Effect of potential waste constituents on the reactivity of Hanford ferrocyanide wastes: Diluent, catalyst, and initiator studies

During the 1980s, scientists at the Hanford Site began considering disposal options for wastes in underground storage tanks. As a result of safety concerns, it was determined that special consideration should be given to ferrocyanide-bearing wastes to ensure their continued safe storage. In addition, Westinghouse Hanford Company (WHC) chartered Pacific Northwest Laboratory (PNL) to determine the conditions necessary for vigorous reactions to occur in the Hanford Site ferrocyanide wastes. As part of those studies, PNL has evaluated the effects of selected potential waste constituents to determine how they might affect the reactivity of the wastes. The authors' investigations of the diluent, catalytic, or initiating effects of potential waste constituents included studies (1) to determine the effect of the oxidant-to-ferrocyanide ratio, (2) to establish the effect of sodium aluminate concentration, (3) to identify materials that could affect the explosivity of a mixture of sodium nickel ferricyanide (a potential aging product of ferrocyanide) and sodium nitrate and nitrite, (4) and to determine the effect of nickel sulfide concentration. They also conducted a thermal sensitivity study and analyzed the results to determine the relative behaviors of sodium nickel ferrocyanide and ferricyanide. A statistical evaluation of the time-to-explosion (TTX) test results from the catalyst and initiator screening study found that the ferricyanide reacted at a faster rate than did the ferrocyanide analog. The thermal analyses indicated that the ferricyanide form is more thermally sensitive, exhibiting exothermic behavior at a lower temperature than the ferrocyanide form. The increased thermal sensitivity of the ferricyanide, which is a potential oxidation product of ferrocyanide, relative to the ferrocyanide analog, does not support the hypothesis that aging independent of the reaction pathway will necessarily reduce the reaction hazard of ferrocyanide wastes