A Modern Interpretation of the Barney Diagram for Aluminum Solubility in Tank Waste

Experimental and modeling studies of aluminum solubility in Hanford tank waste have been developed and refined for many years in efforts to resolve new issues or develop waste treatment flowsheets. The earliest of these studies was conducted by G. Scott Barney, who performed solubility studies in highly concentrated electrolyte solutions to support evaporator campaign flowsheets in the 1970's. The 'Barney Diagram', a term still widely used at Hanford today, suggested gibbsite ({gamma}-Al(OH){sub 3}) was much more soluble in tank waste than in simple sodium hydroxide solutions. These results, which were highly surprising at the time, continue to be applied to new situations where aluminum solubility in tank waste is of interest. Here, we review the history and provide a modern explanation for the large gibbsite solubility observed by Barney, an explanation based on basic research that has been performed and published in the last 30 years. This explanation has both thermodynamic and kinetic aspects. Thermodynamically, saturated salt solutions stabilize soluble aluminate species that are minor components in simple sodium hydroxide solutions. These species are the aluminate dimer and the sodium-aluminate ion-pair. Ion-pairs must be present in the Barney simulants because calculations showed that there was insufficient space between the highly concentrated ions for a water molecule. Thus, most of the ions in the simulants have to be ion-paired. Kinetics likely played a role as well. The simulants were incubated for four to seven days, and more recent data indicate that this was unlikely sufficient time to achieve equilibrium from supersaturation. These results allow us to evaluate applications of the Barney results to current and future tank waste issues or flowsheets