Study of Kβ X-ray emission spectroscopy applied to Mn(2−x)V(1+x)O4 (x=0 and 1/3) oxyspinel and comparison with XANES

X-ray fluorescence determination of the manganese valence state and speciation in manganese ores

“…Parameters of lines preconditioned by the transitions of electrons from the valence levels are most affected by chemical bonding, e.g. MnK β 5 line and some satellites observed in X‐ray spectra of manganese along with the basic plotted lines; and they are not explained by the classical scheme of X‐ray transitions . The most intense satellite is MnK β ′ interpreted as transitions К‐М 2,3 (main MnK β 1,3 line) with a simultaneous ejection of electron from level М 4,5 for manganese atom or as resultant of the exchange coupling between unpaired electrons in the 3p and 3d shells .…”

“…X-ray photoelectron spectroscopy, [5][6][7] X-ray absorption near edge structure, and extended X-Ray absorption fine structure. [8][9][10][11][12][13][14][15] The X-ray photoelectron spectroscopy method provides information only on the substance surface, whereas measurement of absorption spectra requires the beams of high radiation intensity. The capacity to employ the ratios of X-ray spectral line intensities for the electron probe microanalysis determination of the elemental valence state has been reviewed.…”

“…MnKβ 5 line [25,26] and some satellites observed in X-ray spectra of manganese along with the basic plotted lines; and they are not explained by the classical scheme of X-ray transitions. [15,[27][28][29][30][31] The most intense satellite is MnKβ′ interpreted as transitions К-М 2,3 (main MnKβ 1,3 line) with a simultaneous ejection of electron from level М 4,5 for manganese atom [25] or as resultant of the exchange coupling between unpaired electrons in the 3p and 3d shells. [32] Formation of MnKβ′, MnKβ″, and MnKβ x satellites involves the shells of the other elements chemically bound with manganese; therefore, the intensity of these satellites depends on both valence state of manganese and its speciation.…”

“…[33][34][35] The dependence of chemical shift and relative intensity of MnKβ 5 line and MnKβ′ and MnKβ″ satellites on manganese valence state was shown for some compounds. [15,33,[36][37][38][39] Some methods are proposed to define the valence state of manganese in mineral samples, based on the analysis of К-series spectra of X-ray emission spectra. [34,[40][41][42] The method earlier developed for the iron valence state determination in igneous rocks is reported in the articles.…”

“…To determine manganese valence state in minerals, the following X‐ray methods are applied: e.g. X‐ray photoelectron spectroscopy, X‐ray absorption near edge structure, and extended X‐Ray absorption fine structure . The X‐ray photoelectron spectroscopy method provides information only on the substance surface, whereas measurement of absorption spectra requires the beams of high radiation intensity.…”