Aleksandra Marsh

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic–Aqueous Aerosols

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

Group Contribution Approach To Predict the Refractive Index of Pure Organic Components in Ambient Organic Aerosol

We introduce and assess a group contribution scheme by which the refractive index (RI) (λ = 589 nm) of nonabsorbing components common to secondary organic aerosols can be predicted from the molecular formula and chemical functionality. The group contribution method is based on representative values of ratios of the molecular polarizability and molar volume of different functional groups derived from data for a training set of 234 compounds. The training set consists of 106 nonaromatic compounds common to atmospheric aerosols, 64 aromatic compounds, and 64 compounds containing halogens; a separate group contribution model is provided for each of these three classes of compound. The resulting predictive model reproduces the RIs of compounds in the training set with mean errors of ±0.58, ±0.36, and ±0.30% for the nonaromatic, aromatic, and halogen-containing compounds, respectively. We then evaluate predictions from the group contribution model for compounds with no previously reported RI, comparing values with predictions from previous treatments and with measurements from single aerosol particle experiments. We illustrate how such comparisons can be used to further refine the predictive model. We suggest that the accuracy of this model is already sufficient to better constrain the optical properties of organic aerosol of known composition.

Condensation Kinetics of Water on Amorphous Aerosol Particles

Responding to changes in the surrounding environment, aerosol particles can grow by water condensation changing rapidly in composition and changing dramatically in viscosity. The timescale for growth is important to establish for particles undergoing hydration processes in the atmosphere or during inhalation. Using an electrodynamic balance, we report direct measurements at -7.5, 0, and 20 °C of timescales for hygroscopic condensational growth on a range of model hygroscopic aerosol systems. These extend from viscous aerosol particles containing a single saccharide solute (sucrose, glucose, raffinose, or trehalose) and a starting viscosity equivalent to a glass of ∼1012 Pa·s, to nonviscous (∼10-2 Pa·s) tetraethylene glycol particles. The condensation timescales observed in this work indicate that water condensation occurs rapidly at all temperatures examined (<10 s) and for particles of all initial viscosities spanning 10-2 to 1012 Pa·s. Only a marginal delay (<1 order of magnitude) is observed for particles starting as a glass.

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

In order to quantify the kinetics of mass transfer between the gas and condensed phases in aerosol, physicochemical properties of the gas and condensed phases as well as kinetic parameters (mass/thermal accommodation coefficient) 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, temperature) using the previously-developed cylindrical electrode Electrodynamic Balance (EDB) 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 vapour 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.