| 1. |
- Björnehohn, E., et al.
(författare)
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Water at Interfaces
- 2016
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Ingår i: Chemical Reviews. - : American Chemical Society (ACS). - 0009-2665 .- 1520-6890. ; 116:13, s. 7698-7726
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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.
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| 2. |
- Ekholm, Victor, et al.
(författare)
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Anomalous surface behavior of hydrated guanidinium ions due to ion pairing
- 2018
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 148:14
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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.
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| 3. |
- Ekholm, Victor, 1989-, et al.
(författare)
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Strong enrichment of atmospherically relevant organic ions at the aqueous interface : the role of ion pairing and cooperative effects
- 2018
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 20:42, s. 27185-27191
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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.
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| 4. |
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| 5. |
- Marinho, Ricardo R. T., et al.
(författare)
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Ethanol Solvation in Water Studied on a Molecular Scale by Photoelectron Spectroscopy
- 2017
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 121:33, s. 7916-7923
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Tidskriftsartikel (refereegranskat)abstract
- Because of the amphiphilic properties of alcohols, hydrophobic hydration is important in the alcohol water system. In the present paper we employ X-ray photoelectron spectroscopy (XPS) to investigate the bulk and surface molecular structure of ethanol water mixtures from 0.2 to 95 mol %. The observed XPS binding energy splitting between the methyl C is and hydroxymethyl C is groups (BES_[CH3-CH2OH]) as a function of the ethanol molar percentage can be divided into different regions: one below 35 mol % with higher values (about 1.53 eV) and one starting at 60 mol % up to 95 mol % with 1.49 eV as an average value. The chemical shifts agree with previous quantum mechanics/molecular mechanics (QM/MM) calculations [Loytynoja, T.; et al. J. Phys. Chem. B 2014, 118, 13217]. According to these calculations, the BES_[CH3-CH2OH] is related to the number of hydrogen bonds between the ethanol and the surrounding molecules. As the ethanol concentration increases, the average number of hydrogen bonds decreases from 2.5 for water-rich mixtures to 2 for pure ethanol. We give an interpretation for this behavior based on how the hydrogen bonds are distributed according to the mixing ratio. Since our experimental data are surface sensitive, we propose that this effect may also be manifested at the interface. From the ratio between the XPS C is core lines intensities we infer that below 20 mol % the ethanol molecules have their hydroxyl groups more hydrated and possibly facing the solution's bulk. Between 0.1 and 14 mol %, we show the formation of an ethanol monolayer at approximately 2 mol %. Several parameters are derived for the surface region at monolayer coverage.
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| 6. |
- Schmidt, Lisa, et al.
(författare)
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Probing Phase Transitions in Organic Crystals Using Atomistic MD Simulations
- 2023
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Ingår i: ACS PHYSICAL CHEMISTRY AU. - : American Chemical Society (ACS). - 2694-2445. ; 3:1, s. 84-93
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Tidskriftsartikel (refereegranskat)abstract
- A profound understanding of the physicochemical properties of organic crystals is crucial for topics from material science to drug discovery. Using molecular dynamics (MD) simulations with a sufficiently accurate force field, microscopic insight into structure and dynamics can be obtained of materials, including liquids and biomolecules. They are a valuable complement to experimental investigations that are used routinely in drug design, but not very often for studies of organic crystals. Indeed, the often delicate interactions in organic crystals act as a sensitive probe to investigate the accuracy of force fields. Here, we study the structural, dynamic, and thermodynamic properties of 30 organic crystals using the popular general AMBER force field (GAFF). In particular, we investigate both solid-solid and solid-liquid phase transitions. Melting points were determined using extensive solid-liquid coexistence simulations. For many compounds, we detect a phase transition from an ordered to a plastic crystal in the simulations. Based on the translational and rotational dynamics of the compounds, we can rationalize the properties of the plastic crystal phase. MD simulations can therefore help to answer the important question of whether or not organic crystals have a plastic crystal phase, and if so, what are the underlying factors in the molecular structure determining that.
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| 7. |
- Walz, Marie-Madeleine, et al.
(författare)
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Alcohols at the Aqueous Surface : Chain Length and Isomer Effects
- 2016
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 18:9, s. 6648-6656
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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.
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| 8. |
- Walz, Marie-Madeleine, et al.
(författare)
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Direct Link between Structure, Dynamics, and Thermodynamics in Molten Salts
- 2019
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Ingår i: The Journal of Physical Chemistry C. - : AMER CHEMICAL SOC. - 1932-7447 .- 1932-7455. ; 123:42, s. 25596-25602
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Tidskriftsartikel (refereegranskat)abstract
- The strongly increased use of molten salts in the energy industry necessitates knowledge of their physicochemical properties on a microscopic scale to guide the development of new technology. Here, we focus on the eutectic LiCl-KCl mixture and unravel the links between structure, dynamics, and thermodynamics and investigate both mixing and temperature effects. In the mixture, for K-Cl, an elongation of the ionic bond length is accompanied by faster ion dynamics and lower Gibbs energy of activation; the opposite is true for Li-Cl. This leads to the counter-intuitive result of retarded dynamics of the lighter ion, while the heavier ion diffusion is accelerated. In contrast, higher temperatures lead to a shortening of the cation- anion distances accompanied by faster dynamics despite an increase in the Gibbs energy of activation. Ionic bond breaking happens on the picosecond timescale and is suggested to proceed through an associative substitution mechanism because of a negative entropy of activation.
