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

Esther A. Gallmeier; Katharina M. Gallmeier; Joanna McFarlane; Marissa E. Morales-Rodriguez

doi:10.1080/01496395.2019.1606829

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

Esther A. Gallmeier
, Katharina M. Gallmeier
, Joanna McFarlane
, Marissa E. Morales-Rodriguez

Fuel Cycle Chemical Technology

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

The separation of actinides in aqueous solution often involves changes in redox chemistry achieved by reagents such as hydroxylamine nitrate (HAN). Thus, 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 determine the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.

Original language	English
Pages (from-to)	1985-1993
Number of pages	9
Journal	Separation Science and Technology (Philadelphia)
Volume	54
Issue number	12
DOIs	https://doi.org/10.1080/01496395.2019.1606829
State	Published - Aug 13 2019

Funding

The work performed was supported by the Laboratory Director’s Research and Development Program of Oak Ridge National Laboratory. This research was also supported by Oak Ridge National Laboratory through the Math Thesis program of Oak Ridge High School. Particular thanks go to Dr. Franz Gallmeier, Ms. Elisabeth Gallmeier, Mrs. Jessica Williams, and Dr. Deanna Pickel. This work was supported by the Laboratory Director’s Research and Development Program of Oak Ridge National Laboratory. Oak Ridge National Laboratory is operated for the U.S. Department of Energy by UT-Battelle LLC under contract no. DE-AC05-00OR22725. This work was supported by the Laboratory Director?s Research and Development Program of Oak Ridge National Laboratory. Oak Ridge National Laboratory is operated for the U.S. Department of Energy by UT-Battelle?LLC under contract no. DE-AC05-00OR22725. The work performed was supported by the Laboratory Director?s Research and Development Program of Oak Ridge National Laboratory. This research was also supported by Oak Ridge National Laboratory through the Math Thesis program of Oak Ridge High School. Particular thanks go to Dr. Franz Gallmeier, Ms. Elisabeth Gallmeier, Mrs. Jessica Williams, and Dr. Deanna Pickel.

Keywords

Hydroxylamine nitrate reactions
aqueous chemical process monitoring
mid-infrared spectroscopy
off-set spectroscopic measurement
quantum-cascade-laser attenuated-total reflectance sensor

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10.1080/01496395.2019.1606829

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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). Thus, 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{\textquoteright}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 determine the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.",

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AU - Morales-Rodriguez, Marissa E.

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N2 - The separation of actinides in aqueous solution often involves changes in redox chemistry achieved by reagents such as hydroxylamine nitrate (HAN). Thus, 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 determine the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.

AB - The separation of actinides in aqueous solution often involves changes in redox chemistry achieved by reagents such as hydroxylamine nitrate (HAN). Thus, 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 determine the areas of stability of HAN, nitrate/nitrite interactions, and assist process control of actinide separations.

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KW - aqueous chemical process monitoring

KW - mid-infrared spectroscopy

KW - off-set spectroscopic measurement

KW - quantum-cascade-laser attenuated-total reflectance sensor

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M3 - Article

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SN - 0149-6395

VL - 54

SP - 1985

EP - 1993

JO - Separation Science and Technology (Philadelphia)

JF - Separation Science and Technology (Philadelphia)

IS - 12

ER -

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

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