Solvent extraction distribution coefficient

Schugerl 115] has recently furnished a detail analysis of the reactive extraction of penicdlin-G and V and precursors like phenyl and phenoxy acetic acids. Thirty different amines have been studied for reactive extraction of penicillins 116] in various solvents such as butyl acetate, chloroform, di-isopropyl ether, kerosene, dioctyl ether, etc. Tertiary amines in n-butyl acetate were found to be advantageous because of their low reactivity with solvent but the distribution coefficients of their complexes are significantly lower than those of secondary amines. While using quaternary ammonium salts for ion-exchange extraction, re-extraction is difficult and very large amounts of anion (e.g.. Cl ) are needed to recover penicillins. The basic relationship for distribution coefficient and extraction kinetics have now been fairly developed for amine-penicillin systems. 

The distribution coefficient for extraction of a metal complex from aqueous to organic solvents is D = [total metal ()rg/... 

As reviewed by Fidelis and Mioduski57) the formation constant K of a complex with a given" ligand (or the distribution coefficient for extraction in another solvent, or an ion-exchange resin) shows a ratio (in the case of two consecutive lanthanides) which provides perceptible variations (from a constant) not only at the half-filled shell (q = 7) Gd(III) but also at the plateaux q = 3 and 4, as well as 10 and 11. These quarter-shell effects can be rationalized 217,218) by the refined spin-pairing energy theory. If D of Eq. (3) is decreased 1 % (65 cm 1) by the nephelauxetic effect in a... 

Table 15.2-1 Equilibrium Distribution Coefficients for Extraction of Phenol and Higher Phenols from Water with Various Solvents...

In many solvent extraction systems, addition of solutes to the aqueous phase increases the distribution coefficient of extractable components. Data in Table 4.2 and Fig. 4.6 show how addition of nitrates to an aqueous solution of uranyl nitrate increases the distribution coefficient of uranyl nitrate between the aqueous phase and diethyl ether [F2]. The increase in distribution coefficients with increased nitrate concentration is explained as follows Analysis of... 

FIGURE 15.2-4 Concentration-based equilibrium distribution coefficients for extraction of phenol from dilute aqueous solution into a solvent mixture composed of 25% w/w TOPO in DIBK. ... 

In the early days of solvent extraction, the organic diluent was often referred to as inert . With further study it became obvious that the organic diluent was anything but inert. Many orders of magnitude variation was observed in the distribution coefficients of extracted metal ions as a function of the organic solvent. In some systems, the stoichiometry of the extracted species (or the extractant) was altered by... 

Long-chain, aliphatic amines ate effective extractants for separation of carboxylic acids from dilute aqueous solution (Yang et al., 1991). Generally, the amine extractants are dissolved in a diluent, an organic solvent that dilutes the extractant. It controls the viscosity and density of the solvent phase. In order to improve the amine s solvation power, diluents such as oleyl alcohol, chloroform, methyl isobutyl ketone, and 1-octanol have been used. The diluents affect the basicity of the amine, the stabiUty of the acid amine complex formed and its solvation power. The pH of the aqueous phase is an important parameter for the reactive extraction of organic acids (Kahya et al., 2001). In the present study, various pure diluents are used for extraction of propionic acid from aqueous solution. On the basis of distribution coefficients, reactive extraction is also carried out with amine extractant for the recovery of propionic acid. 

It has been shown that this principle applies to any number of stages i.e., the optimum use of adsorbent requires an equal division of that adsorbent among the stages of a crosscurrent cascade. The same principle applies to crosscurrent extraction of systems with mutually insoluble solvents. The solute recovery or removal that results in such cascades is depicted graphically in Figure 7.9. In this plot, m represents the distribution coefficient for extraction or Henry s constant H for adsorption, E is the so-called extraction factor mB/A or HS/L, and Y or x is the effluent concentration from the nth stage of the solution being treated. 

The constant K is termed the distribution or partition coefficient. As a very rough approximation the distribution coefficient may be assumed equal to the ratio of the solubilities in the two solvents. Organic compounds are usually relatively more soluble in organic solvents than in water, hence they may be extracted from aqueous solutions. If electrolytes, e.g., sodium chloride, are added to the aqueous solution, the solubility of the organic substance is lowered, i.e., it will be salted out this will assist the extraction of the organic compound. 

Hence one extraction with 100 ml. of benzene removes 3 0 g. (or 75 per cent.) of the n-butyric acid, whilst three extractions remove 3 5 g. (or 87-5 per cent.) of the total acid. This clearly shows the greater efficiency of extraction obtainable with several extractions when the total volume of solvent is the same. Moreover, the smaller the distribution coefficient between the organic solvent and the water, the larger the number of extractions that will be necessary. 

Miscellaneous Pharmaceutical Processes. Solvent extraction is used for the preparation of many products that ate either isolated from naturally occurring materials or purified during synthesis. Among these are sulfa dmgs, methaqualone [72-44-6] phenobarbital [50-06-6] antihistamines, cortisone [53-06-5] estrogens and other hormones (qv), and reserpine [50-55-5] and alkaloids (qv). Common solvents for these appHcations are chloroform, isoamyl alcohol, diethyl ether, and methylene chloride. Distribution coefficient data for dmg species are important for the design of solvent extraction procedures. These can be determined with a laboratory continuous extraction system (AKUEVE) (244). 

