Metal solid state extraction

Four possible mechanisms for solid-state extraction (a) adsorption onto a solid substrate (b) absorption into a thin polymer or chemical film coated on a solid substrate (c) metal-ligand complexation in which the ligand is covalently bound to the solid substrate and (d) antibody-antigen binding in which the receptor is covalently bound to the solid substrate. 

The choice between the use of solid-state supported extractants and solvent extraction is often made on the basis of the concentration of the desired metal in the aqueous feed. Solvent extraction is usually not effective for treating very dilute feeds because an impracticably large volume of the aqueous phase must be contacted with an organic extractant to achieve concentration of the materials across the circuit. However, solvent extraction is preferred for treating moderately concentrated feeds because most ion-exchange resins and related materials have relatively low metal capacities and very large quantities of resin are required. In this review we will focus on reagents used in solvent extraction because, in the main, the nature of the complexes formed are better understood. 

Suzuki J., Yoshida M., Nakahara C., Sekine K., Kikuchi M., Takamura T., Li mass transfer through a metallic copper film on a carbon fiber during the electrochemical insertion/extraction reaction, Electrochem. and Solid State Lett., (2001), 4 (1), A1-A4. 

To characterize the composition and structure of metal complexes formed in extraction processes (either in the aqueous phase or at the interface), various experimental methods are used. Theoretical methods become helpful in complementing the results if the spectroscopic data are not sufficient to fully describe the structure, if crystals suitable for diffraction studies are not available, etc. Moreover, the calculations can result in reliable structures of the complexes or ligands in solution, which are often different from those observed in the solid state. 

Hitherto we have dealt with model FICs that are mostly useful as solid electrolytes. The other class of compounds of importance as electrode materials in solid state batteries is mixed electronic-ionic conductors (with high ionic conductivity). The conduction arises from reversible electrochemical insertion of the conducting species. In order for such a material to be useful in high-energy batteries, the extent of insertion must be large and the material must sustain repeated insertion-extraction cycles. A number of transition-metal oxide and sulphide systems have been investigated as solid electrodes (Murphy Christian, 1979). 

The high affinity shown by carboxylic acids for copper (II) compared with the remaining divalent metals of the first transition series appears to be due in part to the stabilization of the extracted complexes by the formation of the well-known dimeric structure (1) in which copper(II) carbox-ylates exist in the solid state and in non-donor solvents.54 The axial ligands, L, consist of undissociated carboxylic acid molecules55 or, in the absence of an excess amount of extractant, they may consist of water or other solvent molecules.56 Copper was successfully removed from nickel sulfate solutions on the base-metal plant at Matthey Rustenburg Refiners in South Africa by being extracted into Versatic 10 acid at a controlled pH value. The process is believed to have been discontinued only because improvements in the selective leaching of copper and nickel rendered it unnecessary. 

In the solid state, the metal atoms in bis(salicylaIdoximato)copper(II) show two additional contacts with the oxime oxygens of adjacent molecules, resulting in a distorted octahedral structure. However, the axial Cu—O distance (2.66 A) is much longer than the metal—ligand distances in the square-planar array (Cu—O, 1.92 A and Cu—N, 1.94 A).154 Studies by ESR of copper(II) extracts of the commercial reagent SME 529 (14 R = Me, R = C9H)9) have shown that the copper complex exists as a square-planar species in hydrocarbon solutions, but that five-coordinate adducts are formed in the presence of ammonia or pyridine.155... 

Traditionally, potentiometric sensors are distinguished by the membrane material. Glass electrodes are very well established especially in the detection of H+. However, fine-tuning of the potentiometric response of this type of membrane is chemically difficult. Solid-state membranes such as silver halides or metal sulphides are also well established for a number of cations and anions [25,26]. Their LOD is ideally a direct function of the solubility product of the materials [27], but it is often limited by dissolution of impurities [28-30]. Polymeric membrane-based ISEs are a group of the most versatile and widespread potentiometric sensors. Their versatility is based on the possibility of chemical tuning because the selectivity is based on the extraction of an ion into a polymer and its complexation with a receptor that can be chemically designed. Most research has been done on polymer-based ISEs and the remainder of this work will focus on this sensor type. 

The amazing thing about this salt is its ability to sublimate easily and in doing so, it changes from the solid state directly into vapors of hydrochloric acid and ammonia only to reunite on a cool surface as the solid salt again. It is this extremely corrosive atmosphere that serves to open many of the metals for extraction. 

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