Gas-Phase Oxidation of Cm+ and Cm2+ -- Thermodynamics of neutral and ionized CmO

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Fourier transform ion cyclotron resonance mass spectrometry was employed to study the products and kinetics of gas-phase reactions of Cm+ and Cm2+; parallel studies were carried out with La+/2+, Gd+/2+ and Lu+/2+. Reactions with oxygen-donor molecules provided estimates for the bond dissociation energies, D[M+-O](M = Cm, Gd, Lu). The first ionization energy, IE[CmO], was obtained from the reactivity of CmO+ with dienes, and the second ionization energies, IE[MO+](M = Cm, La, Gd, Lu), from the rates of electron-transfer reactions from neutrals to the MO2+ ions. The following thermodynamic quantities for curium oxide molecules were obtained: IE[CmO]= 6.4+-0.2 eV; IE[CmO+]= 15.8+-0.4 ... continued below

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Gibson, John K; Haire, Richard G.; Santos, Marta; Pires de Matos, Antonio & Marcalo, Joaquim December 8, 2008.

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Fourier transform ion cyclotron resonance mass spectrometry was employed to study the products and kinetics of gas-phase reactions of Cm+ and Cm2+; parallel studies were carried out with La+/2+, Gd+/2+ and Lu+/2+. Reactions with oxygen-donor molecules provided estimates for the bond dissociation energies, D[M+-O](M = Cm, Gd, Lu). The first ionization energy, IE[CmO], was obtained from the reactivity of CmO+ with dienes, and the second ionization energies, IE[MO+](M = Cm, La, Gd, Lu), from the rates of electron-transfer reactions from neutrals to the MO2+ ions. The following thermodynamic quantities for curium oxide molecules were obtained: IE[CmO]= 6.4+-0.2 eV; IE[CmO+]= 15.8+-0.4 eV; D[Cm-O]= 710+-45 kJ mol-1; D[Cm+-O]= 670+-40 kJ mol-1; and D[Cm2+-O]= 342+-55 kJ mol-1. Estimates for the M2+-O bond energies for M = Cm, La, Gd and Lu are all intermediate between D[N2-O]and D[OC-O]--i.e., 167 kJ mol-1< D[M2+-O]< 532 kJ mol-1 -- such that the four MO2+ ions fulfill the thermodynamic requirement for catalytic O-atom transport from N2O to CO. It was demonstrated that the kinetics are also favorable and that the CmO2+, LaO2+, GdO2+ and LuO2+ dipositive ions each catalyze the gas-phase oxidation of CO to CO2 by N2O. The CmO2+ ion appeared during the reaction of Cm+ with O2 when the intermediate, CmO+, was not collisionally cooled -- although its formation is kinetically and/or thermodynamically unfavorable, CmO2+ is a stable species.

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  • Journal Name: The Journal of Physical Chemistry A; Journal Volume: 112; Related Information: Journal Publication Date: November 2008

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  • Report No.: LBNL-1353E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 970328
  • Archival Resource Key: ark:/67531/metadc934652

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  • December 8, 2008

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  • Nov. 13, 2016, 7:26 p.m.

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  • Nov. 18, 2016, 2:45 p.m.

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Gibson, John K; Haire, Richard G.; Santos, Marta; Pires de Matos, Antonio & Marcalo, Joaquim. Gas-Phase Oxidation of Cm+ and Cm2+ -- Thermodynamics of neutral and ionized CmO, article, December 8, 2008; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc934652/: accessed September 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.