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Title: In situ radiolysis time-resolved ESR studies of spin trapping by DMPO: Re-evalution of hydroxyl radical and hydrated electron trapping rates and spin adduct yields

Journal Article · · Journal of Physical Chemistry
DOI:https://doi.org/10.1021/jp953382h· OSTI ID:249668
;  [1]
  1. Univ. of Notre Dame, IN (United States)

The second-order rate constants for the reaction of 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) with radiolytically produced hydroxyl radicals and hydrated electrons have been measured in aqueous solution by direct observation of spin adduct initial yield using time-resolved electron spin resonance. The rate constants are 2.8 x 10{sup 9} mol{sup -1} dm{sup 3} S{sup -1} for the DMPO-hydroxyl radical reaction and 3.2 x 10{sup 9} mol{sup -1} dm{sup 3} s{sup -1} for the reaction of DMPO and hydrated electron, using sodium formate and chloroacetic acid as competitive scavengers of the hydroxyl radical and hydrated electron, respectively. The hydrated electron-DMPO competition study determined the fraction of DMPO-H produced directly from radiolytically produced hydrogen atoms as 0.082 of the total DMPO-H yield, indicating that approximately half of the hydrogen atoms react with DMPO to produce non-aminoxyl products. The fraction of the total hydroxyl radical yield leading to DMPO-OH spin adduct was determined to be 0.94, using the bleach of 2,2,6,6-tetramethylpiperidone-N-oxyl by carbon dioxide radical anion as a reference standard. 36 refs., 8 figs., 1 tab.

OSTI ID:
249668
Journal Information:
Journal of Physical Chemistry, Vol. 100, Issue 18; Other Information: PBD: 2 May 1996
Country of Publication:
United States
Language:
English