TY - JOUR
T1 - Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere
AU - Andersen, Mads Peter Sulbæk
AU - Axson, Jessica
AU - Michelsen, Rebecca
AU - Nielsen, Ole John
AU - Iraci, Laura
PY - 2011/5/5
Y1 - 2011/5/5
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 Henrys law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 103 M atm1 in 75.0 wt % H2SO 4 at 242.5 K to 3.6 × 108 M atm1 in 40.7 wt % H2SO4 at 207.8 K. Measured values of H* for HAc range from 2.2 × 105 M atm1 in 57.8 wt % H 2SO4 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 Henrys law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 103 M atm1 in 75.0 wt % H2SO 4 at 242.5 K to 3.6 × 108 M atm1 in 40.7 wt % H2SO4 at 207.8 K. Measured values of H* for HAc range from 2.2 × 105 M atm1 in 57.8 wt % H 2SO4 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.
M3 - Journal article
SN - 1089-5639
VL - 115
SP - 4388
EP - 4396
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 17
ER -