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On polarimetry

Secondary isotope effects are small. In fact, most of the secondary deuterium KIEs that have been reported are less than 20% and many of them are only a few per cent. In spite of the small size, the same techniques that are used for other kinetic measurements are usually satisfactory for measuring these KIEs. Both competitive methods where both isotopic compounds are present in the same reaction mixture (Westaway and Ali, 1979) and absolute rate measurements, i.e. the separate determination of the rate constant for the single isotopic species (Fang and Westaway, 1991), are employed (Parkin, 1991). Most competitive methods (Melander and Saunders, 1980e) utilize isotope ratio measurements based on mass spectrometry (Shine et al., 1984) or radioactivity measurements by liquid scintillation (Ando et al., 1984 Axelsson et al., 1991). However, some special methods, which are particularly useful for the accurate determination of secondary KIEs, have been developed. These newer methods, which are based on polarimetry, nmr spectroscopy, chromatographic isotopic separation and liquid scintillation, respectively, are described in this section. The accurate measurement of small heavy-atom KIEs is discussed in a recent review by Paneth (1992). [Pg.234]

For a characterization within a series of compounds often polarimetry supersedes CD spectroscopy because the chosen concentration for its measurement is not restricted by a too high absorption. The broad acceptance of the polarimetric standardization of chiral compounds always has been a motivation for improvements of polarimeters. Especially for the daily routine work there is a requirement for instruments with high convenience (see section on Polarimetry and CD detectors in liquid chromatography). [Pg.641]

It is worth noting that quantitative data on the rate of enolization could be obtained by polarimetry measurements since optically active thiazoline-5-ones are now available. [Pg.431]

Polarimetry. Polarimetry, or polarization, is defined as the measure of the optical rotation of the plane of polarized light as it passes through a solution. Specific rotation [ a] is expressed as [cr] = OcjIc where (X is the direct or observed rotation, /is the length in dm of the tube containing the solution, and c is the concentration in g/mL. Specific rotation depends on temperature and wavelength of measurement, and is a characteristic of each sugar it may be used for identification (7). [Pg.9]

Polarization is the most common method for the determination of sugar in sugar-containing commodities as well as many foodstuffs. Polarimetry is apphed in sugar analysis based on the fact that the optical rotation of pure sucrose solutions is a linear function of the sucrose concentration of the solution. Saccharimeters are polarimeters in which the scales have been modified to read directiy in percent sucrose based on the normal sugar solution reading 100%. [Pg.9]

The specific rotation ia water is [0 ] ° — +66.529° (26 g pure sucrose made to 100 cm with water). This property is the basis for measurement of sucrose concentration ia aqueous solution by polarimetry. 100°Z iadicates 100% sucrose on soHds. [Pg.13]

The analytical capability of these matrices has been demonstrated for chiral amines [12, 13]. The procedure is illustrated in Fig. 8-4 for the separation of NapEtNH " CIO . Concentrated methanol/dichloromethane solutions of the racemic mixture were placed on a column containing the chiral macrocycle host. The enantiomers of the ammonium salts were resolved chromatographically with mixtures of methanol and dichloromethane as the mobile phase. The amounts of R and S salts in each fraction were determined by polarimetry. Because the chiral supported macrocycle interacts more strongly with S salts, the R salt passes through the column first and the S salt last, as seen in Fig. 8-4. [Pg.211]

The amount of rotation observed in a polarimetry experiment depends on the number of optically active molecules encountered by the light beam. This number, in turn, depends on sample concentration and sample pathlength. If the concentration of sample is doubled, the observed rotation doubles. If the concentration is kept constant but the length of the sample tube is doubled, the observed rotation is doubled. It also happens that the amount of rotation depends on the wavelength of the light used. [Pg.295]

Unfortunately, in the VUV region no polarimetry data are available, but calculations indicate the degree of circular polarization achieved by the wiggler may be 80%, estimated to be no worse than 70% delivered at the experimental chamber [95, 96]. In PECD experiments, we have calibrated the polarization state by deduction from cross-comparison of results at a few fixed energies previously studied on the SU5 beamline where accurate polarimetry data was available [36]. Because the horizontal magnetic field array in the insertion device is electromagnetic, fast current reversal to switch left- and right-handed elliptical polarizations is possible, with the usual potential benefit for dichroism measurements. [Pg.303]

Most analyses of kinetic data have the object of identifying the constants of a rate equation based on the law of mass action and possibly some mass transfer relation.. The law of mass action Is expressed In terms of concentrations of the participants, so ultimately the chemical composition must be known as a function of time. In the laboratory the chemical composition Is determined by some instrument that is suitably calibrated to provide the needed information. Titration, refractive index, density, chromatography, spectrometry, polarimetry, conductimetry, absorbance, magnetic resonance — all of these are used at one time or another to measure chemical composition. In some cases, the calibration to chemical composition is linear with the reading. [Pg.105]

Preferential crystallisation is one option for optical resolution on a manufacmr-ing scale. Online polarimetry and refractometry have been used to d3mamically optimise the process for resolution of DL-threonine in aqueous solution by variation of process parameters such as degree of supersaturation, seed quantity, initial enantiomeric excess and scale [148]. The method is claimed to be suitable for control of quasi-continuous processes. [Pg.262]

The precision and accuracy of polarimetry critically depends on temperature, solvent, and traces of achiral and chiral impurities. [Pg.153]


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See also in sourсe #XX -- [ Pg.246 ]




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