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Counterions and Adsorption of Ion-Exchange Extractants at the Water/Oil Interface

  • Chapter
The Interface Structure and Electrochemical Processes at the Boundary Between Two Immiscible Liquids

Abstract

This review deals with the relation between the extractant surface activity upon adsorption from the non-aqueous phase at the water-oil interface and the extraction characteristics of the systems. Alkylammonium salts, alkylphosphoric and sulfonic acids and macrocyclic ethers were taken as extractants. The properties of adsorption monolayers were compared for the above extractants at water-air and water-oil interfaces. The method of determining the extractant activity coefficients in low permittivity media from the surface pressure isotherms is discussed.

At present, liquid extraction is widely used to extract and concentrate substances [1]. Other high-efficiency processes utilizing double emulsion membranes, membranes on a porous hydrophobic support [2], and electrodialysis systems with liquid membranes [3] gradually find application in this field. In practice, many inorganic and organic ions are determined by ion-selective electrodes with a liquid membrane [4]. Interface catalysis has also been widely accepted in organic chemistry [5]. The water-oil interface is common to all the above systems. Ion transfer across the interface is of primary importance in describing processes that take place in these systems. Almost all extractants and membrane-active substances of ion-selective electrodes are insoluble in water and display surface activity at the water-oil interface upon adsorption from the non-aqueous phase. The adsorption process at the interface may be viewed as a part of a general process of ion transfer across the interface. Thus, it is only natural to expect a correlation between the extraction and adsorption characteristics in water-oil systems. The concepts developed by Rehbinder [6] serve as a basis for studying the relation between bulk and surface properties of surfactant solutions. In many important cases extraction processes are selected that are based on ion-exchange mechanisms. Liquid anion exchangers are represented by solutions of onium salts (mainly alkylammonium salts [7]) in immiscible diluents, while liquid cation exchangers are mainly represented by alkylphosphoric, carboxylic and some other acids [1]. In interface catalysis, quaternary alkylammonium salts, crown ethers and cryptands [5] are used to transfer inorganic ions to the organic phase. All these compounds are used in ion-selective electrodes [4] as membrane-active substances and in membrane systems for the ion extraction and concentration [2, 3]. The ion exchange extraction may be viewed as an exchange reaction between counterions and the monolayer of the extractant adsorbed at the interface with the subsequent transfer of the resultant compound into the organic phase. According to the modern concepts of ion exchange extraction, the counterion exchange occurs either at the interface or in the adjoining layers of water or the organic phase [8,9]. Hence the interaction of the extractant and counterions in the electrical double layer at the interface, the nature of the counterion and its effect on monolayer properties are essential in interpreting the mechanism of ion transfer across the water-oil interface.

The present review is devoted to the relation between bulk characteristics (extraction constants, extractant association in the non-aqueous medium) of ion-exchange extraction systems and properties of the monolayers adsorbed at the water-oil interface.

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  1. A.N. Frumkin Institute of Electrochemistry, Academy of Sciences of the USSR, Leninsky Prospect, 31, SU-117071, Moscow V-71, USSR

    Vladimir E. Kazarinov

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Popov, A.N. (1987). Counterions and Adsorption of Ion-Exchange Extractants at the Water/Oil Interface. In: Kazarinov, V.E. (eds) The Interface Structure and Electrochemical Processes at the Boundary Between Two Immiscible Liquids. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-71881-6_9

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