The kinetics of radical reactions in the radiolysis of aqueous solutions of organic nitro compounds

• Published in: Russian Journal of Physical Chemistry A Vol. 82; no. 11; pp. 1833 - 1837
• Main Authors: Makarov, I. E., Protasova, E. L., Khaikin, G. I.
• Format: Journal Article
• Language: English
• Published: Dordrecht SP MAIK Nauka/Interperiodica 01.11.2008
• Subjects: Chemistry; Chemistry and Materials Science; Physical Chemistry; Physical Chemistry of Solutions; Organic Nitrate; Hydrated Electron; Nitrotoluenes; Nitro Compound; Pulse Radiolysis
• ISSN: 0036-0244; 1531-863X
• DOI: 10.1134/S0036024408110083

Pulsed radiolysis and computer simulation of gamma radiolytic decomposition of organic nitrates in aqueous solutions were performed to determine the rate constants for reactions with the participation of intermediates determining the mechanism of the process. 2,4,6-Trinitrotoluene, 2,4-dinitrotoluene, and cyclic nitramine, cyclotrimethylene-trinitramine, were used as substrates. The bimolecular rate constants for the reactions of hydrated electrons (e aq − ) and hydroxyl radicals ( • OH) with the substrates and constants for the recombination of electron adducts and carbon-centered radicals (the products of the detachment of the H atom from the nitro compound molecule by the OH radical) were determined by direct measurements with the use of high-speed spectrophotometry. Computer simulation of the reaction scheme was used to estimate the rate constant for significant reactions, monomolecular forward and back reactions of electron adducts and electron transfer to molecular oxygen, and refine the rate constant for the reaction of e aq − with tert -butanol.