Extraction solvating extractants

The organic extractants used for the separation of metal ions broadly fall into three classes, chelating extractants, solvating extractants, and ion-pair extractants. For the first two classes, usually nonpolar organic diluent is preferred. On the other hand, polar diluents are preferred in the case of ion-pair extraction. 

The governing equation for uranium extraction (solvating extraction) by TBP is... 

Marcus, Y., Kertes, A.S., and Yanir, E., lUPAC Chemical Data Series Equilibrium Constants of Liquid-Liquid Distribution Reactions. Part LH Compourui Eorming Extractants, Solvating Extractants and Inert Solvents, Pergamon Press, Oxford, 1977. 

Protein molecules extracted from Escherichia coli ribosomes were examined by viscosity, sedimentation, and diffusion experiments for characterization with respect to molecular weight, hydration, and ellipticity. These dataf are examined in this and the following problem. Use Fig. 9.4a to estimate the axial ratio of the molecules, assuming a solvation of 0.26 g water (g protein)"V At 20°C, [r ] = 27.7 cm g" and P2 = 1.36 for aqueous solutions of this polymer. 

Solvating extractants contain one or more electron donor atoms, usually oxygen, which can supplant or partially supplant the water which is attached to the metal ions. Perhaps the best known example of such an extractant is tri-( -butyl) phosphate) [126-73-8] (TBP), which forms... 

A process developed in Israel (263) uses solvent extraction using a higher alcohol or other solvating solvent. This removes phosphoric acid and some hydrochloric acid from the system driving the equiHbrium of equation 42 to the right. The same principle can be appHed in other salt—acid reactions of the form... 

Neutral Extractants. Many neutral organophosphoms extractants are available phosphate esters, phosphonate esters, phosphinate esters, and phosphine oxides. The most popular neutral extractant is tributylphosphate (TBP), which reacts with RE elements according to a solvation mechanism ... 

Supercritical Fluid Extraction. Supercritical fluid (SCF) extraction is a process in which elevated pressure and temperature conditions are used to make a substance exceed a critical point. Once above this critical point, the gas (CO2 is commonly used) exhibits unique solvating properties. The advantages of SCF extraction in foods are that there is no solvent residue in the extracted products, the process can be performed at low temperature, oxygen is excluded, and there is minimal protein degradation (49). One area in which SCF extraction of Hpids from meats maybe appHed is in the production of low fat dried meat ingredients for further processed items. Its apphcation in fresh meat is less successful because the fresh meat contains relatively high levels of moisture (50). 

A paiticularly attiactive and useful feature of supeicritical fluids is that these materials can have properties somewhere between those of a gas and a hquid (Table 2). A supercritical fluid has more hquid-hke densities, and subsequent solvation strengths, while possessiag transport properties, ie, viscosities and diffusivities, that are more like gases. Thus, an SCF may diffuse iato a matrix more quickly than a Hquid solvent, yet still possess a Hquid-like solvent strength for extracting a component from the matrix. 

Figure 1 shows the mechanistic picture developed by C. M. Starks (1,2) for Hquid—Hquid PTC in a graphical form. The catalyst cation extracts the more hpholilic anion Y from the aqueous to the nonpolar organic phase where it is present in the form of a poorly solvated ion pair Y ]. This then reacts rapidly with RX, and the newly formed ion pair X ] returns to the aqueous phase for another exchange process X — Y . In practice most catalyst cations used are rather lipophilic and do not extract strongly into the aqueous phase so that the anions are exchanged at the phase boundary. 

In this study we examined the influence of concentration conditions, acidity of solutions, and electrolytes inclusions on the liophilic properties of the surfactant-rich phases of polyethoxylated alkylphenols OP-7 and OP-10 at the cloud point temperature. The liophilic properties of micellar phases formed under different conditions were determined by the estimation of effective hydration values and solvatation free energy of methylene and carboxyl groups at cloud-point extraction of aliphatic acids. It was demonstrated that micellar phases formed from the low concentrated aqueous solutions of the surfactant have more hydrophobic properties than the phases resulting from highly concentrated solutions. The influence of media acidity on the liophilic properties of the surfactant phases was also exposed. 

