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Contribution à la compréhension des réactions ion gaz dans les cellules de collision-réaction des ICP-MS : Application à la résolution d’interférences isobariques et poly-atomiques

Alexandre Quemet 1, 2 
1 LANIE - Laboratoire de développement Analytique Nucléaire Isotopique et Elémentaire
SEARS - Service d'études analytiques et de réactivité des surfaces : DEN/DPC
2 LASE - Laboratoire d’analyse en soutien aux exploitants
SEARS - Service d'études analytiques et de réactivité des surfaces : DEN/DPC/SEARS
Abstract : Inductively Coupled Plasma Mass Spectrometry (ICP-MS) emerged as the most essential technique in inorganic analytical chemistry thanks to its numerous assets, particularly its flexibility, its sensitivity and its reproducibility. As part of the elementary and isotopic analysis of irradiated fuel and transmutation target, the analyst is faced with a complex mass spectrum, due to the presence of many radionuclides. ICP-MS can not differentiate ions with the same mass, which induces isobaric and polyatomic interferences when the ions at the same mass are different chemical species. Last generations of ICP-MS have introduced collision reaction cells. It can in situ reduce these isobaric or polyatomic interferences. The cell is a multipol (quadrupole, hexapole or octopole) device filled with a collision and/or reaction gas. The gas molecules collide or possibly react with the ion beam, which eliminates or reduces interferences. Such resolution of interferences is based on the difference of chemical behaviours between the analyte and the interfering species: the choice of the gas is crucial. A better understanding of the “ion – gaz” reaction should help choosing the reacting gases. Three ICP-MS, with the different cell geometries, were used for this study: Perkin Elmer Elan DRC e (quadrupole), Thermo Fischer X serie II (hexapole) and Agilent Technologies 7700x (octopole). The effects of the cell geometry on different experimental parameters and on the resolution of the 56Fe+/40Ar16O+ polyatomic interferences were examined to measure iron at trace or ultra-trace level. This preliminary study was applied to measure iron as impurities in uranium oxide, the method was then validated with a Certified Reference Material. The reactivities of transition metals (Zr, Ru, Pd, Ag, Cd, Sn), lanthanides (La, Ce, Nd, Sm, Eu, Gd, Dy, Er and Yb) and actinides (U, Np, Pu, Am and Cm), elements of interest in the nuclear field, are studied with numerous gases (O2, CO, CO2, N2O, NO, CH4, C2H4, C3H8, NH3, CH3Cl and COS). Among these gases, ammonia appears to be a selective gas for lanthanides and actinides. DFT (Density Functional Theory) and ab initio calculations (MP2 and CCSD(T)) were able to reproduce the reactivity differences among lanthanide cations (La+, Sm+, Eu+ and Gd+). Reaction paths, potential energy surfaces, molecular orbitals and the influence of the electronic configuration along the reaction path are used to propose an explanation for the observed differences in the chemical behaviours. A few experimental results and quantum calculations indicate how to extend these explanations to actinides.
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Submitted on : Wednesday, December 8, 2021 - 2:26:41 PM
Last modification on : Monday, December 13, 2021 - 9:16:53 AM
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Alexandre Quemet. Contribution à la compréhension des réactions ion gaz dans les cellules de collision-réaction des ICP-MS : Application à la résolution d’interférences isobariques et poly-atomiques. Chimie analytique. Université d’Evry Val d’Essonne, 2012. Français. ⟨tel-03470740⟩

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