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| 9. |
- Walz, Marie-Madeleine, et al.
(författare)
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Microscopic origins of conductivity in molten salts unraveled by computer simulations
- 2021
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Ingår i: Communications Chemistry. - : Springer Nature. - 2399-3669. ; 4
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Tidskriftsartikel (refereegranskat)abstract
- Molten salts are crucial materials in energy applications, such as batteries, thermal energy storage systems or concentrated solar power plants. Still, the determination and interpretation of basic physico-chemical properties like ionic conductivity, mobilities and transference numbers cause debate. Here, we explore a method for determination of ionic electrical mobilities based on non-equilibrium computer simulations. Partial conductivities are then determined as a function of system composition and temperature from simulations of molten LiF alpha Cl beta I gamma (with alpha + beta + gamma = 1). High conductivity does not necessarily coincide with high Li+ mobility for molten LiF alpha Cl beta I gamma systems at a given temperature. In salt mixtures, the lighter anions on average drift along with Li+ towards the negative electrode when applying an electric field and only the heavier anions move towards the positive electrode. In conclusion, the microscopic origin of conductivity in molten salts is unraveled here based on accurate ionic electrical mobilities and an analysis of the local structure and kinetics of the materials. Molten salt electrolytes are widely used in energy storage and conversion, but our understanding of conductivity trends remains incomplete. Here, computational approaches are used to determine ionic electrical mobilities, local structures, and kinetics, unravelling the origins of conductivity in molten lithium halide salts.
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| 10. |
- Walz, Marie-Madeleine, et al.
(författare)
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Molten alkali halides - temperature dependence of structure, dynamics and thermodynamics
- 2019
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 21:34, s. 18516-18524
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Tidskriftsartikel (refereegranskat)abstract
- The renewed interest in molten salts in the energy industry fuels the need of a thorough understanding of their physicochemical properties. Alkali halide melts are perhaps the simplest ionic liquids, but they are used as electrolytes in batteries or for thermal energy storage. Although their structure is considered to be well documented and understood, a systematic evaluation of experimental structural data reveals significant discrepancies, while there is only limited experimental information on dynamic properties. Here, we investigate structure, dynamics and thermodynamic properties of pure alkali halide melts using state-of-the-art simulation models at different temperatures. The simulations provide a consistent picture of the structure of alkali halide melts with coordination numbers that lie in between experimental numbers. The simulations reveal a strengthening of the cation-anion bonds with increasing temperature that, somewhat counter-intuitively, coincides with faster dynamics in the melts. The thermodynamic analysis unveils that structure breaking proceeds on the picosecond timescale through an associative substitution mechanism as signified by a negative entropy of activation. The results on ion pair lifetimes contribute to an improved understanding of the microscopic origin of dynamical properties, such as e.g. conductivity of salt melts. The structural analysis provided here contributes to a more coherent picture of the coordination numbers in alkali halides than what is currently available from experimental data.
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| 11. |
- Walz, Marie-Madeleine, et al.
(författare)
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Phase-Transferable Force Field for Alkali Halides
- 2018
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Ingår i: Journal of Chemical Theory and Computation. - : American Chemical Society (ACS). - 1549-9618 .- 1549-9626. ; 14:11, s. 5933-5948
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Tidskriftsartikel (refereegranskat)abstract
- A longstanding goal of computational chemistry is to predict the state of materials in all phases with a single model. This is particularly relevant for materials that are difficult or dangerous to handle or compounds that have not yet been created. Progress toward this goal has been limited, as most work has concentrated on just one phase, often determined by particular applications. In the framework of the development of the Alexandria force field, we present here new polarizable force fields for alkali halides with Gaussian charge distributions for molecular dynamics simulations. We explore different descriptions of the van der Waals interaction, like the commonly applied 12–6 Lennard-Jones (LJ), and compare it to “softer” ones, such as the 8–6 LJ, Buckingham, and a modified Buckingham potential. Our results for physicochemical properties of the gas, liquid, and solid phases of alkali halides are compared to experimental data and calculations with reference polarizable and nonpolarizable force fields. The new polarizable force field that employs a modified Buckingham potential predicts the tested properties for gas, liquid, and solid phases with a very good accuracy. In contrast to reference force fields, this model reproduces the correct crystal structures for all alkali halides at low and high temperature. Seeing that experiments with molten salts may be tedious due to high temperatures and their corrosive nature, the models presented here can contribute significantly to our understanding of alkali halides in general and melts in particular.
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| 12. |
- Walz, Marie-Madeleine, et al.
