Experimental and Theoretical Study of the Kinetics of the OH + Propionaldehyde Reaction between 277 and 375 K at Low Pressure

2015-09-10T00:00:00Z (GMT) by Paul E. Carey Philip S. Stevens
Measurements of the rate constant for the reaction of OH radicals with propionaldehyde as a function of temperature were performed using low-pressure discharge-flow tube techniques coupled with laser-induced fluorescence detection of OH radicals. The measured room-temperature rate constant of (1.51 ± 0.22) × 10<sup>–11</sup> cm<sup>3</sup> molecules<sup>–1</sup> s<sup>–1</sup> at 4 Torr was generally lower but in reasonable agreement with previous absolute and relative rate studies at higher pressures. Measurements as a function of temperature resulted in an Arrhenius expression of (2.3 ± 0.4) × 10<sup>–11</sup> exp[(−110 ± 50)/<i>T</i>] cm<sup>3</sup> molecules<sup>–1</sup> s<sup>–1</sup> between 277 and 375 K at 4 Torr. The observed temperature dependence at low pressure is in contrast to previous measurements of a negative temperature dependence at higher pressures. Ab initio calculations of the potential energy surface for this reaction suggest that the primary reaction pathway involves the formation of a hydrogen-bonded prereactive complex, which could account for the difference in the observed temperature dependence at lower and higher pressures.