A predictive viscosity model for aqueous electrolytes and mixed organic–inorganic aerosol phases

Abstract

Aerosol viscosity is determined by mixture composition and temperature, with a key influence from relative humidity (RH) in modulating aerosol water content. Aerosol particles frequently contain mixtures of water, organic compounds, and inorganic ions, so we have extended the thermodynamics-based group-contribution model AIOMFAC-VISC to predict viscosity for aqueous electrolyte solutions and aqueous organic–inorganic mixtures. For aqueous electrolyte solutions, our new, semi-empirical approach uses a physical expression based on Eyring's absolute rate theory, and we define activation energy for viscous flow as a function of temperature, ion activities, and ionic strength. The AIOMFAC-VISC electrolyte model's ion-specific expressions were simultaneously fitted, which arguably makes this approach more predictive than that of other models. This also enables viscosity calculations for aqueous solutions containing an arbitrary number of cation and anion species, including mixtures that have never been studied experimentally. These predictions achieve an excellent level of accuracy while also providing physically meaningful extrapolations to extremely high electrolyte concentrations, which is essential in the context of microscopic aqueous atmospheric aerosols. For organic–inorganic mixtures, multiple mixing approaches were tested to couple the AIOMFAC-VISC electrolyte model with its existing aqueous organic model. We discuss the best-performing mixing models implemented in AIOMFAC-VISC for reproducing viscosity measurements of aerosol surrogate systems. We present advantages and drawbacks of different model design choices and associated computational costs of these methods, of importance for use of AIOMFAC-VISC in dynamic simulations. Finally, we demonstrate the capabilities of AIOMFAC-VISC predictions for phase-separated organic–inorganic particles equilibrated to observed temperature and relative humidity conditions from atmospheric balloon soundings. The predictions for the studied cases suggest liquid-like viscosities for an aqueous electrolyte-rich particle phase throughout the troposphere, yet a highly viscous or glassy organic-rich phase in the middle and upper troposphere.