(författare)
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Surface behavior of amphiphiles in aqueous solution : a comparison between different pentanol isomers
- 2015
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 17:21, s. 14036-14044
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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.
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| 13. |
- Walz, Marie-Madeleine, et al.
(författare)
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Systematically improved melting point prediction : a detailed physical simulation model is required
- 2019
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Ingår i: Chemical Communications. - : Royal Society of Chemistry (RSC). - 1359-7345 .- 1364-548X. ; 55:80, s. 12044-12047
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Tidskriftsartikel (refereegranskat)abstract
- Accurate prediction of fundamental properties such as melting points using direct physical simulation is challenging. Here, we investigate the melting point (T-m) of alkali halides that are often considered to be the simplest category of salts. Popular force fields that have been examined for this task leave considerable room for improvement. Recently we introduced a new force field for alkali halides (WBK) as part of the Alexandria project, featuring explicit polarisation and distributed charges. This new force field significantly improves the prediction of a large set of physicochemical properties and in this contribution we show that the same is valid for the prediction of T-m. For reference, we calculated T-m using a non-polarisable force field by Joung and Cheatham (JC), and compare our results to existing literature data on the widely used Tosi-Fumi (TF) parameters. In contrast to the predictions of the WBK model, the JC force field consistently overestimates the experimental T-m, while the accuracy of the TF model strongly depends on the investigated salt. Our results show that the inclusion of more realistic physics into a force field opens up the possibility to accurately describe many physicochemical properties over a large range of temperatures, even including phase transitions.
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| 14. |
- Walz, Marie-Madeleine, et al.
(författare)
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The Surface of Ionic Liquids in Water : From an Ionic Tug of War to a Quasi-Ordered Two-Dimensional Layer
- 2024
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Ingår i: ChemPhysChem. - : Wiley-VCH Verlagsgesellschaft. - 1439-4235 .- 1439-7641. ; 25:1
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Tidskriftsartikel (refereegranskat)abstract
- The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations. Ionic liquids are interesting materials for many applications related to sustainable development, but the effects of water on their properties are insufficiently known. Using X-ray photoelectron spectroscopy and molecular dynamics simulations, we show how the surface propensity of four ionic liquids in aqueous solution vary with the molecular structure of the ions, and discuss the underlying driving forces.+image
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| 15. |
- Werner, Josephina, 1985-, et al.
(författare)
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Shifted equilibria of organic acids and bases in the aqueous surface region
- 2018
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 20:36, s. 23281-23293
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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| 16. |
- Werner, Josephina, et al.
(författare)
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Surface Partitioning in Organic-Inorganic Mixtures Contributes to the Size-Dependence of the Phase-State of Atmospheric Nanoparticles
- 2016
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 50:14, s. 7434-7442
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Tidskriftsartikel (refereegranskat)abstract
- Atmospheric particulate matter is one of the main factors governing the Earth's radiative budget, but its exact effects on the global climate are still uncertain. Knowledge on the molecular-scale surface phenomena as well as interactions between atmospheric organic and inorganic compounds is necessary for understanding the role of airborne nanoparticles in the Earth system. In this work, surface composition of aqueous model systems containing succinic acid and sodium chloride or ammonium sulfate is determined using a novel approach combining X-ray photoelectron spectroscopy, surface tension measurements and thermodynamic modeling. It is shown that succinic acid molecules are accumulated in the surface, yielding a 10-fold surface concentration as compared with the bulk for saturated succinic acid solutions. Inorganic salts further enhance this enrichment due to competition for hydration in the bulk. The surface compositions for various mixtures are parametrized to yield generalizable results and used to explain changes in surface tension. The enhanced surface partitioning implies an increased maximum solubility of organic compounds in atmospheric nanoparticles. The results can explain observations of size-dependent phase-state of atmospheric nanoparticles, suggesting that these particles can display drastically different behavior than predicted by bulk properties only.
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| 17. |
- Öhrwall, Gunnar, et al.
(författare)
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Acid-Base Speciation of Carboxylate Ions in the Surface Region of Aqueous Solutions in the Presence of Ammonium and Aminium Ions
- 2015
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Ingår i: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 119:10, s. 4033-4040
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Tidskriftsartikel (refereegranskat)abstract
- The acid base speciation of surface-active carboxylate ions in the surface region of aqueous solutions was studied with synchrotron-radiation-based photoelectron spectroscopy. The protonated form was found at an extraordinarily large fraction compared to that expected from the bulk pH. When adding salts containing the weak acid NH4+ to the solution, the fraction of the acidic form at the surface increases, and to a Much greatet extent than expected from the bulk pH of the solution. We show that ammonium ions also are overrepresented in the surface region, and propose that the interaction between the surface-active anionic carboxylates and cationic ammonium ions creates a carboxylateammonium bilayer close to the surface, which increases the probability of the protonation of the carboxylae ions. By comparing the situation when a salt of the less volatile amine diethanolatnine is used, We also show that the observed evaporation of ammonia that occurs after such an event only affects the equilibrium marginally.
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