scholarly journals Effects of surface tension time-evolution for CCN activation of a complex organic surfactant

2020 ◽  
Vol 22 (2) ◽  
pp. 271-284 ◽  
Author(s):  
Jack J. Lin ◽  
Thomas B. Kristensen ◽  
Silvia M. Calderón ◽  
Jussi Malila ◽  
Nønne L. Prisle
Keyword(s):  
Surface Tension ◽  
Time Evolution ◽  
Water Activity ◽  
Bulk Water ◽  
Organic Surfactant ◽  
Tension Time ◽  
Complex Organic

Time-evolving partitioning effects on surface tension and bulk water activity cancel out in Köhler predictions of CCN activation of mixed NAFA–NaCl particles.

scholarly journals Modeling CCN activity of chemically unresolved model HULIS, including surface tension, non-ideality, and surface partitioning

2018 ◽  
Author(s):  
Nonne L. Prisle ◽  
Bjarke Molgaard
Keyword(s):  
Surface Tension ◽  
Water Activity ◽  
Cloud Droplet ◽  
Tension Reduction ◽  
Surface Tension Reduction ◽  
Surface Partitioning ◽  
Critical Supersaturation ◽  
Surface Active ◽  
Droplet Activation ◽  
Ccn Activity

Abstract. Cloud condensation nuclei (CCN) activity of aerosol particles comprising surface active Nordic Aquatic Fulvic Acid (NAFA) and NaCl was modeled with four different approaches to account for NAFA bulk-to-surface partitioning and the combined influence of NAFA and NaCl on surface tension and water activity of activating droplets. Calculations were made for particles with dry diameters of 30–230 nm and compositions covering the full range of relative NAFA and NaCl mixing ratios. Continuous ternary parametrizations of aqueous surface tension and water activity with respect to independently varying NAFA and NaCl mass concentrations were developed from previous measurements on macroscopic bulk solutions and implemented to a Köhler model framework. This enabled comprehensive thermodynamic predictions of cloud droplet activation, including equilibrium surface partitioning, for particles comprising chemically unresolved organic NAFA mixtures. NAFA here serves as a model for surface active atmospheric humic-like substances (HULIS) and for chemically complex organic aerosol in general. Surfactant effects are gauged via predictions of a suite of properties for activating droplets, including critical supersaturation and droplet size, bulk phase composition, surface tension, Kelvin effect, and water activity. Assuming macroscopic solution properties for activating droplets leads to gross overestimations of reported experimental CCN activation, mainly by overestimating surface tension reduction from NAFA solute in droplets. Failing to account for bulk-to-surface partitioning of NAFA introduces severe biases in evaluated droplet bulk and surface composition and critical size, which here specifically affect cloud activation thermodynamics, but more generally could also impact heterogeneous chemistry on droplet surfaces. Model frameworks based on either including surface partitioning and/or neglecting surface tension reduction give similar results for both critical supersaturation and droplet properties and reproduce reported experimental CCN activity well. These perhaps counterintuitive results reflect how the bulk phase is nearly depleted in surface active organic from surface partitioning in submicron droplets with large surface area for a given bulk volume. As a result, NAFA has very little impact on surface tension and water activity at the point of droplet activation. In other words, the predicted surfactant strength of NAFA is significantly lower in sub-micron activating droplets than in macroscopic aqueous solutions of the same overall composition. These results show similar effects of chemically complex surfactants as have previously been seen only for simple surfactants with well-defined molecular properties and add to the growing appreciation of the complex role of surface activity in cloud droplet activation.

scholarly journals Widening the gap between measurement and modelling of secondary organic aerosol properties?

2010 ◽  
Vol 10 (6) ◽  
pp. 2577-2593 ◽  
Author(s):  
N. Good ◽  
D. O. Topping ◽  
J. Duplissy ◽  
M. Gysel ◽  
N. K. Meyer ◽  
...  
Keyword(s):  
Surface Tension ◽  
Water Activity ◽  
Condensation Nucleus ◽  
Organic Aerosol ◽  
Solute Concentration ◽  
Complex Model ◽  
Cloud Condensation Nucleus ◽  
Saturated Water ◽  
Cloud Activation ◽  
Ccn Activity

Abstract. The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the sub-saturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation could be achieved widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from validated and extensively used instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood and the instrumentation extensively quality assured. It is impossible to say from the results presented here due to the differences in HTDMA data whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

scholarly journals Electrolytes induce long-range orientational order and free energy changes in the H-bond network of bulk water

2016 ◽  
Vol 2 (4) ◽  
pp. e1501891 ◽  
Author(s):  
Yixing Chen ◽  
Halil I. Okur ◽  
Nikolaos Gomopoulos ◽  
Carlos Macias-Romero ◽  
Paul S. Cremer ◽  
...  
Keyword(s):  
Surface Tension ◽  
Hydrogen Bond ◽  
Second Harmonic ◽  
Orientational Order ◽  
Electrolyte Solutions ◽  
Bulk Water ◽  
Atomic Scale ◽  
Dipole Orientation ◽  
Hydrogen Bond Interactions ◽  
Bond Network

