Mass Accommodation Coefficient Research Articles

A reference data set for validating vapor pressure measurement techniques: homologous series of polyethylene glycols

Abstract. To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well-established saturation vapor pressures. However, vapor pressures of semivolatile and low-volatility organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of 2. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem, we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H − (O − CH2 − CH2)n − OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10−7 to 5×10−2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows outlying data to be rejected more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressure values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggests that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about 1 order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest-accuracy data, allowing subsequent extrapolation to atmospheric temperatures.

A sensitivity study of diffusional mass transfer of gases in tropical storm hydrometeors

This paper quantifies mass transfer and diffusional uptake rates of gases in liquid and solid hydrometeors within a cyclonic system. The non-availability of transfer rates for trace gases diffusing into storm hydrometeors, particularly over polluted urban conurbations, often constrain modellers the world over; however, this is an essential requirement to quantify the scavenging rates over the region concerned. The present paper seeks to provide modellers with such rates. Further, all of the earlier studies apply only to temperate regimes, and surprisingly identical formulations are assumed even for tropical conditions. The present analysis fills this research gap and couples cloud morphology with the associated thermodynamics through Weather Research and Forecasting (WRF) runs for cyclone Chapala (27 October 2015–04 November 2015) which battered the coasts of Yemen (Skamarock et al. 2008). It was a good example for undertaking this sensitivity study because the vertical extent spanned from around 0.75 to 16 km—enabling uptake rate calculations over both droplet and ice phases. Many of the diffusing gases were polar; the dipole moment of sulphur dioxide (SO2) and water vapour (H2O) was also included using a full Lennard–Jones model to compute the binary diffusivities of these gases as they diffused into the droplets mixed with water vapour. The first-order uptake rate constants ranged from 2.08 × 10−07 to 3.44 × 10−06 (s−1) and 1.97 × 10−07 to 7.81 × 10−07 (s−1) for H2O and SO2 respectively. The rates are of the order of 10−09 (s−1) for diffusion of water vapour into ice crystals further aloft. Closely linked with the gas uptake rates is another crucial parameter—the mass accommodation coefficient, α. The most widely used values are 1 and 0.036 (Pruppacher and Klett 1998)—the chosen values are restrictive and warrants a closer look. In storm systems, the vertical extents are in the kilometre range. Chapala with a large vertical extent warrants a full profile calculation. This study shows that for H2O vapour, α values range from a low of 0.004 reaching up to 0.046, and for SO2 impacting the liquid droplets, they are 0.004 to 0.077. Using these values in cloud droplet growth equations showed large changes in the positioning of the cloud base height up to about a maximum of 30%—a classic example illustrating the coupling of microphysics with dynamics suggesting that even large-scale models should cautiously use standard un-corrected accommodation and diffusion coefficients. Over polluted environments, aerosol number concentrations are very high—several hundreds of particles in a cubic centimetre—the cumulative effect involving such large-scale scavenging ends up in causing substantive changes in the actual scavenging rates. This is likely to affect overall radiative transfer calculations and must be corrected.

Evaporation Kinetics of Polyol Droplets: Determination of Evaporation Coefficients and Diffusion Constants

AbstractIn order to quantify the kinetics of mass transfer between the gas and condensed phases in aerosol, physicochemical properties of the gas and condensed phases and kinetic parameters (mass/thermal accommodation coefficients) are crucial for estimating mass fluxes over a wide size range from the free molecule to continuum regimes. In this study, we report measurements of the evaporation kinetics of droplets of 1‐butanol, ethylene glycol (EG), diethylene glycol (DEG), and glycerol under well‐controlled conditions (gas flow rates and temperature) using the previously developed cylindrical electrode electrodynamic balance technique. Measurements are compared with a model that captures the heat and mass transfer occurring at the evaporating droplet surface. The aim of these measurements is to clarify the discrepancy in the reported values of mass accommodation coefficient (αM, equals to evaporation coefficient based on microscopic reversibility) for 1‐butanol, EG, and DEG and improve the accuracy of the value of the diffusion coefficient for glycerol in gaseous nitrogen. The uncertainties in the thermophysical and experimental parameters are carefully assessed, the literature values of the vapor pressures of these components are evaluated, and the plausible ranges of the evaporation coefficients for 1‐butanol, EG, and DEG as well as uncertainty in diffusion coefficient for glycerol are reported. Results show that αM should be greater than 0.4, 0.2, and 0.4 for EG, DEG, and 1‐butanol, respectively. The refined values are helpful for accurate prediction of the evaporation/condensation rates.

