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Author(s):   Becerra, R.; Cannady, J.P.; Goulder, O.; Walsh, R.
Title:   Time-Resolved Gas-Phase Kinetic, Quantum Chemical and RRKM Studies of Reactions of Silylene with Cyclic Ethers
Journal:   J. Phys. Chem. A
Volume:   114
Page(s):   784 - 793
Year:   2010
Reference type:   Journal article
Squib:   2010BEC/CAN784-793

Reaction:   Oxirane + SiH2 → Products
Reaction order:   2
Temperature:   294 - 605 K
Pressure:  1.33E-3 - 0.13 bar
Rate expression:   9.3x10-12 [±1.5x10-12 cm3/molecule s] e-5700 [±510 J/mole]/RT
Category:  Experiment
Data type:   RRK(M) extrapolation
Pressure dependence:   Rate constant is high pressure limit
Experimental procedure:   Static or low flow - Data taken vs time
Excitation technique:   Flash photolysis (laser or conventional)
Time resolution:   In real time
Analytical technique:   IR absorption
Comments:   The reaction showed pressure dependence characteristic of a third-body-assisted association reaction. The second-order rate constants obtained by extrapolation to the high-pressure limit at each temperature were fitted with the Arrhenius equation. The reported error limits are single standard deviations. Because of the unknown uncertainties involved in extrapolation, the authors estimate that these Arrhenius parameters may have maximum uncertainties of 0.5 (log Ainf) and 3.6 kJ/mol (Ea).

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
294 9.03E-13
300 9.46E-13
325 1.13E-12
350 1.31E-12
375 1.49E-12
400 1.68E-12
425 1.85E-12
450 2.03E-12
475 2.20E-12
500 2.36E-12
525 2.52E-12
550 2.67E-12
575 2.82E-12
600 2.97E-12
605 2.99E-12