The effects of methanol clustering on methanol-water nucleation

The formation of subcritical methanol clusters in the vapor phase is known to complicate the analysis of nucleation measurements. Here, we investigate how this process affects the onset of binary nucleation as dilute water-methanol mixtures in nitrogen carrier gas expand in a supersonic nozzle. These are the first reported data for water-methanol nucleation in an expansion device. We start by extending an older monomer-dimer-tetramer equilibrium model to include larger clusters, relying on Helmholtz free energy differences derived from Monte Carlo simulations. The model is validated against the pressure/temperature measurements of Laksmono et al. [Phys. Chem. Chem. Phys. 13, 5855 (2011)] for dilute methanol-nitrogen mixtures expanding in a supersonic flow prior to the appearance of liquid droplets. These data are well fit when the maximum cluster size i_max is 6-12. The extended equilibrium model is then used to analyze the current data. On the addition of small amounts of water, heat release prior to particle formation is essentially unchanged from that for pure methanol, but liquid formation proceeds at much higher temperatures. Once water comprises more than ∼24 mol % of the condensable vapor, droplet formation begins at temperatures too high for heat release from subcritical cluster formation to perturb the flow. Comparing the experimental results to binary nucleation theory is challenged by the need to extrapolate data to the subcooled region and by the inapplicability of explicit cluster models that require a minimum of 12 molecules in the critical cluster.