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Title: Real time monitoring of the chemistry of hydroxylamine nitrate and iron as surrogates for nuclear materials processing

Abstract

The separation of actinides in aqueous solution often involves changes in redox chemistry achieved by reagents such as hydroxylamine nitrate (HAN). As a result, in situ monitoring of the chemistry of HAN in contact with plutonium and neptunium in concentrated nitric acid at 35°C is important for the efficacy of Pu-238 extraction. A spectroscopic method of following the chemistry of HAN in contact with iron (as a simulant for plutonium) was developed, using a quantum cascade laser-attenuated total reflectance (QCL-ATR) system. The mid-infrared (3.67–12.5 μm) was chosen for its ability to distinguish the molecular vibrations of analytes and exclude the background absorption of the concentrated HNO3 matrix. The concentrations of chemical species found in the reaction were drawn from the collected QCL power data using Beer’s law after a baseline correction. These data were qualitatively compared to a kinetic rate model based on a simplified reaction mechanism. The QCL-ATR method can help assess the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1511941
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Separation Science and Technology
Additional Journal Information:
Journal Volume: 54; Journal Issue: 12; Journal ID: ISSN 0149-6395
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Hydroxylamine nitrate reactions; quantum-cascade-laser attenuated-total reflectance sensor; mid-infrared spectroscopy; aqueous chemical process monitoring; off-set spectroscopic measurement

Citation Formats

Gallmeier, Esther A., Gallmeier, Katharina M., McFarlane, Joanna, and Morales-Rodriguez, Marissa E. Real time monitoring of the chemistry of hydroxylamine nitrate and iron as surrogates for nuclear materials processing. United States: N. p., 2019. Web. doi:10.1080/01496395.2019.1606829.
Gallmeier, Esther A., Gallmeier, Katharina M., McFarlane, Joanna, & Morales-Rodriguez, Marissa E. Real time monitoring of the chemistry of hydroxylamine nitrate and iron as surrogates for nuclear materials processing. United States. doi:10.1080/01496395.2019.1606829.
Gallmeier, Esther A., Gallmeier, Katharina M., McFarlane, Joanna, and Morales-Rodriguez, Marissa E. Thu . "Real time monitoring of the chemistry of hydroxylamine nitrate and iron as surrogates for nuclear materials processing". United States. doi:10.1080/01496395.2019.1606829. https://www.osti.gov/servlets/purl/1511941.
@article{osti_1511941,
title = {Real time monitoring of the chemistry of hydroxylamine nitrate and iron as surrogates for nuclear materials processing},
author = {Gallmeier, Esther A. and Gallmeier, Katharina M. and McFarlane, Joanna and Morales-Rodriguez, Marissa E.},
abstractNote = {The separation of actinides in aqueous solution often involves changes in redox chemistry achieved by reagents such as hydroxylamine nitrate (HAN). As a result, in situ monitoring of the chemistry of HAN in contact with plutonium and neptunium in concentrated nitric acid at 35°C is important for the efficacy of Pu-238 extraction. A spectroscopic method of following the chemistry of HAN in contact with iron (as a simulant for plutonium) was developed, using a quantum cascade laser-attenuated total reflectance (QCL-ATR) system. The mid-infrared (3.67–12.5 μm) was chosen for its ability to distinguish the molecular vibrations of analytes and exclude the background absorption of the concentrated HNO3 matrix. The concentrations of chemical species found in the reaction were drawn from the collected QCL power data using Beer’s law after a baseline correction. These data were qualitatively compared to a kinetic rate model based on a simplified reaction mechanism. The QCL-ATR method can help assess the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.},
doi = {10.1080/01496395.2019.1606829},
journal = {Separation Science and Technology},
number = 12,
volume = 54,
place = {United States},
year = {2019},
month = {5}
}

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