| 1. |
- Björnehohn, E., et al.
(författare)
-
Water at Interfaces
- 2016
-
Ingår i: Chemical Reviews. - : American Chemical Society (ACS). - 0009-2665 .- 1520-6890. ; 116:13, s. 7698-7726
-
Forskningsöversikt (refereegranskat)abstract
- The interfaces of neat water and aqueous solutions play a prominent role in many technological processes and in the environment. Examples of aqueous interfaces are ultrathin water films that cover most hydrophilic surfaces under ambient relative humidities, the liquid/solid interface which drives many electrochemical reactions, and the liquid/vapor interface, which governs the uptake and release of trace gases by the oceans and cloud droplets. In this article we review some of the recent experimental and theoretical advances in our knowledge of the properties of aqueous interfaces and discuss open questions and gaps in our understanding.
|
|
| 2. |
- Björneholm, Olle, et al.
(författare)
-
Deeper Insight into Depth-Profiling of Aqueous Solutions Using Photoelectron Spectroscopy
- 2014
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 118:50, s. 29333-29339
-
Tidskriftsartikel (refereegranskat)abstract
- X-ray photoelectron spectroscopy (XPS) is widely used to probe properties such as molecular stoichiometry, microscopic distributions relative to the surface by so-called depth-profiling, and molecular orientation. Such studies usually rely on the core-level photoionization cross sections being independent of molecular composition. The validity of this assumption has recently been questioned, as a number of gas-phase molecules have been shown to exhibit photon-energy-dependent nonstochiometric intensity oscillations arising from EXAFS-like modulations of the photoionization cross section. We have studied this phenomenon in trichloroethanol in both gas phase and dissolved in water. The gas-phase species exhibits pronounced intensity oscillations, similar to the ones observed for other gas-phase molecules. These oscillations are also observed for the dissolved species, implying that the effect has to be taken into account when performing depth-profiling experiments of solutions and other condensed matter systems. The similarity between the intensity oscillations for gas phase and dissolved species allows us to determine the photoelectron kinetic energy of maximum surface sensitivity, approximate to 100 eV, which lies in the range of pronounced intensity oscillations.
|
|
| 3. |
- Ekholm, Victor, et al.
(författare)
-
Anomalous surface behavior of hydrated guanidinium ions due to ion pairing
- 2018
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 148:14
-
Tidskriftsartikel (refereegranskat)abstract
- Surface affinity of aqueous guanidinium chloride (GdmCl) is compared to that of aqueous tetrapropylammonium chloride (TPACl) upon addition of sodium chloride (NaCl) or disodium sulfate (Na2SO4). The experimental results have been acquired using the surface sensitive technique X-ray photoelectron spectroscopy on a liquid jet. Molecular dynamics simulations have been used to produce radial distribution functions and surface density plots. The surface affinities of both TPA(+) and Gdm(+) increase upon adding NaCl to the solution. With the addition of Na2SO4, the surface affinity of TPA(+) increases, while that of Gdm(+) decreases. From the results of MD simulations it is seen that Gdm(+) and SO42- ions form pairs. This finding can be used to explain the decreased surface affinity of Gdm(+) when co-dissolved with SO42- ions. Since SO42- ions avoid the surface due to the double charge and strong water interaction, the Gdm(+)-SO42- ion pair resides deeper in the solutions' bulk than the Gdm(+) ions. Since TPA(+) does not form ion pairs with SO42-, the TPA(+) ions are instead enriched at the surface.
|
|
| 4. |
- Ekholm, Victor, 1989-, et al.
(författare)
-
Strong enrichment of atmospherically relevant organic ions at the aqueous interface : the role of ion pairing and cooperative effects
- 2018
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 20:42, s. 27185-27191
-
Tidskriftsartikel (refereegranskat)abstract
- Surface affinity, orientation and ion pairing are investigated in mixed and single solute systems of aqueous sodium hexanoate and hexylammonium chloride. The surface sensitive X-ray photoelectron spectroscopy technique has been used to acquire the experimental results, while the computational data have been calculated using molecular dynamics simulations. By comparing the single solute solutions with the mixed one, we observe a non-linear surface enrichment and reorientation of the organic ions with their alkyl chains pointing out of the aqueous surface. We ascribe this effect to ion paring between the charged functional groups on the respective organic ion and hydrophobic expulsion of the alkyl chains from the surface in combination with van der Waals interactions between the alkyl chains. These cooperative effects lead to a substantial surface enrichment of organic ions, with consequences for aerosol surface properties.
|
|
| 5. |
|
|
| 6. |
- Persson, Ingmar, et al.
