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Abstract  

Li-, Na-, K-, Rb- and Cs-montmorillonites were saturated with benzidine, these organo-clay complexes heated under vacuum to 200°C and IR spectra recorded at various temperatures. Benzidine is mostly bound to interlayer cations through water molecules, except in Cs-clay where bonding to hydrophobic water and to water molecules which are hydrogen bonded to the oxygen plane predominates. During the thermal treatment water is lost and alkali, cations coordinate directly with benzidine. In Cs-, and to some extent also in Rb- and K-montmorillonite, benzidine is oxidized to semiquinone and quinoidal cation during the thermal treatment.

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Abstract  

Transition metal montmorillonites were saturated with benzidine (BEN) and heated gradually to 200°C, in a vacuum cell supported by KBr windows. IR spectra were recorded before and after the thermal treatment and at various temperatures during this treatment. X-ray diffractions were recorded before and after the thermal treatment. Hg clay shows properties similar to those of Mg and Ca clays. In the interlayer BEN is bound to Hg through a water molecule bridge, either by proton accepting (typeA) or by proton donation (typeB). Some BEN is also protonated (typeD). Initially typeA predominates, but after the thermal treatment, when the film is rehydrated, the amounts of typesB andD increase. With Mn-, Co-, Ni-, Zn- and Cd-montmorillonite a direct coordination of the benzidine by the dehydrated metallic cation is obtained (typeC), in addition to small amounts of typesA,B andD. During the thermal treatment water is evolved and associationsA andB are completely transformed toC. At elevated temperatures the following associations were identified in trace amounts, ammonium-amine, BEN bound to non-structured water, hydrophobic adsorbed BEN and BEN bound to the oxygen plane (typesE, F, H andJ, respectively). During the thermal treatment of Co and Cd clays some of the benzidine was oxidized, probably to semiquinone and quinoidal cation.

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