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Published on: June 8, 2022
Complexation of Np(V) with the Dicarboxylates, Malonate, and Succinate: Complex Stoichiometry, Thermodynamic Data,
Martin M Maiwald1,2, Katharina Müller3, Karsten Heim3
1Ruprecht Karls Universität Heidelberg, Physikalisch-Chemisches Institut, Im Neuenheimer Feld 253, 69120 Heidelberg, Germany.
Abstract:
The complexation of Np(V) with malonate and succinate is studied by different spectroscopic techniques, namely, attenuated total reflection Fourier transform infrared (ATR FT-IR) and extended X-ray absorption fine-structure (EXAFS) spectroscopy, as well as by quantum chemistry to determine the speciation, thermodynamic data, and structural information of the formed complexes. For complex stoichiometries and the thermodynamic functions (log β°(Θ), ΔrH°, ΔrS°), near infrared absorption spectroscopy (vis/NIR) is applied. The complexation reactions are investigated as a function of the total concentration of malonate ([Mal2-]total) and succinate ([Succ2-]total), ionic strength [Im = 0.5-4.0 mol kg-1 Na+(Cl-/ClO4-)], and temperature (Θ = 20-85 °C). Besides the solvated NpO2+ ion, the formation of two Np(V) species with the stoichiometry NpO2(L)1-2 (n = 1, 2, L = Mal2-, Succ2-) is observed. With increasing temperature, the molar fractions of both complex species increase and the temperature-dependent conditional stability constants log β'(Θ) at given ionic strengths are determined by the law of mass action. The log β'(Θ) are extrapolated to IUPAC reference-state conditions (Im = 0) according to the specific ion interaction theory (SIT), revealing thermodynamic log β°(Θ) values. For all formed complexes, [NpO2(Mal)-: log β1°(25 °C) = 3.36 ± 0.11, NpO2(Mal)23-: log β2°(25 °C) = 3.95 ± 0.19, NpO2(Succ)-: log β1°(25 °C) = 2.05 ± 0.45, NpO2(Succ)23-: log β2°(25 °C) = 0.75 ± 1.22], an increase of the stability constants with increasing temperature was observed. This confirmed an endothermic complexation reaction. The temperature dependence of the log β°(T) values is described by the integrated Van't Hoff equation, and the standard reaction enthalpies and entropies for the complexation reactions are determined. Furthermore, the sum of the specific binary ion-ion interaction coefficients Δεn°(Θ) for the complexation reactions are obtained as a function of the t from the respective SIT modeling as a function of the temperature. In addition to the thermodynamic data, the structures of the complexes and the coordination modes of malonate and succinate are investigated using EXAFS spectroscopy, ATR-FT-IR spectroscopy, and quantum chemical calculations. The results show that in the case of malonate, six-membered chelate complexes are formed, whereas for succinate, seven-membered rings form. The latter ones are energetically unfavorable due to the limited space in the equatorial plane of the Np(V) ion (as NpO2+ cation).
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