scholarly journals Aerosol hygroscopicity at high (99 to 100%) relative humidities

2010 ◽  
Vol 10 (3) ◽  
pp. 1329-1344 ◽  
Author(s):  
C. R. Ruehl ◽  
P. Y. Chuang ◽  
A. Nenes

Abstract. The hygroscopicity of an aerosol strongly influences its effects on climate and, for smaller particles, atmospheric lifetime. While many aerosol hygroscopicity measurements have been made at lower relative humidities (RH) and under cloud formation conditions (RH>100%), relatively few have been made at high RH (99 to 100%), where the Kelvin (curvature) effect is comparable to the Raoult (solute) effect. We measured the size of droplets at high RH that had formed on particles composed of one of seven compounds with dry diameters between 0.1 and 0.5 μm. We report the hygroscopicity of these compounds using a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term. For inorganic compounds, hygroscopicity could reliably be predicted using water activity data (measured in macroscopic solutions) and assuming a surface tension of pure water. In contrast, most organics exhibited a slight to mild increase in hygroscopicity with droplet diameter. This trend was strongest for sodium dodecyl sulfate (SDS), the most surface-active compound studied. The results suggest that, for single-component aerosols at high RH, partitioning of solute to the particle-air interface reduces particle hygroscopicity by reducing the bulk solute concentration. This partitioning effect is more important than the increase in hygroscopicity due to surface tension reduction. Furthermore, we found no evidence that micellization limits SDS activity in micron-sized solution droplets, as observed in macroscopic solutions. We conclude that while the high-RH hygroscopicity of inorganic compounds can be reliably predicted using readily available data, surface-activity parameters obtained from macroscopic solutions with organic solutes may be inappropriate for calculations involving micron-sized droplets.

2009 ◽  
Vol 9 (4) ◽  
pp. 15595-15640 ◽  
Author(s):  
C. R. Ruehl ◽  
P. Y. Chuang ◽  
A. Nenes

Abstract. The hygroscopicity of an aerosol largely determines its influence on climate and, for smaller particles, atmospheric lifetime. While much aerosol hygroscopicity data is available at lower relative humidities (RH) and under cloud formation conditions (RH>100%), relatively little data is available at high RH (99.2 to 99.9%). We measured the size of droplets at high RH that had formed on particles composed of one of seven compounds with dry diameters between 0.1 and 0.5 μm, and calculated the hygroscopicity of these compounds. We use a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term, to express the hygroscopicity of surface-active compounds. For inorganic compounds, hygroscopicity could reliably be predicted using water activity data and assuming a surface tension of pure water. In contrast, most organics exhibited a slight to mild increase in hygroscopicity with droplet diameter. This trend was strongest for sodium dodecyl sulfate (SDS), the most surface-active compound studied. The results suggest that partitioning of surface-active compounds away from the bulk solution, which reduces hygroscopicity, dominates any increases in hygroscopicity due to reduced surface tension. This is opposite to what is typically assumed for soluble surfactants. Furthermore, we saw no evidence that micellization limits SDS activity in micron-sized solution droplets, as observed in macroscopic solutions. These results suggest that while the high-RH hygroscopicity of inorganic compounds can be reliably predicted using readily available data, surface-activity parameters obtained from macroscopic solutions with organic solutes may be inappropriate for calculations of the hygroscopicity of micron-sized droplets.


2010 ◽  
Vol 10 (12) ◽  
pp. 5625-5639 ◽  
Author(s):  
E. O. Fors ◽  
J. Rissler ◽  
A. Massling ◽  
B. Svenningsson ◽  
M. O. Andreae ◽  
...  

