Since the oxidation potential of cobaltic sulfate is the highest of any of the easily regenerated oxidizing agents which might be used as oxygen carriers in the electrolytic oxidation of organic compounds, a study of its behavior as an oxidizing agent seemed desirable.By the use of organic compounds of varied susceptibilities to oxidation, such a study should give an indication of the feasibility of cobaltic sulfate as an oxygen carrier and should also indicate the type of oxidation for which cobaltic sulfate is best adapted. The work was undertaken with these ideas in mind.The only reference found in a literature search where cobaltic sulfate was used as an oxidizing agent was in a paper by Conant and Aston2 in which they showed that 'isobutyric aldehyde was oxidized to acetone and other products.
ExperimentalAt the beginning of the investigation a method for the preparation of cobaltic sulfate was sought. That which suggested itself immediately was the electrolytic method described by Erich Miiller.3 which consisted in the oxidation of cobaltous sulfate in 8 N sulfuric acid a t a platinum anode. The yields obtained were not entirely satisfactory under these conditions. A study was therefore undertaken to determine the optimum conditions for the preparation in the hope of improving the yield and shortening the time required.The apparatus consisted of a large porous cup of 800 cc. capacity as the anode compartment which was placed in an 1000-cc. beaker. A platinum sheet of 80 sq. cm. area was used as the anode while a sheet of copper of about 300 sq. cm. area on the anode side which surrounded the porous cup served as the cathode.The anolyte consisted of 500 cc. of a saturated solution of cobaltous sulfate in sulfuric acid.In all cases a current of 5 amperes was employed. The anode current density was therefore about 0.06 ampere per sq. cm.Experiments were carried out a t various temperatures and with different concelltrations of sulfuric acid The cobaltic sulfate prepared was always in suspension in the anode liquor, which was so viscous that a sample could not be taken by means of a The catholyte was of the same composition.The temperature was controlled either by a cooling coil or an ice-bathThe results are given in the tables.
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