Equilibrium, chemical between immiscible liquids

Extraction—distribution between immiscible liquid phases Crystallization—melting point or solubility Adsorption—surface sorption Reverse osmosis—diflusivity and solubility Membrane gas separation—diflusivity and solubility Ultrafiltration—molecular size ion exchange—chemical reaction equilibrium Dwlysis—diflusivity... 

Extraction—distribution between immiscible liquid phases Crystallization-melting point or solubility Adsorption-surface sorption Reverse osmosis—diffiisivity and solubility Membrane gas separation—diffusivity and solubility Ultrafiltration—molecular size Ion exchange—chemical reaction equilibrium Dialysis—diffiisivity... 

The equilibrium condition for the distribution of one solute between two liquid phases is conveniently considered in terms of the distribution law. Thus, at equilibrium, the ratio of the concentrations of the solute in the two phases is given by CE/CR = K, where K1 is the distribution constant. This relation will apply accurately only if both solvents are immiscible, and if there is no association or dissociation of the solute. If the solute forms molecules of different molecular weights, then the distribution law holds for each molecular species. Where the concentrations are small, the distribution law usually holds provided no chemical reaction occurs. 

In Fig. 1.2, phase transformations are pnt into their context of physical processes used for separation of mixtures of chemical compounds. However, the figure has been drawn asymmetrically in that two Uqnids (I and II) are indicated. Most people are familiar with several organic Uqnids, Uke kerosene, ether, benzene, etc., that are only partially miscible with water. This lack of miscibility allows an equilibrium between two liquids that are separated from each other by a common phase boundary. Thus the conventional physical system of three phases (gas, liquid, and solid, counting all solid phases as one), which ordinarily are available to all chemists, is expanded to four phases when two immiscible liquids are involved. This can be of great advantage, as will be seen when reading this book. 

When a solute is distributed between two immiscible liquids, different species, formed from the solute, may exist in the two liquids. Thus, when an organic liquid such as benzene or carbon tetrachloride and water are used as the two liquids, a weak acid may dimerize in the organic phase and partially ionize in the aqueous phase. The condition of equilibrium is the equality of the chemical potential of the monomeric, nonionized species in the two phases. If the dimerization is complete, the condition of equilibrium involves half of the chemical potential of the dimer in the organic phase. 

The transfer of chemicals between two or more environmental compartments or phases can be described by equilibrium partitioning, and knowledge of this partitioning is essential for understanding and describing chemical fate in the environment. Chemical partitioning takes place between adjacent phases such as between a solid and a liquid (dissolution), a liquid and a gas (volatilisation), a solution and a solid surface (adsorption) or a solution and an immiscible liquid (solvent... 

One of the fundamental problems in chemistry is understanding at the molecular level the effect of the medium on the rate and the equilibrium of chemical reactions which occur in bulk liquids and at surfaces. Recent advances in experimental techniques[l], such as frequency and time-resolved spectroscopy, and in theoretical methods[2,3], such as statistical mechanics of the liquid state and computer simulations, have contributed significantly to our understanding of chemical reactivity in bulk liquids[4] and at solid interfaces. These techniques are also beginning to be applied to the study of equilibrium and dynamics at liquid interfaces[5]. The purpose of this chapter is to review the progress in the application of molecular dynamics computer simulations to understanding chemical reactions at the interface between two immiscible liquids and at the liquid/vapor interface. 

Limits of miscibility have been determined between lithium and potassium from 63 to 500 °C. Generally, lithium is less miscible with potassium than with sodium the tendency to separate into two immiscible liquids with lithium increases from sodium to caesium. In Li-K, between 63 and 180 °C, a K-rich liquid phase is in equilibrium with solid lithium, while two immiscible liquid phases are present above 180 °C. The solubilities S/(p.p.m. by weight) of K in liquid Li, and of Li in liquid K, determined by chemical analysis of the immiscible phases, are given, respectively, by 38... 