(författare)
-
Solution chemistry in the surface region of aqueous solutions
- 2020
-
Ingår i: Pure and Applied Chemistry. - : WALTER DE GRUYTER GMBH. - 0033-4545 .- 1365-3075. ; 92:10, s. 1553-1561
-
Tidskriftsartikel (refereegranskat)abstract
- Solution chemistry is commonly regarded as the physical chemistry of reactions and chemical equilibria taking place in the bulk of a solvent, and between solutes in solution, and solids or gases in contact with the solution. Our knowledge about such reactions and equilibria in aqueous solution is very detailed such as their physico-chemical constants at varying temperature, pressure, ionic medium and strength. In this paper the solution chemistry in the surface region of aqueous solutions, down to ca. 10 angstrom below the water-air interface, will be discussed. In this region, the density and relative permittivity are significantly smaller than in the aqueous bulk strongly affecting the chemical behaviour of solutes. Surface sensitive X-ray spectroscopic methods have recently been applicable on liquids and solutions by use of liquid jets. This allows the investigation of the speciation of compounds present in the water-air interface and the surface region, a region hardly studied before. Speciation studies show overwhelmingly that neutral molecules are accumulated in the surface region, while charged species are depleted from it. It has been shown that the equilibria between aqueous bulk, surface region, solids and/or air are very fast allowing effective transport of chemicals over the aqueous surface region.
|
|
| 7. |
- Salamanca Blanco, Yina Patricia, et al.
(författare)
-
Chemical equilibria of aqueous ammonium-carboxylate systems in aqueous bulk, close to and at the water-air interface
- 2019
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 21, s. 12434-12445
-
Tidskriftsartikel (refereegranskat)abstract
- Previous studies have shown that the water-air interface and a number of water molecule layers just below it, the surface region, have significantly different physico-chemical properties, such as lower relative permittivity and density, than bulk water. The properties in the surface region of water favor weakly hydrated species as neutral molecules, while ions requiring strong hydration and shielding of their charge are disfavored. In this study the equilibria NH4+(aq) + RCOO-(aq) reversible arrow NH3(aq) + RCOOH(aq) are investigated for R = CnH2n+1, n = 0-8, as open systems, where ammonia and small carboxylic acids in the gas phase above the water surface are removed from the system by a gentle controlled flow of nitrogen to mimic the transport of volatile compounds from water droplets into air. It is shown that this non-equilibrium transport of chemicals can be sufficiently large to cause a change of the chemical content of the aqueous bulk. Furthermore, X-ray photoelectron spectroscopy (XPS) has been used to determine the relative concentration of alkyl carboxylic acids and their conjugated alkyl carboxylates in aqueous surfaces using a micro-jet. These studies confirm that neutral alkyl carboxylic acids are accumulated in the surface region, while charged species, as alkyl carboxylates, are depleted. The XPS studies show also that the hydrophobic alkyl chains are oriented upwards into regions with lower relative permittivity and density, thus perpendicular to the aqueous surface. These combined results show that there are several chemical equilibria between the aqueous bulk and the surface region. The analytical studies show that the release of mainly ammonia is dependent on its concentration in the surface region, as long as the solubility of the carboxylic acid in the surface region is sufficiently high to avoid a precipitation in/on the water-air interface. However, for n-octyl- and n-nonylcarboxylic acid the solubility is sufficiently low to cause precipitation. The combined analytical and surface speciation studies in this work show that the equilibria involving the surface region are fast. The results from this study increase the knowledge about the distribution of chemical species in the surface region at and close to the water-air interface, and the transport of chemicals from water to air in open systems.
|
|
| 8. |
- Salter, Matthew E., et al.
