Temperature-dependent luminescence spectroscopic and mass spectrometric investigations of U(VI) complexation with aqueous silicates in the acidic pH-range

Autor: Henry Lösch, Manuel Raiwa, Norbert Jordan, Michael Steppert, Robin Steudtner, Thorsten Stumpf, Nina Huittinen
Jazyk: angličtina
Rok vydání: 2020
Předmět:
Zdroj: Environment International, Vol 136, Iss , Pp - (2020)
Druh dokumentu: article
ISSN: 0160-4120
45838461
DOI: 10.1016/j.envint.2019.105425
Popis: In this study the complexation of U(VI) with orthosilicic acid (H4SiO4) was investigated between pH 3.5 and 5 by combining electrospray ionization mass spectrometry (ESI-MS) and laser-induced luminescence spectroscopy. The ESI-MS experiments performed at a total silicon concentration of 5 · 10−3 M (exceeding the solubility of amorphous silica at both pH-values) revealed the formation of oligomeric sodium-silicates in addition to the UO2OSi(OH)3+ species. For the luminescence spectroscopic experiments (25 °C), the U(VI) concentration was fixed at 5 · 10−6 M, the silicon concentration was varied between 1.3 · 10−4–1.3 · 10−3 M (reducing the formation of silicon oligomers) and the ionic strength was kept constant at 0.2 M NaClO4. The results confirmed the formation of the aqueous UO2OSi(OH)3+ complex. The conditional complexation constant at 25 °C, log *β = −(0.31 ± 0.24), was extrapolated to infinite dilution using the Davies equation, which led to log *β0 = −(0.06 ± 0.24). Further experiments at different temperatures (1–25 °C) allowed the calculation of the molal enthalpy of reaction ΔrHm0 = 45.8 ± 22.5 kJ·mol−1 and molal entropy of reaction ΔrSm0 = 152.5 ± 78.8 J·K−1·mol−1 using the integrated van’t Hoff equation, corroborating an endothermic and entropy driven complexation process. Keywords: Luminescence, Silicates, Uranium(VI), Complexation, Thermodynamic constants, Temperature dependent
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