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Accessibility information
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.

View full bibliographic record.


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