Molecular beam scattering experiments are used to investigate reactions of SO 2 at the surface of a molten alkali carbonate eutectic at 683 K. We find that two-thirds of the SO 2 molecules that thermalize at the surface of the melt are converted to gaseous CO 2 via the reaction SO 2 ðgÞ þ CO 2− 3 → CO 2 ðgÞ þ SO 2− 3 . The CO 2 product is formed from SO 2 in less than 10 −6 s, implying that the reaction takes place in a shallow liquid region less than 100 Å deep. The reaction probability does not vary between 683 and 883 K, further implying a compensation between decreasing SO 2 residence time in the near-interfacial region and increasing reactivity at higher temperatures. These results demonstrate the remarkable efficiency of SO 2 → CO 2 conversion by molten carbonates, which appear to be much more reactive than dry calcium carbonate or wet slurries commonly used for flue gas desulfurization in coal-burning power plants.flue gas desulfurization | gas scrubbing | gas-liquid reactions | liquid surface | molecular beam scattering T he atmospheric oxidation of sulfur dioxide produced during the combustion of fossil fuels is a significant source of acid rain and of fine aerosol particles harmful to human health (1-3). In coal-burning power plants, 75-98% of the SO 2 generated by combustion is removed by reaction with wet or dry limestone, which is predominantly composed of CaCO 3 (4). The overall reaction is (5):Numerous mechanistic (6-8) and kinetic (9, 10) studies of this reaction have been conducted by using solid CaCO 3 or limestone particles, with reported values of the activation energy ranging from 10 to 150 kJ mol −1 (9, 10). This large variation is probably caused by differences in the composition and porosity of the particles, the presence or absence of water vapor, and the buildup of a product overlayer (9). On the surface of dry CaCO 3 , SO 2 → CO 2 conversion takes place via the direct transfer of O 2− from CO 2− 3 to a physisorbed SO 2 molecule (8). Adsorption of ambient water converts the solid surface into CaðOHÞðCO 3 HÞ, which has been observed to enhance SO 2 uptake (6, 7). In the wet limestone process, SO 2 reacts with H 2 O in the slurry to produce H þ and HSO − 3 ; these acidic species are neutralized by OH − and HCO − 3 from dissolution of CO 2− 3 , a process that generates CO 2 and leaves SO 2− 3 in solution (5). Oldenkamp and Margolin developed an alternative method to remove SO 2 from flue gases by employing a molten eutectic mixture of Li 2 CO 3 , Na 2 CO 3 , and K 2 CO 3 (11). This liquid-phase reagent potentially avoids the wide variations in conditions observed for solid limestone and is regenerable (11,12). When bubbling SO 2 through the carbonate melt at 800 K, nearly 100% of the SO 2 is removed for contact times as short as 0.05 s (12). In practice, this efficiency can be orders of magnitude higher than for solid CaCO 3 at the same reaction time. Measurements by van Houte and Delmon, for example, imply that only 10 −5 % of the SO 2 is removed in 0.05 s, in part because the oxidation o...