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System peaks Selectivity coefficient

Both methods use a low-capacity cation exchanger as a stationary phase and a dilute mineral acid such as hydrochloric or nitric acid as a mobile phase. Although stationary phases and eluents have changed over the years, the principal difference between the methods is the same up to the present day. For his hypothetical experiments. Small kept constant the volume of the stationary phase, the ion-exchange capacity of the separator colunm, the selectivity coefficients for sodium and potassium relative to the hydronium ion, and the injection volume. With these values and the known acid concentration in the mobile phase, it is possible to calculate the elution volumes of sodium and potassium. To further simplify the calculation of the elution profiles, the chromatographic peaks are assumed to be symmetrical, so that they can be described by a Gaussian curve. One can further assume that the membrane-based suppressor system exhibits a very small dead volume and, therefore, subtracts negligibly from the efficiency of the separator column, which is estimated to be 3000 theoretical plates. [Pg.741]

In chromatography techniques, selectivity can be proved by the existence of good separation between the analyte and the other components (such as the matrix, impurities, degradation product(s), and metabolites). A consequence of this requirement is that the resolution of the analyte from the other components should be more than 1.5-2.0. In order to detect the possibility of coelution of other substance(s), the purity of the analyte peak should also be determined. For instance, the UV-Vis spectrum of the analyte peak/spot can be used to determine 4the purity of the analyte peak/spot, in this case the correlation coefficient V (this term is used by the software of DAD System Manager Hitachi, and CATS from Camag). With the same meaning and mathematical equation, other terms are used, such as Match... [Pg.246]

In a typical pulse experiment, a pulse of known size, shape and composition is introduced to a reactor, preferably one with a simple flow pattern, either plug flow or well mixed. The response to the perturbation is then measured behind the reactor. A thermal conductivity detector can be used to compare the shape of the peaks before and after the reactor. This is usually done in the case of non-reacting systems, and moment analysis of the response curve can give information on diffusivities, mass transfer coefficients and adsorption constants. The typical pulse experiment in a reacting system traditionally uses GC analysis by leading the effluent from the reactor directly into a gas chromatographic column. This method yields conversions and selectivities for the total pulse, the time coordinate is lost. [Pg.240]

Monochromatic detection. A schematic of a monochromatic absorbance detector is given in Fig. 3.12. It is composed of a mercury or deuterium light source, a monochromator used to isolate a narrow bandwidth (10 nm) or spectral line (i.e. 254 nm for Hg), a flow cell with a volume of a few pi (optical path 0.1 to 1 cm) and a means of optical detection. This system is an example of a selective detector the intensity of absorption depends on the analyte molar absorption coefficient (see Fig. 3.13). It is thus possible to calculate the concentration of the analytes by measuring directly the peak areas without taking into account the specific absorption coefficients. For compounds that do not possess a significant absorption spectrum, it is possible to perform derivatisation of the analytes prior to detection. [Pg.57]

Sorption of Cu(tfac)2 on a column depends on the amount of the compound injected, the content of the liquid phase in the bed, the nature of the support and temperature. Substantial sorption of Cu(tfac)2 by glass tubing and glass-wool plugs was observed. It was also shown that sorption of the copper chelate by the bed is partialy reversible . The retention data for Cr(dik)3, Co(dik)3 and Al(dik)3 complexes were measured at various temperatures and various flow rates. The results enable one to select conditions for the GC separation of Cr, Al and Co S-diketonates. Retention of tfac and hfac of various metals on various supports were also studied and were widely used for the determination of the metals. Both adsorption and partition coefficients were found to be functions of the average thickness of the film of the stationary phase . Specific retention volumes, adsorption isotherms, molar heats and entropy of solution were determined from the GC data . The retention of metal chelates on various stationary phases is mainly due to adsorption at the gas-liquid interface. However, the classical equation which describes the retention when mixed mechanisms occur is inappropriate to represent the behavior of such systems. This failure occurs because both adsorption and partition coefficients are functions of the average thickness of the film of the stationary phase. It was pointed out that the main problem is lack of stability under GC conditions. Dissociation of the chelates results in a smaller peak and a build-up of reactive metal ions. An improvement of the method could be achieved by addition of tfaH to the carrier gas of the GC equipped with aTCD" orFID" . ... [Pg.701]

Variations in cathodic peak current with the square of the sweep rate [/p,.. = /(v -)] for. selected PACE/electrolyte systems are shown in Figs. 13a and 13b [194]. In all ca.ses the relation is linear and the correlation coefficient tends to unity, especially in the lower ranges of the potential sweep rates. In agreement with numerous researchers [7,9,14,16,24,26,132], we also suggest that the cathodic peak is due to the reduction of quinonelike groups, whereas the anodic wave is due to the oxidation of hydroquinonelike groups in different environments on the active carbon surface of the electrode. These reactions are faradic... [Pg.159]

The blown bitumens do not exhibit peaks in the evaporation range when the system pressure is inereased to 10 bar, except for the dispersion medium of the bitumens 85/40 and 85/25, which demonstrate only an evaporation loss. The Arrhenius coefficients of the blown bitumen showed greater differences than those of the distillation bitumens. In the plot of half life time, versus the inverse Kelvin temperature, the distillation bitumens and their colloid components follow almost parallel lines, whereas the graphs for the blown bitumens and their colloid components diverge. The plot of versus 1 000/T shows the residence time required to achieve a conversion of fifty percent, at a preset reaction temperature, or which temperature is required to achieve a preset conversion at a preset residence time. This information is valuable in thermal processing, for example in selection of the crack severity of the visbreaking process. [Pg.262]

Another method for achieving selective detection of certain types of spin systems is through the application of pulsed magnetic field gradients. This can be used to select particular coherence pathways for spins in a multiple pulse experiment, for example, in multidimensional NMR spectroscopy, to crush unwanted magnetization such as solvent resonance, to measure molecular diffusion coefficients, and, hence, to edit spectra on the basis of the diffusion coefficients of the molecules giving rise to individual peaks. [Pg.3280]

CL is soluble in water, slightly soluble in alcohols, but insoluble in non-polar solvents such as hexane and chloroform. Based on these properties, we selected -butanol and water as a basic solvent system. However, this combination was not suitable by itself, because the CL components were entirely partitioned into the lower aqueous phase. In order to partition the CL components partly into the n-butanol phase, various salts (sodium chloride and sodium sulfate) or acids (hydrochloric acid, sulfuric acid and TFA) were added as a modifier. A desirable effect was obtained by the addition of TFA, where the partition coefficients of CL components rose as the concentration of TFA in the solvent system was increased. As TFA forms an ion pair with amino groups in the molecule of CL, the hydrophobicity of CL components increases with the concentration of TFA, resulting in the partition of components toward the organic phase. In order to determine the optimal concentration of TFA in the solvent system, K values were measured at various TFA concentrations. The K value of each component increases with the TFA concentration and, at 40 mM TFA concentration, the K values of CL-A and CL-B reach 1.5 and 0.6, respectively. At this TFA concentration, the a values between the adjacent peaks are all greater than 1.5,... [Pg.2194]


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See also in sourсe #XX -- [ Pg.84 , Pg.85 , Pg.86 ]




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