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Surface Enrichment and Proton Dynamics in Aqueous Systems Studied by Photoelectron Spectroscopy
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Molecular and Condensed Matter Physics.
2018 (English)Licentiate thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Uppsala University, 2018.
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:uu:diva-341992OAI: oai:DiVA.org:uu-341992DiVA, id: diva2:1183373
Presentation
2018-03-09, Å4001, 10:00 (English)
Opponent
Supervisors
Available from: 2018-02-20 Created: 2018-02-16 Last updated: 2018-02-20
List of papers
1. Shifted Equilibria of Organic Acids and Bases in the Aqueous Surface Region
Open this publication in new window or tab >>Shifted Equilibria of Organic Acids and Bases in the Aqueous Surface Region
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2018 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 20, no 36, p. 23281-23293Article in journal (Refereed) Published
Abstract [en]

Acid-base equilibria of carboxylic acids and alkyl amines in the aqueous surface region were studied using surface-sensitive X-ray photoelectron spectroscopy and molecular dynamics simulations. Solutions of these organic compounds were examined as a function of pH, concentration and chain length to investigate the distribution of acid and base form in the surface region as compared to the aqueous bulk. Results from these experiments show that the neutral forms of the studied acid-base pairs are strongly enriched in the aqueous surface region. Moreover, we show that for species with at least four carbon atoms in their alkyl-chain, their charged forms are also found to be abundant in the surface region. Using a combination of XPS and MD results, a model is proposed that effectively describes the surface composition. Resulting absolute surface concentration estimations show clearly that the total organic mole fractions in the surface region change drastically as a function of solution pH. The origin of the observed surface phenomena, hydronium/hydroxide concentrations in the aqueous surface region and why standard chemical equations, used to describe equilibria in dilute bulk solution are not valid in the aqueous surface region, are discussed in detail. The reported results are of considerable importance especially for the detailed understanding of properties of small aqueous droplets that can be found in the atmosphere.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:uu:diva-341965 (URN)10.1039/c8cp01898g (DOI)000447370600011 ()30191936 (PubMedID)
Funder
Swedish Research Council, 2013-3940EU, Horizon 2020, 717022
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2023-10-31Bibliographically approved
2. The surface of sea spray aerosol under scrutiny: An X-ray photoelectron spectroscopy study
Open this publication in new window or tab >>The surface of sea spray aerosol under scrutiny: An X-ray photoelectron spectroscopy study
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341964 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-18
3. Temperature Dependent Surface Propensity of Halide Salts
Open this publication in new window or tab >>Temperature Dependent Surface Propensity of Halide Salts
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341963 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-25
4. Proton Transfer Closes the Intermolecular Coulombic Decay Channel in Water
Open this publication in new window or tab >>Proton Transfer Closes the Intermolecular Coulombic Decay Channel in Water
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341961 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2018-02-16
5. Signature of ultrafast proton transfer in the Auger spectrum of amorphous ice
Open this publication in new window or tab >>Signature of ultrafast proton transfer in the Auger spectrum of amorphous ice
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(English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences
Identifiers
urn:nbn:se:uu:diva-341962 (URN)
Available from: 2018-02-16 Created: 2018-02-16 Last updated: 2019-08-18

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