Exploring CCN droplet suppression with a higher sensitivity optical particle counter

ABSTRACTThe continuous flow thermal gradient cloud condensation nuclei counter (CCNc) is the instrument currently widely used in exploring the interactions of aerosol with water vapor in the supersaturated regime. In this study we use a CCNc with an optical particle counter (OPC) modified to twice the sensitivity of the default OPC on the standard CCNc built by DMT, Inc. The standard OPC and the modified OPC-β are used to explore the droplet growth of inorganic and organic salts and the effects of cloud condensation nuclei concentrations on the final droplet sizes. We also couple the higher sensitivity OPC-β with the continuous flow streamwise thermal gradient CCNc (CFSTGC) model to estimate the mass accommodation coefficient, α. For inorganic and organic aerosol, a mass accommodation coefficient, α >> 0.2 will yield modeled droplet diameters consistent with experimental and ambient observations. However, using higher sensitivity CCN data, the final droplet diameters of CCN appear independent of aerosol h...

Uptake of Gaseous Alkylamides by Suspended Sulfuric Acid Particles: Formation of Ammonium/Aminium Salts.

Amides represent an important class of nitrogen-containing compounds in the atmosphere that can in theory interact with atmospheric acidic particles and contribute to secondary aerosol formation. In this study, uptake coefficients (γ) of six alkylamides (C1 to C3) by suspended sulfuric acid particles were measured using an aerosol flow tube coupled to a high resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS). At 293 K and < 3% relative humidity (RH), the measured uptake coefficients for six alkylamides were in the range of (4.8-23) × 10-2. A negative dependence upon RH was observed for both N-methylformamide and N,N-dimethylformamide, likely due to decreased mass accommodation coefficients (α) at lower acidities. A negative temperature dependence was observed for N,N-dimethylformamide under < 3% RH, also consistent with the mass accommodation-controlled uptake processes. Chemical analysis of reacted sulfuric acid particles indicates that alkylamides hydrolyzed in the presence of water molecules to form ammonium or aminium. Our results suggest that multiphase uptake of amides will contribute to growth of atmospheric acidic particles and alter their chemical composition.

Direct Measurements of Gas/Particle Partitioning and Mass Accommodation Coefficients in Environmental Chambers.

Secondary organic aerosols (SOA) are a major contributor to fine particulate mass and wield substantial influences on the Earth's climate and human health. Despite extensive research in recent years, many of the fundamental processes of SOA formation and evolution remain poorly understood. Most atmospheric aerosol models use gas/particle equilibrium partitioning theory as a default treatment of gas-aerosol transfer, despite questions about potentially large kinetic effects. We have conducted fundamental SOA formation experiments in a Teflon environmental chamber using a novel method. A simple chemical system produces a very fast burst of low-volatility gas-phase products, which are competitively taken up by liquid organic seed particles and Teflon chamber walls. Clear changes in the species time evolution with differing amounts of seed allow us to quantify the particle uptake processes. We reproduce gas- and aerosol-phase observations using a kinetic box model, from which we quantify the aerosol mass accommodation coefficient (α) as 0.7 on average, with values near unity especially for low volatility species. α appears to decrease as volatility increases. α has historically been a very difficult parameter to measure with reported values varying over 3 orders of magnitude. We use the experimentally constrained model to evaluate the correction factor (Φ) needed for chamber SOA mass yields due to losses of vapors to walls as a function of species volatility and particle condensational sink. Φ ranges from 1-4.

Molecular dynamics study of octane condensation coefficient at room temperature

The condensation coefficient, αc, also called mass accommodation coefficient, of liquid octane, is assumed to be 1.0 in fluid models of thin film evaporation even though it decreases with increasing liquid temperature. The temperature range where αc=1 is valid, is yet to be fully described. In this work, the condensation coefficient of liquid octane was estimated by employing large scale equilibrium classical molecular dynamics simulations and computing the condensation probability as the ratio of the number of octane molecules that condense in the liquid phase to the number of octane molecules incident at the interface from the gas phase. The effect of the model details on the computed value of the condensation coefficient was explored by using two different parameterizations of the octane molecule, the all-atom OPLS and the united-atom TraPPE force fields. The condensation probabilities were computed in the temperature range from 290K to 350K. Bulk properties of liquid octane were also studied via molecular dynamics simulations and the persistent residence times of nearest coordination of octane molecules were determined. At 300K, the temperature of interest in electronics cooling applications, the united-atom molecular model predicted αc=0.96 and the all-atom model predicted αc=0.93. No significant temperature dependence of the condensation coefficient was observed within the studied temperature range, therefore, supporting the assumption of αc=1.0 at room temperature. The two octane models predicted similar liquid structure and condensation probabilities. Compared to the all-atom molecular model, the united-atom model was found to predict shorter residence times in the first coordination shell of bulk octane molecules. This work extends the computational prediction of octane condensation coefficient into room temperature range.

