Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal

Theo Kurtén; Jonas Elm; Nønne L. Prisle; Kurt Valentin Mikkelsen; Christopher J. Kampf; Eleanor M. Waxman; Rainer Volkamer

doi:10.1021/jp510304c

Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal

Theo Kurtén, Jonas Elm, Nønne L. Prisle, Kurt Valentin Mikkelsen, Christopher J. Kampf, Eleanor M. Waxman, Rainer Volkamer

Department of Chemistry

25 Citations (Scopus)

Abstract

We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry's law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.

Original language	English
Journal	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume	119
Issue number	19
Pages (from-to)	4509-4514
Number of pages	6
ISSN	1089-5639
DOIs	https://doi.org/10.1021/jp510304c
Publication status	Published - 14 May 2015

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Kurtén, T., Elm, J., Prisle, N. L., Mikkelsen, K. V., Kampf, C. J., Waxman, E. M., & Volkamer, R. (2015). Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 119(19), 4509-4514. https://doi.org/10.1021/jp510304c

Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal. / Kurtén, Theo; Elm, Jonas; Prisle, Nønne L. et al.

In: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Vol. 119, No. 19, 14.05.2015, p. 4509-4514.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal",

abstract = "We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry's law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.",

author = "Theo Kurt{\'e}n and Jonas Elm and Prisle, {N{\o}nne L.} and Mikkelsen, {Kurt Valentin} and Kampf, {Christopher J.} and Waxman, {Eleanor M.} and Rainer Volkamer",

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doi = "10.1021/jp510304c",

language = "English",

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T1 - Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal

AU - Kurtén, Theo

AU - Elm, Jonas

AU - Prisle, Nønne L.

AU - Mikkelsen, Kurt Valentin

AU - Kampf, Christopher J.

AU - Waxman, Eleanor M.

AU - Volkamer, Rainer

PY - 2015/5/14

Y1 - 2015/5/14

N2 - We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry's law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.

AB - We have used quantum chemical methods to investigate the molecular mechanism behind the recently reported ( Kampf , C. J. ; Environ. Sci. Technol . 2013 , 47 , 4236 - 4244 ) strong dependence of the Henry's law coefficient of glyoxal (C2O2H2) on the sulfate concentration of the aqueous phase. Although the glyoxal molecule interacts only weakly with sulfate, its hydrated forms (C2O3H4 and C2O4H6) form strong complexes with sulfate, displacing water molecules from the solvation shell and increasing the uptake of glyoxal into sulfate-containing aqueous solutions, including sulfate-containing aerosol particles. This promotes the participation of glyoxal in reactions leading to secondary organic aerosol formation, especially in regions with high sulfate concentrations. We used our computed equilibrium constants for the complexation reactions to assess the magnitude of the Henry's law coefficient enhancement and found it to be in reasonable agreement with experimental results. This indicates that the complexation of glyoxal hydrates with sulfate can explain the observed uptake enhancement.

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DO - 10.1021/jp510304c

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SN - 1089-5639

VL - 119

SP - 4509

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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 - 19

ER -

Computational study of the effect of glyoxal-sulfate clustering on the Henry's Law coefficient of glyoxal

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