Diffusional gradient technique

DOSY is a technique that may prove successful in the determination of additives in mixtures [279]. Using different field gradients it is possible to distinguish components in a mixture on the basis of their diffusion coefficients. Morris and Johnson [271] have developed diffusion-ordered 2D NMR experiments for the analysis of mixtures. PFG-NMR can thus be used to identify those components in a mixture that have similar (or overlapping) chemical shifts but different diffusional properties. Multivariate curve resolution (MCR) analysis of DOSY data allows generation of pure spectra of the individual components for identification. The pure spin-echo diffusion decays that are obtained for the individual components may be used to determine the diffusion coefficient/distribution [281]. Mixtures of molecules of very similar sizes can readily be analysed by DOSY. Diffusion-ordered spectroscopy [273,282], which does not require prior separation, is a viable competitor for techniques such as HPLC-NMR that are based on chemical separation. 

Most of the experimental applications of the ZLC technique have been with gaseous systems, and for these systems the technique may now be regarded as a standard method. Based on our experience it is possible to suggest some guidelines as to how the experiments should be carried out. The key parameter is L, which from its definition (Eq. 17) can be considered the ratio of the diffusional and washout time constants R /D and KVs/F. This parameter is also equal to the dimensionless adsorbed phase concentration gradient at the surface of the solid at time zero. From either of these definitions it is evident that L gives an indication of how far removed the system is from equilibrium control. This parameter is proportional to the flow rate, so it can be easily varied, and to extract a reliable time constant, it is necessary to run the experiment at at least two different flow rates. 

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