Kinetic study of the C(10)H(7) + O(2) reaction.
The effect of temperature on the formation of C(10)H(7)O(2) in the C(10)H(7) + O(2) reaction has been investigated at temperatures 299-444 K by directly monitoring the C(10)H(7)O(2) radical in the visible region by cavity ringdown spectrometry (CRDS) using the 2-C(10)H(7)Br as a radical source photolyzing at 193 nm. The first experimentally measured rate constant for the association reaction can be given by k(1) = (1.53 +/- 0.10) x 10(12) exp[(900 +/- 45)/RT] cm(3) mol(-1) s(-1), where R is gas constant and 1.986 cal/mol-K, at a total pressure of 40 Torr in the temperature range studied. Theoretically the association process was computed by B3LYP/6-31+G(d, p) with the energy profile improved at the G2MS level of theory. The excitation energies and oscillator strengths of the association product (2-C(10)H(7)OO) were calculated by using the time-dependent DFT method. The association rate constant of this reaction was predicted by the canonical VTST/RRKM theory with the steady-state and master-equation analyses. The latter method gave a much better agreement with the experimental data.
Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
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Park
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Xu
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Lin