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Absolute rate constant for the reaction of Phenyl radical with Acetylene

✍ Scribed by T. Yu; M. C. Lin; C. F. Melius

Publisher: John Wiley and Sons
Year: 1994
Tongue: English
Weight: 490 KB
Volume: 26
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550261105

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✦ Synopsis

The absolute rate constant for the reaction of phenyl radical with acetylene has been measured at 20 torr total pressure in the temperature range of 297 to 523 K using the cavity-ring-down technique. These new kinetic data could be quantitatively correlated with the data obtained earlier with a relative rate method under low-pressure torr) and high-temperature (1000 -1330 K) conditions. These kinetic data were analyzed in terms of the RRKM theory employing the thermochemical and molecular structure data computed with the BAC-MP4 technique.

The calculated results reveal that the total rate constant for the C6H5 + CzHz reaction ( k t ) is pressureindependent, whereas those for the formation of CsHsCzH ( k b ) and the C6H5CzHz adduct ( k , ) are strongly pressure-dependent. A least-squares analysis of the calculated values for 300 -2000 K at the atmospheric pressure of Nz or Ar can be given by k b = 9.5 X 10-42T9.33 ex P(-1,713/T) k , = 1.8 X 10-7T-'.63 exp(-2,711/T) and kt = 4.1 X 10-i8T'.77 exp(-1,152/T), all in units of cm3/s. The latter equation effectively represents the two sets of experimental data.

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