Extraction, aqueous reagents

As we have seen earlier in this chapter, metal catalysts may be made soluble in water by careful design of the ligands around them. Metal catalysed reactions may also be conducted under phase transfer conditions. Here, by contrast, the metal catalyst usually resides in the organic phase and not the aqueous phase. The use of a phase transfer catalyst in these systems may be to transfer a water-soluble metal catalyst into the organic layer, or else to ensure a supply of water-soluble substrate or reagent to a catalyst already resident in the organic phase. An example of the former is the use of methyltrioctylammonium chloride to extract aqueous RhCL... 

Potassium bromate [7758-01-2] M 167.0. Crystd from distilled H2O(2ml/g) between 100° and 0°. To remove bromide contamination, a 5% soln in distilled H2O, cooled to 10°, has been bubbled with gaseous chlorine for 2h, then filtered and extracted with reagent grade CCI4 until colourless and odourless. After evaporating the aqueous phase to about half its volume, it was cooled again slowly to about 10°. The crystalline KBrOa was separated, washed with 95% EtOH and vacuum dried [Boyd, Cobble and Wexler JACS 74 237 7952]. Another way to remove Br ions was by stirring several times in MeOH and then dried at 150° [Field and Boyd JPC 89 3767 1985]. 

Bird and Ritter isolated, from wood of white oak, a chlorine holocellu-lose which contained all of the 0-acetyl groups present in the wood. Mitchell and Ritter later extracted a chlorine holocellulose from sugar maple with water and obtained a xylan in a yield of 3.4% of the wood. This polysaccharide contained 9.2% of 0-acetyl groups. A xylan which had been obtained in the same way, from aspen, by Wise and Jones, was, on treatment with periodate, oxidized almost to completion. When the wood itself was similarly treated, most of its xylan escaped oxidation. Although it appears evident that all of the xylan in the wood could not possibly have been accessible to the aqueous reagent, it was concluded that the lack of oxidation was most probably due to the fact that the native xylan was partly 0-acetylated. After treatment of wood from Eucalyptus regnans with methanol at 150°, Stewart and coworkers obtained, on extraction with water, a xylan (in a jdeld of 3.7%) which contained 5-6% of acetate... 

Recovery of components through extraction and back-extraction is usually characterized by low energy and reagent consumption but relatively high capital cost. The parameters affecting equipment cost therefore have strong effects on process economics, particularly for low-value products such as mineral acids. Extractant composition affects equipment cost, because (1) the distribution coefficients determine the extractant/aqueous phase volume ratio in extraction and in back-extraction and thereby the... 

All extraction studies were conducted under conditions where the compounds formed by these interacting library members are at equilibrium with each other. In order to confirm that our extraction systems functioned as a dynamic library, it was necessary to ensure that the two-phase system was at equilibrium. To demonstrate this, we compared the extent of metal ion extraction with reagents initially dissolved in either the chloroform or the water layer. A dithizone assay as described herein was used to measure extracted metal ion concentration. As shown in Fig. 2, Cd(II) concentrations distributed into chloroform after 24 or 40 h were identical within experimental error for both sets of conditions, suggesting that the equilibrium was established between the two layers within 24 h. Thus the percentage of metal ion in the organic phase was the same whether the complex extracts from aqueous phase or organic phase. 

Although solvent extraction has been widely appUed in the field of RE separation, there also exist some shortcomings. The main drawback of this process is the loss of the organic phase due to the dissolution of extractant into the aqueous solution. Another shortage is that when solvent extraction is used directly in low RE concentration extraction, more reagent and energy consumption would be needed. To overcome the drawbacks mentioned above, some studies have been focused on... 

This type of extraction depends upon the use of a reagent which reacts chemically with the compound to be extracted, and is generally employed either to remove small amounts of impurities in an organic compound or to separate the components of a mixture. Examples of such reagents include dilute (5 per cent.) aqueous sodium or potassium hydroxide solution, 5 or 10 per cent, sodium carbonate solution, saturated sodium bicarbonate solution (ca. 5 per cent.), dilute hydrochloric or sulphuric acid, and concentrated sulphuric acid. 

Separations based upon differences in the chemical properties of the components. Thus a mixture of toluene and anihne may be separated by extraction with dilute hydrochloric acid the aniline passes into the aqueous layer in the form of the salt, anihne hydrochloride, and may be recovered by neutralisation. Similarly, a mixture of phenol and toluene may be separated by treatment with dilute sodium hydroxide. The above examples are, of comse, simple apphcations of the fact that the various components fah into different solubihty groups (compare Section XI,5). Another example is the separation of a mixture of di-n-butyl ether and chlorobenzene concentrated sulphuric acid dissolves only the w-butyl other and it may be recovered from solution by dilution with water. With some classes of compounds, e.g., unsaturated compounds, concentrated sulphuric acid leads to polymerisation, sulphona-tion, etc., so that the original component cannot be recovered unchanged this solvent, therefore, possesses hmited apphcation. Phenols may be separated from acids (for example, o-cresol from benzoic acid) by a dilute solution of sodium bicarbonate the weakly acidic phenols (and also enols) are not converted into salts by this reagent and may be removed by ether extraction or by other means the acids pass into solution as the sodium salts and may be recovered after acidification. Aldehydes, e.g., benzaldehyde, may be separated from liquid hydrocarbons and other neutral, water-insoluble hquid compounds by shaking with a solution of sodium bisulphite the aldehyde forms a sohd bisulphite compound, which may be filtered off and decomposed with dilute acid or with sodium bicarbonate solution in order to recover the aldehyde. 

Grote s reagent is useful for the determination of 2-aminothiazoie in blood and wine (145), This thiazole may be extracted from its aqueous solution and then titrated in nonaqueous medium (MeOH) with HCIO4 in the presence of a mixed methyl red-methylene blue indicator (146). 

A number of organic compounds, eg, acetylacetone [123-54-6] and cupferron [135-20-6] form compounds with aqueous actinide ions (IV state for reagents mentioned) that can be extracted from aqueous solution by organic solvents (12). The chelate complexes are especially noteworthy and, among these, the ones formed with diketones, such as 3-(2-thiophenoyl)-l,l,l-trifluoroacetone [326-91-0] (C4H2SCOCH2COCF2), are of importance in separation procedures for plutonium. 

A iridine traces in aqueous solution can be determined by reaction with 4-(p-nitroben25l)pyridine [1083-48-3] and potassium carbonate [584-08-7]. Quantitative determination is carried out by photometric measurement of the absorption of the blue dye formed (367,368). Alkylating reagents interfere in the determination. A iridine traces in the air can be detected discontinuously by absorption in Folin s reagent (l,2-naphthoquinone-4-sulfonate) [2066-93-5] (369,370) with subsequent chloroform extraction and hplc analysis of the red dye formed (371,372). The detection limit is ca 0.1 ppm. Nitrogen-specific thermal ionisation detectors can be used for continuous monitoring of the ambient air. 

The use of an extractant depends on loading capacity, extraction rate, pH range, and the cost of the reagent and the diluent. Loss of the extractant must be minimised because of its high cost. Organic losses to the aqueous phase are also undesirable because of the deleterious effect on cathode deposits. Advances in SX—EW processes are described in Reference 38. 

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