Kβ X-Ray Emission and K X-Ray Absorption Spectra of Sulfur in Sulfate Compounds

Abstract

With a two-crystal vacuum spectrometer, the sulfur Kβ emission spectra in fluorescence are measured for a series of alkali, alkaline-earth and hydrated 3d transition-metal salts with the SO4 2- ion. In addition, the sulfur K absorption spectra in a series of hydrated 3d transition-metal sulfates are measured with a bent-quartz-crystal vacuum spectrograph. The measured Kβ emission and K absorption spectra are presented along with the sulfur K absorption spectra of alkali and alkaline-earth sulfates reported previously. It is shown that the Kβ emission and K absorption spectra of sulfur in alkali and alkaline-earth sulfates are influenced by the cations, while those of hydrated 3d transition-metal sulfates are little affected by the metal ions. The sulfur Kβ emission spectra and the sulfur K absorption spectra are interpreted in terms of the molecular orbitals of the SO4 2- ion.

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

“…The fluorescence energies as presented in Table are in good agreement with previously published data from the last 90 years (Figure ). All mean values with the only exception of S Kβ 1 for sulfite (Table ) are within the confidence intervals calculated from the previously published data .…”

“…The fluorescence energies as presented in Table are in good agreement with previously published data from the last 90 years (Figure ). All mean values with the only exception of S Kβ 1 for sulfite (Table ) are within the confidence intervals calculated from the previously published data . For a better comparability of respective fluorescence energies and the possible impact of the historic development of XRF instrumentation, this big amount of 38 data sets was categorised to four time periods: 1920–1949, 1950–1979, 1980–1999 and 2000–2016.…”

“…Energies of X‐ray fluorescence lines for sulfur in different oxidation states: A comparison of values from this work (mean value ± range of dispersion) and previously published data…”

“…All mean values with the only exception of S Kβ 1 for sulfite (Table 3) are within the confidence intervals calculated from the previously published data. For a better comparability of respective fluorescence energies and the possible impact of the historic development of XRF instrumentation, this big amount of 38 data sets was categorised to four time periods: 1920-1949 [7][8][9][10][11][12][13][14][15] , 1950-1979 [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] , 1980-1999 [33][34][35][36][37] and 2000-2016 [6,[38][39][40][41][42][43] . Comparing used instrumentation (see Table S6 for further detailed information) showed that FIGURE 2 Energies of X-ray fluorescence lines for sulfur in different oxidation states: A comparison of values from this work (mean value ± range of dispersion) and previously published data Fluorescence energy (S Kα 1,2 and S Kβ 1 ) and S Kβ′/S Kβ 1 ratio of peak height versus elemental sulfur mass fraction that the main difference between historical and modern devices is their availability.…”

Sulfate Speciation Analysis Using Soft X-ray Emission Spectroscopy

“…Among the sulfates, changes are much less pronounced; small energy shifts and changes in spectral shape are observed in XAS, while the energy position as well as the shape of the S Kα XES spectra are mostly independent of the cation 17 . The information content of XES increases significantly as compared to core to core transitions as in S Kα when investigating transitions involving valence states, i.e., for S Kβ [20][21][22][23][24][25] (probing states with p symmetry) and S L2,3 (probing states with s and d symmetry) XES 7,26,27 . In addition to the observed chemical line shifts, the spectral shapes now vary for different compounds offering high sensitivity for the differentiation of sulfur compounds.…”