We demonstrate that stable and relatively unreactive "environmentally persistent free radicals (PFRs)" can be readily formed in the post-flame and cool-zone regions of combustion systems and other thermal processes. These resonance-stabilized radicals, including semiquinones, phenoxyls, and cyclopentadienyls, can be formed by the thermal decomposition of molecular precursors including catechols, hydroquinones and phenols. Association with the surfaces of fine particles imparts additional stabilization to these radicals such that they can persist almost indefinitely in the environment. A mechanism of chemisorption and electron transfer from the molecular adsorbate to a redox-active transition metal or other receptor is shown through experiment, and supported by molecular orbital calculations, to result in PFR formation. Both oxygen-centered and carbon-centered PFRs are possible that can significantly affect their environmental and biological reactivity.

The formation of radicals from the gas-phase pyrolysis of hydroquinone, catechol, and phenol over a temperature range of 400-750 degrees C was studied using the technique of low-temperature matrix isolation electron paramagnetic resonance (LTMI EPR). Cooling the reactor effluent from pyrolysis in a nitrogen carrier gas to 77 K produces a cryogenic matrix that exhibits poorly resolved EPR spectra. However, using carbon dioxide as a carrier gas formed a matrix that, upon annealing by slowly raising the matrix temperature followed by rapid recooling to 77 K, yielded more resolved, identifiable spectra. Annealed spectra of all three samples resulted in the generation of EPR spectra above 700 degrees C with 6 lines, hyperfine splitting constant approximately 6.0 G, and peak to peak width approximately 3 G that was readily assignable, based on comparison to the literature and theoretical calculations, as that of cyclopentadienyl radical. Pyrolysis at temperatures below 700 degrees C generated a carbon dioxide matrix isolation spectrum with a high g-value (>2.0040) that is attributed to oxygen-containing radicals such as semiquinone or phenoxyl. Conclusive identification of anticipated semiquinone, phenoxyl, and hydroxycyclopentadienyl radicals was complicated by the ability of these radicals to exist in carbon-centered and oxygen-centered resonance structures that can give different EPR spectra.

The formation of radicals from the gas-phase pyrolysis of phenol over a temperature range of 400-1000 degrees C was studied using the technique of low temperature matrix isolation electron paramagnetic resonance (LTMI EPR). Cooling the reactor effluent in a CO2 carrier gas to 77 K produces a cryogenic matrix that exhibits complex EPR spectra. However, annealing by slowly raising the matrix temperature yielded well-resolved, identifiable spectra. All annealed spectra over the temperature range of 700-1000 degrees C resulted in the generation of EPR spectra with six lines, hyperfine splitting constant approximately 6.0 G, g = 2.00430, and peak-to-peak width approximately 3 G that was readily assignable, based on comparison with the literature and theoretical calculations, as that of cyclopentadienyl radical. Annihilation procedures along with microwave power saturation experiments helped to clearly identify phenoxy radicals in the same temperature region. Conclusive identifications of cyclopentadienyl and phenoxy radicals were based on pure spectra of these radicals under the same experimental conditions generated from suitable precursors. Cyclopentadienyl is clearly the dominant radical at temperatures above 700 degrees C and is observed at temperatures as low as 400 degrees C. The low-temperature formation is attributed to heterogeneous initiation of phenol decomposition under very low pressure conditions. The high cyclopentadienyl to phenoxy ratio was consistent with the results of reaction kinetic modeling calculations using the CHEMKIN kinetic package and a phenol pyrolysis model adapted from the literature.

The formation and temperature dependence of the total yields of radicals from the gas-phase pyrolysis of hydroquinone (HQ) over a temperature range of 350−950 °C was studied using the technique of low-temperature matrix isolation electron paramagnetic resonance (LTMI−EPR) spectroscopy. Annihilation procedures along with microwave power saturation studies of the frozen radicals as well as GC−MS analysis of products helped to clearly identify several types of radicals over the temperature range studied. On the basis of these results, three formation temperature regimes could be identified: low-temperature region from 350 to 725 °C, where neutral p-semiquinone (p-SQ) radical is dominant, high-temperature region from 850 to 975 °C, where cyclopentadienyl (CPD) radical is dominant, and an intermediate-temperature region from 725 to 850 °C, where a mixture of p-SQ and CPD radicals exists.

The formation of environmentally persistent free radicals (EPFRs) from the gas-phase pyrolysis of catechol (CT) was studied over a temperature range of 400-750 degrees C using the technique of low-temperature matrix isolation electron paramagnetic resonance (LTMI-EPR) spectroscopy. A split singlet EPR spectrum with a g value of 2.0052 was observed. To aid in the interpretation of this spectrum, a detailed analysis of the potential energy surface of CT decomposition pathways was performed employing CBS-QB3 multilevel and DFT individual methods. The energetically favored channels were the formation of ipso- and alpha-CT isomers of CT as well as o-semiquinone (o-SQ) radicals from ipso- and alpha-CT. ipso-CT as well as open ipso-CT radicals were apparently unstable intermediates that could not be accumulated in sufficiently high concentrations to be detected by EPR. The calculated EPR spectrum of o-SQ radical is consistent with the formation of an oxygen-centered radical with a high g value observed experimentally. The hyperfine splitting of the observed spectrum can be attributed to the formation of hydrogen bonds in radical dimers. The lack of experimental observation of o-benzoquinone, an anticipated pyrolysis product, has been explained based on theoretical calculations.