Evaporation of water and uptake of HCl and HBr through hexanol films at the surface of supercooled sulfuric acid.

Vacuum evaporation and molecular beam scattering experiments have been used to monitor the loss of water and dissolution of HCl and HBr in deuterated sulfuric acid at 213 K containing 0 to 100 mM hexanol. The addition of 1-hexanol to the acid creates a surface film of hexyl species. This film becomes more compact with decreasing acidity, ranging from approximately 62% to approximately 68% of maximum packing on 68 to 56 wt % D(2)SO(4), respectively. D(2)O evaporation from 68 wt % acid remains unaltered by the hexyl film, where it is most porous, but is impeded by approximately 20% from 56 and 60 wt % acid. H --> D exchange experiments further indicate that the hexyl film on 68 wt % acid enhances conversion of HCl and HBr into DCl and DBr, which is interpreted as an increase in HCl and HBr entry into the bulk acid. For this permeable hexyl film, the hydroxyl groups of surface hexanol molecules may assist uptake by providing extra sites for HCl and HBr hydrogen bonding and dissociation. In contrast, HCl --> DCl exchange in 60 wt % D(2)SO(4) at first rises with hexyl surface coverage but then drops back to the bare acid value as the hexyl species pack more tightly. HCl entry is actually diminished by the hexyl film on 56 wt % acid, where the film is most compact. These experiments reveal a transition from a porous hexanol film on 68 wt % sulfuric acid that enhances HCl and HBr uptake to one on 56 wt % acid that slightly impedes HCl and D(2)O transport.