The direct electrochemical generation of I3 -via 3 I → I + 2 e can be excluded since the further precipitation of I2 via Equation 2 would require to first reach an I3 -concentration which would drive disproportionation; hence, I3 -would level off while I2 grows. Instead, in situ Raman and SAXS show steadily and concurrently evolving amounts of I3 -and I2. Based on the equilibrium constant of Equation , the concentration of I3 -is orders of magnitudes higher than the I2 concentration at all times . The generation of large amounts of I2 via precipitation (Equation ) would require extremely high I3 -concentrations, which appears unlikely.