The reaction of C{sub 6}H{sub 5} with CO: Kinetic measurement and theoretical correlation with the reverse process

Journal Article · Thu Feb 17 04:00:00 EST 2000 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp993245a· OSTI ID:20017551

Nam, G J; Xia, W; Park, J; Lin, M C

The kinetics of the C{sub 6}H{sub 5} reaction with CO has been studied by the cavity ring-down spectrometric technique in the temperature range 295--500 K at 12--120 Torr pressure with Ar as the carrier gas. The reaction occurred near the high-pressure limit under the conditions used. A weighted least-squares analysis of all data gives the rate constant for the association reaction, k{sub 1} = 10{sup 11.93{+-}0.14} exp[{minus}(1,507 {+-} 109)/T] cm{sup 3} mole{sup {minus}1} s{sup {minus}1}, where the errors represent two standard deviations. This result can correlate satisfactorily with the kinetic data reported by Solly and Benson for the reverse process (J.Am.Chem.Soc, 1971, 93, 2171) with the Rice-Ramsperger-Kassel-Marcus (RRKM) theory using the transition-state parameters computed quantum mechanically by the MP2 method with the 6--31G(d,p) basis set. Combination of the forward and reverse reaction data gives {Delta}H{sub 1}{degree} = {minus}24.6 {+-} 0.8 kcal/mol at 0 K and k{sub {minus}1}{sup {infinity}} = 5.3 x 10{sup 14} exp({minus}14 600/T) s{sup {minus}1} for the temperature range 300--670 K. The heat of reaction, combining with the known heats of formation of the reactants, leads to {Delta}{sub f}H{sub 0}{degree} (C{sub 6}H{sub 5}CO) = 32.5 {+-} 1.5 kcal/mol.

• Research Organization: Emory Univ., Atlanta, GA (US)
• Sponsoring Organization: US Department of Energy
• DOE Contract Number: FG02-97ER14784
• OSTI ID: 20017551
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 6 Vol. 104; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

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