Separation by extraction

Separation by Extraction.—Separating funnels are again used for this purpose. The substance to be extracted is generally in solution or suspension in water. A solvent which is immiscible with water and in which the substance is soluble is added—in small quantities at first. The funnel is stoppered and agitated, holding the tap and stopper closed, after which it is set aside in a vertical position until the liquids separate. Separation is then effected as above. 

The solvent most commonly employed is ether, but benzene, chloroform, ligroin and amyl alcohol are used in special circumstances. 

In all cases extraction should be carried out more than once, the extracts being added together. The amount of substance which goes into solution in ether, etc., depends on the distribution coefficient, that is, the ratio of the concentrations in the two solvents after equilibrium is attained. This ratio is constant for any given temperature, provided the molecular weight of the solute does not vary in either solvent (see Physical Chemistry, by A. J. Mee). It follows then that extraction may have to be repeated several times, and also that it is more efficient to extract a number of times with successive small quantities of solvent rather than once with a large quantity. 

When a quantity of the substance separates from the solution as an oil, this oil should be separated before extraction is attempted. 

In extraction with ether the following points should be noticed — 

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A certain amount of hydrolysis of the original acetamide to acid and ammonia always occurs, and the final amine always contains traces of ammonia. This is separated by extracting the mixed anhydrous hydrochlorides with absolute ethanol, which dissolves the amine hydrochloride but not the ammonium chloride filtration of the hot ethanolic extract removes the ammonium chloride, whilst the amine hydrochloride crystallises readily from the filtrate on cooling. 

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. 

Using Figure 7.27, explain how an aqueous mixture of Cu +, Pb +, and Cd + can be separated by extraction with dithizone in CCI4. 

Tannins occur in many plants and are separated by extraction. At present, only quebracho extract is used as a mud thinner in significant quantity in the United States. Quebracho is an acidic material and performs best at high pH. It is an excellent thinner for lime-treated and cement-contaminated muds. However, it is not effective at high salt concentrations. Sulfomethylated tannin products are functional over a wide range of pH and salinity and have either been treated with chromium for good thermal stabiUty (58) or are chrome free. Concentrations of tannin additives are ca 1.5—18 kg/m (0.5—6 lb/bbl). 

Polymers containing 8-hydroxyquinoline appear to be selective adsorbents for tungsten in alkaline brines (95). In the presence of tartrate and citrate, quinaldic acid [93-10-7] allows the separation of zinc from gallium and indium (96). Either of these compounds can selectively separate lead and zinc from oxide ores as complexes (97). It is also possible to separate by extraction micro quantities of rhenium(VII), using quinoline in basic solution (98). The... 

Solvent Recovery. A mixture of methanol and methyl acetate is obtained after saponification. The methyl acetate can be sold as a solvent or converted back into acetic acid and methanol using a cationic-exchange resin such as a cross-linked styrene—sulfonic acid gel (273—276). The methyl acetate and methanol mixture is separated by extractive distillation using water or ethylene glycol (277—281). Water is preferred if the methyl acetate is to be hydroly2ed to acetic acid. The resulting acetic acid solution is concentrated by extraction or a2eotropic distillation. 

The C4 stream from steam crackers, unlike its counterpart from a refinery, contains about 45% butadiene by weight. Steam crackers that process significant amounts of Hquid feedstocks have satellite faciUties to recover butadiene from the stream. Conventional distillation techniques are not feasible because the relative volatihty of the chemicals in this stream is very close. Butadiene and butylenes are separated by extractive distillation using polar solvents. 

The picolyl ester has been prepared from amino acids and picolyl alcohol (DCC / CH2CI2, 20°, 16 h, 60% yield) or picolyl chloride (DMF, 90-100°, 2 h, 50% yield). It is cleaved by reduction (H2/Pd-C, aq.= FtOH, 10 h, 98% yield Na/NH3, 1.5 h, 93% yield) and by basic hydrolysis (1 NaOH, dioxane, 20°, 1 h, 93% yield). The basic site in a picolyl ester allows its ready separation by extraction into an acidic medium. ... 

