The electrolytic production of peroxydisulfuric acid using periodically reversed direct current and alternating current superimposed on direct current

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1956
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Virginia Polytechnic Institute
Abstract

It was the purpose of this investigation to study the effect of varying the direct to reverse time ratio of periodically-reversed, direct current from 1.0 to 20.0 at an anode current density of 4.5 amperes per square centimeter, and to study the effect of alternating current of 60, 240, and 500 cycles per second, 0.2 to 4.5 amperes per square centimeter, superimposed on direct current on the electrolytic production of peroxydisulfuric acid.

Electrolyses of 200 milliliters of sulfuric acid of specific gravity 1.4, at a temperature of 5 to 10 °C were performed with direct current. The anode current density was varied. The surface area of platinum anode and lead cathode was 2.0 and 221.8 square centimeters, respectively. For one hour of electrolysis, the yields were 7.9, 14.0, 20.2, and 22.9 grams of peroxydisulfuric acid at the anode current density of 1.5, 3.0, 4.5, and 6.0 amperes per square centimeter, respectively. The current efficiencies corresponding to these anode current densities were 85.0, 77.0, 61.5, and 53.4 per cent. The results showed that the yield was increased and the current efficiency was decreased with increase in the anode current density.

Electrolysis of the same concentration and volume of sulfuric acid using periodically-reversed, direct current yielded 14.2 grams at an anode current density of 4.5 amperes per square centimeter and at a temperature of 5 to 8 °C. The time of electrolysis was one hour and the time ratio of direct to reverse electrolysis was 20. The current efficiency obtained under these conditions was 42.6 per cent. Decreasing the direct to reverse time ratio gave lower yields and current efficiencies. Apparently, there is no advantage in using periodically-reversed, direct current over the use of direct current for this reaction under the above experimental conditions.

Electrolyses of 200 milliliters of sulfuric acid of the same concentration were performed with 60 cycles per second, alternating current superimposed on direct current. The direct current density was 4.5 amperes per square centimeter for the ten tests, but the surface area of the platinum anode was changed from two to one square centimeter and the direct current was decreased from 9.0 to 4.5 amperes. The current efficiency decreased sharply from 61.5 to approximately 31.0 per cent as the ratio of peak alternating to direct current increased from zero to 0.2 and then it remained constant until the ratio reached one. The current efficiency decreased suddenly to almost zero when the ratio was greater than one.

The same sulfuric acid was electrolyzed under the same experimental conditions with 240 and 500 cycles per second, alternating current superimposed on direct current. Both direct and alternating anode current densities were varied. The direct current density was 2.2 and 4.5 amperes per square centimeter. The current efficiencies obtained during these tests were almost the same as that obtained with 60 cycles per second, alternating current within a specific limit of the ratio of peak alternating to direct current. The ratio of peak alternating current to direct current at which the current efficiencies suddenly dropped to zero was 0.75 for 240 cycles per second, and 0.5 for 500 cycles per second, instead of one for 60 cycles per second, superimposed alternating current.

The platinum anode was activated and dissolved into the sulfuric acid when the ratio of peak alternating to direct current was greater than 1.0, 0.75, and 0.5 for 60, 240, and 500 cycles per second, alternating current superimposed on direct current.

Apparently, there is no advantage in using alternating current superimposed on direct current over the use of direct current for electrolytic production of peroxydisulfuric acid.

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