Abstract. HUmic-LIke Substances (HULIS) have been identified as major contributors to the organic carbon in atmospheric aerosol. The term "HULIS" is used to describe the organic material found in aerosol particles that resembles the humic organic material in rivers and sea water and in soils. In this study, two sets of filter samples from atmospheric aerosols were collected at different sites. One set of samples was collected at the K-puszta rural site in Hungary, about 80 km SE of Budapest, and a second was collected at a site in Rondônia, Amazonia, Brazil, during the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC) biomass burning season experiment. HULIS were extracted from the samples and their hygroscopic properties were studied using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) at relative humidity (RH) <100%, and a cloud condensation nucleus counter (CCNC) at RH >100%. The H-TDMA measurements were carried out at a dry diameter of 100 nm and for RH ranging from 30 to 98%. At 90% RH the HULIS samples showed diameter growth factors between 1.04 and 1.07, reaching values of 1.4 at 98% RH. The cloud nucleating properties of the two sets of aerosol samples were analysed using two types of thermal static cloud condensation nucleus counters. Two different parameterization models were applied to investigate the potential effect of HULIS surface activity, both yielding similar results. For the K-puszta winter HULIS sample, the surface tension at the point of activation was estimated to be lowered by between 34% (47.7 mN/m) and 31% (50.3 mN/m) for dry sizes between 50 and 120 nm in comparison to pure water. A moderate lowering was also observed for the entire water soluble aerosol sample, including both organic and inorganic compounds, where the surface tension was decreased by between 2% (71.2 mN/m) and 13% (63.3 mN/m).


Author(s):  
Ashkan Davanlou ◽  
Joshua Lee ◽  
Saptarshi Basu ◽  
Ranganathan Kumar

Pressure-swirl nozzles (simplex nozzles) are used in various field applications such as aero-engines, power generation, spray painting and agricultural irrigation. For this particular nozzle, research in the past decade has dealt with the development of numerical models for predicting droplet distribution profiles. Although these results have been valuable, the experimental results have been contradictory, therefore fundamental understanding of the influence of properties in nozzle is important. This paper experimentally investigates the effect of surfactants on breakup and coalescence. Since most of the fuels and biofuels have low surface tension compared to water, a comparative analysis between a surfactant solution and a liquid fuel is imperative. For this experimental study, a simplex nozzle characterized as flow number 0.4 will be utilized. The injection pressures will range from 0.3–4Mpa while altering the surface tension from 72 to 28mN/m. By applying Phase Doppler Particle Anemometry (PDPA) which is a non-intrusive laser diagnostic technique, the differences in spray characteristics due to spray surface tension can be highlighted. The average droplet diameter decreases for a low surface tension fluid in the axial direction in comparison to pure water. The average velocity of droplets is surprisingly lower in the same spray zone. Measurements made in the radial direction show no significant changes, but at the locations close to the nozzle, water droplets have larger diameter and velocity. The results indicate the breakup and coalescence regimes have been altered when surface tension is lowered. A decrease in surface tension alters the breakup length while increasing the spray angle. Moreover, higher injection pressure shortens the breakup length and decrease in overall diameter of the droplets. By performing this experimental study the fundamentals of spray dynamics, such as spray formation, liquid breakup length, and droplet breakup regimes can be observed as a function of surface tension and how a surrogate fuel compares with a real fuel for experimental purposes. This knowledge potentially will lead to designing a better atomizer or new biofuels.


Author(s):  
Emil Chibowski ◽  
Aleksandra Szcześ ◽  
Lucyna Hołysz

Magnetic Field (MF) effects on water and dispersed systems have been studied for more than half of century. However, so far there is no complete understanding of the observed changes in the properties of studied systems if it is solely based on the classical theories of magnetic field action. In Part I of this paper we presented results of MF influence on the evaporation rate of aqueous solutions of anionic surfactant Sodium Dodecyl Sulphate (SDS) and cationic one Dodecyl Trimethylammonium Bromide (DoTAB). In this paper static magnetic field effects on the surface tension of the above-mentioned surfactants are presented. The concentrations of the solutions used were both below and above their Critical Micelle Concentration (CMC). The solutions were under the MF action for 60 min in a closed vessel and were stirred by hand every 15 min. Previously it was found that the surface tension of pure water (distilled in a quartz apparatus) decreased by 2.1 mN/m after similar the MF treatment. Moreover, the memory effect lasted longer than 60 min. In case of the surfactant solutions the surface tension changed depending both on the kind of surfactant and its concentration. Bigger changes were observed for cationic DoTAB. In the solutions below their CMC the surface tension was lower after MF treatment. However, the surface tension of DoTAB solution at CMC increased several mN/m after the MF treatment. In the solutions concentrated above the CMC, respectively, the MF effects were practically vanishing. The observed changes are discussed in detail considering the structure of the surfactant adsorbed layers and acceleration force acting on the ions which was calculated from the Lorentz equation. To our knowledge, such results are published in the literature for the first time and they should be considered as preliminary ones. More systematic experiments are needed to better understand the observed changes.


