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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 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.
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:
OSTI Identifier:
1329809
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