Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere

Mads Peter Sulbæk Andersen; Jessica Axson; Rebecca Michelsen; Ole John Nielsen; Laura Iraci

Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere

Mads Peter Sulbæk Andersen, Jessica Axson, Rebecca Michelsen, Ole John Nielsen, Laura Iraci

Kemisk Institut

Abstract

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.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry A
Vol/bind	115
Udgave nummer	17
Sider (fra-til)	4388-4396
Antal sider	9
ISSN	1089-5639
Status	Udgivet - 5 maj 2011

Citationsformater

Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere. / Andersen, Mads Peter Sulbæk; Axson, Jessica; Michelsen, Rebecca et al.

I: Journal of Physical Chemistry A, Bind 115, Nr. 17, 05.05.2011, s. 4388-4396.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

@article{8da842db986d4476b0fb84818e980564,

title = "Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere",

abstract = "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.",

author = "Andersen, {Mads Peter Sulb{\ae}k} and Jessica Axson and Rebecca Michelsen and Nielsen, {Ole John} and Laura Iraci",

year = "2011",

month = may,

day = "5",

language = "English",

volume = "115",

pages = "4388--4396",

journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "17",

}

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 Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

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

IS - 17

ER -

Solubility of Acetic Acid and Trifluoroacetic Acid in Low-Temperature (207-245 K) Sulfuric Acid Solutions: Implications for the Upper Troposphere and Lower Stratosphere

Abstract

Fingeraftryk

Citationsformater