Dilution and packing of anionic liquid surfactant in presence of divalent and trivalent counter-ions

Rothe, M. and Quintard, G. and Kronseder, M. and Bauduin, P. and Zemb, T. and Kunz, W. (2023) Dilution and packing of anionic liquid surfactant in presence of divalent and trivalent counter-ions. JOURNAL OF MOLECULAR LIQUIDS, 384: 122195. ISSN 0167-7322, 1873-3166

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Abstract

Alkyl ether carboxylates are part of a new class of ionic liquids based on the Concept of Melting Point Lowering due to Ethoxylation (COMPLET) and possess unique aggregation behaviour due to the simultaneous anionic and non-ionic nature of the surfactant anion. Previous publications on H[C8E8c] (Polyoxyethylene(8) octyl ether carboxylic acid) and its monovalent salts have shown a variety of phases in aqueous systems with a transition from small spherical micelles at high water contents towards a phase of interdigitated head groups at low water contents. In the present paper, we examine the shorter homologue H[C8E5c] (Polyoxyethylene(5) octyl ether carboxylic acid) and its di-and trivalent transition and rare earth metal salts using X-ray scattering methods in the small-and wide-angle range (SWAXS). These measurements confirm the presence of spherical micelles in diluted aqueous systems which aggregate and whose head groups interdigitate at higher concentrations of the isotropic, non-birefringent ionic liquid. Swelling experiments yield two-dimensional swelling of the microstructure, and combined with the scattering pattern, the data infer prolate spheroidal direct (o/w) micelles with interdigitated head groups, which align to form short linear chains. These chains are offset to form a localised hexagonal close -like packing of the micelles. Most interesting, within this packing, the metal cations are confined into channels between the micelles in linear chains with ion-ion distances of 0.4-1.1 nm. In particular, in the water-free ionic liquid, this confinement may be responsible for some of the unique properties of these systems. It is suggested that the confinement of the cations leads to strong ion-ion aggregation that could be at the origin of the very peculiar magnetic properties of these simple one-component liquids, which contrasts with classical ferrofluids, in which magnetic nanoparticles are dispersed in another liquid.

Item Type: Article
Uncontrolled Keywords: OLIGOETHER CARBOXYLATES; MICELLE; WATER; Surface-active ionic liquids; Polyvalent ionic liquids; Surfactants; Structure; Swelling; Ion confinement
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > Prof. Dr. Werner Kunz
Depositing User: Dr. Gernot Deinzer
Date Deposited: 30 Jan 2024 11:09
Last Modified: 30 Jan 2024 11:09
URI: https://pred.uni-regensburg.de/id/eprint/59679

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