This research has focused on new liquid-liquid extraction chemistry applicable to separation of major sodium salts from alkaline tank waste. It was the overall goal to provide the scientific foundation upon which the feasibility of liquid-liquid extraction chemistry for bulk reduction of the volume of tank waste can be evaluated. Sodium hydroxide represented the initial test case and primary focus. It is a primary component of the waste1 and has the most value for recycle. A full explanation of the relevance of this research to USDOE Environmental Management needs will be given in the Relevance, Impact, and Technology Transfer section below. It should be noted that this effort was predicated on the need for sodium removal primarily from low-activity waste, whereas evolving needs have shifted attention to volume reduction of the high-activity waste. The results of the research to date apply to both applications, though treatment of high-activity wastes raises new questions that will be addressed in the renewal period. Toward understanding the extractive chemistry of sodium hydroxide and other sodium salts, it was the intent to identify candidate extractants and determine their applicable basic properties regarding selectivity, efficiency, speciation, and structure. A hierarchical strategy was to be employed in which the type of liquid-liquid-extraction system varied in sophistication from simple, single-component solvents to solvents containing designer host molecules. As an aid in directing this investigation toward addressing the fundamental questions having the most value, a conceptualization of an ideal process was advanced. Accordingly, achieving adequate selectivity for sodium hydroxide represented a primary goal, but this result is worthwhile for waste applications only if certain conditions are met.