The kinetics of the reaction of hydrogen atoms with propyne (pC 2 H 4 ) was experimentally studied in a shock tube at temperatures ranging from 1200 to 1400 K and pressures between 1.3 and 4.0 bar with Ar as the bath gas. The hydrogen atoms (initial mole fraction 0.5-2.0 ppm) were produced by pyrolysis of C 2 H 5 I and monitored by atomic resonance absorption spectrometry under pseudo-first-order conditions with respect to propyne (initial mole fraction 5-20 ppm). From the hydrogen atom time profiles, overall rate coefficients k ov ≡= -([pC 3 H 4 ][H] -1 × d[H]/dt for the reaction H + pC 3 H 4 → products (≠ H) were deduced; the following temperature dependence was obtained: k ov = 1.2 × 10 -10 exp(-2270 K/T) cm 3 -1 with an estimated uncertainty of ±20%. A pressure dependence was not observed. The results are analyzed in terms of statistical rate theory with molecular and transition state data from quantum chemical calculations. Geometries were optimized using density functional theory at the B3LYP/6-31G(d) level, and single-point energies were computed at the QCISD(T)/cc-pVTZ level of theory. It is confirmed that the reaction proceeds via an addition-elimination mechanism to yield C 2 H 2 + CH 3 and via a parallel direct abstraction to give C 3 H 3 + H 2 . Furthermore, it is shown that a hydrogen atom catalyzed isomerization channel to allene (aC 3 H 4 ), H + pC 3 H 4 → aC 3 H 4 + H, is also important. Kinetic parameters to describe the channel branching of these reactions are deduced.
|Original language||English (US)|
|Number of pages||7|
|Journal||Journal of Physical Chemistry A|
|State||Published - May 17 2007|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry