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The speciation, thermodynamics and structure of the Np(v) (as the NpO2+ cation) complexes with oxalate (Ox2-) are studied by different spectroscopic techniques. Near infrared absorption spectroscopy (Vis/NIR) is used to investigate complexation reactions as a function of the total ligand concentration ([Ox2-]total), ionic strength (Im = 0.5-4.0 mol kg-1 Na+(Cl-/ClO4-)) and temperature (T = 20-85 °C) for determination of the complex stoichiometry and thermodynamic functions (log β0n(T), ΔrH0n, ΔrS0n). Besides the solvated NpO2+ ion, two Np