Mass spectrometric studies of physical, thermochemical and reactive properties of xenon fluorides, xenon oxides and xenon oxyfluorides

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Eur. J. Mass Spectrom. 8, 233 - 246 (2002)
DOI: 10.1255/ejms.495

Mass spectrometric studies of physical, thermochemical and reactive properties of xenon fluorides, xenon oxides and xenon oxyfluorides

Vladislav V. Zelenov,^* Elena V. Aparina, Alexander V. Loboda, Alexander S. Kukui and Alexander F. Dodonov
Institute of Energy Problems of Chemical Physics (Branch), Russian Academy of Sciences, 142432 Chernogolovka, Russia E-mail:
Sergei A. Kashtanov and Nicolai N. Aleinikov
Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Russia

ABSTRACT:

Using a reactor with a flowing diffusion cloud coupled to a high-resolution, low-energy electron-impact ionization mass spectrometer, mechanistic, kinetic and thermochemical characteristics of gas-phase reactions with the participation of charged and neutral xenon oxides, xenon fluorides and xenon oxyfluorides have been investigated. Ionization energies for XeF, XeF₂, XeF₄, XeO₃, XeO₄, XeOF₄ molecules and appearance energies for the ions formed from these molecules were obtained. Based on experimental and reference data, the enthalpies of XeO₃ and XeOF₄ formation were refined and a number of binding energies in the parent and fragment ions were calculated. For electron-impact ionization, the ionization cross-sections for Xe, XeF₂, XeF₄ and XeOF₄ proved to correlate with a semi-empirical principle of full ionization. Based on the temperature dependencies of saturated vapor pressures for XeO₄, XeOF₄ and XeO₂F₂, their enthalpies of evaporation, sublimation and melting were determined. The mechanisms of gas-phase reactions between H atoms and neutral XeF₂, XeF₄, XeF₆, XeO₄ and XeOF₄ were studied.

Keywords: xenon fluorides, xenon oxides, xenon oxyfluorides, ionization energy, appearance energy, enthalpy of formation, enthalpy of evaporation, enthalpy of sublimation, binding energy, gas-phase reaction

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