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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
Reference reaction:
CH2=C(CH3)CH=CH2 + ·OH → Products
Reference reaction order:
2
Temperature:
240 - 340
K
Pressure: 1.33E-3 - 1.47E-3 bar
Rate expression:
2.98±5.1x10-1 e349 [±382 J/mole]/RT
Category: Experiment
Data type:
Relative rate value measured
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 relative rate expression was derived from a least squares analysis performed at NIST from the data reported in Table 1 of the paper. The listed uncertainties are 2 sigma and are statistical only.
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.
View full bibliographic record.
Rate constant values calculated from the Arrhenius expression:
| T (K) | k(T) [] |
|---|---|
| 240 | 3.55E0 |
| 250 | 3.53E0 |
| 275 | 3.47E0 |
| 300 | 3.43E0 |
| 325 | 3.39E0 |
| 340 | 3.37E0 |