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Title: The role of organic solvent radical cations in separations ligand degradation

The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M -1 s -1 in dodecane/0.10 M CH 2Cl 2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO 3 complex formed in the acid contacted solvent.
Authors:
 [1] ;  [2] ;  [3] ;  [3] ;  [3]
  1. California State Univ. (CalState), Long Beach, CA (United States)
  2. Idaho National Lab. (INL), Idaho Falls, ID (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Report Number(s):
BNL-112756-2016-JA
Journal ID: ISSN 0236-5731; R&D Project: CO031; KC0304030
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Journal of Radioanalytical and Nuclear Chemistry
Additional Journal Information:
Journal Volume: 307; Journal Issue: 3; Journal ID: ISSN 0236-5731
Publisher:
Springer
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
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; Dodecane radical cation; ps pulse radiolysis; CMPO; TODGA; Acid contact
OSTI Identifier:
1329809

Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, and Wishart, James F.. The role of organic solvent radical cations in separations ligand degradation. United States: N. p., Web. doi:10.1007/s10967-015-4582-7.
Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, & Wishart, James F.. The role of organic solvent radical cations in separations ligand degradation. United States. doi:10.1007/s10967-015-4582-7.
Mezyk, Stephen P., Mincher, Bruce J., Dhiman, Surajdevprakash B., Layne, Bobby, and Wishart, James F.. 2015. "The role of organic solvent radical cations in separations ligand degradation". United States. doi:10.1007/s10967-015-4582-7. https://www.osti.gov/servlets/purl/1329809.
@article{osti_1329809,
title = {The role of organic solvent radical cations in separations ligand degradation},
author = {Mezyk, Stephen P. and Mincher, Bruce J. and Dhiman, Surajdevprakash B. and Layne, Bobby and Wishart, James F.},
abstractNote = {The dodecane radical cation reaction rate constant with CMPO was measured using ps electron pulse radiolysis/absorption spectroscopy as k = (1.30 ± 0.11) x 1010 M-1 s-1 in dodecane/0.10 M CH2Cl2 solution. No reactivity increase occurred when these solutions were pre-contacted with nitric acid, similar to the behavior observed for TODGA. To corroborate these kinetic data with steady-state radiolysis measurements, where acid pre contacted CMPO showed significantly less degradation, it is proposed that the dodecane radical cation always reacts directly with TODGA, but for CMPO the charge-transfer occurs with the CMPO•HNO3 complex formed in the acid contacted solvent.},
doi = {10.1007/s10967-015-4582-7},
journal = {Journal of Radioanalytical and Nuclear Chemistry},
number = 3,
volume = 307,
place = {United States},
year = {2015},
month = {11}
}