Metal chelate extraction

The complex species is more soluble in organic solvents than in water. Many examples are quoted in the literature, with special emphasis on metal chelates extraction. 

RECOMMENDED pH LIMITATIONS FOR APDC - METAL CHELATE EXTRACTIONS... 

Yes we can, and we utilize all of the above equations to do so. This is an instructive exercise that can be found in a number of analytical chemistry texts that introduce the topic of metal chelate extraction. Usually the derivation itself is not included and only the final equation is given and interpreted. In the derivation that follows, we find that we do not need to add any more simplifying assumptions to those already given to reach the final working equation. 

CA Liquid-Liquid Extractions Involving Metal Chelators... 

Scheme for the liquid-liquid extraction of a metal ion by a metal chelator. 

Liquid-liquid extractions using ammonium pyrrolidine dithiocarbamate (APDC) as a metal chelating agent are commonly encountered in the analysis of metal ions in aqueous samples. The sample and APDC are mixed together, and the resulting metal-ligand complexes are extracted into methyl isobutyl ketone before analysis. 

Pentanedione is widely used in extraction processes for the separation and purification of metals because of its abiUty to form covalent metal chelates. It is also used as an intermediate in the production of heterocycHc substances and dyes, as a fuel additive (324), and in metal plating and resin modification. 

An on-line concentration, isolation, and Hquid chromatographic separation method for the analysis of trace organics in natural waters has been described (63). Concentration and isolation are accompHshed with two precolumns connected in series the first acts as a filter for removal of interferences the second actually concentrates target solutes. The technique is appHcable even if no selective sorbent is available for the specific analyte of interest. Detection limits of less than 0.1 ppb were achieved for polar herbicides (qv) in the chlorotriazine and phenylurea classes. A novel method for deterrnination of tetracyclines in animal tissues and fluids was developed with sample extraction and cleanup based on tendency of tetracyclines to chelate with divalent metal ions (64). The metal chelate affinity precolumn was connected on-line to reversed-phase hplc column, and detection limits for several different tetracyclines in a variety of matrices were in the 10—50 ppb range. 

J. Stary, The S olvent Extraction of Metal Chelates, The MacmiUan Co., New York, 1964. 

In the case of inorganic solutes we are concerned largely with samples in aqueous solution so that it is necessary to produce substances, such as neutral metal chelates and ion-association complexes, which are capable of extraction into organic solvents. For organic solutes, however, the extraction system may sometimes involve two immiscible organic solvents rather than the aqueous-organic type of extraction. 

The choice of a satisfactory chelating agent for a particular separation should, of course, take all the above factors into account. The critical influence of pH on the solvent extraction of metal chelates is discussed in the following section. 

The solvent extraction of a neutral metal chelate complex formed from a chelating agent HR according to the equation... 

An alternative to the formation of neutral metal chelates for solvent extraction is that in which the species of analytical interest associates with oppositely charged ions to form a neutral extractable species.6 Such complexes may form clusters with increasing concentration which are larger than just simple ion pairs, particularly in organic solvents of low dielectric constant. The following types of ion association complexes may be recognised. 

Multi-element analyses involving solvent extraction and high performance liquid chromatography (HPLC) have also been described. The extracts, containing metal-chelate complexes with sulphur-containing reagents, such as dithizone and diethyldithiocarbamate, were used directly for determination of the metals by HPLC.14... 

J Stary, The Solvent Extraction of Metal Chelates, Pergamon Press, Oxford, 1964... 

Kinetics and mechanism of metal chelation processes via solvent extraction techniques. H. Freiser, Acc. Chem. Res., 1984,17,126-131 (40). 

A normal-phase HPLC separation seems to be useful to separate major chlorophyll derivatives, but it is not compatible with samples in water-containing solvents an additional extraction step is required to eliminate water from the extract since its presence rednces chromatographic resolution and interferes with retention times. Besides that, the analysis cannot be considered quantitative due to the difhculty in transferring componnds from the acetone solution into the ether phase. On the other hand, an advantage of the normal-phase method is its efficacy to separate magne-sinm-chlorophyll chelates from other metal-chelated chlorophyll derivatives. ... 

