Spontaneous Iodide Activation at the Air–Water Interface of Aqueous Droplets

We present experimental evidence that atomic and molecular iodine, I and I₂, are produced spontaneously in the dark at the air-water interface of iodide-containing droplets without any added catalysts, oxidants, or irradiation. Specifically, we observe I₃^- formation within droplets, and I₂ emission into the gas phase from NaI-containing droplets over a range of droplet sizes. The formation of both products is enhanced in the presence of electron scavengers, either in the gas phase or in solution, and it clearly follows a Langmuir-Hinshelwood mechanism, suggesting an interfacial process. These observations are consistent with iodide oxidation at the interface, possibly initiated by the strong intrinsic electric field present there, followed by well-known solution-phase reactions of the iodine atom. This interfacial chemistry could be important in many contexts, including atmospheric aerosols.