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Title: Molybdenum(VI) Coordination in Tributyl Phosphate Chloride Based System

Abstract

Fundamental coordination chemistry of Mo(VI) at its macroconcentrations in solvent extraction systems is of great importance for industrial processes that require the purification or recovery of large concentrations of Mo. The coordination of Mo(VI) in tri-n-butyl phosphate (TBP) from solutions of hydrochloric acid and up to 0.3 M Mo was investigated using UV, FTIR, and P-31 NMR spectroscopies, as well as EXAFS. From these techniques we resolved near-neighbor atoms, speciation, structural information on the coordination environment, and thermodynamic parameters affiliated with the solvent extraction of Mo(VI) and HCl. The solvated extracted form of Mo(VI) as MoO2Cl2 center dot 2TBP was identified. High extraction yield of Mo at >5 M HCl concentration is driven by replacing HCl in the organic phase by Mo. The existence of additional organic Mo adducts is also discussed with the aid of density functional theory, however no evidence of dimeric or polymeric Mo species was found to be present in TBP.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]
  1. Argonne National Laboratory, Nuclear Engineering Division, Argonne, Illinois 60439, United States
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1461441
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Industrial and Engineering Chemistry Research
Additional Journal Information:
Journal Volume: 57; Journal Issue: 16; Journal ID: ISSN 0888-5885
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Tkac, Peter, Momen, Md Abdul, Breshears, Andrew T., Brown, M. Alex, and Vandegrift, George F. Molybdenum(VI) Coordination in Tributyl Phosphate Chloride Based System. United States: N. p., 2018. Web. doi:10.1021/acs.iecr.8b00590.
Tkac, Peter, Momen, Md Abdul, Breshears, Andrew T., Brown, M. Alex, & Vandegrift, George F. Molybdenum(VI) Coordination in Tributyl Phosphate Chloride Based System. United States. doi:10.1021/acs.iecr.8b00590.
Tkac, Peter, Momen, Md Abdul, Breshears, Andrew T., Brown, M. Alex, and Vandegrift, George F. Wed . "Molybdenum(VI) Coordination in Tributyl Phosphate Chloride Based System". United States. doi:10.1021/acs.iecr.8b00590.
@article{osti_1461441,
title = {Molybdenum(VI) Coordination in Tributyl Phosphate Chloride Based System},
author = {Tkac, Peter and Momen, Md Abdul and Breshears, Andrew T. and Brown, M. Alex and Vandegrift, George F.},
abstractNote = {Fundamental coordination chemistry of Mo(VI) at its macroconcentrations in solvent extraction systems is of great importance for industrial processes that require the purification or recovery of large concentrations of Mo. The coordination of Mo(VI) in tri-n-butyl phosphate (TBP) from solutions of hydrochloric acid and up to 0.3 M Mo was investigated using UV, FTIR, and P-31 NMR spectroscopies, as well as EXAFS. From these techniques we resolved near-neighbor atoms, speciation, structural information on the coordination environment, and thermodynamic parameters affiliated with the solvent extraction of Mo(VI) and HCl. The solvated extracted form of Mo(VI) as MoO2Cl2 center dot 2TBP was identified. High extraction yield of Mo at >5 M HCl concentration is driven by replacing HCl in the organic phase by Mo. The existence of additional organic Mo adducts is also discussed with the aid of density functional theory, however no evidence of dimeric or polymeric Mo species was found to be present in TBP.},
doi = {10.1021/acs.iecr.8b00590},
journal = {Industrial and Engineering Chemistry Research},
issn = {0888-5885},
number = 16,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}