Extraction factor, partitioning

Extraction factor, partitioning between metal and salt phase.390-97... 

Neptunium and plutonium are partitioned by reducing Pu(IV) or Pu(VI) to inextractable Pu(III) neptunium is simultaneously reduced to Np(IV). Neptunium is kept in the organic phase by adjusting the acid in the aqueous strip solution (1BX) and the organic-to-aqueous flow ratio to maintain the extraction factor of neptunium greater than one. 

A sample contains a weak acid analyte, HA, and a weak acid interferent, HB. The acid dissociation constants and partition coefficients for the weak acids are as follows Ra.HA = 1.0 X 10 Ra HB = 1.0 X f0 , RpjHA D,HB 500. (a) Calculate the extraction efficiency for HA and HB when 50.0 mF of sampk buffered to a pH of 7.0, is extracted with 50.0 mF of the organic solvent, (b) Which phase is enriched in the analyte (c) What are the recoveries for the analyte and interferent in this phase (d) What is the separation factor (e) A quantitative analysis is conducted on the contents of the phase enriched in analyte. What is the expected relative erroi if the selectivity coefficient, Rha.hb> is 0.500 and the initial ratio ofHB/HA was lO.O ... 

An interesting consequence of selective sorption is that conditions for partition chromatography arise which may enhance the normal ion exchange separation factors. This aspect has been utilised by Korkisch34 for separation of inorganic ions by the so-called combined ion exchange-solvent extraction method (CISE). 

A cosolvent used as a miscible additive to CO2 changed the properties of the supercritical gas phase. The addition of a cosolvent resulted in increased viscosity and density of the gas mixture and enhanced extraction of the oil compounds into the C02-rich phase. Gas phase properties were measured in an equilibrium cell with a capillary viscometer and a high-pressure densitometer. Cosolvent miscibility with CO2, brine solubility, cosolvent volatility, and relative quantity of the cosolvent partitioning into the oil phase are factors that must be considered for the successful application of cosolvents. The results indicate that lower-molecular-weight additives, such as propane, are the most effective cosolvents to increase oil recovery [1472]. 

The polarity index is a measure of the polarity of the solvent, which is often the most important factor in the solvent choice for the particular application. In extraction processes, the tenet that like dissolves like (and conversely, opposites do not attract ) is the primary consideration in choosing the solvent for extraction, partitioning, and/or analytical conditions. For example, hexane often provides a selective extraction for nonpolar analytes, and toluene may provide more selectivity for aromatic analytes. 

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. 

Microwave-assisted extraction (MAE) of analytes from various matrices using organic solvents has been operative since 1986 [128], In this process microwave energy is used to heat solvents in contact with a solid sample uniformly and to partition compounds of analytical interest from the sample matrix into the solvent. The way in which microwaves enhance extraction is not fully understood. The main factors to consider include improved transport properties of molecules, molecular agitation, the heating of solvents above their boiling points and, in some cases, product selectivity. 

The partition of a solute between two immiscible liquid phases provides the basis for simple solvent extraction techniques. The polarity of both solute and solvent are important factors in determining the solubility of the solute, and polar solutes will dissolve more readily in polar solvents than in nonpolar solvents. 

The formation of two aqueous phases can be exploited in the recovery of proteins using liquid-liquid extraction techniques. Many factors contribute to the distribution of a protein between the two phases. Smaller solutes, such as amino acids, partition almost equally between the two phases, whereas larger proteins are more unevenly distributed. This effect becomes more pronounced as protein size increases. Increasing the polymer molecular weight in one phase decreases partitioning of the protein to that phase. The variation in surface properties between different proteins can be exploited to improve selectivity and yield. The use of more hydrophobic polymer systems, such as fatty acid esters of PEG added to the PEG phase, favors the distribution of more hydrophobic proteins to this phase. In Fig. 10.13, partition coefficients for several proteins in a dextran-PEG system are given [27]. 

The use of a volatile solvent, e.g., pentane, was not explored because of inherent limitations. Concentration of such extracts was not possible because of the volatility of the sample components. Therefore the maximum concentration factor that could have been achieved was limited by the partition coefficients of the compounds into the solvent used in the extraction. For most compounds this factor was estimated to be about 10 1. Furthermore, with CRMS and other general detectors, the solvent masking problem would still preclude observation of many compounds. Therefore, the method would be limited to detectors that are not responsive to the solvent used in the extraction. Recent work (3.4,5) has indicated that extraction with a volatile solvent is a viable approach for the analysis of a small set of compounds, e.g., the trihalomethanes, with an electron capture detector in drinking water samples where concentration factors of 10 1 or less are acceptable. 

With the use of the regression models a partition coefficient for each compound and a selectivity for each pair of substances can be predicted in each composition of the extraction liquid within the factor space. Figure 7.1 demonstrates the response surfaces of the partition coefficients of two compounds i and j in a binary extraction liquid i.e. an extraction liquid composed of two solvents). The compositions where the partition coefficients of i and j are optimal are represented by O, and 0, respectively. The optimal compositions with regard to the selectivity is represented by 0 . Two situations are given. 

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