Precipitation techniques separation technique

Many precipitation reactions that are useful as separation techniques for gravimetric analysis fail to meet one or both of two requirements for titrimetry ... 

Particulate interferents can be separated from dissolved analytes by filtration, using a filter whose pore size retains the interferent. This separation technique is important in the analysis of many natural waters, for which the presence of suspended solids may interfere in the analysis. Filtration also can be used to isolate analytes present as solid particulates from dissolved ions in the sample matrix. For example, this is a necessary step in gravimetry, in which the analyte is isolated as a precipitate. A more detailed description of the types of available filters is found in the discussion of precipitation gravimetry and particulate gravimetry in Chapter 8. 

Lime-Sulfuric. Recovery of citric acid by calcium salt precipitation is shown in Figure 3. Although the chemistry is straightforward, the engineering principles, separation techniques, and unit operations employed result in a complex commercial process. The fermentation broth, which has been separated from the insoluble biomass, is treated with a calcium hydroxide (lime) slurry to precipitate calcium citrate. After sufficient reaction time, the calcium citrate slurry is filtered and the filter cake washed free of soluble impurities. The clean calcium citrate cake is reslurried and acidified with sulfuric acid, converting the calcium citrate to soluble citric acid and insoluble calcium sulfate. Both the calcium citrate and calcium sulfate reactions are generally performed in agitated reaction vessels made of 316 stainless steel and filtered on commercially available filtration equipment. 

The mixture of diastereomers has been separated into its two principal components by Izatt, Haymore, Bradshaw and Christensen who had previously identified the two principal diastereomers as the cis-syn-cis and cis-anti-cis isomers. Their previous separation technique involved a protracted chromatography on alumina but the new method relied upon the difference in water solubility between the lead perchlorate and hydroniur perchlorate complexes. The lead perchlorate complex is essentially insoluble in aqueous solution and precipitates from it. Using this method, one may obtain 39% of the high-melting polymorph (mp 83—84°) and 44% of the low-melting compound (mp 62—63°). Note that the former also exists in a second crystalline form, mp 69—70°. 

Chemical Precipitation. If physical separation techniques do not work, separation may be achieved by chemical conversion to a soluble precipitate. 

Second, Schneider s article reviews recent work (notably by Rowlinson, Kohn and co-workers) on phase relations in binary liquid systems where one of the components is much more volatile than the other (D1, D2, E3, M8, R9). Such systems may have lower critical solution temperatures for these systems, an increase in temperature (and, indirectly, pressure) causes precipitation of the heavy component, thereby providing a possible separation technique, e.g., for the fractionation of polymers. 

Tewes et al., using both precipitation and extraction separation techniques, observed essentially complete exchange within the separation time (1 min) during an isotopic study ( V) of this exchange. The media ranged from 0.3 M perchloric acid to 7 M hydrochloric acid reactant concentrations were 10 M. 

Polissar has observed 100 % exchange between Mn(III), as the oxalato ion Mn(Ox)J, and manganous sulphate. Adamson, using manganic chloride as the source of Mn(III), has observed the exchange to be incomplete in a time 15 sec with reactant concentrations 10 M. Both workers used a separation technique based on the precipitation of Mn(IV), present via the equilibrium... 

The precipitated metal hydroxide can then be removed from the wastewater by clarification or other solid-water separation techniques.52... 

Clarification by either sedimentation or dissolved air flotation is the most common solid-water separation technique used for the removal of precipitates. In this process application, clarification... 

Purify the biotinylated protein or molecule using dialysis or gel filtration. For small molecule biotinylation where these separation methods may not be appropriate, other procedures may have to be developed, such as reverse-phase chromatography or organic precipitation techniques. 

The development of modem separation techniques has affected the purification procedures employed for D-galacturonanases. Fractional precipitation with ammonium sulfate and with organic solvents are now used only in combination with new separation techniques. To separate fractions having D-galacturonanase activity, adsorption to pectate or calcium pectate gel has been used in several instances.157-207... 

If it were possible to identify or quantitatively determine any element or compound by simple measurement no matter what its concentration or the complexity of the matrix, separation techniques would be of no value to the analytical chemist. Most procedures fall short of this ideal because of interference with the required measurement by other constituents of the sample. Many techniques for separating and concentrating the species of interest have thus been devised. Such techniques are aimed at exploiting differences in physico-chemical properties between the various components of a mixture. Volatility, solubility, charge, molecular size, shape and polarity are the most useful in this respect. A change of phase, as occurs during distillation, or the formation of a new phase, as in precipitation, can provide a simple means of isolating a desired component. Usually, however, more complex separation procedures are required for multi-component samples. Most depend on the selective transfer of materials between two immiscible phases. The most widely used techniques and the phase systems associated with them are summarized in Table 4.1. 