Conventional approaches based on electrochemical techniques, surface tension, and extraction methods have allowed the estabhshment of thermodynamic and kinetic information concerning partition equilibrium, rate of charge transfer, and adsorption of surfactant and ionic species at the hquid/Uquid interface [4—6]. In particular, electrochemical methods are tremendously sensitive to charge transfer processes at this interface. For instance, conventional instm-mentation allowed the monitoring of ion transfer across a hquid/hquid interface supported on a single micron-sized hole [7, 8]. On the other hand, the concentration profile of species reacting at the interface can be accurately monitored by scanning electrochemical microscopy [9, 10]. However, a detailed picture of the chemical environment at the junction between the two immiscible liquids caimot be directly accessed by purely electrochemical means. The implementation of in-situ spectroscopic techniques has allowed access to key information such as ... 

The liquid-liquid extraction process is based on the specific distribution of dissolved components between two immiscible fluids, for instance, between aqueous and organic liquids. The process refers to a mass exchange processes in which the mass transport of component (j) from phase (1) to phase (2) by means of convection or molecular diffusion acts to achieve the chemical potential (p) equilibrium (134) ... 

Chemical separations are often either a question of equilibrium established in two immiscible phases across the contact between the two phases. In the case of true distillation, the equilibrium is established in the reflux process where the condensed material returning to the pot is in contact with the vapor rising from the pot. It is a gas-liquid interface. In an extraction, the equilibrium is established by motion of the solute molecules across the interface between the immiscible layers. It is a liquid-liquid, interface. If one adds a finely divided solid to a liquid phase and molecules are then distributed in equilibrium between the solid surface and the liquid, it is a liquid-solid interface (Table 1). 

A three component system consisting of a solvent (0) and two further components (1 and 2) can be considered. The phase equilibrium between the solid (s) and liquid (1) phases is characterized by equality of the chemical potentials of a given component in the two phases. Supposing that the component are completely immiscible in the solid phase we obtain from the condition of equality of chemical potentials ... 

In a static partition, the atom (necessarily radioactive in the present context) is distributed between two immiscible phases (liquid and/or solid). Since this procedure is sequential, the accuracy in the measurement of the average concentrations increases with the number of trials. For a given system, under given conditions, the determination of one partition coefficient (D) requires numerous repetitive experiments, even for the more simple case involving only one chemical species in each phase. The experimental conditions must always ensure that at the end of the experiment, the atom has reached permanent partition equilibrium between the two phases. Moreover, the short half-life of the nucleus does not bring any perturbation since there is only one alternative either the measurement indicates in which phase the atom is or the atom has disintegrated before the measurement and no information is obtained. 

Distribution potential established when ionic species are partitioned in equilibrium between the aqueous and organic phases, W and O, is a fundamental quantity in electrochemistry at liquid-liquid interfaces, through which the equilibrium properties of the system are determined. In any system composed of two immiscible electrolyte solutions in contact with each other, the equilibrium is characterized by the equality of the electrochemical or chemical potentials for each ionic or neutral species, respectively, commonly distributed in the two phases [4]. It follows from the former equality that the distribution potential Aq inner electrical potential of the aqueous phase, 0, with respect to the inner potential of the organic phase, 0°, is given by the Nernst equation [17,18],... 

Extraction or separation of dissolved chemical component [X]A from liquid phase A is accomplished by bringing liquid solution of [X]B into contact with a second phase B that is totally immiscible. A distribution of the component between the immiscible phases occurs. After the analyte is distributed between the two phases, the extracting analyte is released and/or recovered from phase A for analysis. The theory of chemical equilibrium leads us to a reversible distribution coefficient as follows ... 

Inclusion of this technique to the BOHLM has to be explained. Solvent extraction or partition of the solute between two immiscible phases is an equilibrium-based separation process. So, the membrane-based or nondispersive solvent extraction process has to be equilibrium based also. Liquid membrane separation is a rate process and the separation occurs due to a chemical potential gradient, not by equilibrium between phases [114]. According to these definitions, many authors who refer to their works as membrane-based or nondispersive solvent extraction processes are not correct. 

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