Extraction principles distribution

The principle of solvent extraction—the distribution of chemical species between two immiscible liquid phases—has been applied to many areas of chemistry. A typical one is liquid partition chromatography, where the principle of solvent extraction provides the most efficient separation process available to organic chemistry today its huge application has become a field (and an industry ) of its own. The design of ion selective electrodes is another application of the solvent extraction principle it also has become an independent field. Both these applications are only briefly touched upon in the chapter of this book on analytical applications (Chapter 14), as we consider them outside the scope of... 

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... 

See also Countercurrent Chromatography Solvent Extraction with a Helical Column. Extraction Solvent Extraction Principles Solvent Extraction Multistage Countercurrent Distribution Pressurized Fluid Extraction Supercritical Fluid Extraction. 

See also Atomic Absorption Spectrometry Interferences and Background Correction. Atomic Emission Spectrometry Principles and Instrumentation Interferences and Background Correction Flame Photometry Inductively Coupled Plasma Microwave-Induced Plasma. Atomic Mass Spectrometry Inductively Coupled Plasma Laser Microprobe. Countercurrent Chromatography Solvent Extraction with a Helical Column. Derivatization of Analytes. Elemental Speciation Overview Practicalities and Instrumentation. Extraction Solvent Extraction Principles Solvent Extraction Multistage Countercurrent Distribution Microwave-Assisted Solvent Extraction Pressurized Fluid Extraction Solid-Phase Extraction Solid-Phase Microextraction. Gas Chromatography Ovenriew. Isotope Dilution Analysis. Liquid Chromatography Ovenriew. 

An example for the principle of extracting a distribution function from an LIF spectrum is shown in Figure 7.6. 

For preparative purposes batch fractionation is often employed. Although fractional crystallization may be included in a list of batch fractionation methods, we shall consider only those methods based on the phase separation of polymer solutions fractional precipitation and coacervate extraction. The general principles for these methods were presented in the last section. In this section we shall develop these ideas more fully with the objective of obtaining a more narrow distribution of molecular weights from a polydisperse system. Note that the final product of fractionation still contains a distribution of chain lengths however, the ratio M /M is smaller than for the unfractionated sample. 

Ultrasonic Spectroscopy. Information on size distribution maybe obtained from the attenuation of sound waves traveling through a particle dispersion. Two distinct approaches are being used to extract particle size data from the attenuation spectmm an empirical approach based on the Bouguer-Lambert-Beerlaw (63) and a more fundamental or first-principle approach (64—66). The first-principle approach implies that no caHbration is required, but certain physical constants of both phases, ie, speed of sound, density, thermal coefficient of expansion, heat capacity, thermal conductivity. 

The study of the mechanism of cloud point micellar extractions by phases of non-ionic surfactant (NS) is an aspect often disregarded in most literature reports and, thus, is of general interest. The effective application of the micellar extraction in the analysis is connected with the principled and the least studied problem about the influence of hydrophobicity, stmcture and substrate charge on the distribution between the water and non-ionic surfactant-rich phase. 

To understand the fundamental principles of extraction, the various terms used for expressing the effectiveness of a separation must first be considered. For a solute A distributed between two immiscible phases a and b, the Nernst Distribution (or Partition) Law states that, provided its molecular state is the same in both liquids and that the temperature is constant ... 

In principle, the electronic quadrupole can also be extracted from the calculated valence charge distribution. This is a tensor quantity and its components are defined by the matrix... 

An additional method of increasing the efficiency of liquid-liquid extraction is based on the countercurrent distribution principle [80-861 Early countercurrent distribution apparatus... 

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. 

Using MS detection relaxes the constraints on LC resolution, because additional separation occurs in the mass domain. In principle, LC-MS may yield a complete 2D distribution of a polymer according to chemical composition and molar mass. If MS detection is employed, the efficient cleaning in the LC step makes it possible to use total ion monitoring and even to identify unknown compounds from the sample. As extracts often contain interfering compounds, mass spectrometry in selective ion mode is a practical detector. Fully automated multidimensional LC-MS-MS-MS systems are available. 

We shall also outline how bond distances and information pertaining to the distribution of electron density may, in principle, be extracted from measurements carried out using electron microscopy. Finally we touch upon future possible lines of development likely to be of value to the inorganic, surface and analytical chemist. 

Although in principle stationary and transport-specific energy chains can be analysed, here the assessment of the latter is explained in more detail, and is then referred to as well-to-wheel (WTW) analysis. The primary focus of WTW analysis in Europe is on global environmental impact, i.e., greenhouse-gas emissions expressed as C02-equivalents. Other issues of interest are (a) primary energy demand (which equals resource utilisation), (b) local pollutant emissions and (c) full energy or fuel supply costs. Well-to-wheel analysis covers the entire fuel supply chain from feedstock extraction, feedstock transportation, fuel manufacturing and fuel distribution to fuel use in a vehicle. 

