Quantitative determination of volatile products formed in electrolyses of organic compounds

Article abstract of DOI:10.1021/ac00063a037

A straightforward and accurate procedure has been developed for the quantitation of volatile products that are formed from electrolyses of organic compounds. This methodology, which eliminates the need for external cold traps, utilizes an internal standard that is present in both the solution and gas phases of a gas-tight electrochemical cell. By sampling the gas and solution phases of the cell at the end of an electrolysis and by using gas chromatography to determine the quantities of the various volatile products in each phase with respect to the internal standard, one can ascertain the absolute yield of each product derived from the electrolysis of the starting material. In this paper, we present the theoretical background for this technique, including the formulation and use of experimentally measured gas chromatographic response factors, and we demonstrate the applicability of the approach for the quantitation of seven volatile products that are formed by the electrolytic reduction of 1,4-dibromobutane at a reticulated vitreous carbon cathode in dimethylformamide containing tetramethylammonium perchlorate. This method can be readily adapted to any compound whose electrolysis gives rise to volatile products.