Modeling the surface tension of complex, reactive organic–inorganic mixtures

Abstract. Atmospheric aerosols can contain thousands of organic compounds which impact aerosol surface tension, affecting aerosol properties such as cloud condensation nuclei (CCN) ability. We present new experimental data for the surface tension of complex, reactive organic-inorganic aqueous mixtures mimicking tropospheric aerosols. Each solution contained 2–6 organic compounds, including methylglyoxal, glyoxal, formaldehyde, acetaldehyde, oxalic acid, succinic acid, leucine, alanine, glycine, and serine, with and without ammonium sulfate. We test two surface tension models and find that most reactive, complex, aqueous organic mixtures which do not contain salt are well-described by a weighted Szyszkowski–Langmuir (S–L) model which was first presented by Henning et al. (2005). Two approaches for modeling the effects of salt were tested: (1) the Tuckermann approach (an extension of the Henning model with an additional explicit salt term), and (2) a new implicit method proposed here which employs experimental surface tension data obtained for each organic species in the presence of salt used with the Henning model. We recommend the use of method (2) for surface tension modeling because the Henning model (using data obtained from organic-inorganic systems) and Tuckermann approach provide similar modeling fits and goodness of fit (χ2) values, yet the Henning model is a simpler and more physical approach to modeling the effects of salt, requiring less empirically determined parameters.

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Mechanism of oxidation/deoxidation of liquid silicon: theoretical analysis and interpretation of experimental surface tension data

Journal of Crystal Growth ◽

10.1016/s0022-0248(00)00496-6 ◽

2000 ◽

Vol 217 (3) ◽

pp. 233-249 ◽

Cited By ~ 48

Author(s):

M. Ratto ◽

E. Ricci ◽

E. Arato

Keyword(s):

Surface Tension ◽

Theoretical Analysis ◽

Liquid Silicon ◽

Surface Tension Data ◽

Experimental Surface ◽

Mechanism Of Oxidation

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Systematic Optimization of Water Models Using Liquid/Vapor Surface Tension Data

10.26434/chemrxiv.8016293 ◽

2019 ◽

Author(s):

Yudong Qiu ◽

Paul S. Nerenberg ◽

Teresa Head-Gordon ◽

Lee-Ping Wang

Keyword(s):

Surface Tension ◽

Optimization Procedure ◽

Kinetic Properties ◽

Molecular Liquids ◽

Surface Tension Data ◽

Heat Of Vaporization ◽

Experimental Surface ◽

Temperature Of Maximum Density ◽

Water Models ◽

First Time

<div> <div> <div> <p>In this work we investigate whether experimental surface tension measurements, which are less sensitive to quantum and self-polarization corrections, are able to replace the usual reliance on the heat of vaporization as experimental reference data for fitting force field models of molecular liquids. To test this hypothesis we develop the fitting protocol necessary to utilize surface tension measurements in the ForceBalance optimization procedure in order to determine revised parameters for both three-point and four-point water models, TIP3P-ST and TIP4P-ST. We find that the incorporation of surface tension in the fit results in a rigid three-point model that reproduces the correct temperature of maximum density of water for the first time, but also leads to over-structuring of the liquid and less accurate transport properties. The rigid four-point TIP4P-ST model is highly accurate for a broad range of thermodynamic and kinetic properties, with similar performance compared to recently developed four- point water models. The results show surface tension to be a useful fitting property in general, especially when self-polarization corrections or nuclear quantum corrections are not readily available for correcting the heat of vaporization as is the case for other molecular liquids. </p> </div> </div> </div>

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New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

Atmospheric Chemistry and Physics ◽

10.5194/acp-11-9155-2011 ◽

2011 ◽

Vol 11 (17) ◽

pp. 9155-9206 ◽

Cited By ~ 196

Author(s):

A. Zuend ◽

C. Marcolli ◽

A. M. Booth ◽

D. M. Lienhard ◽

V. Soonsin ◽

...

