Studies of aqueous U(iv) equilibrium and nanoparticle formation kinetics using spectrophotometric reaction modeling analysis

Abstract

Hydrolysis of tetravalent uranium (U(IV)) and U(IV)-nanoparticle formation kinetics were examined over a wide range of temperatures using spectrophotometric reaction modeling analysis. The characteristic absorption bands representing U⁴⁺, U(OH)³⁺, and a proposed oxohydroxo species were newly identified in the UV region (190–300 nm). Dynamic absorption band changes in the UV and visible regions (360–800 nm) were explored to reevaluate the binary ion interaction coefficients for U(IV) ions and the thermodynamic constants of the primary hydrolysis reaction, including complexation constants, enthalpy, and entropy. No further hydrolysis equilibrium beyond the formation of U(OH)³⁺ was identified. Instead, an irreversible transformation of U(IV) ions to U(IV)-nanoparticles (NPs) was found to occur exclusively via the formation of a new intermediate species possessing characteristic absorption bands. The kinetic analysis, based on a two-step, pseudo-first-order reaction model, revealed that the rate of the initial step producing the intermediates is highly temperature-dependent with the measured kinetic energy barrier of ∼188 kJ mol⁻¹. With additional experimental evidence, we conclude that the intermediates are oligomeric oxohydroxo U(IV) species occurring from the condensation of U(IV) ions and simultaneously participating in the nucleation and growth process of UO₂(cr)-NPs.