Co (I I) complex formation is the essential part of copper wet analysis. The latter involves several chemical unit operations. In a concrete example, eight such operations were combined - two-phase formation, mixing, chelating reaction, solvent extraction, phase separation, three-phase formation, decomposition of co-existing metal chelates and removal of these chelates and reagents [28]. Accordingly, Co (I I) complex formation serves as a test reaction to perform multiple unit operations on one chip, i.e. as a chemical investigation to validate the Lab-on-a-Chip concept. 

Liquid chromatographic methods are well suited to the separation and determination of metal chelates that can be extracted into organic solvents. Many chelates also absorb strongly in the UV onAisible regions, facilitating detection. The... 

The given structure shows two molecules of TTA to have reacted with a cobalt ion to form the cobalt-TTA complex, in which the cobalt atom forms a valence bond solid lines) with one, and a coordinate bond (broken lines) with the other, oxygen atom of each TTA molecule. Thus, in the cobalt-TTA complex there is a six-membered ring formed by each TTA molecule with the cobalt atom. Metal chelate complexes of this type have good stability, they are nonpolar and soluble in the organic phase. The usefulness of the chelating extractants in solvent extraction is therefore obvious. 

Chelates Heavy metals or bases Chelating agents such as by extraction of the metal ions Formation of stable metal chelates ... 

When a 350 ml seawater sample was spiked with 54Mn and taken through the chelation, extraction, and back-extraction procedures, the observed recovery of the radio-tracer was 100.6%. Estimates of detection limits for manganese based on sets of both shipboard and shore laboratory separations are of the order of 0.1 nmol/1. The accuracy of the technique is demonstrated by data from the ICES fifth-round intercalibration exercise for trace metals in seawater [449 ]. 

Rodionova and Ivanov [667] used chelate extraction in the determination of copper, bismuth, lead, cadmium, and zinc in seawater. The metal complexes of diethyl and dithiophosphates are extracted in carbon tetrachloride prior to determination by atomic absorption spectrometry. 

Cadmium, copper, and silver have been determined by an ammonium pyrrolidine dithiocarbamate chelation, followed by a methyl isobutyl ketone extraction of the metal chelate from the aqueous phase [677], and finally followed by graphite furnace atomic absorption spectrometry. The detection limits of this technique for 1% absorption were 0.03 pmol/1 (copper), 2 nmol/1 (cadmium), and 2 nmol/1 (silver). 

A variety of preconcentration procedures has been used, including solvent extraction of metal chelates, coprecipitation, chelating ion exchange, adsorption onto other solids such as silica-bonded organic complexing agents, and liquid-liquid extraction. 

Certain lead(II) complexes were shown to display reversible redox behavior on the CV scale. Examples are Pb(II) complexes of 2(o-hydroxyphenyliminomethyl)-pyrrole and 2(o-hydroxyphenyliminomethyl)-thiophene. Their stability constants were also determined by polarography140. Anodic exchange reactions of extracted metal chelates were carried out with 1-pyrrolidinecarbodithioic acid in isobutyl methyl ketone141. 

The best way to take advantage of the organic solvent effect without simultaneously diluting the sample is by employing solvent extraction. By this method the element to be analyzed can actually be concentrated and a solution of the element is obtained in essentially pure organic solvent. One of the most commonly used systems involves formation of the metal chelate with ammonium 1-pyrro-lidinecarbodithioate (APDC) and then extracting this into methylisobutyl ketone (MIBK). APDC chelates of many elements form and extract into MIBK from acid solution. 

Efficiency of Extraction. Selectivity of Extraction. Extraction Systems. Extraction of Uncharged Metal Chelates. Methods of Extraction. Applications of Solvent Extraction. 

Thus, for a given reagent and solvent, the extraction of the metal chelate is dependent only upon pH and the concentration of reagent in the organic phase and is independent of the initial metal concentration. 

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