Coefficient distribution

Distribution coefficients, like selectivity coefficients, arc a measure of the alfinily of the resin for a particular solute ion. A large distribution coefficient indicates that an ion-exchanger has a greater affinity of an ion. 

Some workers have used a volume distribution coefficient,.  

Experimentally, the weight distribution coefficient of an ion A in a given eluent is measured by equilibrating a known volume of standard solution with a known weight of resin and calculating the results from Eq. 5.7. The volume distribution coefficient, Dy, of an ion is calculated from its retention volume from a column with a given eluent  

The distribution coefficient K (also called partition coefficient) corresponds to the distribution of the analyte (X) between the stationary (s) and mobile (m) phases, as it elutes through the column. In equation form, K corresponds to the ratio of the concentration of the analyte [X] in the stationary phase over the concentration of the analyte in the mobile phase. 

SAMPLE PREPARATION SOLVENT AND SOLID-PHASE EXTRACTION 

Neutral organics distribute from water into organic solvents. Like dissolves like.  

Many substances are partially ionized in the aqueous layer as weak acids. This introduces a pH effect on the extraction. Consider, for example, the extraction of benzoic acid from an aqueous solution. Benzoic acid (HBz) is a weak acid in water with a particular ionization constant Ka (given by Equation 18.4). The distribution coefficient is given by 

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Two further examples of type I ternary systems are shown in Figure 19 which presents calculated and observed selectivities. For successful extraction, selectivity is often a more important index than the distribution coefficient. Calculations are shown for the case where binary data alone are used and where binary data are used together with a single ternary tie line. It is evident that calculated selectivities are substantially improved by including limited ternary tie-line data in data reduction. 

The ternary diagrams shown in Figure 22 and the selectivi-ties and distribution coefficients shown in Figure 23 indicate very good correlation of the ternary data with the UNIQUAC equation. More important, however, Table 5 shows calculated and experimental quarternary tie-line compositions for five of Henty s twenty measurements. The root-mean-squared deviations for all twenty measurements show excellent agreement between calculated and predicted quarternary equilibria. 

Figure 4-23. Calculated and experimental selectivities and distribution coefficients for the type-I ternaries in the 2,2,4-trimethyl pentane-cyclohexane-furfural-benzene system.

The most widely used descriptor for the hydrophobicity term in toxicology is the distribution coefficient between octanol and water, log Pq< - (the environmental scientists would rather call it log The bulk solvent octanol is of course a... 

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. 

In practice, it is more convenient to predict the behavior of an ion, for any chosen set of conditions, by employing a much simpler distribution coefficient, which is defined as the concentration of a solute in the resin phase divided by its concentration in the liquid phase, or ... 

By comparing the ratio of the distribution coefficients for a pair of ions, a separation factor (or relative retention) is obtained for a specific experimental condition. 

Instead of using separation data may be expressed in terms of a volume distribution coefficient ) , which is defined as the amount of solution in the exchanger per cubic centimeter of resin bed divided by the amount per cubic centimeter in the liquid phase. The relation between and is given by ... 

Intelligent inspection of the relevant distribution coefficients will show whether a separation is feasible and what the most favorable eluant concentration is likely to be. In the columnar mode, an ion, even if not eluted, may move down the column a considerable distance and with the next eluant may appear in the eluate much earlier than indicated by the coefficient in the first eluant alone. A... 

The principle of headspace sampling is introduced in this experiment using a mixture of methanol, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, benzene, toluene, and p-xylene. Directions are given for evaluating the distribution coefficient for the partitioning of a volatile species between the liquid and vapor phase and for its quantitative analysis in the liquid phase. Both packed (OV-101) and capillary (5% phenyl silicone) columns were used. The GG is equipped with a flame ionization detector. 

Distribution Coefficients. Gel-permeation stationary-phase chromatography normally exhibits symmetrical (Gaussian) peaks because the partitioning of the solute between mobile and stationary phases is linear. Criteria more sophisticated than those represented in Figure 8 are seldom used (34). 

The distribution coefficient, represents the fractional volume of a specific stationary phase explored by a given solute, represented by equation 3 ... 

Salt Effects. The definition of a capacity factor k in hydrophobic interaction chromatography is analogous to the distribution coefficient, in gel permeation chromatography ... 

