Abstract

Electrospray-ionization (ESI) time-of-flight mass spectrometry has been used to investigate the pH-dependent behavior of phosphotungstates in solution from pH = 2.7 to 8.0. Mass spectra are reported for the first time for H₃PW₁₁O₃₉^4-, H₄PW₁₁O₃₉^3-, and H₅PW₁₁O₃₉^2-. The pH dependence of phosphotungstate species as measured by electrospray is compared with that measured by ³¹P NMR. The pH ranges of species are similar (±1 pH unit) when measured by these two methods. Protonation and solvation of phosphotungstate species measured by ESI differ from those observed by ³¹P NMR. However, the core phosphotungstate species are measured correctly by ESI.

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