Does the UO2(CH3COO)3-complex really exist: a spectroscopic study


Does the UO2(CH3COO)3-complex really exist: a spectroscopic study

Brinkmann, H.; Moll, H.; Stumpf, T.

The coordination chemistry of radionuclides (RN) with organic components is of great interest since latter can affect the mobility as well as the sorption behavior adversely. Acetate (AcO-) can be a biotic or abiotic degradation product of organic material present in nuclear waste. Additionally it is often declared as model compound for more complex organic structures. A large number of studies is available which investigated the speciation of uranium(VI) in the presence of acetate under acidic conditions. From potentiometric titrations it seems to be very clear that three uranyl-acetate species are formed under acidic conditions: UO2AcO+ (1:1), UO2(AcO)2 (1:2) and UO2(AcO)3- (1:3).
Spectroscopic methods (e.g. IR and EXAFS) provide no certainty whether the 1:3 complex exists or not. TRLFS and UV-vis spectroscopy were mainly applied to characterize the formation of the 1:1 complex. In this study TRLFS, ATR-FT-IR and UV-vis spectroscopy were applied to determine the speciation of uranium(VI) in the presence of acetate and to fill the gap of missing spectroscopic data for the other formed species. Experimental conditions were chosen so that all three previous identified species should be formed. Data evaluation was performed on the basis of factor analysis resulting in single component spectra and stability constants. The findings led us to the conclusion that the 1:3 complex was not formed. In addition the detailed evaluation of ATR-FT-IR spectra show that an approximation used in potentiometric studies should be treated with caution. All these indications reinforce the doubts with respect to the existence of the UO2(AcO)3- species.

Keywords: Acetate; Uranyl; TRLFS; UV-vis; ATR-FT-IR

  • Poster
    GDCh-Wissenschaftsforum Chemie 2017, 10.-14.09.2017, Berlin, Deutschland

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Publ.-Id: 25289