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Author(s):   Li, Z.J.; Nguyen, P.; de Leon, M.F.; Wang, J.H.; Han, K.L.; He, G.Z.
Title:   Experimental and theoretical study of reaction of OH with 1,3-butadiene
Journal:   J. Phys. Chem. A
Volume:   110
Page(s):   2698 - 2708
Year:   2006
Reference type:   Journal article
Squib:   2006LI/NGU2698-2708

Reaction:   1,3-Butadiene + ·OH → Products
Reaction order:   2
Temperature:   298 K
Pressure:  1.33E-3 - 1.47E-3 bar
Rate expression:   6.93x10-11 [±4.8x10-12 cm3/molecule s]
Category:  Experiment
Data type:   Relative value normalized by a reference value
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:   OH radicals were produced from the F + H2O -> OH + HF reaction with F atoms generated in a discharge flow system. The reaction rate was determined relative to those for the reference compounds isoprene and propionaldehyde. The rate constants at 298 K for the reactions of hydroxyl radical with propionaldehyde and isoprene were taken from the literature as 1.98x10-11 and 9.99 x 10-11 cm3 molecule-1 s-1, respectively.

The authors derived the rate expression after averaging the data from the reference compounds isoprene and propionaldehyde. Listed uncertainties are 2 sigma and take into account the scatter of data and uncertainty of the experimental parameters such as pressure, temperature, and flow rates..

Ab initio molecular orbital calculations were carried out at the MP2/6-311++G-(d,p) level of theory and structures and vibrational frequencies of the reactants, products, and transition state complexes are reported. The results suggest that both addition of OH to 1,3-butadiene and the abstraction of hydrogen atom from 1,3-butadiene by the OH radical are exothermic processes. Addition of OH to the terminal carbon of the 1,3-butadiene is predicted to be the most energetically favored reaction pathway and is calculated to have an activation energy of 0.7 kcal mol-1.

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