Chemical kinetics of the reaction of the hydroxyl radical with acetic acid

The reaction between the hydroxyl radical (OH) and acetic acid (CH 3 COOH) is important in upper troposphere/lower stratosphere, its role comparable to the reaction of OH with methane in controlling the tropospheric oxidative capacity. Existing experimental data on the kinetics of this reaction show large uncertainties that have impacts on atmospheric models and our understanding of HO x chemistry. Harvard's High Pressure Flow System (HPFS) is optimized for studying gas-phase radical reactions free of heterogeneous interferences. Its ability to access a wide range of temperatures and pressures, combined with a Fourier transform infrared spectroscopy and high sensitivity for OH detection achieved via laser-induced fluorescence allows for highly accurate rate constants to be measured under atmospheric conditions. Thus, the HPFS is ideally suited for addressing the poorly understood temperature and pressure dependencies of the OH + CH 3 COOH reaction. The reaction rate for OH + CH 3 COOH is first measured at 7 Torr and found to have a strong negative temperature dependence. An Arrhenius expression of k (T) = (5.38 ± 0.28) × 10 -14 exp (740 ± 51 / T) cm 3 molecule -1 s -1 is obtained. At 93 Torr, the rate has a similar negative temperature dependence and is expressed by k (T) = (2.44 ± 0.22) × 10 -14 exp (0027 ± 24) / T)) cm 3 molecule -1 s -1 . Comparing the two data sets yields a noticeable pressure dependence that is experimentally observed for the first time. This finding is in accordance with a complex-formation mechanism. A problem in the decay plot origin limits the ability to acquire data at low temperatures. The cause of the problem is probed with isotopically-labeled experiments, kinetics experiments under different flow conditions, and data analysis. A bias in acetic acid monomer concentration due to the radial temperature gradient is the most likely explanation. The problem can be corrected by using the dimer concentration to infer the monomer concentration in the core of the flow. Conclusions and future research directions are discussed in the final chapter.