Molecular simulation of steady-state evaporation and condensation: Validity of the Schrage relationships

The accuracy, or even the validity, of the Schrage relationships expressing the rate of evaporation and condensation in terms of local interfacial thermodynamics properties and the mass accommodation coefficient is a subject of significant discussion. In this work, we carry out molecular dynamics (MD) simulations of evaporation and condensation of fluid Ar in a nanochannel. By adjusting the temperature difference, ΔT, between the evaporating and condensing surfaces, we control the steady-state evaporation and condensation fluxes (JMD). We find that across a wide ΔT range studied, JMD is always in excellent agreement with the prediction from the exact Schrage relationships. Furthermore, if the temperature difference between the two liquid surfaces in the nanochannel is less than ∼20% of the average absolute temperature, we find that both energy and mass fluxes at the interface are proportional to ΔT. Our analysis indicates that in the case of steady-state evaporation and condensation processes, the exact Schrage relationships satisfy the conservation of mass, momentum and energy, and provides accurate predictions of the rates of the associated processes.

Estimates of the organic aerosol volatility in a boreal forest using two independent methods

Abstract. The volatility distribution of secondary organic aerosols that formed and had undergone aging – i.e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase – was characterized in a boreal forest environment of Hyytiälä, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40 % of the organics in particles were semi-volatile, 34 % were low-volatility organics and 26 % were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (ΔHVAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol−1 were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m∕z 43 (f43) and m∕z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when ΔHVAP = 80 kJ mol−1 was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16 % (R2) of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.

The effect of viscosity and diffusion on the HO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; uptake by sucrose and secondary organic aerosol particles

Abstract. We report the first measurements of HO2 uptake coefficients, γ, for secondary organic aerosol (SOA) particles and for the well-studied model compound sucrose which we doped with copper(II). Above 65 % relative humidity (RH), γ for copper(II)-doped sucrose aerosol particles equalled the surface mass accommodation coefficient α = 0.22 ± 0.06, but it decreased to γ = 0.012 ± 0.007 upon decreasing the RH to 17 %. The trend of γ with RH can be explained by an increase in aerosol viscosity and the contribution of a surface reaction, as demonstrated using the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). At high RH the total uptake was driven by reaction in the near-surface bulk and limited by mass accommodation, whilst at low RH it was limited by surface reaction. SOA from two different precursors, α-pinene and 1,3,5-trimethylbenzene (TMB), was investigated, yielding low uptake coefficients of γ &lt; 0.001 and γ = 0.004 ± 0.002, respectively. It is postulated that the larger values measured for TMB-derived SOA compared to α-pinene-derived SOA are either due to differing viscosity, a different liquid water content of the aerosol particles, or an HO2 + RO2 reaction occurring within the aerosol particles.

Phase State and Saturation Vapor Pressure of Submicron Particles of meso-Erythritol at Ambient Conditions.

meso-Erythritol is a sugar alcohol identified in atmospheric aerosol particles. In this work, evaporation of submicron-sized particles of meso-erythritol was studied in a TDMA system including a laminar flow tube under dry conditions at five temperatures (278-308 K) and ambient pressure. A complex behavior was observed and attributed to the formation of particles of three different phase states: (1) crystalline, (2) subcooled liquid or amorphous, and (3) mixed. With respect to saturation vapor pressure, the subcooled liquid and amorphous states are treated to be the same. The particle phase state was linked to initial particle size and flow tube temperature. Saturation vapor pressures of two phase states attributed to the crystalline and subcooled liquid state respectively are reported. Our results suggest a mass accommodation coefficient close to one for both states.

Experimental evidence supporting the insensitivity of cloud droplet formation to the mass accommodation coefficient for condensation of water vapor to liquid water

AbstractThe mass accommodation coefficient for uptake of water vapor to liquid water, αM, has been constrained using photoacoustic measurements of aqueous absorbing aerosol. Measurements performed over a range of relative humidities and pressures were compared to detailed model calculations treating coupled heat and mass transfer occurring during photoacoustic laser heating cycles. The strengths and weaknesses of this technique are very different to those for droplet growth/evaporation experiments that have typically been applied to these measurements, making this a useful complement to existing studies. Our measurements provide robust evidence that αM is greater than 0.1 for all humidities tested and greater than 0.3 for data obtained at relative humidities greater than 88% where the aerosol surface was most like pure water. These values of αM are above the threshold at which kinetic limitations are expected to impact the activation and growth of aerosol particles in warm cloud formation.