2004 ◽  
Vol 4 (6) ◽  
pp. 7667-7689 ◽  
Author(s):  
G. Kiss ◽  
H.-C. Hansson

Abstract. A simple approach is suggested here to give reliable estimates on the Raoult term of the Köhler equation when calculating critical supersaturation (Sc) for real atmospheric samples. Water activity is calculated from osmolality and thus the original Köhler equation can be applied avoiding the difficulties with unknown molecular weights, solubilities, van't Hoff factors of aerosol constituents and also the interactions in the growing droplet. First, water activity calculated from osmolality data was compared to literature values both for electrolytes and a non-electrolyte. Then the applicability of the approach was demonstrated by generating Köhler curves from osmolality derived and literature activity data as well as by using the simplified Köhler equation. Sc values calculated with the osmolality approach fitted those obtained by using literature water activity data within a relative deviation of less than 0.3%, 0.8%, 1.1% and 3.4% for sucrose, CaCl2, NaCl and H2SO4, respectively, while the corresponding errors with the simplified Köhler equation were 11%, 8.5%, 4.5% and 19% in the dry nucleus size range of 20 nm to 100 nm. Finally, the osmolality method was used to show how considerably Sc is underestimated for organic acids if complete dissociation is assumed. The method described in this paper can be applied to real atmospheric samples (aerosol extracts, fog water or cloud water) thus improving the reliability of estimates on critical supersaturation and critical droplet diameter in atmospheric modelling.


2018 ◽  
Vol 180 ◽  
pp. 02118 ◽  
Author(s):  
Václav Vinš ◽  
Jiří Hykl ◽  
Zbyněk Nikl ◽  
Miroslav Čenský ◽  
Jan Hrubý

An experimental apparatus originally developed for the measurement of surface tension of supercooled water was modified such that it allows for measurement of binary aqueous mixtures. The measuring principle based on the capillary rise technique is similar to that employed in the previous measurements with pure water [J. Hrubý et al., J. Phys. Chem. Lett. 5 (2014) 425 and V. Vinš et al., J. Phys. Chem. B 119 (2015) 5567]. The temperature dependence of the surface tension is determined from the measured height of the liquid column elevated in a vertical capillary tube with an inner diameter of 0.32 mm. The aqueous liquid rises to a height of 60 mm to 95 mm depending on the solute concentration and the temperature. Preliminary tests performed with the binary mixtures of water with methanol, ethanol, and n-propanol at various concentrations and temperatures down to –28 °C approved functionality of the measuring technique. Some difficulties, such as influence of impurities on the liquid column elevation or formation of bubbles in the liquid column, were observed. The experimental apparatus is further being modified in order to obtain more accurate data for various aqueous mixtures.


