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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:   2
Temperature:   299 - 477 K
Pressure:  0.27 bar
Rate expression:   3.24x10-14 [cm3/molecule s] e12430 [±1040 J/mole]/RT
Uncertainty:   1.40999997
Bath gas:   SF6
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure dependent
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:   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.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
299 4.81E-12
300 4.73E-12
325 3.22E-12
350 2.32E-12
375 1.75E-12
400 1.36E-12
425 1.09E-12
450 8.98E-13
475 7.54E-13
477 7.44E-13