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

Abstract

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:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1329809
Report Number(s):
BNL-112756-2016-JA
Journal ID: ISSN 0236-5731; R&D Project: CO031; KC0304030
Grant/Contract Number:  
SC00112704
Resource 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
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

Citation Formats

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., 2015. 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. Wed . "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}
}

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