Thermodynamic consistency of Raoult’s Law and Henry’s Law approaches for multiphase organic aerosol partitioning

Partitioning of semivolatile organic compounds between gas, organic aerosol, and aqueous aerosol phases has been described in atmospheric models using Raoult’s Law and/or Henry’s Law, with activity coefficients accounting for nonideal behavior in the aerosol solutions. Raoult’s Law and Henry’s Law are thermodynamically consistent with each other as long as the parameters defining their different reference states are accurately known. Unfortunately, saturation vapor pressures, Henry’s law constants, and activity coefficients for organic aerosol compounds must typically be estimated. As a result, thermodynamic inconsistencies can arise when using Raoult’s and Henry’s Law approaches together due to errors in estimation methods. A test of predicted partitioning parameters for representative semivolatile organics suggests overall errors of at least an order of magnitude. Box model simulations with a simplified partitioning scenario demonstrate that these estimation errors can significantly alter partitioning for many compounds and, more importantly, that thermodynamic inconsistencies will lead to even greater errors than those due solely to uncertain parameters. To avoid these errors, a common reference state should be used to define equilibrium among all phases, improved estimation methods and measurements should continue to be pursued, and alternative reference states that better represent typical organic aerosol mixtures should be explored.