Among the properties sought in the solvent are low cost, avadabihty, stabiUty, low volatiUty at ambient temperature, limited miscibility in aqueous systems present in the process, no solvent capacity for the salts, good solvent capacity for the acids, and sufficient difference in distribution coefficient of the two acids to permit their separation in the solvent-extraction operation. Practical solvents are C, C, and alcohols. For industrial process, alcohols are the best choice (see Amyl alcohols). Small quantities of potassium nitrate continue to be produced from natural sources, eg, the caUche deposits in Chile. 

The equihbrium distribution coefficient can be calculated by material balance, using the weight of the feed F, raffinate R, and extract E, plus the weight-fraction solute in the feed xy and raffinate iv, when the weight-fraction solute in the extraction solvent y, is zero [Eq. (15-8)]. 

Extraction from Aqueous Solutions Critical Fluid Technologies, Inc. has developed a continuous countercurrent extraction process based on a 0.5-oy 10-m column to extract residual organic solvents such as trichloroethylene, methylene chloride, benzene, and chloroform from industrial wastewater streams. Typical solvents include supercritical CO9 and near-critical propane. The economics of these processes are largely driven by the hydrophihcity of the product, which has a large influence on the distribution coefficient. For example, at 16°C, the partition coefficient between liquid CO9 and water is 0.4 for methanol, 1.8 for /i-butanol, and 31 for /i-heptanol. 

This may be illustrated by the following example. Suppose that 50 mL of water containing 0.1 g of iodine are shaken with 25 mL of carbon tetrachloride. The distribution coefficient of iodine between water and carbon tetrachloride at the ordinary laboratory temperature is 1 /85, i.e. at equilibrium the iodine concentration in the aqueous layer is 1 /85th of that in the carbon tetrachloride layer. The weight of iodine remaining in the aqueous layer after one extraction with 25 mL, and also after three extractions with 8.33 mL of the solvent, can be calculated by application of the above formula. In the first case, if x, g of iodine remains in the 50 mL of water, its concentration is x,/50 gmL 1 the concentration in the carbon tetrachloride layer will be (0.1 —x1)/25gmL 1. 

The effect of irradiation on the extractability of sulfoxides towards plutonium, uranium and some fission products were studied by Subramanian and coworkers . They studied mainly the effect of irradiation on dihexyl sulfoxide (DHSO) and found that irradiation did not change the distribution coefficient for Ru, Eu and Ce but increases the distribution coefficient for Zr and Pu. When comparing DHSO and tributyl phosphate (TBP), the usual solvent for the recovery and purification of plutonium and uranium from spent nuclear fuels, the effect of irradiation to deteriorate the extraction capability is much larger in TBP. Lan and coworkers studied diphenyl sulfoxides as protectors for the gamma radiolysis of TBP. It was found that diphenyl sulfoxide can accept energy from two different kinds of excited TBP and thus inhibits the decomposition of the latter. 

When the distribution coefficient for the desired solute from aqueous solutions into even the best of solvents is unfavourable it may become attractive to superimpose reaction. Consider the. separation of citric acid from aqueous solutions, for which physical extraction is unattractive. Here we can use a bulky tertiary amine, e.g. tri-2-ethylhexylamine, which has a very low solubility in water, and dissolve it in a suitable, water-insoluble solvent this will... 

Equation (31) is true only when standard chemical potentials, i.e., chemical solvation energies, of cations and anions are identical in both phases. Indeed, this occurs when two solutions in the same solvent are separated by a membrane. Hence, the Donnan equilibrium expressed in the form of Eq. (32) can be considered as a particular case of the Nernst distribution equilibrium. The distribution coefficients or distribution constants of the ions, 5 (M+) and B X ), are related to the extraction constant the... 

When using any solvent extraction system, one of the most important decisions is the selection of the solvent to be used. The properties which should be considered when choosing the appropriate solvent are selectivity distribution coefficients insolubility recoverability density interfacial tension chemical reactivity viscosity vapour pressure freezing point safety and cost. A balance must be obtained between the efficiency of extraction (the yield), the stability of the additive under the extraction conditions, the (instrumental and analyst) time required and cost of the equipment. Once extracted the functionality is lost and... 

Essentially, extraction of an analyte from one phase into a second phase is dependent upon two main factors solubility and equilibrium. The principle by which solvent extraction is successful is that like dissolves like . To identify which solvent performs best in which system, a number of chemical properties must be considered to determine the efficiency and success of an extraction [77]. Separation of a solute from solid, liquid or gaseous sample by using a suitable solvent is reliant upon the relationship described by Nemst s distribution or partition law. The traditional distribution or partition coefficient is defined as Kn = Cs/C, where Cs is the concentration of the solute in the solid and Ci is the species concentration in the liquid. A small Kd value stands for a more powerful solvent which is more likely to accumulate the target analyte. The shape of the partition isotherm can be used to deduce the behaviour of the solute in the extracting solvent. In theory, partitioning of the analyte between polymer and solvent prevents complete extraction. However, as the quantity of extracting solvent is much larger than that of the polymeric material, and the partition coefficients usually favour the solvent, in practice at equilibrium very low levels in the polymer will result. 

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