TY - JOUR

T1 - Solubility of Acetic Add and Trifluoroacetic Add in Low-Temperature (207-245 K) Sulfuric Add Solutions

T2 - Implications for the Upper Troposphere and Lower Stratosphere

AU - Andersen, Mads P. Sulbaek

AU - Axson, Jessica L.

AU - Michelsen, Rebecca R. H.

AU - Nielsen, Ole John

AU - Iraci, Laura T.

PY - 2011

Y1 - 2011

N2 - The solubility of gas-phase acetic acid (CH3COOH, HAc) and trifluoroacetic acid (CF3COOH, TFA) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (207−245 K) and acid composition (40−75 wt %, H2SO4). For both HAc and TFA, the effective Henry’s law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 103 M atm−1 in 75.0 wt % H2SO4 at 242.5 K to 3.6 × 108 M atm−1 in 40.7 wt % H2SO4 at 207.8 K. Measured values of H* for HAc range from 2.2 × 105 M atm−1 in 57.8 wt % H2SO4 at 245.0 K to 3.8 × 108 M atm−1 in 74.4 wt % H2SO4 at 219.6 K. The solubility of HAc increases with increasing H2SO4 concentration and is higher in strong sulfuric acid than in water. In contrast, the solubility of TFA decreases with increasing sulfuric acid concentration. The equilibrium concentration of HAc in UT/LS aerosol particles is estimated from our measurements and is found to be up to several orders of magnitude higher than those determined for common alcohols and small carbonyl compounds. On the basis of our measured solubility, we determine that HAc in the upper troposphere undergoes aerosol partitioning, though the role of H2SO4 aerosol particles as a sink for HAc in the upper troposphere and lower stratosphere will only be discernible under high atmospheric sulfate perturbations.

AB - The solubility of gas-phase acetic acid (CH3COOH, HAc) and trifluoroacetic acid (CF3COOH, TFA) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (207−245 K) and acid composition (40−75 wt %, H2SO4). For both HAc and TFA, the effective Henry’s law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 103 M atm−1 in 75.0 wt % H2SO4 at 242.5 K to 3.6 × 108 M atm−1 in 40.7 wt % H2SO4 at 207.8 K. Measured values of H* for HAc range from 2.2 × 105 M atm−1 in 57.8 wt % H2SO4 at 245.0 K to 3.8 × 108 M atm−1 in 74.4 wt % H2SO4 at 219.6 K. The solubility of HAc increases with increasing H2SO4 concentration and is higher in strong sulfuric acid than in water. In contrast, the solubility of TFA decreases with increasing sulfuric acid concentration. The equilibrium concentration of HAc in UT/LS aerosol particles is estimated from our measurements and is found to be up to several orders of magnitude higher than those determined for common alcohols and small carbonyl compounds. On the basis of our measured solubility, we determine that HAc in the upper troposphere undergoes aerosol partitioning, though the role of H2SO4 aerosol particles as a sink for HAc in the upper troposphere and lower stratosphere will only be discernible under high atmospheric sulfate perturbations.

U2 - 10.1021/jp200118g

DO - 10.1021/jp200118g

M3 - Journal article

VL - 115

SP - 4388

EP - 4396

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 17

ER -