bismuthate Ion in Nitric Acid Systems},
author = {Einkauf, Jeffrey D. and Wilcox, Andrew J. and Burns, Jonathan D.},
abstractNote = {Here, the dissolution rate and solubility of NaBiO3 have been investigated in nitric acid systems ranging from 4–6 M HNO3, and were found to be 58–76 µg/cm2·d and 490–830 mM, respectively. The presence of 50 mM U(VI) drastically increased the solubility to 540–1200 mM, while rates of dissolu-tion were relatively unchanged. The solubility of NaBiO3 increased with an increase in U(VI) con-centrations at 4 M HNO3, with log-log analysis indicating a one-to-one complex between Bi and U and IR spectroscopic evidence monitoring uranyl stretching suggesting complex formation. Absorb-ance spectra were obtained experimentally and computationally with an absorbance band in the range of 450–600 nm that has been attributed to Bi(V). The ingrowth and decay of Bi(V) in solution was also studied as a function of mass of solid NaBiO3 present, acidity, and temperature. The ac-tivation energies of dissolution and decomposition were calculated to be 39 ± 4 and 61 ± 6 kJ/mol, re-spectively. Furthermore, these results indicate that dissolution of NaBiO3 into the respective Na+ and BiO3– is occur-ring prior to undergoing reduction, a process which conventionally has been believed to occur in the reverse order.},
doi = {10.1021/acs.inorgchem.8b02672},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 24,
volume = 57,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
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