ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 (10-3-10-2 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 + C2H2 reaction (kt) is pressure-independent, whereas those for the formation of C6H5C2H (kb) and the C6H5C2H2 adduct (kc) are strongly pressure-dependent. A least-squares analysis of the calculated values for 300-2000 K at the atmospheric pressure of N2 or Ar can be given by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_b = 9.5 \times {\rm 10}^{{\rm - 42}} T^{9.33} \exp \left({- 1,713/T} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_C = 1.8 \times {\rm 10}^{{\rm - 7}} T^{-1.63} \exp \left({- 2,711/T} \right) $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ k_t = 4.1 \times {\rm 10}^{{\rm - 18}} T^{1.77} \exp \left({- 1,152/T} \right) $$\end{document} all in units of cm3/s. The latter equation effectively represents the two sets of experimental data. © 1994 John Wiley & Sons, Inc.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550261105
