Kinetics and Products of Vinyl + 1,3-Butadiene, a Potential Route to Benzene
The reaction between vinyl radical, C 2 H3, and 1,3-butadiene, 1,3-C 4 H 6 , has long been recognized as a potential route to benzene, particularly in 1,3-butadiene flames, but the lack of reliable rate coefficients has hindered assessments of its true contribution. Here, by using laser flash photolysis and visible laser absorbance (λ = 423.2 nm), we measured the overall rate coefficient for C 2 H 3 + 1,3-C 4 H 6 , k 1 , at 297 K ≤ T ≤ 494 K and 4 ≤ P ≤ 100 Torr. k 1 was in the high-pressure limit in this range and could be fit by the simple Arrhenius expression k1 = (1.1 ± 0.2) × 10 –12 cm 3 molecule –1 s –1 exp(–9.9 ± 0.6 kJ mol –1 /RT). Using photoionization time-of-flight mass spectrometry, we also investigated the products formed. At T ≤ 494 K and P = 25 Torr, we found only C 6 H 9 adduct species, while at 494 K ≤ T ≤ 700 K and P = 4 Torr, we observed ≤~10% branching to cyclohexadiene in addition to C 6 H 9 . Quantum chemistry master-equation calculations using the modified strong collision model indicate that n-C 6 H 9 is the dominant product at low temperature, consistent with our experimental results, and predict the rate coefficient and branching ratios at higher T where chemically activated channels become important. Predictions of k 1 are in close agreement with our experimental results, allowing us to recommend the following modified Arrhenius expression in the high-pressure limit from 300 to 2000 K: k 1 = 6.5 × 10 –20 cm 3 molecule –1 s –1 T 2.40 exp(–1.76 kJ mol –1 /RT).