The stabiHty criteria for ternary and more complex systems may be obtained from a detailed analysis involving chemical potentials (23). The activity of each component is the same in the two Hquid phases at equiHbrium, but in general the equiHbrium mole fractions are greatiy different because of the different activity coefficients. The distribution coefficient m based on mole fractions, of a consolute component C between solvents B and A can thus be expressed... 

This is the important rule of additivity of resistances. In practice, and are often of the same order of magnitude, but the distribution coefficient m can vary considerably. For solutes which preferentially distribute toward solvent B, m is large and the controlling resistance Hes in phased. Conversely, if the distribution favors solvent A the controlling mass-transfer resistance Hes in phase B. 

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). 

S. W. Karickhoff and D. S. Brown, determination of Octanol Water Distribution Coefficients, Water Solubilities, and Sediment/Water Partitions Coefficientsfor Hydrophobic Organic Pollutants, EPA-600/4-79-032, report, EPA, Washington, D.C., 1979. 

In extraction (qv), the distribution coefficient value is the slope of the equiUbrium line. In practice, the slope of the operating line is set at a value somewhat less than the distribution coefficient to provide driving force and fix the required theoretical extraction stages at some reasonable number. 

Liquid—Liquid Extraction. The tiquid—tiquid extraction process for the rare-earth separation was discovered by Fischer (14). Extraction of REE using an alcohol, ether, or ketone gives separation factors of up to 1.5. The selectivity of the distribution of two rare-earth elements, REI and RE2, between two nonmiscible tiquid phases is given by the ratio of the distribution coefficients DI and D2 ... 

Therefore the extent of extraction or back-extraction is governed by the concentration of X ia the aqueous phase, the distribution coefficients, and selectivities depending on the anion. In nitrate solutions, the distribution coefficient decreases as the atomic number of the REE increases, whereas ia thiocyanate solutions, the distribution coefficient roughly increases as the atomic number of the REE increases. The position of yttrium in the lanthanide series is not the same in nitrate and thiocyanate solutions, and this phenomenon has been used for high purity yttrium manufacture in the past. A combination of extraction by carboxyUc acids then by ammonium salts is also utilized for production of high purity yttrium. 

The distribution of highly extractable solutes such as and Pu between the aqueous and organic phases is strongly dependent upon the nitrate anion concentration in the aqueous phase. This salting effect permits extraction or reextraction (stripping) of the solute by controlling the nitric acid concentration in the aqueous phase. The distribution coefficient, D, of the solute is expressed as... 

Two ions a and b can be separated by countercurrent extraction as long as the ratio of the distribution coefficients, that is, the separation factor Q, is not unity ... 

Relative values for the various TBP distribution coefficients of the feed constituents are as follows ... 

These variations permit the separation of other components, if desired. Additional data on uranium, plutonium, and nitric acid distribution coefficients as a function of TBP concentration, solvent saturation, and salting strength are available (24,25). Algorithms have also been developed for the prediction of fission product distributions in the PUREX process (23). 

Information on ionization energies, solubiUties, diffusion coefficients, and soHd—Hquid distribution coefficients is available for many impurities from nearly all columns of the Periodic Table (86). Extrinsic Ge and Si have been used almost exclusively for infrared detector appHcations. Of the impurities,... 

In most cases, the activator impurity must be incorporated during crystal growth. An appropriate amount of impurity element is dissolved in the molten Ge and, as crystal growth proceeds, enters the crystal at a concentration that depends on the magnitude of the distribution coefficient. For volatile impurities, eg, Zn, Cd, and Hg, special precautions must be taken to maintain a constant impurity concentration in the melt. Growth occurs either in a sealed tube to prevent escape of the impurity vapor or in a flow system in which loss caused by vaporization from the melt is replenished from an upstream reservoir. 

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. 

For many modeling purposes, Nhas been assumed to be 1 (42), resulting in a simplified equation, S = C, where is the linear distribution coefficient. This assumption usually works for hydrophobic polycycHc aromatic compounds sorbed on sediments, if the equdibrium solution concentration is <10 M (43). For many pesticides, the error introduced by the assumption of linearity depends on the deviation from linearity. 

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