A proposed mechanism of action of permanent modifiers for molecular absorption spectrometry: the case of calcium monofluoride
- High-Resolution Continuum Source Molecular Absorption Spectrometry (HR-CS-MAS) with graphite furnace atomizers has been successfully used for the analytical determination of non-metals. The use of permanent modifiers (or coatings) for molecule formation is necessary, but their mechanisms of action remain unclear. In order to understand and improve the current analytical methods, we present a comprehensive mechanistic study of molecule formation in graphite furnaces: a key step into the recovery of analytical signals. Therefore, a well-known system for fluorine determination was studied: the molecule formation of CaF, with Zr as permanent modifier. Through a kinetic approach, an Arrhenius plot showed a pseudo first order reaction respect to F-. By spectroscopic methods (XPS, XAS, EDX) it was possible to elucidate an intermediate state. Here a mechanism is proposed, where ZrO2 works as heterogeneous catalyst: after a pyrolytic step, it is activated to the intermediate state of ZrO(OCaF)High-Resolution Continuum Source Molecular Absorption Spectrometry (HR-CS-MAS) with graphite furnace atomizers has been successfully used for the analytical determination of non-metals. The use of permanent modifiers (or coatings) for molecule formation is necessary, but their mechanisms of action remain unclear. In order to understand and improve the current analytical methods, we present a comprehensive mechanistic study of molecule formation in graphite furnaces: a key step into the recovery of analytical signals. Therefore, a well-known system for fluorine determination was studied: the molecule formation of CaF, with Zr as permanent modifier. Through a kinetic approach, an Arrhenius plot showed a pseudo first order reaction respect to F-. By spectroscopic methods (XPS, XAS, EDX) it was possible to elucidate an intermediate state. Here a mechanism is proposed, where ZrO2 works as heterogeneous catalyst: after a pyrolytic step, it is activated to the intermediate state of ZrO(OCaF) and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. With this analytical information, improved surface modifications and coatings for graphite furnaces can be designed and some of them, for example with Zr nanoparticle and Zr xerogels are here presented.…
Autor*innen: | Carlos Enrique Abad AndradeORCiD |
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Weitere Person: | Ana de Oliveira Guilherme BuzanichORCiD, Martin RadtkeORCiD, Andreas Lippitz, Sigrid Benemann, Hans-Joachim Heinrich, Sebastian RecknagelORCiD, Norbert JakubowskiORCiD, M.-D. Huang, S. Florek, H. Becker-Ross |
Dokumenttyp: | Vortrag |
Veröffentlichungsform: | Präsentation |
Sprache: | Englisch |
Jahr der Erstveröffentlichung: | 2017 |
DDC-Klassifikation: | Naturwissenschaften und Mathematik / Chemie / Analytische Chemie |
Freie Schlagwörter: | Coating; Fluorine; HR-CS-MAS; High-resolution continuum source Molecular Absorption Spectrometry; Modifier; Zirconium oxide |
Veranstaltung: | ANAKON 2017 |
Veranstaltungsort: | Tübingen, Germany |
Beginndatum der Veranstaltung: | 03.04.2017 |
Enddatum der Veranstaltung: | 06.04.2017 |
Verfügbarkeit des Dokuments: | Datei im Netzwerk der BAM verfügbar ("Closed Access") |
Datum der Freischaltung: | 21.04.2017 |
Referierte Publikation: | Nein |
Eingeladener Vortrag: | Nein |