Freezing of Dilute Aqueous-Alcohol Nanodroplets: The Effect of Molecular Structure

We investigate vapor-liquid nucleation and subsequent freezing of aqueous-alcohol nanodroplets containing 1-pentanol, 1-hexanol, and their 3-isomers. The aerosols are produced in a supersonic nozzle, where condensation and freezing are characterized by static pressure and Fourier transform Infrared (FTIR) spectroscopy measurements. At fixed water concentrations, the presence of alcohol enables particle formation at higher temperatures since both the equilibrium vapor pressure above the critical clusters and the cluster interfacial free energy are decreased relative to the pure water case. The disappearance of a small free OH peak, observed for pure water droplets, when alcohols are added and shifts in the CH peaks as a function of alcohol chain length reveal varying surface partitioning preferences of the alcohols. Changes in the FTIR spectra during freezing, as well as changes in the ice component derived from self-modeling curve resolution analysis, show that 1-hexanol and 1-pentanol perturb freezing less than their branched isomers do. This behavior may reflect the molecular footprints of the alcohols, the available surface area of the droplets, and not only alcohol solubility. The presence of alcohols also lowers the freezing temperature relative to that of pure water, but when there is clear evidence for the formation of ice, the ice nucleation rates change by less than a factor of similar to 2-3 for all cases studied.

Automated summary

This study investigates the vapor-liquid nucleation and freezing of aqueous-alcohol nanodroplets, revealing that the presence of alcohol affects particle formation temperatures and surface partitioning preferences. The freezing process is perturbed less by 1-hexanol and 1-pentanol compared to their branched isomers. Furthermore, the presence of alcohols lowers the freezing temperature relative to pure water, but ice nucleation rates change by less than a factor of 2-3 for all cases studied.