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Title: Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

Abstract

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance of the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Idaho National Laboratory (INL)
Sponsoring Org.:
DOE - NE
OSTI Identifier:
912432
Report Number(s):
INL/JOU-05-00866
Journal ID: ISSN 0013-936X; ESTHAG; TRN: US0800386
DOE Contract Number:  
DE-AC07-99ID-13727
Resource Type:
Journal Article
Resource Relation:
Journal Name: Environmental Science and Technology; Journal Volume: 41; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CARBON; CHEMISTRY; CHLORIDES; COMPUTERS; ELECTRON ATTACHMENT; ELECTRONS; HYDRATION; HYDROXYL RADICALS; IRRADIATION; KINETICS; NITRATES; RADIATION DOSES; RADICALS; RADIOLYSIS; SOLVATED ELECTRONS; STERILIZATION; TRANSIENTS

Citation Formats

B. J. Mincher, S. K. Cole, W. J. Cooper, R. V. Fox, P. R. Gardinali, S. P. Mezyk, and K. E. O'Shea. Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin). United States: N. p., 2007. Web.
B. J. Mincher, S. K. Cole, W. J. Cooper, R. V. Fox, P. R. Gardinali, S. P. Mezyk, & K. E. O'Shea. Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin). United States.
B. J. Mincher, S. K. Cole, W. J. Cooper, R. V. Fox, P. R. Gardinali, S. P. Mezyk, and K. E. O'Shea. Thu . "Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)". United States. doi:.
@article{osti_912432,
title = {Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)},
author = {B. J. Mincher and S. K. Cole and W. J. Cooper and R. V. Fox and P. R. Gardinali and S. P. Mezyk and K. E. O'Shea},
abstractNote = {Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance of the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.},
doi = {},
journal = {Environmental Science and Technology},
number = 3,
volume = 41,
place = {United States},
year = {Thu Feb 01 00:00:00 EST 2007},
month = {Thu Feb 01 00:00:00 EST 2007}
}