Reduction of <i>N</i>-Nitrosodimethylamine with Granular Iron and Nickel-Enhanced Iron. 2. Mechanistic Studies

Abstract

To elucidate the reduction mechanism of N-nitrosodimethylamine (NDMA) by granular iron, various electrochemical experiments using a mercury electrode were conducted. The studies included differential pulse voltammetry and exhaustive potentiostatic electrolysis. The results of the NDMA electroreduction experiments were compared with the results obtained in the column and batch experiments of Part 1 of this study. The results show that (1) electroreduction of NDMA occurs at potentials more negative than −1.3 V and this potential cannot be achieved under the conditions of the column and batch experiments and (2) different reduction products of NDMA were observed in the electrochemical tests relative to the column and batch tests. That is, dimethylamine (DMA) and nitrous oxide were formed in the electrochemical reduction experiments, whereas ammonia and DMA were produced in the column and batch experiments. The difference in product formation and more importantly the fact that the iron cannot reach the potentials required for electroreduction indicate that the reduction of NDMA on iron cannot take place by direct electron transfer. The process of catalytic hydrogenation was found to be consistent with all experimental observations and is proposed as the alternative mechanism.