The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis
Abstract
Here, Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to α-irradiation using a He-ion beam, 244Cm isotopic α-rays, and He and Li ions created by the n,α reaction of 10B in a nuclear reactor. Post-irradiation samples were analyzed for the radiolytically-induced decrease in CMPO concentration, the appearance of degradation products, and their Am solvent extraction distribution ratios. The –G CMPO-value for the radiolytic degradation of CMPO was found to be very low compared to values previously reported for γ-irradiation. Additionally, isotopic irradiation to absorbed α-doses as high as 600 kGy in aerated solution had no effect on Am solvent extraction or stripping. The main CMPO radiolysis products identified in He-ion beam irradiated samples by ESI-MS include amides, an acidic amide, and amines produced by bond rupture on either side of the CMPO carbonyl group. Deaerated samples irradiated using the reactor in the absence of an aqueous phase, or with a dilute nitric acid aqueous phase showed small but measurable decreases in CMPO concentration with increasing absorbed doses. Higher concentrations of nitric acid resulted in lower decomposition rates for the CMPO. The radio-protection by dissolved oxygen and nitric acid previously found for γ-irradiated CMPO also occurs for α-irradiation. This suggests thatmore »
- Authors:
-
- Idaho National Lab. (INL), Idaho Falls, ID (United States). Aqueous Separations and Radiochemistry Dept.
- California State Univ. (CalState), Long Beach, CA (United States). Dept. of Chemistry and Biochemistry
- Idaho National Lab. (INL), Idaho Falls, ID (United States). Chemistry and Radiation Measurements Dept.
- Univ. of Notre Dame, IN (United States). Dept. of Physics
- Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science
- Publication Date:
- Research Org.:
- Idaho National Lab. (INL), Idaho Falls, ID (United States); Univ. of California, Irvine, CA (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1454602
- Report Number(s):
- INL/JOU-13-29077
Journal ID: ISSN 0736-6299; TRN: US1901086
- Grant/Contract Number:
- NA0000979; AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Solvent Extraction and Ion Exchange
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 2; Journal ID: ISSN 0736-6299
- Publisher:
- Taylor and Francis
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; CMPO; free radicals; alpha irradiation; solvent extraction
Citation Formats
Mincher, Bruce J., Mezyk, Stephen P., Elias, Gracy, Groenewold, Gary S., LaVerne, Jay A., Nilsson, Mikael, Pearson, Jeremy, Schmitt, Nicholas C., Tillotson, Richard D., and Olson, Lonnie G. The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis. United States: N. p., 2014.
Web. doi:10.1080/07366299.2013.850300.
Mincher, Bruce J., Mezyk, Stephen P., Elias, Gracy, Groenewold, Gary S., LaVerne, Jay A., Nilsson, Mikael, Pearson, Jeremy, Schmitt, Nicholas C., Tillotson, Richard D., & Olson, Lonnie G. The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis. United States. https://doi.org/10.1080/07366299.2013.850300
Mincher, Bruce J., Mezyk, Stephen P., Elias, Gracy, Groenewold, Gary S., LaVerne, Jay A., Nilsson, Mikael, Pearson, Jeremy, Schmitt, Nicholas C., Tillotson, Richard D., and Olson, Lonnie G. Fri .
"The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis". United States. https://doi.org/10.1080/07366299.2013.850300. https://www.osti.gov/servlets/purl/1454602.
@article{osti_1454602,
title = {The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis},
author = {Mincher, Bruce J. and Mezyk, Stephen P. and Elias, Gracy and Groenewold, Gary S. and LaVerne, Jay A. and Nilsson, Mikael and Pearson, Jeremy and Schmitt, Nicholas C. and Tillotson, Richard D. and Olson, Lonnie G.},
abstractNote = {Here, Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to α-irradiation using a He-ion beam, 244Cm isotopic α-rays, and He and Li ions created by the n,α reaction of 10B in a nuclear reactor. Post-irradiation samples were analyzed for the radiolytically-induced decrease in CMPO concentration, the appearance of degradation products, and their Am solvent extraction distribution ratios. The –G CMPO-value for the radiolytic degradation of CMPO was found to be very low compared to values previously reported for γ-irradiation. Additionally, isotopic irradiation to absorbed α-doses as high as 600 kGy in aerated solution had no effect on Am solvent extraction or stripping. The main CMPO radiolysis products identified in He-ion beam irradiated samples by ESI-MS include amides, an acidic amide, and amines produced by bond rupture on either side of the CMPO carbonyl group. Deaerated samples irradiated using the reactor in the absence of an aqueous phase, or with a dilute nitric acid aqueous phase showed small but measurable decreases in CMPO concentration with increasing absorbed doses. Higher concentrations of nitric acid resulted in lower decomposition rates for the CMPO. The radio-protection by dissolved oxygen and nitric acid previously found for γ-irradiated CMPO also occurs for α-irradiation. This suggests that similar free-radical mechanisms operate in the high-LET system, but with lower degradation yields due to the lower overall radical concentrations produced.},
doi = {10.1080/07366299.2013.850300},
journal = {Solvent Extraction and Ion Exchange},
number = 2,
volume = 32,
place = {United States},
year = {Fri Jan 24 00:00:00 EST 2014},
month = {Fri Jan 24 00:00:00 EST 2014}
}
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