Electrolytes interact with water in many ways: changing dipole orientation, inducing charge transfer, and distorting the hydrogen-bond network in the bulk and at interfaces. Numerous experiments and computations have detected short-range perturbations that extend up to three hydration shells around individual ions. We report a multiscale investigation of the bulk and surface of aqueous electrolyte solutions that extends from the atomic scale (using atomistic modeling) to nanoscopic length scales (using bulk and interfacial femtosecond second harmonic measurements) to the macroscopic scale (using surface tension experiments). Electrolytes induce orientational order at concentrations starting at 10 μM that causes nonspecific changes in the surface tension of dilute electrolyte solutions. Aside from ion-dipole interactions, collective hydrogen-bond interactions are crucial and explain the observed difference of a factor of 6 between light water and heavy water.

scholarly journals Reactivity in interstellar ice analogs: role of the structural evolution

2018 ◽  
Vol 614 ◽  
pp. A107 ◽  
Author(s):  
P. Ghesquière ◽  
A. Ivlev ◽  
J. A. Noble ◽  
P. Theulé
Keyword(s):  
Structural Changes ◽  
Organic Molecules ◽  
Structural Evolution ◽  
Bulk Water ◽  
Pore Collapse ◽  
Water Ice ◽  
Bulk Diffusivity ◽  
Diffusion Limited ◽  
Interstellar Ice ◽  
Complex Organic

Context. The synthesis of interstellar complex organic molecules in ice involves several types of reactions between molecules and/or radicals that are usually considered to be diffusion controlled. Aims. We aim to understand the coupling between diffusion and reactivity in the interstellar ice mantle using a model binary reaction in the diffusion-limited regime. Methods. We performed isothermal kinetic laboratory experiments on interstellar ice analogs at low temperatures, using the NH3:CO2:H2O model system where reactants NH3 and CO2 have a low reaction barrier and are diluted in a water-dominated ice. Results. We found that in the diffusion-limited regime, the reaction kinetics is not determined by the intrinsic bulk diffusivity of reactants. Instead, reactions are driven by structural changes evolving in amorphous water ice, such as pore collapse and crystallization. Diffusion of reactants in this case likely occurs along the surface of (tiny) cracks generated by the structural changes. Conclusions. The reactivity driven by the structural changes breaks the conventional picture of reactant molecules/radicals diffusing in a bulk water ice. This phenomenon is expected to lead to a dramatic increase in production rates of interstellar complex organic molecules in star-forming regions.

scholarly journals Convex dynamics in Hele-Shaw cells

2002 ◽  
Vol 31 (11) ◽  
pp. 639-650 ◽  
Author(s):  
Dmitri Prokhorov ◽  
Alexander Vasil'ev
Keyword(s):  
Surface Tension ◽  
Time Evolution ◽  
Isoperimetric Inequalities ◽  
Logarithmic Capacity ◽  
Geometric Properties ◽  
Area Change ◽  
Finite Source

We study geometric properties of a contracting bubble driven by a homogeneous source at infinity and surface tension. The properties that are preserved during the time evolution are under consideration. In particular, we study convex dynamics of the bubble and prove that the rate of the area change is controlled by variation of the bubble logarithmic capacity. Next we consider injection through a single finite source and study some isoperimetric inequalities that correspond to the convex andα-convex dynamics.

scholarly journals Widening the gap between measurement and modelling of secondary organic aerosol properties?

2009 ◽  
Vol 9 (5) ◽  
pp. 22619-22657
Author(s):  
N. Good ◽  
D. O. Topping ◽  
J. Duplissy ◽  
M. Gysel ◽  
N. K. Meyer ◽  
...  
Keyword(s):  
Surface Tension ◽  
Water Activity ◽  
Condensation Nucleus ◽  
Organic Aerosol ◽  
Solute Concentration ◽  
Complex Model ◽  
Cloud Condensation Nucleus ◽  
Saturated Water ◽  
Cloud Activation ◽  
Ccn Activity

Abstract. The link between measured sub-saturated hygroscopicity and cloud activation potential of secondary organic aerosol particles produced by the chamber photo-oxidation of α-pinene in the presence or absence of ammonium sulphate seed aerosol was investigated using two models of varying complexity. A simple single hygroscopicity parameter model and a more complex model (incorporating surface effects) were used to assess the detail required to predict the cloud condensation nucleus (CCN) activity from the sub-saturated water uptake. Sub-saturated water uptake measured by three hygroscopicity tandem differential mobility analyser (HTDMA) instruments was used to determine the water activity for use in the models. The predicted CCN activity was compared to the measured CCN activation potential using a continuous flow CCN counter. Reconciliation using the more complex model formulation with measured cloud activation required widely different assumed surface tension behavior of the growing droplet; this was entirely determined by the instrument used as the source of water activity data. This unreliable derivation of the water activity as a function of solute concentration from sub-saturated hygroscopicity data indicates a limitation in the use of such data in predicting cloud condensation nucleus behavior of particles with a significant organic fraction. Similarly, the ability of the simpler single parameter model to predict cloud activation behaviour was dependent on the instrument used to measure sub-saturated hygroscopicity and the relative humidity used to provide the model input. However, agreement was observed for inorganic salt solution particles, which were measured by all instruments in agreement with theory. The difference in HTDMA data from proven instruments means that it cannot be stated with certainty the detail required to predict the CCN activity from sub-saturated hygroscopicity. In order to narrow the gap between measurements of hygroscopic growth and CCN activity the processes involved must be understood. It is impossible to say from the results presented here whether: i) Surface tension suppression occurs ii) Bulk to surface partitioning is important iii) The water activity coefficient changes significantly as a function of the solute concentration.

