经典电解分析法不适用于有机物质,因为大多数场合下,有机物质电解还原或电解氧化产物的量不可能测定。作者拟出了可以相当精确地测定含量在5.10~(-10)克分子以下的某些有机物和无机物的电解分析法。方法是根据在汞阴极或某种其他阴极上将物质(离子或分子)电解还原时,在铂阳极上同时析出当量的碘。电解进行到被分析的物质完全还原为止,这可以由电流的下降来判断。被分析物质的量由滴定在阳极上析出的碘量(用硫代硫酸钠滴定)来决定。为了使析出碘的当量与被还原物质的当量相等,阴极和阳极过程的电流效率必须达至100%。从析出碘的方面来看,这一条件即使在很大的电流密度下仍能实现。但阴极反应要达 Classical electrolytic analysis is not applicable to organic materials because in most cases it is impossible to determine the amount of electrolytic reduction or electrolytic oxidation of organic materials. The authors have developed an analytical method for the determination of certain organics and inorganics with a very accurate determination of 5.10 to (-10) moles. The method is based on the simultaneous precipitation of an equivalent amount of iodine on a platinum anode as the material (ions or molecules) is electrolytically reduced on a mercury cathode or some other cathode. The electrolysis takes place until the analyte is completely reduced, which can be judged by the drop in current. The amount of analyte is determined by titrating the amount of iodide precipitated on the anode (titrated with sodium thiosulfate). In order to equalize the equivalent amount of precipitated iodine to that of the reduced material, the current efficiency of the cathode and anode processes must be up to 100%. From the perspective of precipitation of iodine, this condition can be achieved even at high current densities. But the cathode reaction to reach