Title: Kinetics of the CH3+HCl/DCl→CH4/CH3D+Cl and CD3+HCl/DCl→CD3H/CD4+Cl reactions: An experimental H atom tunneling investigation
Abstract: The kinetics of the radical reactions of CH3 with HCl or DCl and CD3 with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH3 (or CD3) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH3COCH3 (or CD3COCD3). The decay of CH3/CD3 was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH3 and CD3 reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (−Ea/RT) (error limits stated are 1σ + Students t values, units in cm3 molecule−1 s−1): k(CH3 + HCl) = [1.004 + 85.64 exp (−0.02438 × T/K)] × (3.3 ± 1.3) × 10−13 exp [−(4.8 ± 0.6) kJ mol−1/RT] and k(CD3 + HCl) = [1.002 + 73.31 exp (−0.02505 × T/K)] × (2.7 ± 1.2) × 10−13 exp [−(3.5 ± 0.5) kJ mol−1/RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (−Ea/RT) (error limits stated are 1σ + Students t values, units in cm3 molecule−1 s−1): k(CH3 + DCl) = (2.4 ± 1.6) × 10−13 exp [−(7.8 ± 1.4) kJ mol−1/RT] and k(CD3 + DCl) = (1.2 ± 0.4) × 10−13 exp [−(5.2 ± 0.2) kJ mol−1/RT] cm3 molecule−1 s−1. Curvature in the Arrhenius plots of the H-atom abstraction reactions at low temperatures was analyzed by considering H-atom tunneling through the reaction barrier and primary kinetic isotope effect. Contribution of tunneling in it was concluded to be negligible. In addition, secondary isotope effect was measured.
Publication Year: 2006
Publication Date: 2006-10-05
Language: en
Type: article
Indexed In: ['crossref']
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Cited By Count: 14
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