Pulsed field gradient self

A more sophisticated method which has found wide application in the study of intracrystalline diffusion in zeolites is the nuclear magnetic resonance (NMR) pulsed field gradient self-diffusion method. The method, which is limited to hydrocarbons and other sorbates with a sufficient density of unpaired nuclear spins, depends on measuring directly the mean square distance traveled by molecules,... 

FIGURE 5.4. The sequence of pulses used in the pulsed field gradient self-diffusion measure, ment. (a) rf pulse (i) Gradient pulse sequence (90°, 180°) (c) Response signal. (From ref. 22, with permission.)... 

We finish this section by comparing our results with NMR and incoherent neutron scattering experiments on water dynamics. Self-diffusion constants on the millisecond time scale have been measured by NMR with the pulsed field gradient spin echo (PFGSE) method. Applying this technique to oriented egg phosphatidylcholine bilayers, Wassail [68] demonstrated that the water motion was highly anisotropic, with diffusion in the plane of the bilayers hundreds of times greater than out of the plane. The anisotropy of... 

W. Brown, R. Johnsen, P. Stilbs, B. Lindman. Size and shape of nonionic amphiphile (Ci2Eg) micelles in dilute aqueous solutions as derived from quasielastic and intensity of light scattering, sedimentation and pulsed-field-gradient nuclear magnetic resonance self-diffusion data. J Phys Chem 87 4548-4553, 1983. 

There are a number of NMR methods available for evaluation of self-diffusion coefficients, all of which use the same basic measurement principle [60]. Namely, they are all based on the application of the spin-echo technique under conditions of either a static or a pulsed magnetic field gradient. Essentially, a spin-echo pulse sequence is applied to a nucleus in the ion of interest while at the same time a constant or pulsed field gradient is applied to the nucleus. The spin echo of this nucleus is then measured and its attenuation due to the diffusion of the nucleus in the field gradient is used to determine its self-diffusion coefficient. The self-diffusion coefficient data for a variety of ionic liquids are given in Table 3.6-6. 

Brown, W Stilbs, P Lindstrom, T, Self-Diffusion of Small Molecules in Cellulose Gels using FT-Pulsed Field Gradient NMR, Journal of Applied Polymer Science 29, 823,1984. Brownstein, KR Tarr, CE, Importance of Classical Diffusion in NMR Studies of Water in Biological Cells, Physical Review A 19, 2446, 1979. 

Hadden, DA, Master of Science Thesis, Florida State University, Tallahassee, FL, 1999. Hadden, D Rill, RL McFadden, L Locke, BR, Oligonucleotide and Water Self-Diffusion in Pluronic Triblock Copolymer Gels and Solutions by Pulsed Field Gradient Nuclear Magnetic Resonance, Macromolecules 33, 4235, 2000. 

While the nuclear magnetic resonance (NMR) technique has widely been used to study diffusion processes of normal liquids, solids, or colloidal systems, there are only a few applications to molten salts. The spin echo self-diffusion method with pulsed field gradients was applied to molten salts by Herdlicka et al. "" There is no need to set up or maintain a concentration gradient. 

Pulsed field gradient NMR (PFG-NMR) spectroscopy has been successfully used for probing interactions in several research fields.44-53 The method was developed by Stejskal and Tanner more than 40 years ago54 and allows the measurement of self-diffusion coefficient, D, which is defined as the diffusion coefficient in absence of chemical potential gradient. 

Nafion absorbs MeOH more selectively than water, and the MeOH diffusion flow is higher than the osmotic water flow in Nafion membranes. Diffusion coefficients of Nafion 117 determined by different techniques have been reported. Ren et al. measured MeOH diffusion coefficients in Nafion 117 membranes exposed to 1.0 M MeOH solutions using pulsed field gradient (PPG) NMR techniques. The MeOH self-diffusion coefficient was 6 x 10 cm S and roughly independent of concentration over the range of 0.5-8.0 M at 30°C. A similar diffusion coefficient was obtained for Nafion 117 at 22°C by Hietala, Maunu, and Sundholm with the same technique. Kauranen and Skou determined the MeOH diffusion coefficient of 4.9 x 10 cm for Nafion... 

Water self-diffusion coefficients (Dh o) have been determined by pulse field gradient NMR for Nation (Nil/) , BPSH, and SPEEKK and have been shown to increase with increasing acid and water content. At high water contents, the values for PEMs approach the corresponding value for pure water. This is due to the increase in volume fraction of free water. At low water content, however. Nation exhibits greater Dnp values than either BPSH or SPEEKK. In corranon with the observations for EOD, this has been attributed to the smaller channels in aromatic-based polymers, leading to a considerably lower dielectric constant for the water in the channels. 

