Chemical effect on intensity ratios of K‐series x‐rays in vanadium, chromium and manganese compounds

Abstract

Kα and Kβ x‐ray fluorescence spectra of various V, Cr and Mn compounds were measured with a Bragg spectrometer. The relative intensities of the Kβ1,3, Kβ2, Kβ′ and Kβ″ lines with respect to the Kα line were determined to confirm the chemical effect on the Kβ/Kα intensity ratio obtained using a Si(Li) detector. Chemical effects on each component line are discussed with respect to the oxidation state of the metal ions. The relative importance of an increase in transition probabilities of the Kβ2 group (Kβ2 and Kβ″) was evaluated in the determination of the overall Kβ/Kα ratio.

Chemical state analysis employing sub‐natural linewidth resolution PIXE measurements of Kα diagram lines

“…This is consistent with the previous measurements of photoinduced x-ray fluorescence spectra measured by Kawai et al 17 Also, available data for Cr, V and Mn compounds confirm that the measured K˛shifts are generally less than about 0.5 eV. 3,6,9 For the CuO and Cu 2 O oxides, energy shifts of 0.11 and 0.13 eV have been reported, 18 whereas maximum energy shifts up to š0.2 eV have been measured for many Ni intermetallic compounds and alloys. 19 This trend of small K˛energy shifts for the 3d transition and late transition elements has therefore been also confirmed by our experiment.…”

“…Therefore, it seems more appropriate that for the 3d transition elements chemical speciation has to be carried out via the Kˇ1 ,3 emission lines, where the observed energy shifts range from about 0.4 eV up to more than 1 eV, or through other characteristics of the emission spectra than energy shifts. 1,3,6…”

Analytical Aspects of Metal Enolates

“…K α and K β XRF spectra of Cr(acac) 3 and other Cr compounds were measured with a Bragg spectrometer. The relative intensities of the K β1.3 , K β2 , K β and K β lines with respect to the K α line confirm the chemical effect on the K β /K α intensity ratio obtained using a Si(Li) detector 55 .…”

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

“…Formation of MnK β ′, MnK β ″, and MnK β 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 . The dependence of chemical shift and relative intensity of MnK β 5 line and MnK β ′ and MnK β ″ satellites on manganese valence state was shown for some compounds . 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 …”