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Author(s):   Pokidova, T.S.; Denisov, E.T.; Shestakov, A.F.
Title:   Kinetic Parameters and Geometry of the Transition State of Acyl Radical Decarbonylation
Journal:   Kinet. Catal.
Volume:   50
Page(s):   647 - 655
Year:   2009
Reference type:   Journal article
Squib:   2009POK/DEN647-655

Reaction:   CO + tert-C4H9 → (CH3)3CC(O)·
Reaction order:   2
Temperature:   298 K
Rate expression:   2.99x10-13 [cm3/molecule s] e-21500 [J/mole]/RT
Category:  Theory
Data type:   Estimated: thermochemical, kinetic, or other
Pressure dependence:   Rate constant is high pressure limit
Comments:   Experimental data on acyl radical decomposition reactions (RCO → R + CO, where R = alkyl or aryl) were analyzed in terms of the intersecting parabolas method. A semiempirical algorithm was constructed for calculating the transition state geometry for the decomposition of acyl radicals and for the reverse reactions of R addition to CO. Kinetic parameters were calculated for 18 decomposition reactions of structurally different acyl radicals. Arrhenius parameters are reported without the temperature range of validity; rate constants are calculated for the temperature of 298 K.

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