Hydrogen-Bond Breaking and Proton Exchange in Collisions of Gaseous Formic Acid with Liquid Sulfuric Acid

Gas-liquid scattering experiments provide direct observations of the fate of hydrogen-bonding molecules striking the surfaces of acidic liquids. Collisions of gaseous formic acid with concentrated sulfuric acid show that impinging monomers (HCOOH and DCOOD) scatter inelastically from the interface or become trapped by surface H2SO4. Most trapped DCOOD molecules undergo proton exchange before desorbing from the acid, indicating that gas-surface accommodation almost always leads to reaction with H2SO4 molecules. This proton transfer is not inhibited by dimerization of the formic acid: The dimers readily undergo intramolecular hydrogen bond cleavage and D-H exchange before desorbing from the acid.