Ionization and Dissociation of Perchlorylfluoride by Electron Impact

Abstract

Relative abundances and appearance potentials are reported for both positive and negative ions observed in the mass spectrum of perchlorylfluoride. Appearance potentials of the atom ions result in a value for ΔHf(ClO3F) of nearly zero within the experimental uncertainty. Bond dissociation energies and ionization potentials of the chloryl radicals are estimated from appearance potentials of the polyatomic ions. The energetics of probable ionization-dissociation processes are compared with observed data.

Structural and Energetic Properties of Closed Shell XFn(X = Cl, Br, and I;n= 1–7) and XOnFm(X = Cl, Br, and I;n= 1–3;m= 0–6) Molecules and Ions Leading to Stability Predictions for Yet Unknown Compounds

“…The best calculated value (Q5) is more positive than the experimental values and just outside of the error bars. For ClO 3 F, three experimental values have been reported for the heat of formation. ,,, Our best computed value for the heat of formation is −2.3 kcal/mol from the Q5 CBS extrapolation, which is too positive as compared to experiment by about 3 kcal/mol and just outside the error bars of the calculation and experiment. Du et al reported the heat of formation of ClO 3 F as 1.5 kcal/mol at the G3 level, slightly more positive than our DTQ extrapolated value of 0.7 kcal/mol.…”

“… a Calculations from DTQ CV extrapolated results are given in parentheses for compounds with Br. b Reference . c Reference . d Reference . e Reference . f Reference g Values obtained from reference . h Reference . i Reference . …”

Mass spectrometry study of intermediates in thermal decomposition of perchloric acid and chlorine dioxide

“…Indirect estimates of the ionization potentials of Cl02 and ClO have been made from electron impact studies on the ionization and dissociation of perchloryl fluoride. 16 Dibeler et aZ. 16 estimated I(Cl0z) to be 11-1 eV from the appearance potential of ClOi from FClOs.…”

“…16 Dibeler et aZ. 16 estimated I(Cl0z) to be 11-1 eV from the appearance potential of ClOi from FClOs. Dibeler's value of A(C1O;) = 15.7+0.5 eV gave an upper limit to AH'j(Cl0;) of 281flOkcalmole-1, the error quoted being in the appearance potential measurement.…”

Отрицательные Ионы

“…Действительно, ток отрицательных ионов, обра-зующихся при энергии электронов, близкой к нулю, более чем в 2 раза превосходит ток наиболее распространенного положительного иона СЮз-При этом ClOgF исключительно стоек термически] и химически инертен 109 . Процессы прилипания электронов с энергией, близкой к нулю, могут идти в очень узкой области энергий.…”