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FT-IR Investigation of the State of Iron(III) Chloride Clusters Confined in AOT Reverse Micelles Dispersed in Carbon Tetrachloride
Authors:Leopoldo Ceraulo  Serena Fanara  Angela Ruggirello  Vincenzo Turco Liveri
Institution:(1) Dipartimento di Chimica e Tecnologie Farmaceutiche, Università di Palermo, via Archirafi n. 32, 90123 Palermo, Italy;(2) Department of Physical Chemistry, University of Palermo, Viale delle Scienze Parco D’Orleans II, 90128 Palermo, Italy
Abstract:The state of the water-soluble salt iron(III) chloride in AOT reverse micelles dispersed in carbon tetrachloride has been investigated by FT-IR spectroscopy. Interestingly, while the entrapment of a lot of water-soluble inorganic salts in AOT reverse micelles requires preliminarily the presence of significant amounts of water within the micellar core, solubilization of FeCl3 occurs without the need to add water in the micellar solution reaching the very high solubility value, expressed as the maximum salt-to-surfactant molar ratio, of 1.30. The analysis of the spectral features of the investigated samples leads to hypothesize that iron(III) chloride is confined within the reverse micellar core as small size melted clusters of ionic species arising from the reactions

$$ {\text{FeCl}}_{{\text{3}}} + {\text{FeCl}}_{{\text{3}}} \to {\text{FeCl}}^{ + }_{{\text{2}}} + {\text{FeCl}}^{ - }_{{\text{4}}} {\text{ }} $$

$$ {\text{FeCl}}_{{\text{3}}} + {\text{FeCl}}^{ - }_{{\text{4}}} \to {\text{Fe}}_{{\text{2}}} {\text{Cl}}^{ - }_{{\text{7}}} $$
accompanied by a marked structural rearrangement of the AOT head group domain surrounding the micellar core and a shift of the sodium counterion from the micellar core surface to its interior. This picture has been further corroborated by conductivity measurements of FeCl3/AOT/CCl4 solutions as a function of the salt-to-surfactant molar ratio.
Keywords:Solubilization  Confinement effects  Ferric chloride  AOT reverse micelles  Ionic clusters
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