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Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension

Werner, Josephina; Julin, Jan; Dalirian, Maryam; Prisle, Nonne L.; Öhrwall, Gunnar LU ; Persson, Ingmar; Bjorneholm, Olle and Riipinen, Ilona (2014) In Physical Chemistry Chemical Physics 16(39). p.21486-21495
Abstract
The water vapor interface of aqueous solutions of succinic acid, where pH values and bulk concentrations were varied, has been studied using surface sensitive X-ray photoelectron spectroscopy (XPS) and molecular dynamics (MD) simulations. It was found that succinic acid has a considerably higher propensity to reside in the aqueous surface region than its deprotonated form, which is effectively depleted from the surface due to the two strongly hydrated carboxylate groups. From both XPS experiments and MD simulations a strongly increased concentration of the acid form in the surface region compared to the bulk concentration was found and quantified. Detailed analysis of the surface of succinic acid solutions at different bulk concentrations... (More)
The water vapor interface of aqueous solutions of succinic acid, where pH values and bulk concentrations were varied, has been studied using surface sensitive X-ray photoelectron spectroscopy (XPS) and molecular dynamics (MD) simulations. It was found that succinic acid has a considerably higher propensity to reside in the aqueous surface region than its deprotonated form, which is effectively depleted from the surface due to the two strongly hydrated carboxylate groups. From both XPS experiments and MD simulations a strongly increased concentration of the acid form in the surface region compared to the bulk concentration was found and quantified. Detailed analysis of the surface of succinic acid solutions at different bulk concentrations led to the conclusion that succinic acid saturates the aqueous surface at high bulk concentrations. With the aid of MD simulations the thickness of the surface layer could be estimated, which enabled the quantification of surface concentration of succinic acid as a multiple of the known bulk concentration. The obtained enrichment factors were successfully used to model the surface tension of these binary aqueous solutions using two different models that account for the surface enrichment. This underlines the close correlation of increased concentration at the surface relative to the bulk and reduced surface tension of aqueous solutions of succinic acid. The results of this study shed light on the microscopic origin of surface tension, a macroscopic property. Furthermore, the impact of the results from this study on atmospheric modeling is discussed. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
16
issue
39
pages
21486 - 21495
publisher
Royal Society of Chemistry
external identifiers
  • wos:000343072900050
  • scopus:84907829341
ISSN
1463-9084
DOI
10.1039/c4cp02776k
language
English
LU publication?
yes
id
b9f93519-0048-4293-ab2d-45a0923f7faa (old id 4784087)
date added to LUP
2014-11-21 12:10:51
date last changed
2017-01-01 06:17:38
@article{b9f93519-0048-4293-ab2d-45a0923f7faa,
  abstract     = {The water vapor interface of aqueous solutions of succinic acid, where pH values and bulk concentrations were varied, has been studied using surface sensitive X-ray photoelectron spectroscopy (XPS) and molecular dynamics (MD) simulations. It was found that succinic acid has a considerably higher propensity to reside in the aqueous surface region than its deprotonated form, which is effectively depleted from the surface due to the two strongly hydrated carboxylate groups. From both XPS experiments and MD simulations a strongly increased concentration of the acid form in the surface region compared to the bulk concentration was found and quantified. Detailed analysis of the surface of succinic acid solutions at different bulk concentrations led to the conclusion that succinic acid saturates the aqueous surface at high bulk concentrations. With the aid of MD simulations the thickness of the surface layer could be estimated, which enabled the quantification of surface concentration of succinic acid as a multiple of the known bulk concentration. The obtained enrichment factors were successfully used to model the surface tension of these binary aqueous solutions using two different models that account for the surface enrichment. This underlines the close correlation of increased concentration at the surface relative to the bulk and reduced surface tension of aqueous solutions of succinic acid. The results of this study shed light on the microscopic origin of surface tension, a macroscopic property. Furthermore, the impact of the results from this study on atmospheric modeling is discussed.},
  author       = {Werner, Josephina and Julin, Jan and Dalirian, Maryam and Prisle, Nonne L. and Öhrwall, Gunnar and Persson, Ingmar and Bjorneholm, Olle and Riipinen, Ilona},
  issn         = {1463-9084},
  language     = {eng},
  number       = {39},
  pages        = {21486--21495},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {Succinic acid in aqueous solution: connecting microscopic surface composition and macroscopic surface tension},
  url          = {http://dx.doi.org/10.1039/c4cp02776k},
  volume       = {16},
  year         = {2014},
}