Experimental Evidence for the Pressure Dependence of the Reaction Rate between Acetic Acid and Hydroxyl Radicals

Yi-wen Huang, Timothy J. Dransfield, and James G. Anderson. Experimental Evidence for the Pressure Dependence of the Reaction Rate Constant between Acetic Acid and Hydroxyl Radicals. The Journal of Physical Chemistry A 2010 114 (43), 11538-11544

The reaction rate constant of acetic acid with the hydroxyl radical is measured at 93 Torr with our high-pressure flow system (HPFS) and found to display a negative temperature dependence that can be described by the Arrhenius expression, k(T) = (2.44 ± 0.22) × 10(-14) exp ((1027 ± 24)/T)) cm(3) molecule(-1) s(-1). Compared with our previously reported 7 Torr data, we find a noticeable pressure dependence. This dependence is observed to increase with decreasing temperature. This finding is consistent with a termolecular reaction mechanism. It is the first experimental evidence of the pressure dependence for this rate constant. A kinetics model is constructed, and the model results agree qualitatively with our experimental data. The extrapolated rate constant of the title reaction would be faster than previously believed at conditions of the upper troposphere/lower stratosphere, suggesting that the importance of acetic acid in its impact on HO(x) chemistry is currently underestimated.