Speciation of Main-Group Metal Ions by Electrospray Mass Spectrometry. 1. Investigation of Aqueous Polyselenide Species and Effects of Cations and pH
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Abstract
Polyselenide anion speciation in aqueous solution has been investigated by electrospray mass spectrometry (ESMS). Two methods of control over this speciation are reported: countercation substitutions and pH adjustments. The countercation has been found to affect the degree of disproportionation or comproportionation. Solutions of sodium tetraselenide displayed numerous Sen2- and HSen- species in neutral and basic soluions. In potassium solutions, the dominant species was Se42-·H2O. Solutions of cesium pentaselenide also showed preference for higher-order polyselenides. The pH dependence has been analyzed in terms of the percent Sen (n = 2−5) present. Di-, tri-, tetra-, and pentaselenide species were present over the entire pH range investigated, and trends in selenide species versus pH were developed. For example, at pH > 9, tetraselenide species were dominant.
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