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Title: In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy

Abstract

Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to effectively analyze solvent extraction systems are lacking in that they are commonly off-line. Thus, a method to effectively investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modelling has been developed to allow for on-line analysis and monitoring. Kinetic parameters of interfacial mass transfer for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured in by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Resulting concentration data, derived from a chemometric model using Raman spectra as the base set, allowed for the calculation of kinetic parameters in the system when paired with extraction time. The forward and reverse interfacial mass transfer coefficients, kf and kr, were determined for solutions that were process relevant and of pro-cess interest, where kf was calculated as 5.3 (± 0.3) × 10-3 cm min 1 and kr was calculated as 2.9 (± 0.2) × 10-2 cm min-1. The information obtained regarding solvent extraction parameters and transfer can be applied in the further studymore » of systems of higher complexity involving complex formation and their transfer across a liquid:liquid interface.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [1];  [1];  [1];  [1];  [1]
  1. BATTELLE (PACIFIC NW LAB)
  2. TRADEWIND SERVICES LLC
  3. WASHINGTON STATE UNIV
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1558418
Report Number(s):
PNNL-SA-128863
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Solvent Extraction and Ion Exchange
Additional Journal Information:
Journal Volume: 37; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
extraction, interfacial transport, Lewis Cell, Liquid:liquid, TBP

Citation Formats

Asmussen, Susan E., Lines, Amanda M., Bottenus, Daniel R., Heller, Forrest D., Bryan, Samuel A., Delegard, Calvin H., Louie, Christina A., Lumetta, Gregg J., Pellegrini, Kristi L., Pitts, William K., Clark, Sue B., and Casella, Amanda J. In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy. United States: N. p., 2019. Web. doi:10.1080/07366299.2019.1630071.
Asmussen, Susan E., Lines, Amanda M., Bottenus, Daniel R., Heller, Forrest D., Bryan, Samuel A., Delegard, Calvin H., Louie, Christina A., Lumetta, Gregg J., Pellegrini, Kristi L., Pitts, William K., Clark, Sue B., & Casella, Amanda J. In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy. United States. doi:10.1080/07366299.2019.1630071.
Asmussen, Susan E., Lines, Amanda M., Bottenus, Daniel R., Heller, Forrest D., Bryan, Samuel A., Delegard, Calvin H., Louie, Christina A., Lumetta, Gregg J., Pellegrini, Kristi L., Pitts, William K., Clark, Sue B., and Casella, Amanda J. Mon . "In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy". United States. doi:10.1080/07366299.2019.1630071.
@article{osti_1558418,
title = {In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in n-Dodecane using Raman Spectroscopy},
author = {Asmussen, Susan E. and Lines, Amanda M. and Bottenus, Daniel R. and Heller, Forrest D. and Bryan, Samuel A. and Delegard, Calvin H. and Louie, Christina A. and Lumetta, Gregg J. and Pellegrini, Kristi L. and Pitts, William K. and Clark, Sue B. and Casella, Amanda J.},
abstractNote = {Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to effectively analyze solvent extraction systems are lacking in that they are commonly off-line. Thus, a method to effectively investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modelling has been developed to allow for on-line analysis and monitoring. Kinetic parameters of interfacial mass transfer for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured in by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Resulting concentration data, derived from a chemometric model using Raman spectra as the base set, allowed for the calculation of kinetic parameters in the system when paired with extraction time. The forward and reverse interfacial mass transfer coefficients, kf and kr, were determined for solutions that were process relevant and of pro-cess interest, where kf was calculated as 5.3 (± 0.3) × 10-3 cm min 1 and kr was calculated as 2.9 (± 0.2) × 10-2 cm min-1. The information obtained regarding solvent extraction parameters and transfer can be applied in the further study of systems of higher complexity involving complex formation and their transfer across a liquid:liquid interface.},
doi = {10.1080/07366299.2019.1630071},
journal = {Solvent Extraction and Ion Exchange},
number = 2,
volume = 37,
place = {United States},
year = {2019},
month = {7}
}

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