Vibrational spectroscopy can help us escape from this predicament due to the exquisite sensitivity of vibrational frequencies, particularly of the OH stretch, to local molecular environments. Thus, very roughly, one can think of the infrared or Raman spectrum of liquid water as reflecting the distribution of vibrational frequencies sampled by the ensemble of molecules, which reflects the distribution of local molecular environments. This picture is oversimplified, in part as a result of the phenomenon of motional narrowing The vibrational frequencies fluctuate in time (as local molecular environments rearrange), which causes the line shape to be narrower than the distribution of frequencies [3]. Thus in principle, in addition to information about liquid structure, one can obtain information about molecular dynamics from vibrational line shapes. In practice, however, it is often hard to extract this information. Recent and important advances in ultrafast vibrational spectroscopy provide much more useful methods for probing dynamic frequency fluctuations, a process often referred to as spectral diffusion. Ultrafast vibrational spectroscopy of water has also been used to probe molecular rotation and vibrational energy relaxation. The latter process, while fundamental and important, will not be discussed in this chapter, but instead will be covered in a separate review [4],... 

In amorphous solids there is a considerable disorder and it is impossible to give a description of their structure comparable to that applicable to crystals. In a crystal indeed the identification of all the atoms in the unit cell, at least in principle, is possible with a precise determination of their coordinates. For a glass, only a statistical description may be obtained to this end different experimental techniques are useful and often complementary to each other. Especially important are the methods based on diffraction experiments only these will be briefly mentioned here. The diffraction pattern of an amorphous alloy does not show sharp diffraction peaks as for crystalline materials but only a few broadened peaks. Much more limited information can thus be extracted and only a statistical description of the structure may be obtained. The so-called radial distribution function is defined as ... 

The principle of solvent extraction is illustrated in Fig. 1.1. The vessel (a separatory funnel) contains two layers of liquids, one that is generally water (Sa,) and the other generally an organic solvent (S g). In the example shown, the organic solvent is lighter (i.e., has a lower density) than water, but the opposite situation is also possible. The solute A, which initially is dissolved in only one of the two liquids, eventually distributes between the two phases. When this distribution reaches equilibrium, the solute is at concentration [A]a, in the aqueous layer and at concentration [AJ g in the organic layer. The distribution ratio of the solute... 

Consider first the extraction of hexafluoroacetylacetone (HFA) by TOPO by Example 1, and, second, the extraction of nitric acid by TBP (Example 7). The principles of volume and water-structure effects, discussed for the solute A in section 4.4, are also important in the distribution of the adducts. 

Dyrssen and Sill6n [68] pointed ont that distribntion ratios obtained by conventional batchwise techniques are often too scattered to allow the determination of as many parameters as used in Examples 15 and 16. They suggested a simplified graphic treatment of the data, based on the assnmption that there is a constant ratio between successive stability constants, i.e., KJK i = 10 , and that all distribntion cnrves can be normalized so that A log Pn = where N is the number of ligands A in the extracted complex. Thns, the distribution curve log Du vs. log[A ] is described by the two parameters a and b, and the distribution constant of the complex, Tdc- The principle can be nsefnl for estimations when there is insnfficient reliable experimental data. 

The general principles established for extraction apply to stripping, although of course distribution ratios are sought that are significantly less than unity in order to accomplish the strip as efficiently as possible. 

Molecules in the gas phase provide an electron diffraction pattern which can be analyzed in order to obtain relative interatomic distances in molecules. Some of the distances depend on molecular conformation and, in principle, it is possible to extract conformational data (conformer structure and population). Rough estimates of energy barriers may also be obtained from the peak widths by comparing calculated and experimental distribution functions. Uncertainties on populations are rather high ( 10-15%). 

Although theoretical considerations are helpful to an understanding of the principles involved and may be useful for studying and predicting simple extractions of pure substances, an empirical approach ultimately must be resorted to for cases involving such complex and undefinable mixtures as kerosenes and lubricating oils. The ideal distribution law which states that the ratio of concentrations of a component distributed between two mutually insoluble phases is a constant dependent only on the temperature (K = C1/C2), is analogous to Henry s law for absorption and is rarely valid for commercial extraction problems. 

The mixture to be separated and analyzed may be either a gas, liquid, or a solid in some instances. All that is required is that the materials be stable, have a vapor pressure of 0.1 torr at the operating temperature and interact with the column material (either a solid adsorbent or a liquid stationary phase) and the mobile phase (carrier gas). The result of this interaction is the differing distribution of the sample components between the two phases, resulting in the separation of the sample components into zones or bands. The principle that governs the chromatographic separation is the foundation of most physical methods of separation, for example, distillation and liquid-liquid extraction. 

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