Photoionization Efficiency Spectrum, Ionization Energy, and Heat of Formation of Br2O
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Abstract
The photoionization efficiency (PIE) spectrum of Br2O was measured over the wavelength range λ = 100−125 nm by using a photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. A value of 10.264 ± 0.011 eV was obtained for the adiabatic ionization energy of Br2O from analysis of the photoionization thresholds. Also, the appearance energy (AE) of BrO+ (from the dissociative ionization of Br2O) was determined from the PIE spectrum of BrO+ over the wavelength range λ = 104−110 nm. Combining the AE298 value, 11.714 ± 0.014 eV, with known thermodynamic quantities yields a value for ΔfH°298(Br2O) = 107.1 ± 3.5 kJ mol-1. The value for ΔfH°298(Br2O) may be related to ΔfH°298(HOBr) through the equilibrium constant for the reaction Br2O + H2O ⇌ 2HOBr. This leads to ΔfH°298(HOBr) = −60.0 ± 3.5 kJ mol-1.
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