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Title: Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water

Comparison of experimental measurements of the yield of molecular hydrogen produced in the gamma radiolysis of water and aqueous nitrate solutions with predictions of a Monte Carlo track chemistry model shows that the nitrate anion scavenging of the hydrated electron, its precursor, and hydrogen atom cannot account for the observed decrease in the yield at high nitrate anion concentrations. Inclusion of the quenching of excited states of water (formed by either direct excitation or reaction of the water radical cation with the precursor to the hydrated electron) by the nitrate anion into the reaction scheme provides excellent agreement between the stochastic calculations and experiment demonstrating the existence of this short-lived species and its importance in water radiolysis. Energy transfer from the excited states of water to the nitrate anion producing an excited state provides an additional pathway for the production of nitrogen containing products not accounted for in traditional radiation chemistry scenarios. Such reactions are of central importance in predicting the behavior of liquors common in the reprocessing of spent nuclear fuel and the storage of highly radioactive liquid waste prior to vitrification.
Authors:
ORCiD logo [1] ;  [2] ;  [3]
  1. California State Univ. (CalState), Long Beach, CA (United States); Univ. of Notre Dame, IN (United States). Radiation Laboratory
  2. Univ. of Manchester (United Kingdom). Dalton Cumbrian Facility and School of Chemistry
  3. Univ. of Notre Dame, IN (United States). Radiation Laboratory and Department of Physics
Publication Date:
Grant/Contract Number:
NE0008406; AC07-05ID14517; FC02-04ER15533
Type:
Published Article
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 21; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
California State Univ. (CalState), Long Beach, CA (United States). Long Beach Research Foundation
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
OSTI Identifier:
1417675
Alternate Identifier(s):
OSTI ID: 1424731

Horne, Gregory P., Pimblott, Simon M., and LaVerne, Jay A.. Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water. United States: N. p., Web. doi:10.1021/acs.jpcb.7b02775.
Horne, Gregory P., Pimblott, Simon M., & LaVerne, Jay A.. Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water. United States. doi:10.1021/acs.jpcb.7b02775.
Horne, Gregory P., Pimblott, Simon M., and LaVerne, Jay A.. 2017. "Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water". United States. doi:10.1021/acs.jpcb.7b02775.
@article{osti_1417675,
title = {Inhibition of Radiolytic Molecular Hydrogen Formation by Quenching of Excited State Water},
author = {Horne, Gregory P. and Pimblott, Simon M. and LaVerne, Jay A.},
abstractNote = {Comparison of experimental measurements of the yield of molecular hydrogen produced in the gamma radiolysis of water and aqueous nitrate solutions with predictions of a Monte Carlo track chemistry model shows that the nitrate anion scavenging of the hydrated electron, its precursor, and hydrogen atom cannot account for the observed decrease in the yield at high nitrate anion concentrations. Inclusion of the quenching of excited states of water (formed by either direct excitation or reaction of the water radical cation with the precursor to the hydrated electron) by the nitrate anion into the reaction scheme provides excellent agreement between the stochastic calculations and experiment demonstrating the existence of this short-lived species and its importance in water radiolysis. Energy transfer from the excited states of water to the nitrate anion producing an excited state provides an additional pathway for the production of nitrogen containing products not accounted for in traditional radiation chemistry scenarios. Such reactions are of central importance in predicting the behavior of liquors common in the reprocessing of spent nuclear fuel and the storage of highly radioactive liquid waste prior to vitrification.},
doi = {10.1021/acs.jpcb.7b02775},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 21,
volume = 121,
place = {United States},
year = {2017},
month = {5}
}