Keyword(s):

Liquid Phase ◽

Functional Groups ◽

Organic Compounds ◽

Activity Coefficients ◽

Atmospheric Aerosols ◽

Atmospheric Chemistry ◽

Inorganic Ions ◽

Aqueous Mixtures ◽

Organic Functional Groups ◽

Ether Ester

Abstract. We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

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New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-11-15297-2011 ◽

2011 ◽

Vol 11 (5) ◽

pp. 15297-15416 ◽

Cited By ~ 3

Author(s):

A. Zuend ◽

C. Marcolli ◽

A. M. Booth ◽

D. M. Lienhard ◽

V. Soonsin ◽

...

Keyword(s):

Liquid Phase ◽

Functional Groups ◽

Organic Compounds ◽

Activity Coefficients ◽

Atmospheric Aerosols ◽

Atmospheric Chemistry ◽

Inorganic Ions ◽

Aqueous Mixtures ◽

Organic Functional Groups ◽

Ether Ester

Abstract. We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

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Applicability of the Gibbs Adsorption Isotherm to the analysis of experimental surface-tension data for ionic and nonionic surfactants

Advances in Colloid and Interface Science ◽

10.1016/j.cis.2017.07.018 ◽

2017 ◽

Vol 247 ◽

pp. 178-184 ◽

Cited By ~ 21

Author(s):

L. Martínez-Balbuena ◽

Araceli Arteaga-Jiménez ◽

Ernesto Hernández-Zapata ◽

César Márquez-Beltrán

Keyword(s):

Surface Tension ◽

Adsorption Isotherm ◽

Nonionic Surfactants ◽

Surface Tension Data ◽

Experimental Surface

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The role of surfactants in Köhler theory reconsidered

Atmospheric Chemistry and Physics ◽

10.5194/acp-4-2107-2004 ◽

2004 ◽

Vol 4 (8) ◽

pp. 2107-2117 ◽

Cited By ~ 173

Author(s):

R. Sorjamaa ◽

B. Svenningsson ◽

T. Raatikainen ◽

S. Henning ◽

M. Bilde ◽

...

Keyword(s):

Surface Tension ◽

Organic Compounds ◽

Inorganic Compounds ◽

Sodium Dodecyl ◽

Cloud Droplet ◽

Droplet Surface ◽

Cloud Condensation Nucleus ◽

Hygroscopic Properties ◽

Critical Supersaturation ◽

Droplet Activation

Abstract. Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is the organic compounds that are surface active i.e. tend to concentrate on droplet surface and decrease the surface tension. Gibbsian surface thermodynamics was used to find out how partitioning between droplet surface and the bulk of the droplet affects the surface tension and the surfactant bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate (SDS) was used together with sodium chloride to investigate the effect of surfactant partitioning on the Raoult effect (solute effect). While accounting for the surface to bulk partitioning is known to lead to lowered bulk surfactant concentration and thereby to increased surface tension compared to a case in which the partitioning is neglected, the present results show that the partitioning also alters the Raoult effect, and that the change is large enough to further increase the critical supersaturation and hence decrease cloud droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solutions were studied in order to study the partitioning with compounds found in the atmosphere and to find out the combined effects of dissolution and partitioning behavior. The results show that the partitioning consideration presented in this paper alters the shape of the Köhler curve when compared to calculations in which the partitioning is neglected either completely or in the Raoult effect. In addition, critical supersaturation was measured for SDS particles with dry radii of 25-60nm using a static parallel plate Cloud Condensation Nucleus Counter. The experimentally determined critical supersaturations agree very well with theoretical calculations taking the surface to bulk partitioning fully into account and are much higher than those calculated neglecting the partitioning.