Based on the calculation of the solvatation free energy of methylene fragment with carboxyl at the aliphatic carboxylic acids extraction, the uniqueness of cloud-point phases was demonstrated, manifested in their ability to energetically profitably extract both hydrophilic and hydrophobic molecules of substrates. The conclusion is made about the universality of this phenomenon and its applicability to other kinds of organized media on the surfactant base. 

Polarity. The increase in the polarity of the plasticizer (e.g. existence of polar groups, substitution of aryl groups by alkyl ones) reduces softening efficiency, worsens low-temperature properties of the plasticized polymers, improves solvation, and reduces extractability by aliphatic solvents. 

The mode of extraction in these oxonium systems may be illustrated by considering the ether extraction of iron(III) from strong hydrochloric acid solution. In the aqueous phase chloride ions replace the water molecules coordinated to the Fe3+ ion, yielding the tetrahedral FeCl ion. It is recognised that the hydrated hydronium ion, H30 + (H20)3 or HgO,, normally pairs with the complex halo-anions, but in the presence of the organic solvent, solvent molecules enter the aqueous phase and compete with water for positions in the solvation shell of the proton. On this basis the primary species extracted into the ether (R20) phase is considered to be [H30(R20)3, FeCl ] although aggregation of this species may occur in solvents of low dielectric constant. 

Solvated polymers are approaching "gels" in properties, depending on the mobility of the molecules. In some cases the action of a binder and of a separator are combined. By extraction of one of the components and refilling the voids with a liquid, a two-phase system can be created (Bellcore). There are irreversible and re-... 

The ion pair extraction by flow injection analysis (FIA) has been used to analyze sodium dodecyl sulfate and sodium dodecyl ether (3 EO) sulfate among other anionic surfactants. The solvating agent was methanol and the phase-separating system was designed with a PTFE porous membrane permeable to chloroform but impermeable to the aqueous solution. The method is applicable to concentrations up to 1.25 mM with a detection limit of 15 pM [304]. 

FIGURE 37.5 General refining techniques for production of distillate aromatic extract (DAE), mild extraction solvate (MES), and treated distillate aromatic extract (TDAE). (From Joona, M., High-aromatic tire extender oils implications and future, ITEC, OH, 2004.)... 

Apart from the study of physicochemical aspects such as ion solvation, and bio-mimetic aspects such as photosynthesis or carrier-mediated ion transfer (Volkov et al., 1996, 1998), there are several areas of potential applications of electrochemical IBTILE measurements comprising electroanalysis, lipophilicity assessment of drugs, phase transfer catalysis, electro-assisted extraction, and electrocatalysis. 

Statishcal criteria of Eq. (24) are too good the standard deviation, which was created on the basis of different measurements by various authors, is much less than even the experimental error of determinahon. This could be due to mutual intercorrelation of descriptors leading to over-ophmistic statistics [18]. Another reason may be the lack of diversity in the training set. The applicahon of the solvation equation to data extracted from the MEDchem97 database gave much more modest results n = 8844, = 0.83, root mean square error = 0.674, F = 8416... 

Accelerated solvent extraction (ASE) is a technique which attempts to merge the beneficial solvation properties of SFE with traditional organic solvents. Specifically, the sample is placed in an extraction vessel which can withstand high pressures while being maintained at a constant temperature. Extraction is carried out by pumping the extraction solvent through the samples for a limited time. As an example of the use of ASE, Richter and Covino extracted PCBs from a 10-g fish tissue sample with hexane... 

Clearly, then, the chemical and physical properties of liquid interfaces represent a significant interdisciplinary research area for a broad range of investigators, such as those who have contributed to this book. The chapters are organized into three parts. The first deals with the chemical and physical structure of oil-water interfaces and membrane surfaces. Eighteen chapters present discussion of interfacial potentials, ion solvation, electrostatic instabilities in double layers, theory of adsorption, nonlinear optics, interfacial kinetics, microstructure effects, ultramicroelectrode techniques, catalysis, and extraction. 

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