Reaction Dynamics and Isotope Exchange Kinetics of Niobium and Uranium Oxide Complexes

The work contained in this dissertation covers the topic of exchange dynamics in metal oxide complexes in aqueous solution. The first project covered involves a nanometer-sized polyoxoniobate with 19 non-equivalent oxygen sites. The rate of isotopic oxygen exchange was followed using 17O NMR. The remainder of the work presented here involves oxide complexes with uranium, beginning with a paper on isotopic oxygen exchange in a uranyl tetrahydroxide ion. Efforts to relate these experimentally determined activation volumes to computationally determined partial molar volumes in order to elucidate reaction mechanisms are also presented. To further the work on uranium complexes, ligand exchange in a uranyl tricarbonate species is explored. These projects finally build up to observing the reaction dynamics of a large uranyl-peroxo species in aqueous solution.;The purpose of this work is to provide a better understanding the fundamentals of how metal oxide materials react in solution so that these materials can be used more efficiently as catalysts in energy production. Furthermore fundamental work is necessary for determining the fate of radioactive waste in the environment, storing of radioactive waste and increasing the efficiency nuclear energy processes.;Permission to reuse published work was requested from the publishers of each respective journal prior to printing of this dissertation.