Abstract
The kinetics, mechanisms, and stable products produced for the nitration of aryl alkyl mild ortho-para director toluene in irradiated nitric acid and neutral nitrite solutions were investigated using γ and pulse radiolysis. Electron pulse radiolysis was used to determine the bimolecular rate constants for the reaction of toluene with different transient species produced by irradiation. HPLC with UV detection, GC-MS and LC-MS, were used to assess the stable reaction products. Free-radical based nitration reaction products were found in irradiated acidic and neutral media. In 6.0M HNO3, ring substitution, side chain substitution, and oxidation, produced different nitrated toluene products. For ring substitution, nitrogen oxide radicals were added mainly to cyclohexadienyl radicals, whereas for side chain substitution, these radicals were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite solutions, radiolytically-induced ring nitration products approached a statistically random distribution, suggesting a direct free-radical reaction involving addition of the NO2 radical.
| Original language | English |
|---|---|
| Pages (from-to) | 554-560 |
| Number of pages | 7 |
| Journal | Radiation Physics and Chemistry |
| Volume | 80 |
| Issue number | 4 |
| DOIs | |
| State | Published - Apr 2011 |
Funding
This research was funded by the INL-Laboratory Directed Research and Development Program, sponsored by the U.S. Department of Energy (DOE), Office of Nuclear Energy, Science and Technology under the 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, U. S. Department of Energy.
Keywords
- Electrophilic substitution
- Free-radicals
- HPLC
- LC-MS
- Toluene radiolysis
- UV spectra