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Title: The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis

Abstract

Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to a-irradiation using a He-ion beam, 244 Cm isotopic a-rays, and He and Li ions created by the n,a 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 ?-irradiation. Additionally, isotopic irradiation to absorbed a-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 ?-irradiated CMPO also occurs for a-irradiation. This suggests thatmore » similar free-radical mechanisms operate in the high-LET system, but with lower degradation yields due to the lower overall radical concentrations produced.« less

Authors:
; ; ; ; ; ; ; ; ;
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:
1122108
Report Number(s):
INL/JOU-13-29077
Journal ID: ISSN 0736-6299
DOE Contract Number:  
NA0000979; AC07-05ID14517
Resource Type:
Journal Article
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:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; alpha radiation; CMPO; free radicals; high LET; radiation chemistry; solvent etxraction

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. 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., and Olson, Lonnie G. Fri . "The Radiation Chemistry of CMPO: Part 2. Alpha Radiolysis". United States. doi:10.1080/07366299.2013.850300.
@article{osti_1122108,
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 = {Octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) dissolved in dodecane was subjected to a-irradiation using a He-ion beam, 244 Cm isotopic a-rays, and He and Li ions created by the n,a 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 ?-irradiation. Additionally, isotopic irradiation to absorbed a-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 ?-irradiated CMPO also occurs for a-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},
issn = {0736-6299},
number = 2,
volume = 32,
place = {United States},
year = {2014},
month = {1}
}

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