The mixture is then slowly heated to the boiling point of toluene and kept boiling for one hour under reflux. After the mixture has been allowed to cool the sodium chloride which precipitates is separated by extraction with water. The solution of toluene is then extracted with dilute hydrochloric acid. From the hydrochloric acid extract the basic substance is separated in the form of an oil by means of caustic soda solution and is introduced into ether. The ethereal solution Is dried with the aid of potassium carbonate and then distilled. 

For a further separation of the sulfonated surfactants the latter are heated for 4 h with 2 N HC1. The methyl ester sulfonates are split into methanol and a-sulfo fatty acids, which form disodium salts after neutralization with NaOH. The product mixture from acid hydrolysis can be separated by extraction with petroleum ether. For example, the fatty alcohols formed from fatty alcohol sulfo-... 

Despite its widespread application [31,32], the kinetic resolution has two major drawbacks (i) the maximum theoretical yield is 50% owing to the consumption of only one enantiomer, (ii) the separation of the product and the remaining starting material may be laborious. The separation is usually carried out by chromatography, which is inefficient on a large scale, and several alternative methods have been developed (Figure 6.2). For example, when a cyclic anhydride is the acyl donor in an esterification reaction, the water-soluble monoester monoacid is separable by extraction with an aqueous alkaline solution [33,34]. Also, fiuorous phase separation techniques have been combined with enzymatic kinetic resolutions [35]. To overcome the 50% yield limitation, one of the enantiomers may, in some cases, be racemized and resubmitted to the resolution procedure. 

To study the cell wall alterations diiring processing in detail, total pectic fractions were separated by extraction of AIR from fresh, blanched and sterilized beans with acetate buffer, CDTA and NajCOj. Analysis showed that sterilization caused a lai e increase in the amount of buffer soluble pectins (Figure 1). 

The ammonium difluorophosphate which is better soluble in ethanol is separated by extraction with this solvent 34). The reactions (22) 54) and (23) (55) which are run at higher temperatures do not give purer products ... 

Limited yield by racemic dynamic kinetic resolution separation by extraction... 

Most studies of micellar effects upon rates or products of organic reactions have been made with very low concentrations of reactants, and this small scale of work is not very encouraging for the synthetic organic chemist. An additional disadvantage is that surfactants complicate product separation by extraction or distillation, and to date most studies in this general area have been exploratory and have been aimed at solving these problems. 

Thallium has been determined in 10 ml of ashed serum or in urine by extracting with sodium diethyldithiocarbamate into MIBK n°). More recently, Savory and co-workers 1131 described a wet digestion procedure for 50 ml of urine or 5 ml of serum in which the thallium is separated by extracting the bromide into ether, evaporating the ether and then taking up in dilute acid for aspiration. As little as 0.1 ppm is determined in urine. Curry et al.114) determined less than 1 ng of thallium in 200 /d of urine by using the tantalum sample boat technique. The sample in the boat is dried by holding the boat 1 cm from the flame and then it is inserted into the flame where it is vaporized. A similar procedure is used for >3 ng of thallium in 50-100/al of blood, except that the blood is preashed with 3 drops of nitric acid. Since the tantalum boat method is susceptible to interelement interferences, the method of standard additions is used for calibration. 

Devoto 115)has described an indirect procedure for the determination of 0.1 ppm arsenic in urine. The arsenomolybdic acid complex is formed and extracted from 1 ml of urine at pH 2 into 10 ml of cyclohexanone. The molybdenum in the complex is then measured. Before extracting the arsenic, phosphate in the urine is separated by extracting the phosphomolybdic acid complex at pH 1 into isobutyl acetate. The direct determination of arsenic in biological material and blood and urine is best done using a nitrous oxide-acetylene flame 116>. The background absorption by this flame is low at 1937 A, and interferences are minimized due to the high temperature of the flame. 

