The determination of the thermodynamic constants of MgUO2(CO3)32- complex in NaClO4 and NaCl media by time-resolved luminescence spectroscopy, and applications in different geochemical contexts

被引:6
|
作者
Shang, Chengming [1 ]
Reiller, Pascal E. [1 ]
机构
[1] Univ Paris Saclay, Serv Etud Analyt & React Surfaces SEARS, CEA, F-91191 Gif Sur Yvette, France
关键词
Geochemistry - Optical properties - Ionic strength - Laser spectroscopy - Laser theory - Sodium chloride - Luminescence;
D O I
10.1039/d0dt04124f
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The formation constants and specific ion interaction coefficients of MgUO2(CO3)(3)(2-) complex were determined in 0.1 to 1.0 mol kg(w)(-1) NaCl and 0.10 to 2.21 mol kg(w)(-1) NaClO4 media in the framework of the specific ion interaction theory (SIT), by time-resolved laser-induced luminescence spectroscopy. The upper limits of ionic strength were chosen in order to limit luminescence quenching effects generated by high concentrations of Cl- and ClO4- already observed during our earlier studies on CanUO2(CO3)(3)((4-2n)-) complexes (Shang & Reiller, Dalton Trans., 49, 466; Shang et al., Dalton Trans., 49, 15443). The cumulative formation constant determined is , and the specific ion interaction coefficients are epsilon(MgUO2(CO3)(3)(2-), Na+) = 0.19 +/- 0.11 kg(w) mol(-1) in NaClO4 and epsilon(MgUO2(CO3)(3)(2-), Na+) = 0.09 +/- 0.16 kg(w) mol(-1) in NaCl. Two gratings of 300 and 1800 lines per mm were used to acquire MgUO2(CO3)(3)(2-) luminescence spectra, where the high-resolution 1800 lines per mm grating detected slight spectral shifts for the principal luminescent bands relative to CanUO2(CO3)(3)((4-2n)-). The applications of the consistent set of thermodynamic constants and epsilon values for MnUO2(CO3)(3)((4-2n)-) (M = Mg and Ca) were examined in different geochemical contexts, where Mg over Ca concentration ratio varies to help defining the relative importance of these species.
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页码:4363 / 4379
页数:17
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