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Author(s):   Vereecken, L.; Peeters, J.
Title:   Enhanced H-atom Abstraction from Pinonaldehyde, Pinonic Acid, Pinic Acid, and Related Compounds: Theoretical Study of C-H Bond Strengths
Journal:   Phys. Chem. Chem. Phys.
Volume:   4
Page(s):   467 - 472
Year:   2002
Reference type:   Journal article
Squib:   2002VER/PEE467-472

Reaction:   (CH3)2CO + ·OHCH3C(O)CH2(·) + H2O
Reaction order:   2
Reference reaction:   (CH3)2CO + ·OH → Products
Reference reaction order:   2
Temperature:   290 K
Rate expression:   9.5x10-1
Rate constant is a lower limit.
Category:  Experiment
Data type:   Mechanistic information only
Pressure dependence:   None reported
Experimental procedure:   Flow tube - Data taken vs distance
Excitation technique:   Discharge
Time resolution:   By end product analysis
Analytical technique:   Mass spectrometry
Comments:   The possible OH addition/CH3 elimination channel was found to be < 5% of reaction, with no significant formation of acetic acid detected. Reaction proceeds via H abstraction.

In addition to the experimental work, the potential energy surface was characterized at the B3LYP-DFT/6-31G(d,p) and B3LYP-DFT/6-311++G(d,p) levels of theory, with single-point CCSD(T)/6-311++G(2d,2p) energy calculations. At all levels, the barrier for OH-addition was found to be 6±0.5 kcal/mol, at least 2.5 kcal/mol higher than that for the H-abstraction channels. Transition state theory and RRKM - master equation calculations suggest the OH-addition channel is negligible at all relevant atmospheric temperatures.

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