Ion extraction, metals

Extraction of metal ions Extraction processes Extraction resistance Extractive distillation... 

Metal ion extraction with crown ethers containing linear lateral groups capable of acid ionization 98PAC2393. 

Macrocyclic ligands such as crown ethers have been widely used for metal ion extraction, the basis for metal ion selectivity being the structure and cavity size of the crown ether. The hydrophobicity of the ligand can be adjusted by attachment of alkyl or aromatic ligands to the crown. Impressive results have been obtained with dicyclohexano-18-crown-6 as an extractant for Sr in [RMIM][(CF3S02)2N] IL/aque-... 

The presence of residual unbound transition-metal ions on a dyed substrate is a potential health hazard. Various eco standards quote maximum permissible residual metal levels. These values are a measure of the amount of free metal ions extracted by a perspiration solution [53]. Histidine (5.67) is an essential amino acid that is naturally present as a component of perspiration. It is recognised to play a part in the desorption of metal-complex dyes in perspiration fastness problems and in the fading of such chromogens by the combined effects of perspiration and sunlight. The absorption of histidine by cellophane film from aqueous solution was measured as a function of time of immersion at various pH values. On addition of histidine to an aqueous solution of a copper-complex azo reactive dye, copper-histidine coordination bonds were formed and the stability constants of the species present were determined [54]. Variations of absorption spectra with pH that accompanied coordination of histidine with copper-complex azo dyes in solution were attributable to replacement of the dihydroxyazo dye molecule by the histidine ligand [55]. 

Metal ion Extractant Complex in organic phase Extraction constant Ref. 

Recently, reports have appeared on a class of ILs known as task specific ionic liquids (TSIL). The term was introduced by J. H. Davis, Jr s group to refer to those ILs which have functional groups attached to them so as to give specific properties and functionalities. Thus, they not only perform specific functions like metal ion extraction,catalysisand capture of but also maintain the desired physical characteristics such as physical state, non-volatility, viscosity, etc. The implementation of TSILs further enhances the versatility of classical ILs where both reagent and medium are coupled. The union of reagent with medium has been... 

Given all these attractive features, it is easy to understand the increasing interest in the application of ILs in solvent extraction. The review gives an introduction into the rapidly growing area it focuses on the extraction of organic compounds, metal ion extraction being considered in Chapter 10 of this book. 

We see that the distribution coefficient for metal ion extraction depends on pH and ligand concentration. It is often possible to select a pH where D is large for one metal and small for another. For example. Figure 23-4 shows that Cu2+ could be separated from Pb2+ and Zn2+ by extraction with dithizone at pH 5. Demonstration 23-1 illustrates the pH dependence of an extraction with dithizone. Box 23-1 describes crown ethers that are used to extract polar reagents into nonpolar solvents for chemical reactions. 

The metal ion extraction should increase with the increase in extractant concentration as well as with nitrate ion concentration. With the increasing concentration of nitric acid, beyond a point however, a decrease in metal ion extraction is observed, which is ascribed primarily to the (i) formation of anionic actinide complexes, and (ii) decrease of extractant concentration caused by nitric acid extractant complex formation. The latter is represented as ... 

QSPR Modeling of Metal/Ligand Complexation and Metal Ion Extraction... 

Luo et al.90 have described yet another approach to reducing the impact of ion exchange in metal ion extraction by neutral extractants in ILs, one which relies on modifying neither the structure of the IL nor the properties of the extractant. Instead, a sacrificial species that transfers in preference to the IL cation upon metal ion extraction (thereby reducing loss of the IL) is added to the IL phase. Ideally, the sacrificial species should exhibit no affinity for the extractant (in order not to interfere with extraction of the metal ion of interest) and be more hydrophilic than the IL cation (in order to favor its loss to the aqueous phase upon metal ion transfer). Tests with sodium tetraphenylborate indicate that its addition to a solution of a calix-crown ether in [C4mim+][Tf2N ] reduces the loss of the IL induced by cesium extraction by nearly one-quarter with no adverse effect on the efficiency of cesium extraction. 

No attempt was made to reduce the ash content of the humic acid samples, since drastic purification methods can cause abnormal changes in humate characteristics, and it was believed that most organic acids in their natural environment would be in salt form and associated with other colloidal matter. Though competition from displaced cations may have contributed to the smaller uptake by humic acid (HA II) in the adsorption stage (as shown in Table 2.1), any residual counterions should have had little effect on the metal-ion extraction step. 

Inert systems are used for two reasons. Purification of proteins can be contaminated and enzymes can be deactivated with metals ions extracted out of stainless steel. Also, inert systems are resistant to concentrated salt solutions. Some protein purifications require in excess of 150 mM salt. 

It follows from flux Equation (11.12) that the concentration of the counter hydrogen ion and the equilibrium coefficient K for a particular metal ion will affect the metal ion flux. The effect of these factors can best be understood by looking at curves of metal ion extraction versus pH. Examples are shown in Figure 11.10 for copper and other metals using the carrier LIX 64N [43], The counter ion... 

A plot of the temperatures required for clouding versus surfactant concentration typically exhibits a minimum in the case of nonionic surfactants (or a maximum in the case of zwitterionics) in its coexistence curve, with the temperature and surfactant concentration at which the minimum (or maximum) occurs being referred to as the critical temperature and concentration, respectively. This type of behavior is also exhibited by other nonionic surfactants, that is, nonionic polymers, // - a I k y I s u I Any lalcoh o I s, hydroxymethyl or ethyl celluloses, dimethylalkylphosphine oxides, or, most commonly, alkyl (or aryl) polyoxyethylene ethers. Likewise, certain zwitterionic surfactant solutions can also exhibit critical behavior in which an upper rather than a lower consolute boundary is present. Previously, metal ions (in the form of metal chelate complexes) were extracted and enriched from aqueous media using such a cloud point extraction approach with nonionic surfactants. Extraction efficiencies in excess of 98% for such metal ion extraction techniques were achieved with enrichment factors in the range of 45-200. In addition to metal ion enrichments, this type of micellar cloud point extraction approach has been reported to be useful for the separation of hydrophobic from hydrophilic proteins, both originally present in an aqueous solution, and also for the preconcentration of the former type of proteins. 

---