On the optimum conditions for the reduction of nitrate to nitrite by cadmium.

The variables of direct importance in the reduction of nitrate to nitrite by a metallic reductant such as cadmium used in a reductor column are discussed with special reference to the determination of nitrate as nitrite in very dilute solutions, e.g., natural waters. As a result of these considerations the effect of flow-rate (expressed as bed-volumes min ), pH, temperature, chloride concentration and various types of reductor cadmium on the yield of nitrite is investigated. The effect of dissolved oxygen in the sample solution on pH and cadmium concentration in the reduced solution is demonstrated. At constant pH a maximum yield of nitrite is obtained at a certain flow-rate, which is explained as the result of a rapid formation and simultaneously proceeding slow reduction of nitrite. With increasing pH this maximum is shifted to lower flow-rates, and grows broader whilst the yield at maximum approaches 100%; at pH 9.5 a yield of 99.9 +/- 0.1% is obtained. The temperature has little effect on the reduction rate in the interval 20-30 degrees but at 10 degrees the reduction is noticeably slower. Chloride ions have a strongly retarding effect on the reduction rate but the yield at maximum is not affected. Electrolytically precipitated cadmium, filings of pure cadmium or amalgamated pure cadmium all give practically the same yield at maximum though some differences in reduction rate are observed. Impure cadmium or copper-cadmium and silver-cadmium, owing to the formation of galvanic cells with higher reducing power, give a high reduction rate, which also applies to nitrite, causing a poorer yield at maximum. The practical consequences of the results are thoroughly discussed.