Glyoxal and methylglyoxal Setschenow salting constants in sulfate, nitrate, and chloride solutions: measurements and Gibbs energies
Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Standard
Glyoxal and methylglyoxal Setschenow salting constants in sulfate, nitrate, and chloride solutions : measurements and Gibbs energies. / Waxman, Eleanor M.; Elm, Jonas; Kurtén, Theo; Mikkelsen, Kurt Valentin; Ziemann, Paul J.; Volkamer, Rainer.
I: Environmental Science & Technology, Bind 49, Nr. 19, 2015, s. 11500-11508.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
Harvard
APA
Vancouver
Author
Bibtex
}
RIS
TY - JOUR
T1 - Glyoxal and methylglyoxal Setschenow salting constants in sulfate, nitrate, and chloride solutions
T2 - measurements and Gibbs energies
AU - Waxman, Eleanor M.
AU - Elm, Jonas
AU - Kurtén, Theo
AU - Mikkelsen, Kurt Valentin
AU - Ziemann, Paul J.
AU - Volkamer, Rainer
PY - 2015
Y1 - 2015
N2 - Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects.
AB - Knowledge about Setschenow salting constants, KS, the exponential dependence of Henry's Law coefficients on salt concentration, is of particular importance to predict secondary organic aerosol (SOA) formation from soluble species in atmospheric waters with high salt concentrations, such as aerosols. We have measured KS of glyoxal and methylglyoxal for the atmospherically relevant salts (NH4)2SO4, NH4NO3, NaNO3, and NaCl and find that glyoxal consistently "salts-in" (KS of -0.16, -0.06, -0.065, -0.1 molality(-1), respectively) while methylglyoxal "salts-out" (KS of +0.16, +0.075, +0.02, +0.06 molality(-1)). We show that KS values for different salts are additive and present an equation for use in atmospheric models. Additionally, we have performed a series of quantum chemical calculations to determine the interactions between glyoxal/methylglyoxal monohydrate with Cl(-), NO3(-), SO4(2-), Na(+), and NH4(+) and find Gibbs free energies of water displacement of -10.9, -22.0, -22.9, 2.09, and 1.2 kJ/mol for glyoxal monohydrate and -3.1, -10.3, -7.91, 6.11, and 1.6 kJ/mol for methylglyoxal monohydrate with uncertainties of 8 kJ/mol. The quantum chemical calculations support that SO4(2-), NO3(-), and Cl(-) modify partitioning, while cations do not. Other factors such as ion charge or partitioning volume effects likely need to be considered to fully explain salting effects.
U2 - 10.1021/acs.est.5b02782
DO - 10.1021/acs.est.5b02782
M3 - Journal article
C2 - 26335375
VL - 49
SP - 11500
EP - 11508
JO - Environmental Science & Technology
JF - Environmental Science & Technology
SN - 0013-936X
IS - 19
ER -
ID: 147086145