Extraction effective diffusivity method

Thus, for many of the compounds that are extracted by this method, the equilibrium state does not quantitatively remove the analyte from solution. Rather from 2 to 20% of the analyte may be removed (Louch et al., 1992), although the application may be quantitative if standards are treated in an identical way. Another important point brought out in this study is that at high K values (>1000) the time to equilibrium is much longer than at lower K values. This effect is the result of the slow diffusion of the nonpolar analytes into the coated phase (Louch et al., 1992). Thus, for compounds with high K values (>1000) a thin film is used, 7 pm (Supelco) in order to attain quick equilibrium conditions. In the case of headspace analysis where sorption occurs from the gaseous state rather than the liquid state, the rate of equilibrium is much faster because of faster diffusion rates around the fiber and the lack of the water boundary layer. Thus, equilibrium for headspace analysis is approximately 10 times faster than the liquid-state sorption. 

In an effective properties model, the porous microstructures of the SOFC electrodes are treated as continua and microstructural properties such as porosity, tortuosity, grain size, and composition are used to calculate the effective transport and reaction parameters for the model. The microstmctural properties are determined by a number of methods, including fabrication data such as composition and mass fractions of the solid species, characteristic features extracted from micrographs such as particle sizes, pore size, and porosity, experimental measurements, and smaller meso- and nanoscale modeling. Effective transport and reaction parameters are calculated from the measured properties of the porous electrodes and used in the governing equations of the ceU-level model. For example, the effective diffusion coefficients of the porous electrodes are typically calculated from the diffusion coefficient of Eq. (26.4), and the porosity ( gas) and tortuosity I of the electrode ... 

For SDS, the reaction proceeded to a reproducible end point rapidly —viz., 1 to 2 minutes—when nonionic surface active impurities such as parent dodecyl alcohol, DOH, were removed by ethyl ether extractions. This impurity effect was verified by adding traces of alkyl alcohol—viz., 1 X 10 9 mole per liter—to purified SDS, whereupon the penetration reaction rate was halved. A possible explanation for this behavior is that formation of an SDS-DOH interfacial complex reduced the SDS activity in the interface and consequently its rate of reaction with the protein monolayer. The reasons for the somewhat slower rate of reaction of Cetab with the protein film are more obscure. The reaction rate did not increase after extracting the detergent repeatedly. Two possible reasons for the time dependence in this case may have been that (1) the ether extraction method was not effective in removing surface active impurities, or (2) because of the greater bulk of the Cetab hydrocarbon chain, Ci6 vs. Ci2 for SDS, more time was required for diffusion and appropriate orientation before complex formation. 

Turning to assays using sensors that require more than a simple cut in the sample, Bergann et al. [37] paid considerable attention to sample preparation in attempts to measure lactate in meat with a sensor (not thick film) based on reaction of hydrogen peroxide with a platinum electrode or on the reaction of ferrocene carboxylate with the active site of lactate oxidase. Sample preparation entailed extraction into buffer following grinding. In some cases, ground samples were left to allow the lactate to diffuse into the buffer solution. This was quite effective but slow (up to 90 min). Ultimately, the quality of the assay was dependent on the method of sample preparation. 

One of the important aspects of any analytical method is its calibration and, therefore, much effort has been put into SPME calibration. As it is not always practicable to employ traditional calibration methods (external standards, internal standards, and standard addition) owing to the sometimes significant matrix effects in complex samples, equilibrium calibration has been suggested as an alternative. In SPME, however, it would normally take rather a long time to achieve equilibrium calibration. If sensitivity were not a concern in an analysis, reduction of extraction time would be desirable, that is, the extraction could be stopped before equilibrium but this would thus demand a new approach to calibration. In this regard, as a way of circumventing matrix effects in environmental analysis, several diffusion-based calibration methods have been recently developed for quantification in SPME.30... 

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