Equilibrium liquid extraction

In a simple liquid-liquid extraction the solute is partitioned between two immiscible phases. In most cases one of the phases is aqueous, and the other phase is an organic solvent such as diethyl ether or chloroform. Because the phases are immiscible, they form two layers, with the denser phase on the bottom. The solute is initially present in one phase, but after extraction it is present in both phases. The efficiency of a liquid-liquid extraction is determined by the equilibrium constant for the solute s partitioning between the two phases. Extraction efficiency is also influenced by any secondary reactions involving the solute. Examples of secondary reactions include acid-base and complexation equilibria. 

In a liquid-liquid extraction, the analyte (or interferent) is extracted from one liquid phase into a second, immiscible liquid phase. When the analyte is involved in secondary equilibrium reactions, it is often possible to improve selectivity by carefully adjusting the composition of one or both phases. 

Separation module for a flow injection analysis using a liquid-liquid extraction (inset shows the equilibrium reaction). 

The separation of components by liquid-liquid extraction depends primarily on the thermodynamic equilibrium partition of those components between the two liquid phases. Knowledge of these partition relationships is essential for selecting the ratio or extraction solvent to feed that enters an extraction process and for evaluating the mass-transfer rates or theoretical stage efficiencies achieved in process equipment. Since two liquid phases that are immiscible are used, the thermodynamic equilibrium involves considerable evaluation of nonideal solutions. In the simplest case a feed solvent F contains a solute that is to be transferred into an extraction solvent S. 

When the equihbrium line is not straight, Treybal Liquid Extraction, 2d ed., McGraw-Hill, New York, 1963) recommends that the geometric mean value of m be used. The geometric mean of the slope of the equilibrium hue at the concentration leaving the feed state and at the raffinate concentration leaving the raffinate stage is... 

For liquid/liquid extraction, data on mass transfer rate of the system at typical operating conditions are required. Also required are an applicable liquid/liquid equilibrium curve and data on chemical reactions occurring after mass transfer in the mixer. 

Steady State Equilibrium Stage. Liquid-liquid extractions are used in many different... 

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) ... 

Fig. 119. Diagram of one- stage liquid-liquid extraction (1 - equilibrium curve, 2 - one-stage process)...

In processing, it is frequently necessary to separate a mixture into its components and, in a physical process, differences in a particular property are exploited as the basis for the separation process. Thus, fractional distillation depends on differences in volatility. gas absorption on differences in solubility of the gases in a selective absorbent and, similarly, liquid-liquid extraction is based on on the selectivity of an immiscible liquid solvent for one of the constituents. The rate at which the process takes place is dependent both on the driving force (concentration difference) and on the mass transfer resistance. In most of these applications, mass transfer takes place across a phase boundary where the concentrations on either side of the interface are related by the phase equilibrium relationship. Where a chemical reaction takes place during the course of the mass transfer process, the overall transfer rate depends on both the chemical kinetics of the reaction and on the mass transfer resistance, and it is important to understand the relative significance of these two factors in any practical application. 

Depicted in Fig. 2, microemulsion-based liquid liquid extraction (LLE) of biomolecules consists of the contacting of a biomolecule-containing aqueous solution with a surfactant-containing lipophilic phase. Upon contact, some of the water and biomolecules will transfer to the organic phase, depending on the phase equilibrium position, resulting in a biphasic Winsor II system (w/o-ME phase in equilibrium with an excess aqueous phase). Besides serving as a means to solubilize biomolecules in w/o-MEs, LLE has been frequently used to isolate and separate amino acids, peptides and proteins [4, and references therein]. In addition, LLE has recently been employed to isolate vitamins, antibiotics, and nucleotides [6,19,40,77-79]. Industrially relevant applications of LLE are listed in Table 2 [14,15,20,80-90]. 

The problems relating to mass transfer may be elucidated out by two clear-cut yet different methods one using the concept of equilibrium stages, and the other built on diffusional rate processes. The selection of a method depends on the type of device in which the operation is performed. Distillation (and sometimes also liquid extraction) are carried out in equipment such as mixer settler trains, diffusion batteries, or plate towers which contain a series of discrete processing units, and problems in these spheres are usually solved by equilibrium-stage calculation. Gas absorption and other operations which are performed in packed towers and similar devices are usually dealt with utilizing the concept of a diffusional process. All mass transfer calculations, however, involve a knowledge of the equilibrium relationships between phases. 

Perry et al. (1997) give a useful summary of solubility data. Liquid-liquid equilibrium compositions can be predicted from vapour-liquid equilibrium data, but the predictions are seldom accurate enough for use in the design of liquid-liquid extraction processes. 

Solvent extraction, sometimes called liquid-liquid extraction, involves the selective transfer of a substance from one liquid phase to another. Usually, an aqueous solution of the sample is extracted with an immiscible organic solvent. For example, if an aqueous solution of iodine and sodium chloride is shaken with carbon tetrachloride, and the liquids allowed to separate, most of the iodine will be transferred to the carbon tetrachloride layer, whilst the sodium chloride will remain in the aqueous layer. The extraction of a solute in this manner is governed by the Nernstpartition or distribution law which states that at equilibrium, a given solute will always be distributed between two essentially immiscible liquids in the same proportions. Thus, for solute A distributing between an aqueous and an organic solvent,... 

