Toluene nitration in irradiated nitric acid and nitrite solution

Journal Article · Fri Apr 01 00:00:00 EDT 2011 · Radiation Physics and Chemistry

DOI:https://doi.org/10.1016/j.radphyschem.2010.12.005· OSTI ID:1007250

Elias, Gracy; Mincher, Bruce J; Mezyk, Stephen P; Muller, Jim; Martin, Leigh R

The kinetics, mechanisms, and stable products produced for the aryl alkyl mild ortho-para director - toluene, in irradiated nitric acid and neutral nitrite solutions were investigated using ?, 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 was primarily used to assess the stable reaction products. GC-MS and LC-MS were used to confirm the results from HPLC. Free-radical nitration reaction products were found in irradiated acidic and neutral media. In acidic medium, the ring substitution and side chain substitution and oxidation produced different nitro products. In ring substitution, nitrogen oxide radicals were added mainly to hydroxyl radical-produced cyclohexadienyl radical, and in side chain substitution they were added to the carbon-centered benzyl radical produced by H-atom abstraction. In neutral nitrite toluene solution, radiolytic ring nitration products approached a statistically random distribution, suggesting a free-radical reaction involving addition of the •NO2 radical.

• Research Organization: Idaho National Lab. (INL), Idaho Falls, ID (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: DE-AC07-05ID14517
• OSTI ID: 1007250
• Report Number(s): INL/JOU-10-19718; TRN: US1101300
• Journal Information: Radiation Physics and Chemistry, Vol. 80, Issue 4; ISSN 0969-806X
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
BENZYL RADICALS
CHAINS
DETECTION
DISTRIBUTION
ELECTRONS
HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY
IRRADIATION
KINETICS
NITRATION
NITRIC ACID
NITRITES
NITROGEN OXIDES
OXIDATION
RADICALS
RADIOLYSIS
TOLUENE
radiolysis
HPLC
UV spectra
LC-MS
free-radicals