A mixture of acetone and chloroform is to be separated into pure products [Hostrup et al. (1999)]. Since they also form an azeotrope, one alternative to satisfy the separation objective is to find a suitable solvent for separation by extractive distillation. This type of problem in product design is usually encountered during the purification or recovery of products, by-products, reactants or removal of undesirable products from the process. Also, it can be noted that failure to find a suitable solvent may result in the discard of the product. Alternatively, a functional chemical product manufacturer may be interested to find, design and develop a new solvent. In this case, the solvent is the chemical product. 

The decomposition of N,N,N-trimethylcyclooctylammo-nium hydroxide forms a mixture of cis- and fions-cyclooctenes which contains ca. 60% of the trans- and 40% of the cfx-isomer (see Note 19). The mixture is separated by extraction of the /ra x-isomer with aqueous silver nitrate. ... 

Technetium and molybdenum can also be separated by extracting molybdate with ethyl ether from a medium 1.2 M in both NH SCN and HCl Mo (VI) and Tc (VII) undergo reduction and complex formation in this medium. After extraction pure technetium is left in the aqueous phase in 80% yield. 

The products were weakly soluble in the ionic phase. They were separated by extraction with ether. The viscous ionic liquid could be reused in five runs without any loss of activity after thorough washing with ether and drying at 80°C after each run. In contrast, the reaction did not proceed in the polar organic solvents DMF and 7V-methylpyrrolidine, even at higher temperatures (75-80°C). The ionic liquids [Bu4N]C1 and [BMIM]C1 were also found to be ineffective. 

The qualitative analysis is quite simple if the homopolymers differ in their solubility, for example, when one homopolymer is soluble in a solvent where the other is not. In this case a sample of the materieil is extracted with that solvent. The reprecipitated extracts and residues are examined for composition. The extraction must, however, be very carefully carried out and repeated several times since polymer mixtures are frequently quite difficult to separate by extraction. If no pure homopolymer is isolated in this way one can be sure that the sample is a genuine copolymer. If the solubility properties of the original homopolymers are insufficiently different it is sometimes possible to induce such differences through chemical transformation, for example, by oxidation and/or hydrolysis. 

The liquid product is separated by extraction with ether. The ether solution is dried over anhydrous potassium carbonate. After filtration, the ether is removed by evaporation and the residue is distilled, a fraction being collected between 126°C and 126.5°C (6 mm Hg), n 1.4587, dd° 1.0151 yield 5.18 gm (55%). 

Ferrocene, like thiophene, furan, and other so-called superaromatic systems, reacts readily with mercuric acetate to form mercurated derivatives. Nes-meyanov and coworkers first reported that ferrocene could be mercurated under relatively mild conditions in either ethyl ether-alcohol or benzene-alcohol solution (63). The acetoxymercuriferrocenes formed in this manner are usually treated with an alcoholic solution of an alkali metal halide. The resulting products, chloro-mercuriferrocene (XXVII) and l,l -di(chloromercuri)ferrocene (XXVIII), can be conveniently separated by extraction with n-butyl alcohol. 

Carbonation and subsequent hydrolysis of either lithiated or sodiated metallocenes lead to the corresponding carboxylic acids. Ferrocenecarboxylic acid and ferrocene-1,1 -dicarboxylic acid are readily produced in this manner and can be conveniently separated by extraction of the former with ethyl ether or benzene. The reaction of metalated ferrocenes with various chlorosilanes has led to a variety of triaryl- or trialkvlsilylferrocenes (3, 28, 90). 

Because of their very similar boiling points and azeotrope formation, the components of the C4 fraction cannot be separated by distillation. Instead, other physical and chemical methods must be used. 1,3-Butadiene is recovered by complex formation or by extractive distillation.143-146 Since the reactivity of isobutylene is higher than that of n-butenes, it is separated next by chemical transformations. It is converted with water or methyl alcohol to form, respectively, tert-butyl alcohol and tert-butyl methyl ether, or by oligomerization and polymerization. The remaining n-butenes may be isomerized to yield additional isobutylene. Alternatively, 1-butene in the butadiene-free C4 fraction is isomerized to 2-butenes. The difference between the boiling points of 2-butenes and isobutylene is sufficient to separate them by distillation. n-Butenes and butane may also be separated by extractive distillation.147... 

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