Extractions, partition coefficient measurement

The following physico-chemical properties of the analyte(s) are important in method development considerations vapor pressure, ultraviolet (UV) absorption spectrum, solubility in water and in solvents, dissociation constant(s), n-octanol/water partition coefficient, stability vs hydrolysis and possible thermal, photo- or chemical degradation. These valuable data enable the analytical chemist to develop the most promising analytical approach, drawing from the literature and from his or her experience with related analytical problems, as exemplified below. Gas chromatography (GC) methods, for example, require a measurable vapor pressure and a certain thermal stability as the analytes move as vaporized molecules within the mobile phase. On the other hand, compounds that have a high vapor pressure will require careful extract concentration by evaporation of volatile solvents. 

MHE can be used for substances of high volatility with a small partition coefficient. Method is based on a stepwise gas extraction at equal time intervals. Normal headspace chromatogram is run, a fraction of the gas phase exhausted, and a second headspace chromatogram is run. -The difference in petUc areas provides a measure of the total peak area of the analyte. 

Lower molecular-weight quaternary ammonium halides, which partition across the two-phase system, transfer anions in measurable concentrations from the aqueous to the organic phase but, in contrast, many of the higher-molecular-weight quaternary ammonium halides with more than ca. 30 carbon atoms are virtually insoluble in aqueous media and their partition coefficients between aqueous and organic phases preclude the transfer of anions efficiently across the interface by the extraction process and yet catalysts, such as Aliquat 336 and Adogen 464, are extremely effective catalysts. 

Partition Coefficients of nonvl-phenyl-poly-(ethoxy)-ethanol (NPE) Surfactants. The solubility of surfactants in water and hydrophobic solvents is well documented (11,12,22), but only a few attempts at measuring partition coefficients between immiscible liquids have been reported (2,4,9,10). Partition coefficients of surfactants are of theoretical interest because of their relation to observed surfactant properties such as emulsification, wetting and detergency. Partition coefficients (K ) may be also of considerable practical value for predicting surfactant recov and recycling in industrial processes. For example, in the cold water extraction of tar sand, an effective surfactant with a high Kp could be efficiently recycled in the process water and would not follow the bitumen into the upgrading stream. 

Using the rules of the propagation of errors [33,34] a measure of the robustness of the partition coefficient (C, ) and the robustness of the selectivity (C ) can be obtained. Below, a derivation of robustness of the partition coefficient P, of a compound i and the selectivity Uij for two compounds i and j with respect to variation in extraction liquid composition is given. The general form of a (Special Cubic) mixture model for three-component mixtures is given by ... 

For correct determination of the recoveries and the partition coefficients, each tube was weighed separately before and after the extraction solvent dispensing step (to give w, ) and before and after phase separation (to give out)- Kn was calculated from w, and from the density of the extraction liquid considered. This way the exact volumes used could be measured, which were used to calculate the partition coefficients ... 

Why discuss distribution coefficients Most everyone is familiar with the demonstration of iodine distributed between an organic and an aqueous layer. However, distribution equilibria are at the heart of many separation processes from liquid-liquid extractions to virtually every type of chromatography in which the distribution of the solute between the mobile phase and the stationary phase determines the effectiveness of the separation. In the practice of analytical chromatography, distribution coefficients are often called partition coefficients but the concept is identical, only the names have changed. The temperature dependence of a distribution coefficient is at the heart of temperature programming in gas-liquid chromatography (GC), and analyses of the temperature behavior depend on the heats of solution of the distributed solutes. Indeed, GC measurements have been used to measure heats of solution. 

Selective extractions can be carried out by careful selection of pH. When extracting organic species it must be remembered that compounds may exist as different species, depending on the pH. Pnw, the partition coefficient of a solute between octanol and water, is a common measure of hydrophobicity. High values of log Pow are favorable for extraction. Reversed-phase HPLC has also been extensively used. 

Whereas several specific soil attributes are advocated as being responsible for DOC sorption in the mineral soil (Table V), it appears that the greater the clay or aluminum and iron oxide content of a soil, the greater its adsorptive capacity for DOC. For example, there is a positive correlation between m (the measure of the affinity of a substance for the sorbent or the partition coefficient) and soil clay content, dithionite extractable iron (Fej), and oxalate extractable aluminum (Al0) (Moore et al., 1992 Nelson et al., 1993 Kaiser and Zech, 1998). Direct measurements of the surface area of soil particles also correlate very well with DOC adsorption capacity (Nelson et al., 1993). Furthermore, Nelson et al. (1993) report that riverine DOC concentrations are negatively correlated to the clay content of watershed... 

The partition coefficient for pentazocine has been measured between various organic and aqueous phases. The results of four studies are shown in Table 4. The first value was obtained by a single extraction using 50 mL of each phase while the second value is from a countercurrent distribution study with pentazocine added to the aqueous phase and extracted eight times into benzene. The third value was obtained by the single extraction method with the additional definition of a distribution ratio, DnOH for pentazocine using the partition coefficient k NOH) in the relation ... 

The performance of SLM extraction is characterized by two measures the enrichment factor (Ec) and the extraction efficiency (E). E measures how much of the analyte in the sample is recovered on the acceptor side after extraction E = (CA/CS) x (VJV%), and Et reflects how many times the concentration in the acceptor is increased compared to the initial sample concentration Ee = (CA/CS). CA and Cs are the final acceptor and initial sample concentrations, respectively. Similarly, VA and Vs are the acceptor and sample volumes, respectively. A more comprehensive elaboration of SLM principles63 and mass transfer kinetics,62 64 as well as the role of the octanol-water partition coefficient in SLM extraction of ionizable compounds,65 is given elsewhere. 

The octanol-water partition coefficient (Kow), characterizing distribution of a non-ionized compound between an octanol (o) and an immiscible aqueous (w) layer, may function as a measure of lipophilicity, that is often listed as its logarithmic value (log P). Therefore, log P may be used as a predictor of extractability in LLE. Table 1 presents log P values of TA calculated by the Molinspiration software [25] using SMILES notation for chemical structures. The SMILES concept is addressed in the next section [26], Conformity of calculated (calc.) and experimental (exp.) log P values is satisfying, as exemplarily shown for atropine (1.83 exp. [27] 1.77 calc.) and scopolamine (0.98 exp. [22] 1.05 calc.). 

Micelle-water partition coefficients are extracted by micelle chromatography (high performance liquid chromatography, HPLC) using micelle aqueous solution as mobile phase. For determination of retention times are measured using a usual HPLC system at various concentrations of micelle in the aqueous mobile phase and then estimated from the following equation ... 

Partition coefficients (octanol/ water) Vanillin, acetaminophen, metoprolol Octanol UV-Vis Wet film extraction in a capillary flow system measurements in both phases [192]... 

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