Shang Chengming, Reiller Pascal E
Université Paris-Saclay, CEA, Service d'Études Analytiques et de Réactivité des Surfaces (SEARS), F-91191 Gif-sur-Yvette CEDEX, France.
Dalton Trans. 2021 Mar 28;50(12):4363-4379. doi: 10.1039/d0dt04124f. Epub 2021 Mar 11.
The formation constants and specific ion interaction coefficients of MgUO(CO) complex were determined in 0.1 to 1.0 mol kg NaCl and 0.10 to 2.21 mol kg NaClO 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 ClO already observed during our earlier studies on CaUO(CO) 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 ε(MgUO(CO), Na) = 0.19 ± 0.11 kg mol in NaClO and ε(MgUO(CO), Na) = 0.09 ± 0.16 kg mol in NaCl. Two gratings of 300 and 1800 lines per mm were used to acquire MgUO(CO) luminescence spectra, where the high-resolution 1800 lines per mm grating detected slight spectral shifts for the principal luminescent bands relative to CaUO(CO). The applications of the consistent set of thermodynamic constants and ε values for MUO(CO) (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.
在特定离子相互作用理论（SIT）框架下，通过时间分辨激光诱导发光光谱法，在0.1至1.0 mol·kg⁻¹的NaCl和0.10至2.21 mol·kg⁻¹的NaClO介质中测定了MgUO(CO)配合物的形成常数和特定离子相互作用系数。选择离子强度上限是为了限制在我们早期对CaUO(CO)配合物的研究中已经观察到的高浓度Cl⁻和ClO⁻产生的发光猝灭效应（Shang & Reiller，《道尔顿汇刊》，49，466；Shang等人，《道尔顿汇刊》，49，15443）。测定的累积形成常数为 ，特定离子相互作用系数为：在NaClO中ε(MgUO(CO), Na⁺) = 0.19 ± 0.11 kg·mol⁻¹，在NaCl中ε(MgUO(CO), Na⁺) = 0.09 ± 0.16 kg·mol⁻¹。使用每毫米300线和1800线的两个光栅采集MgUO(CO)发光光谱，其中每毫米1800线的高分辨率光栅检测到相对于CaUO(CO)的主要发光带存在轻微的光谱位移。在不同的地球化学环境中研究了MUO(CO)（M = Mg和Ca）的一组一致的热力学常数和ε值的应用，其中Mg与Ca的浓度比变化，以帮助确定这些物种的相对重要性。