scholarly journals Modelling the cloud condensation nucleus activity of organic acids

2007 ◽  
Vol 7 (2) ◽  
pp. 5341-5364 ◽  
Author(s):  
Z. Varga ◽  
G. Kiss ◽  
H.-C. Hansson
Keyword(s):  
Surface Tension ◽  
Organic Acids ◽  
Water Activity ◽  
Adipic Acid ◽  
Early Phase ◽  
Carbon Number ◽  
Droplet Formation ◽  
Cloud Condensation Nucleus ◽  
Minor Effect ◽  
Critical Supersaturation

Abstract. In this study vapour pressure osmometry was used to determine water activity in solutions of organic acids. The surface tension of the solutions was also monitored in parallel and then Köhler curves were calculated for nine organic acids (oxalic, malonic, succinic, glutaric, adipic acid, maleic acid, malic acid, citric acid and pinonic acid). Surface tension depression is negligible for most of the organic acids in dilute (≤1 w/w%) solutions. Therefore, these compounds affect the supersaturation only in the beginning phase of droplet formation but not necessarily at the critical size. An exception is cis-pinonic acid which remarkably depress surface tension also in dilute (0.1 w/w%) solution and hence at the critical point. The surface tension of organic acid solutions is influenced by the solubility of the compound, the length of the carbon chain and also by the polar functional groups present in the molecule. Similarly to surface tension solubility plays an important role also in water activity: compounds with higher solubility (e.g. malonic, maleic, and glutaric acid) reduce water activity significantly in the early phase of droplet formation while less soluble acids (e.g. succinic and adipic acid) are saturated in small droplets and the solution starts diluting only in bigger droplets. As a consequence, compounds with lower solubility have a minor effect on water activity in the early phase of droplet formation. To deduce the total effect Köhler curves were calculated and critical supersaturations were determined for the organic acids using measured surface tension and water activity. It was found that critical supersaturation grew with growing carbon number. Oxalic acid had the lowest critical supersaturation in the size range studied and it was comparable to the activation of ammonium sulfate. The Sc values obtained in this study were compared to data from CCNC measurements. In most cases good agreement was found.

scholarly journals Joint effect of organic acids and inorganic salts on cloud droplet activation

2010 ◽  
Vol 10 (7) ◽  
pp. 17981-18023
Author(s):  
M. Frosch ◽  
N. L. Prisle ◽  
M. Bilde ◽  
Z. Varga ◽  
G. Kiss
Keyword(s):  
Surface Tension ◽  
Sodium Chloride ◽  
Organic Acids ◽  
Organic Acid ◽  
Water Activity ◽  
Inorganic Salt ◽  
Cloud Droplet ◽  
Surface Partitioning ◽  
Kohler Theory ◽  
Droplet Activation

Abstract. We have investigated CCN properties of internally mixed particles composed of one organic acid (oxalic acid, succinic acid, adipic acid, citric acid, cis-pinonic acid, or nordic reference fulvic acid) and one inorganic salt (sodium chloride or ammonium sulphate). Surface tension and water activity of aqueous model solutions with concentrations relevant for CCN activation were measured using a tensiometer and osmometry, respectively. The measurements were used to calculate Köhler curves, which were compared to measured critical supersaturations of particles with the same chemical compositions, determined with a cloud condensation nucleus counter. Surfactant surface partitioning was not accounted for. For the mixtures containing cis-pinonic acid or fulvic acid, a depression of surface tension was observed, but for the remaining mixtures the effect on surface tension was negligle at concentrations relevant for cloud droplet activation, and water activity was the more significant term in the Köhler equation. The surface tension depression of aqueous solutions containing both organic acid and inorganic salt was approximately the same as or smaller than that of aqueous solutions containing the same mass of the corresponding pure organic acids. Water activity was found to be highly dependent on the type and amount of inorganic salt. Sodium chloride was able to decrease water activity more than ammonium sulphate and both inorganic compounds had a higher effect on water activity than the studied organic acids, and increasing the mass ratio of the inorganic compound led to a decrease in water activity. Water activity measurements were compared to results from the E-AIM model and values estimated from both constant and variable van't Hoff factors to evaluate the performance of these approaches. The correspondence between measuments and estimates was overall good, except for highly concentrated solutions. Critical supersaturations calculated with Köhler theory based on measured water activity and surface tension, but not accounting for surface partitioning, compared well with measurements, except for the solutions containing sodium chloride or one of the more surface active organic compounds. In such cases, significantly lower values were obtained from Köhler theory than the measured critical supersaturations, suggesting that surfactant partitioning and/or an effect of sodium chloride on solubility of the organic component is important.

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