Electrochemical decomposition of choline chloride based ionic liquid analogues

Ionic liquids are studied intensively for electrochemical applications and more specifically for the electrodeposition of metals. In this paper the electrochemical stability of a deep-eutectic solvent based on choline chloride and ethylene glycol is studied over longer periods of electrolysis. The formation of several decomposition products such as 2-methyl-1,3-dioxolane was observed. Possible mechanisms for the formation of these products are given: some products involve a reaction at either the anode or the cathode, while others can be explained by consecutive reactions of reaction products formed at both electrodes. A range of chlorinated products like chloromethane, dichloromethane and chloroform could be detected as well. This is remarkable as evolution of chlorine gas at the anode is not observed. The formation of the chlorinated products is ascribed to the existence of the Cl-3(-) ion in the solution. The presence of the Cl-3(-) ion was observed photometrically. The presence of chlorinated products gives rise to a larger environmental impact and higher risks for health and safety, and it questions the "greenness" of these ionic liquid analogues. To reduce the decomposition of the solvent, water and easily oxidizable acids were added as 'sacrificial agents'. Their influence on the formation of 2-methyl-1,3-dioxolane was quantified. However, the addition of the sacrificial agents did not improve the stability of the solvent. Addition of formic acid reduced the formation of 2-methyl-1,3-dioxolane but chlorinated products could still be detected. Water reduced the formation of chlorinated products.