Anisole Nitration During Gamma-Irradiation of Aqueous Nitrite and Nitrate Solutions: Free Radical Versus Ionic Mechanisms
The nitration of aromatic compounds in the condensed phase is of interest to nuclear waste treatment applications. This chapter discusses our investigation of radiolytic aromatic nitration mechanisms in the condensed phase toward understanding the nitration products created during nuclear fuel reprocessing. The nitration reactions of anisole, a model aromatic compound, were studied in ?-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. Neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Irradiation of neutral nitrite anisole solution resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the •NO2 radical.
- Research Organization:
- Idaho National Laboratory (INL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC07-05ID14517
- OSTI ID:
- 1003880
- Report Number(s):
- INL/JOU-10-17599
- Journal Information:
- Environmental Chemistry, Journal Name: Environmental Chemistry Journal Issue: 2 Vol. 7; ISSN 1448-2517
- Country of Publication:
- United States
- Language:
- English
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