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Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Journal Article


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Abstract


  • Low-temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165, and 295 K is found to be relatively constant over this temperature range, (3.9−4.9) × 10−10 cm3 molecule−1 s−1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a rate coefficient of 1.3 × 10−10 cm3 molecule−1 s−1 at 105 K. At room temperature, nonexponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta, and para isomers of cyanotoluene because of their similar ionization energies and the 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn’s moon Titan (100 K) and are also likely to proceed at the temperature of interstellar clouds (10−20 K).

Authors


  •   Trevitt, Adam J.
  •   Goulay, Fabien (external author)
  •   Taatjes, Craig A. (external author)
  •   Osborn, David L. (external author)
  •   Leone, Stephen R. (external author)

Publication Date


  • 2010

Citation


  • Trevitt, A. J., Goulay, F., Taatjes, C. A., Osborn, D. L. & Leone, S. R. (2010). Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics. The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 114 (4), 1749-1755.

Scopus Eid


  • 2-s2.0-77249168722

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1500&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/461

Has Global Citation Frequency


Number Of Pages


  • 6

Start Page


  • 1749

End Page


  • 1755

Volume


  • 114

Issue


  • 4

Abstract


  • Low-temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165, and 295 K is found to be relatively constant over this temperature range, (3.9−4.9) × 10−10 cm3 molecule−1 s−1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a rate coefficient of 1.3 × 10−10 cm3 molecule−1 s−1 at 105 K. At room temperature, nonexponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta, and para isomers of cyanotoluene because of their similar ionization energies and the 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn’s moon Titan (100 K) and are also likely to proceed at the temperature of interstellar clouds (10−20 K).

Authors


  •   Trevitt, Adam J.
  •   Goulay, Fabien (external author)
  •   Taatjes, Craig A. (external author)
  •   Osborn, David L. (external author)
  •   Leone, Stephen R. (external author)

Publication Date


  • 2010

Citation


  • Trevitt, A. J., Goulay, F., Taatjes, C. A., Osborn, D. L. & Leone, S. R. (2010). Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics. The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 114 (4), 1749-1755.

Scopus Eid


  • 2-s2.0-77249168722

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=1500&context=scipapers

Ro Metadata Url


  • http://ro.uow.edu.au/scipapers/461

Has Global Citation Frequency


Number Of Pages


  • 6

Start Page


  • 1749

End Page


  • 1755

Volume


  • 114

Issue


  • 4