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Author(s):   Galano, A.; Alvarez-Idaboy, J.R.; Ruiz-Santoyo, M.E.; Vivier-Bunge, A.
Title:   Mechanism and kinetics of the reaction of OH radicals with glyoxal and methylglyoxal: A quantum chemistry plus CVT/SCT approach
Journal:   ChemPhysChem
Volume:   5
Page(s):   1379 - 1388
Year:   2004
Reference type:   Journal article
Squib:   2004GAL/ALV1379-1388

Reaction:   CH3C(O)CHO + ·OH → CH3C(O)C(O)· + H2O
Reaction order:   2
Temperature:   200 - 500 K
Rate expression:   3.93x10-13 [±1.1x10-14 cm3/molecule s] e8813 [±66.52 J/mole]/RT
Category:  Theory
Data type:   Ab initio
Comments:   A theoretical study of the kinetics of the hydrogen abstractions from glyoxal and methylglyoxal by OH at several levels of theory is reported. Geometries, frequencies, and gradients were calculated at the BHandHLYP/6-311++G(d,p) level of theory with PES energies obtained using CCSD(T)/6-311++G(d,p) calculations. Rate coefficients were calculated using CVT/SCT methodology.

Only abstraction of the aldehydic H is found to be important over the studied range of 200-500 K. Results suggest the formation of a reactive complex and are in excellent agreement with experimental data. Calculations performed assuming a direct abstacion (no complex) are in significantly poorer agreement..

Uncertainties represent 2 standard deviations of the analytical expression from the actual calculated values.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [cm3/molecule s]
200 7.87E-11
225 4.37E-11
250 2.73E-11
275 1.86E-11
300 1.35E-11
325 1.03E-11
350 8.12E-12
375 6.64E-12
400 5.56E-12
425 4.76E-12
450 4.14E-12
475 3.66E-12
500 3.27E-12