1963•OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information)Requires access
RADIATION-CHEMICAL OXIDATION OF POTASSIUM FERROCYANIDE IN AQUEOUS SOLUTIONS
A.V. Egunov, П.И. Дoлин
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Abstract
The Bodenstein-Semenov kinetics method was used for clarifying the mechanism of the radiation-chemical oxidation of the ferrocyanide ion. There are no satisfactory literature data concerning the reaction of this ion with the radiolytic H/sub 2/O/sub 2/. Solutions containing 0.8N H/sub 2/SO/sub 4/ and not more than 3 x 10/sup -2/ mole/ltter ferrocyanide and 10/sup -3/ mole/ liter H/sub 2/O/sub 2/ were used in the tests which involved also the determination of the reaction rate on the basis of the spectrometricaily measured ferricyanide concentration. The solutions were irradiated by a Co/sup 60/ gamma -source at a dose rate of 3.66 x 1O/sup 15/ ev/ml sec. The mechanism was found to be a first- order reaction; its rate constant was found to be K/sub o/ = (2.4 plus or minus 0.4) x 10/sup -5/ sec/sup -1/, agreeing well with the results of B. B. Lal (J. Ind. Chem. Soc., 18: 321(1939)). The oxidation process was stoichiometric and the oxidation yield was found to increase with increasing ferrocyanide concentrations. The delayed effect, observed in the case of radiolysis of aqueous ferrocyanide solutions in the presence of atmospheric O may be more » due to the H + O/sub 2/ yields HO/sub 2/; 2HO/sub 2/ yields H/sub 2/O/sub 2/ reactions. There were no sufficient data concerning the mechanism of the charge transfer to the OH radical by the (Fe(CN)/sub 6/)/sup 4-/ ion during the oxidation. (TTT) « less