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Author(s):   Becerra, R.; Cannady, J.P.; Walsh, R.
Title:   Time-resolved gas-phase kinetic and quantum chemical studies of reactions of silylene with chlorine-containing species. 2. CH3Cl
Journal:   J. Phys. Chem. A
Volume:   110
Page(s):   6680 - 6686
Year:   2006
Reference type:   Journal article
Squib:   2006BEC/CAN6680-6686

Reaction:   CH3Cl + SiH2 → Products
Reaction order:   2
Temperature:   398 - 606 K
Pressure:  2.00E-5 - 1.37E-3 bar
Rate expression:   8.13x10-13 [cm3/molecule s] e-2810 [±1450 J/mole]/RT
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure independent
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   Vis-UV absorption
Comments:   Rate constants displayed weak dependence on the intensity of the photolyzing laser, which impies a contribution of side reactions to the SiH2 decay, which was estimated to be approximately 30%. Exact pressure values are not given. Total reactor pressure was determined by the sum of partical pressures of the radical precursor (2.0 - 5.7 Torr), chloromethane (0-35 Torr), and SF6 (0 - 100 Torr). Overall temperature dependence is non-Arrhenius, with a minimum on the Arrhenius plot.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
398 3.48E-13
400 3.49E-13
425 3.67E-13
450 3.84E-13
475 3.99E-13
500 4.14E-13
525 4.27E-13
550 4.40E-13
575 4.52E-13
600 4.63E-13
606 4.65E-13