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Author(s):   Becerra, R.; Cannady, J.P.; Walsh, R.
Title:   Silylene Does React with Carbon Monoxide: Some Gas-Phase Kinetic and Theoretical Studies
Journal:   J. Phys. Chem. A
Volume:   105
Page(s):   1897 - 1903
Year:   2001
Reference type:   Journal article
Squib:   2001BEC/CAN1897-1903

Reaction:   CO + SiH2 → SiH2CO
Reaction order:   3
Temperature:   299 - 477 K
Rate expression:   1.18x10-32 [cm6/molecule2 s] e10870 [±1700 J/mole]/RT
Uncertainty:   1.25
Bath gas:   SF6
Category:  Experiment
Data type:   RRK(M) extrapolation
Pressure dependence:   Rate constant is low pressure limit
Comments:   SiH2 generated by 193 nm excimer laser photolysis of Phenylsilane. SiH2 detected with CW dye laser at 17259.5 cm-1 vib-rot band. Typically used 0-20 torr CO, 1.5-6.5 torr PhSiH3. Studied pressure dependent rate constant over 10-500 torr SF6, 299-477 K. RRKM analysis indicates reactions is very far from high pressure limit ?k/kinf = 1% at 100 torr and 299 K. A lowest pressures 10 torr near low pressure limit.

Rate expression provided by abstractor from fit to low pressure ko(T) data given in paper. ko(299K) 9.0E-31 ko(337K) 5.4E-31 ko(397K) 4.0E-31 ko(477K) 1.6E-31 cm6/(molecules2*s). Apparent curvature in data but too much scatter and too narrow temperature range to use extended Arrhenius form fit.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm6/molecule2 s]
299 9.35E-31
300 9.21E-31
325 6.59E-31
350 4.94E-31
375 3.85E-31
400 3.10E-31
425 2.56E-31
450 2.16E-31
475 1.85E-31
477 1.83E-31