TY - JOUR
T1 - The reaction of C 6 H 5 with CO
T2 - Kinetic measurement and theoretical correlation with the reverse process
AU - Nam, Gi Jung
AU - Xia, Wensheng
AU - Park, J.
AU - Lin, Ming-Chang
PY - 2000/12/17
Y1 - 2000/12/17
N2 - The kinetics of the C6H5 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, k1 = 1011.93±0.14 exp[-(1507 ±109)77] cm3 mole-1 s-1), where the errors represent two standard deviations. Our result can correlated 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 ΔH°1 = -24.6 ± 0.8 kcal/mol at 0 K and k-1∞, = 5.3 × 1014 exp(-14 600/T) s-1 for the temperature range 300-670 K. The heat of reaction, combining with the known heats of formation of the reactants, leads to ΔfH°0 (C6H5CO) = 32.5 ± 1.5 kcal/mol.
AB - The kinetics of the C6H5 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, k1 = 1011.93±0.14 exp[-(1507 ±109)77] cm3 mole-1 s-1), where the errors represent two standard deviations. Our result can correlated 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 ΔH°1 = -24.6 ± 0.8 kcal/mol at 0 K and k-1∞, = 5.3 × 1014 exp(-14 600/T) s-1 for the temperature range 300-670 K. The heat of reaction, combining with the known heats of formation of the reactants, leads to ΔfH°0 (C6H5CO) = 32.5 ± 1.5 kcal/mol.
UR - http://www.scopus.com/inward/record.url?scp=0034677577&partnerID=8YFLogxK
U2 - 10.1021/jp993245a
DO - 10.1021/jp993245a
M3 - Article
AN - SCOPUS:0034677577
SN - 1089-5639
VL - 104
SP - 1233
EP - 1239
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 6
ER -