Anisole nitration during gamma-irradiation of aqueous nitrite and nitrate solutions: free radical versus ionic mechanisms
Gracy Elias A , Bruce J. Mincher A C , Stephen P. Mezyk B , Thomas D. Cullen B and Leigh R. Martin AA Idaho National Laboratory, PO Box 1625, Idaho Falls, ID 83415-6180, USA.
B California State University, Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840, USA.
C Corresponding author. Email: bruce.mincher@inl.gov
Environmental Chemistry 7(2) 183-189 https://doi.org/10.1071/EN09109
Submitted: 28 August 2009 Accepted: 3 February 2010 Published: 22 April 2010
Environmental context. The nitration of aromatic compounds is an important source of toxic, carcinogenic, and mutagenic species in the atmosphere. Gas phase nitration typically occurs by free radical reactions. Condensed-phase free radical reactions may also be relevant in fog and cloud water in polluted areas, in urban aerosols with low pH, in water treatment using advanced oxidation processes such as e-beam irradiation, and in nuclear waste treatment applications. This paper discusses research towards an improved understanding of nitration of aromatic compounds in the condensed phase under conditions conducive to free radical formation.
Abstract. In the irradiated, acidic condensed phase, radiation-enhanced nitrous acid-catalysed, nitrosonium ion, electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions for anisole. This ionic mechanism would predominate in urban atmospheric aerosols and nuclear fuel dissolutions. Irradiated neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Solutions such as these might be encountered in water treatment by e-beam irradiation. Irradiation of neutral nitrite anisole solutions resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the •NO2 radical. Although often proposed as an atmospheric nitrating agent, NO2 radical is unlikely to have an important effect in the acidic condensed phase in the presence of more reactive, competing species such as nitrous acid.
Additional keywords: N-centred radicals, nitronium ion, nitrosonium ion, radical chemistry.
Acknowledgements
This research was funded by the INL-LDRD program, sponsored by the USA Department of Energy (DOE), Office of Nuclear Energy, Science and Technology under DOE Idaho Operations Office contract DE-AC07–99ID13727. Kinetics experiments were performed at the Radiation Laboratory, University of Notre Dame, which is supported by the Office of Basic Energy Sciences, USA Department of Energy. Special thanks are due to H. Sims for helpful discussions concerning the chemistry of irradiated nitric acid.
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