The physicochemical properties of the potassium neptunate K₂NpO₄ have been investigated in this work using X-ray diffraction, X-ray absorption near edge structure (XANES) spectroscopy at the Np-L₃ edge, and low-temperature heat capacity measurements. A Rietveld refinement of the crystal structure is reported for the first time. The Np(VI) valence state has been confirmed by the XANES data, and the absorption edge threshold of the XANES spectrum has been correlated to the Mössbauer isomer shift value reported in the literature. The standard entropy and heat capacity of K₂NpO₄ have been derived at 298.15 K from the low-temperature heat capacity data. The latter suggest the existence of a magnetic ordering transition around 25.9 K, most probably of the ferromagnetic type.

The physical and chemical properties at low temperatures of hexavalent disodium neptunate α-Na₂NpO₄ are investigated for the first time in this work using Mössbauer spectroscopy, magnetization, magnetic susceptibility, and heat capacity measurements. The Np(VI) valence state is confirmed by the isomer shift value of the Mössbauer spectra, and the local structural environment around the neptunium cation is related to the fitted quadrupole coupling constant and asymmetry parameters. Moreover, magnetic hyperfine splitting is reported below 12.5 K, which could indicate magnetic ordering at this temperature. This interpretation is further substantiated by the existence of a λ-peak at 12.5 K in the heat capacity curve, which is shifted to lower temperatures with the application of a magnetic field, suggesting antiferromagnetic ordering. However, the absence of any anomaly in the magnetization and magnetic susceptibility data shows that the observed transition is more intricate. In addition, the heat capacity measurements suggest the existence of a Schottky-type anomaly above 15 K associated with a low-lying electronic doublet found about 60 cm^-1 above the ground state doublet. The possibility of a quadrupolar transition associated with a ground state pseudoquartet is thereafter discussed. The present results finally bring new insights into the complex magnetic and electronic peculiarities of α-Na₂NpO₄.