Accurate Measurements of Aerosol Hygroscopic Growth over a Wide Range in Relative Humidity

Using a comparative evaporation kinetics approach, we describe a new and accurate method for determining the equilibrium hygroscopic growth of aerosol droplets. The time-evolving size of an aqueous droplet, as it evaporates to a steady size and composition that is in equilibrium with the gas phase relative humidity, is used to determine the time-dependent mass flux of water, yielding information on the vapor pressure of water above the droplet surface at every instant in time. Accurate characterization of the gas phase relative humidity is provided from a control measurement of the evaporation profile of a droplet of know equilibrium properties, either a pure water droplet or a sodium chloride droplet. In combination, and by comparison with simulations that account for both the heat and mass transport governing the droplet evaporation kinetics, these measurements allow accurate retrieval of the equilibrium properties of the solution droplet (i.e., the variations with water activity in the mass fraction of solute, diameter growth factor, osmotic coefficient or number of water molecules per solute molecule). Hygroscopicity measurements can be made over a wide range in water activity (from >0.99 to, in principle, <0.05) on time scales of <10 s for droplets containing involatile or volatile solutes. The approach is benchmarked for binary and ternary inorganic solution aerosols with typical uncertainties in water activity of <±0.2% at water activities >0.9 and ∼±1% below 80% RH, and maximum uncertainties in diameter growth factor of ±0.7%. For all of the inorganic systems examined, the time-dependent data are consistent with large values of the mass accommodation (or evaporation) coefficient (>0.1).

Carbon Density Is an Indicator of Mass Accommodation Coefficient of Water on Organic-Coated Water Surface.

The condensational growth of a water droplet follows water vapor accommodation and is described by the mass accommodation coefficient, α. To determine α for droplets coated by straight chain and branched alcohols, we perform molecular dynamics simulations with umbrella sampling and direct impinging. The free energy profiles of water from gas phase to bulk water coated by organic are estimated by the former method. These free energy profiles exhibit a barrier to accommodation in the monolayers containing alcohols with zero and one-level of branching. However, the barrier is not observed for monolayers containing alcohols with two-levels of branching. These profiles and friction coefficients estimated from simulation are used to calculate α from the transition state and Grote-Hynes theory. Results are compared with sticking probabilities estimated from direct impinging simulations, and their differences are interpreted through processes included in each theory. At a low surface coverage of these surface active molecules, the underlying bulk solution is exposed and the resistance to vapor accommodation is reduced. We estimate the carbon density in water surfaces coated by straight-chain alcohols, branched alcohols, and straight-chain fatty acids used in study by Takahama and Russell,1 and show that this quantity is related monotonically to the mass accommodation coefficient.

Organics Substantially Reduce HO2 Uptake onto Aerosols Containing Transition Metal ions.

A HO2 mass accommodation coefficient of α = 0.23 ± 0.07 was measured onto submicron copper(II)-doped ammonium sulfate aerosols at a relative humidity of 60 ± 3%, at 293 ± 2 K and at an initial HO2 concentration of ∼ 1 × 10(9) molecules cm(-3) by using an aerosol flow tube coupled to a sensitive fluorescence assay by gas expansion (FAGE) HO2 detection system. The effect upon the HO2 uptake coefficient γ of adding different organic species (malonic acid, citric acid, 1,2-diaminoethane, tartronic acid, ethylenediaminetetraacetic acid (EDTA), and oxalic acid) into the copper(II)-doped aerosols was investigated. The HO2 uptake coefficient decreased steadily from the mass accommodation value to γ = 0.008 ± 0.009 when EDTA was added in a one-to-one molar ratio with the copper(II) ions, and to γ = 0.003 ± 0.004 when oxalic acid was added into the aerosol in a ten-to-one molar ratio with the copper(II). EDTA binds strongly to copper(II) ions, potentially making them unavailable for catalytic destruction of HO2, and could also be acting as a surfactant or changing the viscosity of the aerosol. The addition of oxalic acid to the aerosol potentially forms low-volatility copper-oxalate complexes that reduce the uptake of HO2 either by changing the viscosity of the aerosol or by causing precipitation out of the aerosol forming a coating. It is likely that there is a high enough oxalate to copper(II) ion ratio in many types of atmospheric aerosols to decrease the HO2 uptake coefficient. No observable change in the HO2 uptake coefficient was measured when the other organic species (malonic acid, citric acid, 1,2-diaminoethane, and tartronic acid) were added in a ten-to-one molar ratio with the copper(II) ions.