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On the Calculation of Liquid–Vapor Interfacial Thickness Using Experimental Surface Tension Data

Journal of Solution Chemistry ◽

10.1007/s10953-009-9401-8 ◽

2009 ◽

Vol 38 (6) ◽

pp. 685-694 ◽

Cited By ~ 3

Author(s):

M. Najafi ◽

A. Maghari

Keyword(s):

Surface Tension ◽

Surface Tension Data ◽

Experimental Surface ◽

Liquid Vapor

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Systematic Optimization of Water Models Using Liquid/Vapor Surface Tension Data

10.26434/chemrxiv.8016293.v1 ◽

2019 ◽

Author(s):

Yudong Qiu ◽

Paul S. Nerenberg ◽

Teresa Head-Gordon ◽

Lee-Ping Wang

Keyword(s):

Surface Tension ◽

Optimization Procedure ◽

Kinetic Properties ◽

Molecular Liquids ◽

Surface Tension Data ◽

Heat Of Vaporization ◽

Experimental Surface ◽

Temperature Of Maximum Density ◽

Water Models ◽

First Time

<div> <div> <div> <p>In this work we investigate whether experimental surface tension measurements, which are less sensitive to quantum and self-polarization corrections, are able to replace the usual reliance on the heat of vaporization as experimental reference data for fitting force field models of molecular liquids. To test this hypothesis we develop the fitting protocol necessary to utilize surface tension measurements in the ForceBalance optimization procedure in order to determine revised parameters for both three-point and four-point water models, TIP3P-ST and TIP4P-ST. We find that the incorporation of surface tension in the fit results in a rigid three-point model that reproduces the correct temperature of maximum density of water for the first time, but also leads to over-structuring of the liquid and less accurate transport properties. The rigid four-point TIP4P-ST model is highly accurate for a broad range of thermodynamic and kinetic properties, with similar performance compared to recently developed four- point water models. The results show surface tension to be a useful fitting property in general, especially when self-polarization corrections or nuclear quantum corrections are not readily available for correcting the heat of vaporization as is the case for other molecular liquids. </p> </div> </div> </div>

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The role of surfactants in Köhler theory reconsidered

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-4-2781-2004 ◽

2004 ◽

Vol 4 (3) ◽

pp. 2781-2804 ◽

Cited By ~ 5

Author(s):

R. Sorjamaa ◽

T. Raatikainen ◽

A. Laaksonen

Keyword(s):

Surface Tension ◽

Organic Compounds ◽

Inorganic Compounds ◽

Cloud Condensation Nuclei ◽

Sodium Dodecyl ◽

Cloud Droplet ◽

Droplet Surface ◽

Surface Thermodynamics ◽

Hygroscopic Properties ◽

Droplet Activation

Abstract. Atmospheric aerosol particles typically consist of inorganic salts and organic material. The inorganic compounds as well as their hygroscopic properties are well defined, but the effect of organic compounds on cloud droplet activation is still poorly characterized. The focus of the present study is in the organic compounds that are surface active i.e. they concentrate on droplet surface and decrease droplet surface tension. Gibbsian surface thermodynamics were used to find out how partitioning in binary and ternary aqueous solutions affects the droplet surface tension and the droplet bulk concentration in droplets large enough to act as cloud condensation nuclei. Sodium dodecyl sulfate was used as a model compound together with sodium chloride to find out the effect the correct evaluation of surfactant partitioning has on the solute effect (Raoult effect). While the partitioning is known to lead to higher surface tension compared to a case in which partitioning is neglected, the present results show that the partitioning also alters the solute effect, and that the change is large enough to further increase the critical supersaturation and hence decrease the droplet activation. The fraction of surfactant partitioned to droplet surface increases with decreasing droplet size, which suggests that surfactants might enhance the activation of larger particles relatively more thus leading to less dense clouds. Cis-pinonic acid-ammonium sulfate aqueous solution was studied in order to relate the partitioning to more realistic atmospheric situation and to find out the combined effects of dissolution and partitioning behaviour. The results show that correct partitioning consideration alters the shape of the Köhler curve when compared to a situation in which the partitioning is neglected either completely or in the Raoult effect.

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