Fourier transform‐infrared studies of thin H₂SO₄/H₂O films: Formation, water uptake, and solid‐liquid phase changes

Abstract

Fourier transform‐infrared (FTIR) spectroscopy was used to examine films representative of stratospheric sulfuric acid aerosols. Thin films of sulfuric acid were formed in situ by the condensed phase reaction of SO 3 with H 2 O. FTIR spectra show that the sulfuric acid films absorb water while cooling in the presence of water vapor. Using stratospheric water pressures, the most dilute solutions observed were >40 wt % before simultaneous ice formation and sulfuric acid freezing occurred. FTIR spectra also revealed that the sulfuric acid films crystallized mainly as sulfuric acid tetrahydrate (SAT). Crystallization occurred either when the composition was about 60 wt % H 2 SO 4 or after ice formed on the films at temperatures 1–4 K below the ice frost point. Finally, we determined that the melting point for SAT depended on the background water pressure and was 216–219 K in the presence of 4 × 10 −4 Torr H 2 O. Our results suggest that once frozen, sulfuric acid aerosols in the stratosphere are likely to melt at these temperatures, 30 K colder than previously thought.