2010 ◽  
Vol 10 (12) ◽  
pp. 5663-5683 ◽  
Author(s):  
N. L. Prisle ◽  
T. Raatikainen ◽  
A. Laaksonen ◽  
M. Bilde

Abstract. Organic compounds with surfactant properties are commonly found in atmospheric aerosol particles. Surface activity can significantly influence the cloud droplet forming ability of these particles. We have studied the cloud droplet formation by two-component particles comprising one of the organic surfactants sodium octanoate, sodium decanoate, sodium dodecanoate, and sodium dodecyl sulfate, mixed with sodium chloride. Critical supersaturations were measured with a static diffusion cloud condensation nucleus counter (Wyoming CCNC-100B). Results were modeled from Köhler theory applying three different representations of surfactant properties in terms of surfactant surface partitioning and reduced droplet surface tension. We here confirm previous results for single-component organic surfactant particles, that experimental critical supersaturations are greatly underpredicted, if reduced surface tension is used while ignoring the effects of surface partitioning in droplets. Furthermore, disregarding surfactant properties by ignoring surface partitioning and assuming the constant surface tension of pure water can also lead to significant underpredictions of experimental critical supersaturations. For the mixed particles comprising less than 50% by mass of surfactant, this approach however still provides a good description of the observed droplet activation. A comprehensive account for surfactant properties, including both surface tension reduction and effects of surface partitioning in activating droplets, generally predicts experimental critical supersaturations well.


2004 ◽  
Vol 4 (8) ◽  
pp. 2107-2117 ◽  
Author(s):  
R. Sorjamaa ◽  
B. Svenningsson ◽  
T. Raatikainen ◽  
S. Henning ◽  
M. Bilde ◽  
...  

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.


2009 ◽  
Vol 9 (6) ◽  
pp. 26925-26967 ◽  
Author(s):  
E. O. Fors ◽  
J. Rissler ◽  
A. Massling ◽  
B. Svenningsson ◽  
M. O. Andreae ◽  
...  

Abstract. HUmic-LIke Substances (HULIS) have been identified as major contributors to the organic carbon in atmospheric aerosol. The term HULIS is used to describe the organic material found in aerosol particles which resembles the humic organic material in river and sea water and in soils. In this study two sets of filter samples from atmospheric aerosols were collected at different sites. One sample was collected at the K-puszta rural site in Hungary, about 80 km SE of Budapest, and a second set of samples was collected at a site in Rondônia, Amazonia, Brazil, during the LBA-SMOCC biomass burning season experiment. HULIS were extracted from the samples, and their hygroscopic properties were studied using a Hygroscopicity Tandem Differential Mobility Analyzer (H-TDMA) at relative humidity (RH) <100%, and a cloud condensation nucleus counter (CCNC) at RH >100%. The H-TDMA measurements were carried out at a dry diameter of 100 nm and for RH ranging from 30 to 98%. At 90% RH the HULIS samples showed diameter growth factors between 1.04 and 1.07, reaching values of 1.4 at 98% RH. The cloud nucleating properties of the two sets of aerosol samples were analyzed using two types of thermal static cloud condensation nucleus counters (CCNC). Two different parameterization models were used to investigate the potential effect of HULIS surface activity, both yielding similar results. For the K-puszta winter HULIS sample, the surface tension at the point of activation was estimated to be lowered by between 34% (47.7 mN/m) and 31% (50.3 mN/m) for dry sizes between 50 and 120 nm in comparison to pure water. A moderate lowering was also observed for the entire water soluble aerosol sample, including both organic and inorganic compounds, where the surface tension was decreased by between 2% (71.2 mN/m) and 13% (63.3 mN/m).


BIBECHANA ◽  
2014 ◽  
Vol 11 ◽  
pp. 103-112 ◽  
Author(s):  
Tulasi Prasad Niraula ◽  
Ajaya Bhattarai ◽  
Sujeet Kumar Chatterjee

Careful measurements of surface tension and viscosity of sodium dodecyl sulphate (SDS) in presence and absence of KCl in pure water and methanol-water mixed solvent media containing 0.1, 0.2, 0.3 and 0.4 volume fractions of methanol at 308.15 K are reported. The concentration of KCl is 0.01M. The concentration of SDS varies from 4.86×10-3 to 29.56×10-3 mol.l-1. The critical micelle concentration (cmc) increases with increase in percentage of methanol and decreases with addition of salt. DOI: http://dx.doi.org/10.3126/bibechana.v11i0.10388 BIBECHANA 11(1) (2014) 103-112


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