Liquid-liquid extraction is a form of solvent extraction in which the solvents produce two immiscible liquid phases. The separation of analytes from the liquid matrix occurs when the analyte partitions from the matrix-liquid phase to the other. The partition of analytes between the two phases is based on their solubilities when equilibrium is reached. Usually, one of the phases is aqueous and the other is an immiscible organic solvent. Large, bulky hydrophobic molecules like to partition into an organic solvent, while polar and/or ionic compounds prefer the aqueous phase. 

This model of liquid extraction is symmetrical to fractional crystallization and has attracted renewed interest after the demonstration by Johnson et al. (1990) that REE distributions in abyssal peridotite clinopyroxene cannot be accounted for by equilibrium melting processes. The solid is supposed to maintain its chemical homogeneity while liquid is continuously extracted. Only the last drop of liquid is supposed to be in equilibrium with the residue. 

The mechanism of transfer of solute from one phase to the second is one of molecular and eddy diffusion and the concepts of phase equilibrium, interfacial area, and surface renewal are all similar in principle to those met in distillation and absorption, even though, in liquid-liquid extraction, dispersion is effected by mechanical means including pumping and agitation, except in standard packed columns. 

Liquid-Liquid Extraction Principle. If a liquid solvent which is either immiscible or only partially miscible is mixed with a solution containing solute A, the solute will distribute between the two liquids until equilibrium is established. The solute s concentration in the two phases at equilibrium will depend on its relative affinity for the two solvents. Although... 

One method which is little known, but very useful for purifying intractable liquids, is fractional precipitation it is an equilibrium method and is a form of liquid-liquid extraction. 

The basic for developing a high pressure liquid extraction unit is the phase equilibrium for the (at least) ternary system, made up of compound A and compound B, which have to be separated by the supercritical fluid C. Changing pressure and temperature influences on one hand the area of the two phase region, where extraction takes place, and on the other hand the connodes, representing the equilibrium between extract and raffinate phase. 

J. Wisniak and A. Tamir, Liquid-Liquid Equilibrium and Extraction Bibliography, Elsevier, New York, 1980. 

Inlerfacial Contact Area and Approach to Equilibrium. Experimental extraction cells such as the original Lewis stirred cell are often operated with a flat liquid-liquid interface the area of which can easily he measured. In the single-drop apparatus, a regular sequence of drops uf known diameter is released through the continuous phase. These units are useful for the direct calculation of the mass flux N and hence the mass-transfer coefficient for a given system. In industrial equipment, however, it is usually necessary to create a dispersion of drops in order to achieve a large specific inlerfacial area. u. defined as the inlerfacial conlael area per unit volume of two-phase dispersion. Thus the mass-lransler rale obtainable per unit volume... 

Wisniak, J. and A. Tamil Liquid-Liquid Equilibrium and Extraction, Elsevier... 

Water-to-droplet MT of 2-ferrocenyl-2-propanol (FeCp-PrOH) has been also studied in detail, as a t dependence of Q(t) (Figure 19). The Q(t) value almost saturates to 0.75 nC at t 30 s for the droplet (C0 = 0.047 M) with r = 4.3 fim. Q(t) at the distribution reequilibrium (Qeq), calculated on the basis of a droplet radius (Keq = 700) and the contact angle of an NB droplet on an Au electrode ( 120°), is 1.3 nC, so that the value is larger than the observed saturated Q(t) value in Figure 19. Liquid/liquid extraction experiments of FeCp-PrOH for a large number of NB droplets indicate that the time required for the distribution equilibrium is > 103 s. Clearly, water-to-... 

Wisniak, J., and Tamir, A. (1980, 1981). Liquid-Liquid Equilibrium and Extraction A Literature Source Book. Amsterdam Elsevier. 

Treybal, in his book Liquid Extraction [1], works equilibrium material balances with triangular coordinates. The most unique and simple way to show three-phase equilibrium is a triangular diagram (Fig. 7.1), which is used for extraction unit operation in cumene synthesis plants [2], In this process benzene liquid is used as the solvent to extract acetic acid (the solute) from the liquid water phase (the feed-raffinate). The curve D,S,P,F,M is the equilibrium curve. Note that every point inside the triangle has some amount of each of the three components. Points A,... 

Static headspace extraction is also known as equilibrium headspace extraction or simply as headspace. It is one of the most common techniques for the quantitative and qualitative analysis of volatile organic compounds from a variety of matrices. This technique has been available for over 30 years [9], so the instrumentation is both mature and reliable. With the current availability of computer-controlled instrumentation, automated analysis with accurate control of all instrument parameters has become routine. The method of extraction is straightforward A sample, either solid or liquid, is placed in a headspace autosampler (HSAS) vial, typically 10 or 20 mL, and the volatile analytes diffuse into the headspace of the vial as shown in Figure 4.1. Once the concentration of the analyte in the headspace of the vial reaches equilibrium with the concentration in the sample matrix, a portion of the headspace is swept into a gas chromatograph for analysis. This can be done by either manual injection as shown in Figure 4.1 or by use of an autosampler. 

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