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Adsorption of Cr(NH3)63+ and Cr(en)33+ on Clay Minerals and the Characterization of Chromium by X-Ray Photoelectron Spectroscopy

Published online by Cambridge University Press:  01 July 2024

M. H. Koppelman  and
J. G. Dillard
M. H. Koppelman*
Affiliation:
Department of Chemistry, Virginia Polytechnic Institute and State University, 24061, Blacksburg, Virginia, USA
J. G. Dillard
Affiliation:
Department of Chemistry, Virginia Polytechnic Institute and State University, 24061, Blacksburg, Virginia, USA
*
1Present address: Georgia Kaolin Research, 25 Route 22, East, 07081, Springfield, New Jersey, USA
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Abstract

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The nature of Cr(NH3)63+ and Cr(en)33+ (en = ethylenediamine) adsorbed on chlorite, illite, and kaolinite has been studied by X-ray photoelectron spectroscopy (XPS). The interaction of the chromium complexes with the clays began at pH 3. During the 7-day interaction time the pH of the complex-clay suspension increased to 8 for illite and chlorite. For kaolinite the pH increased to about 3.6 with Cr(NH3)63+ and to 6.4 with Cr(en)33+. These pH changes appear to be associated with a clay-catalyzed hydrolysis of the chromium-amine complexes. XPS binding-energy data for adsorbed chromium indicate that the dominant species are chromium aqua complexes. Nitrogen/chromium atom ratios, calculated from the XPS photopeak intensities, are less than 6:1 for complexes adsorbed on the clays, suggesting that chromium complexes are initially adsorbed but subsequently hydrolyze to produce aqua-chromium surface species.

Резюме

Резюме

С помощью рентгеновской фотоэлектронной спектроскопии (РФС) изучалась природа Cr(NH3)63+ и Сг(эн)з3+(эн = этилендиамин), адсорбированных хлоритом, иллитом, и каолинитом. Взаимодействие соединений хрома с глинами началось при pH = 3. За период взаимодействия в течение 7 дней pH суспензии глины (иллита или хлорита) и рассматриваемых соединений увеличилось до 8. При использовании каолинита pH увеличилось примерно до 3,6 с Cr(NH3)63+и до 6,4 с Сг(эн)з3+. Эти изменения pH, по-видимому, связаны с гидролизом хром-аминовых соединений, причем глина выступала как катализатор. Данные РЭС о связующей энергии для адсорбированного хрома указывают на то, что преобладающими видами являются водные соединения хрома. Отношения атомов азота к атомам хрома, вычисленных по данным интенсивностей фотопиков РФС, оказались меньше, чем 6:1 для соединений, адсорбированных глинами. Это позволяет предположить, что соединения хрома сначала адсорбируются, но потом гидролизуются, образовывая водно-хромовые поверхностные виды. [N. R.]

Resümee

Resümee

Die Natur von Cr(NH3)63+ und Cr(en)33+ (En = Åthylendiamin), die am Chlorit, Illit sowie Kaolinit adsorbiert waren, wurden mittels Röntgenphotoelektronen-Spektroskopie (XPS) untersucht. Die Einwirkung der Chromkomplexe auf die Tone wurde bei pH 3 begonnen. Während der 7-tägigen Einwirkungszeit wuchs der pH der Komplex-Tonsuspension bei Illit und Chlorit auf 8. Bei Kaolinit wuchs der pH mit Cr(NH3)63+ auf etwa 3,6 und mit Cr(en)33+ auf 6,4. Die pH-Veränderungen scheinen mit einer durch den Ton katalysierten Hydrolyse des Chrom-Aminkomplexes zusammenzuhängen. XPS-Bindungsener- giedaten für adsorbiertes Chrom zeigen, daß die vorherrschenden Arten Chrom-Wasserkomplexe sind. N/ Cr-Atomverhältnisse, die aus den XPS-Peakintensitäten berechnet wurden, sind kleiner als 6:1 bei Komplexen, die an den Tonen adsorbiert sind. Dieses Ergebnis deutet darauf hin, daß die Chromkomplexe in ihrem ursprünglichen Zustand adsorbiert werden, aber anschließend hydrolysieren und Wasser-ChromOberflächenarten bilden. [U.W.]

Résumé

Résumé

La nature de Cr(NH3)63+ et de Cr(en)33+ (en = éthylenediamine) adsorbée sur la chlorite, l'illite, et la kaolinite a été étudiée par spectroscopie photoélectronique aux rayons-X (XPS). L'interaction des complexes de chromium avec les argiles a commencé au pH 3. Pendant le temps d'interaction de 7 jours, le pH de la suspension de complex d'argile a augmenté à 8 pour l'illite et la chlorite. Pour la kaolinite, le pH a augmenté à à peu près 3,6 avec Cr(NH3)63+ et à 6,4 avec Cr(en)33+. Ces changements de pH semblent être associés avec une hydrolyse des complexes chromium amine catalysée par l'argile. Les données de l’énergie de liaison de XPS pour le chromium adsorbé indique que les espèces dominantes sont des complexes aquaachromium. Les proportions nitrogène/chromium, calculées d'après les intensités des sommets XPS, sont sous 6:1 pour les complexes adsorbés sur les argiles, suggérant que les complexes chromium sont initialement adsorbés, mais ensuite hydrolisent pour produire des espèces de surface aqua chromium. [D. J.]

Keywords

AdsorptionChloriteChromiumComplex ionsIlliteKaoliniteX-ray photoelectron spectroscopy
Type
Research Article
Information
Clays and Clay Minerals , Volume 28 , Issue 3 , June 1980 , pp. 211 - 216
Copyright
Copyright © Clay Minerals Society 1980

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