A stochiometric approach was applied by Van Koten and co-workers [29], who used chiral carbosilane dendrimers as soluble supports in the in situ ester enolate-imine condensation in the synthesis of /Mactams (e.g. 19, Scheme 20). The formation of the /Mactam products proceeded with high trans selectivity, and with the same level of stereoinduction as was earlier established in reactions without the dendritic supports, (i.e. the use of the enantiopure dendritic support did not affect the enantioselectivity of the C-C bond formation). After the reaction, the dendrimer species could be separated from the product by precipitation or GPC techniques and reused again. 

Some separation techniques rely on the physical removal of one of the fractions charcoal will strongly adsorb the free fraction allowing its ready removal by centrifugation the addition of dextran reduces the tendency of charcoal to strip bound antigen from the complex alternatively, the bound fraction may be precipitated by the addition of suitable concentrations of various protein precipitants such as alcohol, ammonium sulphate and polyethylene glycol (PEG). 

Though there are hardly any restrictions to choosing a target, pharmacological receptors are investigated most frequently. The nature of the receptor, v hether it is membrane-bound or soluble, determines which separation technique is used to terminate the binding assay. For the former, filtration or centrifugation are favored as separation steps, while for the latter suitable methods are gel filtration, equilibrium dialysis, precipitation or adsorption of the nonbound marker by charcoal [23, 24]. 

Further evidence for the presence of l-(4-pyridyl) pyridinium ion in the reaction mixtures was provided by a separation technique based on the precipitation of the l-(4-pyridyl)pyridinium ion in the presence of pyridine with Ph4B in a solution with a pH of 8. This procedure was necessary, since the ultraviolet spectrum of l-(4-pyridyl)pyridinium ion in a solution prepared by acid hydrolysis of the crude reaction products was completely obscured by the intense spectrum of pyridinium ion, which also was formed by the hydrolysis of the reaction products. However, as shown in Figure 3, the l-(4-pyridyl) pyridinium ion was easily identified after its separation as the tetraphenylborate(III) salt... 

Procedures for the determination of 11 elements in coal—Sb, As, Br, Cd, Cs, Ga, Hg, Rb, Se, U, and Zn—by neutron activation analysis with radiochemical separation are summarized. Separation techniques include direct combustion, distillation, precipitation, ion exchange, and solvent extraction. The evaluation of the radiochemical neutron activation analysis for the determination of mercury in coal used by the Bureau of Mines in its mercury round-robin program is discussed. Neutron activation analysis has played an important role in recent programs to evaluate and test analysis methods and to develop standards for trace elements in coal carried out by the National Bureau of Standards and the Environmental Protection Agency. 

Peri and Pompei (35,36) have helped verify the methods elaborated here (9,21), and they have extended them by adapting cinchonine precipitation to separate tannins from nontannins. Thus, in a mixture of the two tannins precipitated by cinchonine they were able to redissolve them and quantitate tannic acid separately from grape seed tannin because of tannic acids failure to precipitate with formaldehyde and by appropriate application of the F-C analysis. They applied these techniques to analysis of... 

The extraction, in combination with fractional separation of extracts in a multi-stage separation system, results in high-quality volatile oils [42,44]. Recently, this fractional separation technique has been refined by Reverchon and co-workers for selective precipitation of cuticular waxes and volatile oils [43,56],... 

The post-bombardment processing of the activated sample may follow either a nondestructive assay of the radioactivity in the sample (gamma-ray scintillation spectrometry is used most often for this) or a chemical processing of the sample prior to the radioactivity assay. Techniques involving either precipitation, electrodeposition. solvent extraction, and ion exchange or some combination of these form the basts of the radio-chemical separation techniques used in activation analysis. 

One of the key steps in any isotope dilution analysis concerns the isolation and purification of the diluted activity, plus the measurement of its specific activity. Two techniques are usually preferred for the separation precipitation and solvent extraction. As a purification step, precipitation has the advantage that the precipitate can easily be weighed at the time of separation, thereby allowing a quick determination of the specific activity. The main problem with the use of precipitation techniques involves the occurrence of co-precipitation phenomena, in which unwanted materials are precipitated along with the desired substance, thus altering the sample specific activity. Precipitation techniques are used for the isolation of inorganic components. 

The oldest, most well-established chemical separation technique is precipitation. Because the amount of the radionuclide present may be very small, carriers are frequently used. The carrier is added in macroscopic quantities and ensures the radioactive species will be part of a kinetic and thermodynamic equilibrium system. Recovery of the carrier also serves as a measure of the yield of the separation. It is important that there is an isotopic exchange between the carrier and the radionuclide. There is the related phenomenon of co-precipitation wherein the radionuclide is incorporated into or adsorbed on the surface of a precipitate that does not involve an isotope of the radionuclide or isomorphously replaces one of the elements in the precipitate. Examples of this behavior are the sorption of radionuclides by Fe(OH)3 or the co-precipitation of the actinides with LaF3. Separation by precipitation is largely restricted to laboratory procedures and apart from the bismuth phosphate process used in World War II to purify Pu, has little commercial application. 

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