Study on sublimation of solid electrolyte (AgI)0.5‐(AgPO3)0.5 with Knudsen effusion mass spectrometry

Knudsen high‐temperature mass spectrometry was used to study the process of sublimation of a solid electrolyte (AgI)_0.5‐(AgPO₃)_0.5. Monoatomic iodine ions were found to be the dominant species in the electron ionization mass spectra below 600°C. With an increase in temperature, the relative content of phosphorus oxide ions, mainly [PO]⁺ and [P₄O₁₀]⁺, increased. Under further heating, we observed silver iodide and iodine dimer ions together with phosphorus dimer and tetramer ions and clusters [IPO₂]⁺, [IP₂]⁺, [I₃P]⁺. Using the experimental logarithmic dependencies of ion signal intensities versus the reciprocal absolute temperature of the effusion cell, the apparent sublimation enthalpies Δ_sH of the ions giving the most intense signals were estimated. Copyright © 2008 John Wiley & Sons, Ltd.