Dong, L., Kim, Y. S., Wang, F, Hickner, M., Glass, T. E. and McGrath, J. E. 2003. Self-diffusion of water in sulfonated poly(arylene ether sulfone) copolymers by pulse field gradient NMR. Polymer Preprints 44 355. 

Pulsed field gradient (PFG)-NMR experiments have been employed in the groups of Zawodzinski and Kreuer to measure the self-diffusivity of water in the membrane as a function of the water content. From QENS, the typical time and length scales of the molecular motions can be evaluated. It was observed that water mobility increases with water content up to almost bulk-like values above T 10, where the water content A = nn o/ nsojH is defined as the ratio of the number of moles of water molecules per moles of acid head groups (-SO3H). In Perrin et al., QENS data for hydrated Nation were analyzed with a Gaussian model for localized translational diffusion. Typical sizes of confining domains and diffusion coefficients, as well as characteristic times for the elementary jump processes, were obtained as functions of A the results were discussed with respect to membrane structure and sorption characteristics. ... 

Abbreviations D, self-diffusion coefficient ge, gradient-echo IR, inversion recovery IRFT, inversion recovery fourier transform MRS, magnetic resonance spectroscopy PD, proton density PFGSE, pulsed field gradient spin echo se, spin-echo. 

Figure 1 Self-diffusion coefficients of benzene in zeolite NaX at 458 K from techniques n.m.r. pulsed field gradient (0,D) [70] n.m.r.

Umecky, T, Kanakubo, M., and Ikushima, Y., Self-diffusion coefficients of l-butyl-3-methylimidazolium hexafluorophosphate with pulsed-field gradient spin-echo NMR technique. Fluid Phase Equilib., 228-229, 329, 2005. 

Investigations of self-diffusion coefficients have been carried out by Parravano et al. (252) and Karger et at. (259, 275-278) using pulsed-field-gradient NMR techniques. The residence time t of a molecule in a particular... 

Packer and Rees [3] extended the work of Tanner and Stejskal by the development of a theoretical model using a log-normal size distribution function. Measurements made on two water-in-oil emulsions are used to obtain the self-diffusion coefficient, D, of the water in the droplets as well as the parameters a and D0 0. Since then, NMR has been widely used for studying the conformation and dynamics of molecules in a variety of systems, but NMR studies on emulsions are sparse. In first instance pulsed field gradient NMR was used to measure sdf-diffusion coefficients of water in plant cells (e.g. ref. [10]). In 1983 Callaghan... 

Fleisher et al. [12] studied the self-diffusion of oil and water in rape seeds. The selfdiffusion of oil was found to be completely restricted. The experiments could be explained in toms of the model of diffusion within spherical droplets and a Gaussian mass distribution of the droplet radii. At the same time Van den Enden et al. [9] introduced the technique described above. It is a rapid method for the determination of water droplet size distributions in spreads by using low resolution pulsed field gradient NMR. Their method was based on the recognition that a set of echo attenuation values (R) as a function of the field gradient pulsed width, obtained under conditions where R is independent of the time allowed for diffusion, contains all the necessary information on the water droplet size distribution (see above). A log-normal distribution of water droplet sizes was assumed. 

The diffusion of small molecules in rubbers is of both theoretical and practical importance. The theories of diffusion based on consideration of free volume can be tested by measurement of self-diffusion using methods such as pulsed field gradient NMR. Selfdiffusion of small molecules must be understood for applications of rubbers as seals in contact with solvents, and for example for diffusion of plasticisers and other small molecules. 

The NMR technique for measuring self-diffusion in liquids was first reported in 1965390, and its variant for multicomponent mixtures became available with the introduction of the Fourier transform. Wider use had to wait until pulsed field gradients became generally... 

Using pulsed field gradient spin echo NMR, Guering and Lindman [14] and, independently, Clarkson et al. [15] measured the self-diffusion coefficients of the components of microemulsions of sodium dodecyl sulfate (SDS), toluene, butanol, and NaCl brine. The results (Fig. 8) establish unequivocally the existence of bicontinous microemulsion. 

Pulsed Field Gradient (PFG) Self Diffusion Measurement(24)... 

Zielinski and Hanley [AlChE J. 45,1 (1999)] developed a model to predict multicomponent diffusivities from self-diffusion coefficients and thermodynamic information. Their model was tested by estimated experimental diffusivity values for ternary systems, predicting drying behavior of ternary systems, and reconciling ternary selfdiffusion data measured by pulsed-field gradient NMR. 

Pulsed field gradient NMR (PFG-NMR) is a powerful, nondestructive technique of measuring self-diffusion coefficients in a colloidal dispersion [69-71]. Molecules associated with an aggregate or a particle will diffuse more slowly than their free dissolving state. More specifically, when a water-soluble species is partially adsorbed onto an abrasive particle, the measured overall diffusion coefficient (D ) of the species is decreased. If the diffusion coefficient of the free dissolving species can be measured in the absence... 

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