[논문]Temperature-Dependent Hydrolysis Reactions of U(VI) Studied by TRLFS

Lee, J.Y.; Yun, J.I.

doi:10.7733/jnfcwt.2013.1.1.65

[국내논문] Temperature-Dependent Hydrolysis Reactions of U(VI) Studied by TRLFS 원문보기

Journal of nuclear fuel cycle and waste technology, v.1 no.1, 2013년, pp.65 - 73

Lee, J.Y. (Korea Advanced Institute of Science and Technology) , Yun, J.I. (Korea Advanced Institute of Science and Technology)

Abstract ▼ AI-Helper

Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

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문제 정의

Therefore, more detailed investigation regarding chemical behavior of aqueous U(VI) species is needed for reliable safety assessment of deep geologic disposal affected by significant temperature effects [8]. The objective of this study is to investigate the temperaturedependent hydrolysis reactions of aqueous U(VI) species using time-resolved laser fluorescence spectroscopy (TRLFS). The fluorescence spectra of the U(VI) species were measured in the temperature range from 15 to 75℃ under acidic to neutral pH conditions.

이론/모형

The reaction enthalpies and entropies of the U(VI) hydroxide species were calculated using the van’t Hoff equation coupled with the Gibbs free energy equation.
The computational methods for the temperature-dependent formation constants of the U(VI) hydroxide species were employed with the reaction enthalpy and entropy obtained by combining the van’t Hoff equation and the Gibbs free energy equation.
The temperature-dependent hydrolysis reactions were analyzed by determining the formation constants at various temperatures (15 - 75℃) and cross-checked by employing several computational methods, e.g. the DQUANT model [9] and constant enthalpy equation [10]. The formation constants for the U(VI) hydroxide species were determined to be log K⁰₂₂ = -4.

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