Determining Aerosol Volatility Parameters Using a “Dual Thermodenuder” System: Application to Laboratory-Generated Organic Aerosols

Thermodenuders (TD) are a tool widely used for measuring aerosol volatility in the laboratory and field. Extracting the parameters that dictate organic aerosol volatility from TD data is challenging because gas-particle partitioning rarely reaches equilibrium inside a TD operating under atmospheric conditions, thus a wide variety of parameter sets can explain observed evaporation. Component volatilities (as represented by saturation vapor pressure, Csat), cannot be directly extracted due to uncertainties in potential limitations to mass transfer (represented by mass accommodation coefficient, α) and components’ enthalpies of evaporation (ΔHvap). To address these limitations, we have developed a “dual TD” experimental approach in which one line uses a temperature-stepping TD (TS-TD) with a relatively long residence time (RT) and the other operates isothermally at variable residence time (VRT-TD). Data from this approach are used in tandem with an optimizing evaporation kinetics model to extract the values ...

Measurements of the HO2 uptake coefficients onto single component organic aerosols.

Measurements of HO2 uptake coefficients (γ) were made onto a variety of organic aerosols derived from glutaric acid, glyoxal, malonic acid, stearic acid, oleic acid, squalene, monoethanol amine sulfate, monomethyl amine sulfate, and two sources of humic acid, for an initial HO2 concentration of 1 × 10(9) molecules cm(-3), room temperature and at atmospheric pressure. Values in the range of γ < 0.004 to γ = 0.008 ± 0.004 were measured for all of the aerosols apart from the aerosols from the two sources of humic acid. For humic acid aerosols, uptake coefficients in the range of γ = 0.007 ± 0.002 to γ = 0.09 ± 0.03 were measured. Elevated concentrations of copper (16 ± 1 and 380 ± 20 ppb) and iron (600 ± 30 and 51 000 ± 3000 ppb) ions were measured in the humic acid atomizer solutions compared to the other organics that can explain the higher uptake values measured. A strong dependence upon relative humidity was also observed for uptake onto humic acid, with larger uptake coefficients seen at higher humidities. Possible hypotheses for the humidity dependence include the changing liquid water content of the aerosol, a change in the mass accommodation coefficient or in the Henry's law constant.

Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.

We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment.

A Laser Trapping-Spectroscopy Study on Mass Transfer Processes Across a Single Micro-Droplet/Air Interface

Clouds regulate the earth's energy balance by reflecting and scattering solar radiation and by absorbing the earth's infrared radiation. The fundamental knowledge about mass transfer processes across a micro-droplet/air interface is very important to give mathematical equations that describe the growth process of clouds for climate models. So far, experimental studies on the condensation growth of water droplets have been conducted by using either an aerosol flow tube or a vibrating orifice aerosol generator. However, the mass accommodation coefficients evaluated by such techniques are very scattered and, therefore, the detailed mechanisms of condensation growth of micrometer-sized water droplets are still controversial. The primary reason for this is difficulties in observing the growth processes of single water droplets in air. In this study, we demonstrate a novel approach for in situ observation of the evaporation and condensation processes of single water droplets levitated in air by means of a laser trapping technique.

Suppression in droplet growth kinetics by the addition of organics to sulfate particles

AbstractAerosol‐cloud interactions are affected by the rate at which water vapor condenses onto particles during cloud droplet growth. Changes in droplet growth rates can impact cloud droplet number and size distribution. The current study investigated droplet growth kinetics of acidic and neutral sulfate particles which contained various amounts and types of organic compounds, from model compounds (carbonyls) to complex mixtures (α‐pinene secondary organic aerosol and diesel engine exhaust). In most cases, the formed droplet size distributions were shifted to smaller sizes relative to control experiments (pure sulfate particles), due to suppression in droplet growth rates in the cloud condensation nuclei counter. The shift to smaller droplets correlated with increasing amounts of organic material, with the largest effect observed for acidic seed particles at low relative humidity. For all organics incorporated onto acidic particles, formation of high molecular weight compounds was observed, probably by acid‐catalyzed Aldol condensation reactions in the case of carbonyls. To test the reversibility of this process, carbonyl experiments were conducted with acidic particles exposed to higher relative humidity. High molecular weight compounds were not measured in this case and no shift in droplet sizes was observed, suggesting that high molecular weight compounds are the species affecting the rate of water uptake. While these results provide laboratory evidence that organic compounds can slow droplet growth rates, the modeled mass accommodation coefficient of water on these particles (α &gt; 0.1) indicates that this effect is unlikely to significantly affect cloud properties, consistent with infrequent field observations of slower droplet growth rates.