(författare)
-
Calcium enrichment in sea spray aerosol particles
- 2016
-
Ingår i: Geophysical Research Letters. - : Blackwell Publishing. - 0094-8276 .- 1944-8007. ; 43:15, s. 8277-8285
-
Tidskriftsartikel (refereegranskat)abstract
- Sea spray aerosol particles are an integral part of the Earth's radiation budget. To date, the inorganic composition of nascent sea spray aerosol particles has widely been assumed to be equivalent to the inorganic composition of seawater. Here we challenge this assumption using a laboratory sea spray chamber containing both natural and artificial seawater, as well as with ambient aerosol samples collected over the central Arctic Ocean during summer. We observe significant enrichment of calcium in submicrometer (<1 μm in diameter) sea spray aerosol particles when particles are generated from both seawater sources in the laboratory as well as in the ambient aerosols samples. We also observe a tendency for increasing calcium enrichment with decreasing particle size. Our results suggest that calcium enrichment in sea spray aerosol particles may be environmentally significant with implications for our understanding of sea spray aerosol, its impact on Earth's climate, as well as the chemistry of the marine atmosphere.
|
|
| 9. |
- Walz, Marie-Madeleine, et al.
(författare)
-
Alcohols at the Aqueous Surface : Chain Length and Isomer Effects
- 2016
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 18:9, s. 6648-6656
-
Tidskriftsartikel (refereegranskat)abstract
- Surface-active organic molecules at the liquid-vapor interface are of great importance in atmospheric science. Therefore, we studied the surface behavior of alcohol isomers with different chain lengths (C4-C6) in aqueous solution with surface- and chemically sensitive X-ray photoelectron spectroscopy (XPS), which reveals information about the surface structure on a molecular level. Gibbs free energies of adsorption and surface concentrations are determined from the XPS results using a standard Langmuir adsorption isotherm model. The free energies of adsorption, ranging from around -15 to -19 kJ/mol (C4-C6), scale linearly with the number of carbon atoms within the alcohols with ΔGAds/CH2 ≈ -2 kJ/mol. While for the linear alcohols, surface concentrations lie around 2.4 x 1014 molecules/cm2 at the bulk concentrations where monolayers are formed, the studied branched alcohols show lower surface concentrations of around 1.6 x 1014 molecules/cm2, both of which are in line with the molecular structure and their orientation at the interface. Interestingly, we find that there is a maximum in the surface enrichment factor for linear alcohols at low concentrations, which is not observed for the shorter branched alcohols. This is interpreted in terms of a cooperative effect, which we suggest to be the result of more effective van der Waals interactions between the linear alcohol alkyl chains at the aqueous surface, making it energetically even more favorable to reside at the liquid-vapor interface.
|
|
| 10. |
- Walz, Marie-Madeleine, et al.
(författare)
-
Surface behavior of amphiphiles in aqueous solution : a comparison between different pentanol isomers
- 2015
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 17:21, s. 14036-14044
-
Tidskriftsartikel (refereegranskat)abstract
- Position isomerism is ubiquitous in atmospheric oxidation reactions. Therefore, we have compared surface-active oxygenated amphiphilic isomers (1- and 3-pentanol) at the aqueous surface with surface- and chemically sensitive X-ray photoelectron spectroscopy (XPS), which reveals information about the surface structure on a molecular level. The experimental data are complemented with molecular dynamics (MD) simulations. A concentration-dependent orientation and solvation of the amphiphiles at the aqueous surface is observed. At bulk concentrations as low as around 100 mM, a monolayer starts to form for both isomers, with the hydroxyl groups pointing towards the bulk water and the alkyl chains pointing towards the vacuum. The monolayer (ML) packing density of 3-pentanol is approx. 70% of the one observed for 1-pentanol, with a molar surface concentration that is approx. 90 times higher than the bulk concentration for both molecules. The molecular area at ML coverage (approximate to 100 mM) was calculated to be around 32 +/- 2 angstrom(2) per molecule for 1-pentanol and around 46 +/- 2 angstrom(2) per molecule for 3-pentanol, which results in a higher surface concentration (molecules per cm(2)) for the linear isomer. In general we conclude therefore that isomers - with comparable surface activities - that have smaller molecular areas will be more abundant at the interface in comparison to isomers with larger molecular areas, which might be of crucial importance for the understanding of key properties of aerosols, such as evaporation and uptake capabilities as well as their reactivity.
|
|
