Sodium self-diffusivity

Lin T. H. and Yund R. A. (1972). Potassium and sodium self-diffusion in alkali feldspar. Contrib. Mineral Petrol, 34 177-184. 

Light transmission L. L. Schramm and J.C.T. Kwak, op. cit. Electrophoretic mobility P. Bar-On, I. Shainberg, and I. Michaeli, Electrophoretic mobility of montmorillonite particles saturated with Na/Ca ions, J. Colloid Interface Sci. 33 471 (1970). Intrinsic viscosity I. Shainberg and H. Otoh, op. cit. Chloride exclusion volume J. E. Dufey, A. Banin, H. G. Laudelout, juid Y. Chen, Particle shape and sodium self-diffusion coefficient in mixed sodium-calcium montmorillonite. Soil Sci. Soc. Am. J. 40 310 (1976). 

The ESR spectrum of the pyridazine radical anion, generated by the action of sodium or potassium, has been reported, and oxidation of 6-hydroxypyridazin-3(2//)-one with cerium(IV) sulfate in sulfuric acid results in an intense ESR spectrum (79TL2821). The self-diffusion coefficient and activation energy, the half-wave potential (-2.16 eV) magnetic susceptibility and room temperature fluorescence in-solution (Amax = 23 800cm life time 2.6 X 10 s) are reported. 

Mechanisms of micellar reactions have been studied by a kinetic study of the state of the proton at the surface of dodecyl sulfate micelles [191]. Surface diffusion constants of Ni(II) on a sodium dodecyl sulfate micelle were studied by electron spin resonance (ESR). The lateral diffusion constant of Ni(II) was found to be three orders of magnitude less than that in ordinary aqueous solutions [192]. Migration and self-diffusion coefficients of divalent counterions in micellar solutions containing monovalent counterions were studied for solutions of Be2+ in lithium dodecyl sulfate and for solutions of Ca2+ in sodium dodecyl sulfate [193]. The structural disposition of the porphyrin complex and the conformation of the surfactant molecules inside the micellar cavity was studied by NMR on aqueous sodium dodecyl sulfate micelles [194]. 

The last, and less extensively studied field variable driving percolation effects is chemical potential. Salinity was examined in the seminal NMR self-diffusion paper of Clarkson et al. [12] as a component in brine, toluene, and SDS (sodium dodecylsulfate) microemulsions. Decreasing levels of salinity were found to be sufficient to drive the microemulsion microstructure from water-in-oil to irregular bicontinuous to oil-in-water. This paper was... 

Sodium chloride structure crystals have all octahedral sites filled, and so cation diffusion will be dependent upon vacancies on octahedral sites. In the zinc blende (sphalerite) structure, adopted by ZnS, for example, half of the tetrahedral sites are empty, as are all of the octahedral sites, so that self-diffusion can take place without the intervention of a population of defects. 

Staunton S, Nye PH. 1983. The self-diffusion of sodium in a naturally aggregated soil. 

To dearly distinguish between these two modes of solvent penetration of the gel, we immersed poly(acrylamide-co-sodium methacrylate) gels swollen with water and equilibrated with either pH 4.0 HQ or pH 9.2 NaOH solution into limited volumes of solutions of 10 wt % deuterium oxide (DzO) in water at the same pHs. By measuring the decline in density of the solution with time using a densitometer, we extracted the diffusion coefficient of D20 into the gel using a least squares curve fit of the exact solution for this diffusion problem to the data [121,149]. The curve fit in each case was excellent, and the diffusion coefficients obtained were 2.3 x 10 5cm2/s into the ionized pH 9.2 gel and 2.4 x 10 5 cm2/s into the nonionized pH 4.0 gel. These compare favorably with the self diffusion coefficient of D20, which is 2.6 x 10 5 cm2/s, since the presence of the polymer can be expected to reduce the diffusion coefficient about 10% in these cases [150], In short, these experiments show that individual solvent molecules can rapidly redistribute between the solution and the gel by a Fickian diffusion process with diffusion coefficients slightly less than in the free solution. 

Spiegler has used the friction model to describe a system consisting of sodium ions (1), chloride ions (2), water (3) and a charged matrix (4). He neglects the interaction of the sodium ions with the chloride ions. Then five independent measurements are needed to calculate the friction coefficients. Spiegler chose to be measured the self-diffusion coefficient... 

Fig. 2.11. Self-diffusion coefficients of water ( ), sodium ions ( ), dodecyisul-fate ion ( ) and micelles ( ) in SDS solutions. Data from Refs.37-110- 2>...

The self-diffusion of the individual components is strongly affected by the formation of micelles in the solution. This applies to the surfactant, the counterion, the water, and to solubilized molecules. As illustrated in Fig. 2.11 for sodium dodecyl sulfate, surfactant and counterion diffusion are very weakly dependent on concentration below the CMC while a marked decrease in the micellar region is observed for the surfactant and a less marked one for the counterion37. Water diffusion shows a stronger concentration dependence below the CMC than above it. Self-diffusion studies using radioactive tracers have been performed to obtain information on CMC, on counterion binding, on hydration and on intermicellar interactions and shape changes. 

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. 

Figure 8. Self-diffusion coefficients of the components of a microemulsion of sodium dodecyl sulfate (SDS), butanol, toluene, and NaCl brine. Vertical lines denote 2,3 and 3,2 phase transitions. Reprinted with permission from P. Guering and B. Lindman, Langmuir 1,464 (1985) [14]. Copyright 1985 American Chemical Society.

Oh et al. [16] have demonstrated that a microemulsion based on a nonionic surfactant is an efficient reaction system for the synthesis of decyl sulfonate from decyl bromide and sodium sulfite (Scheme 1 of Fig. 2). Whereas at room temperature almost no reaction occurred in a two-phase system without surfactant added, the reaction proceeded smoothly in a micro emulsion. A range of microemulsions was tested with the oil-to-water ratio varying between 9 1 and 1 1 and with approximately constant surfactant concentration. NMR self-diffusion measurements showed that the 9 1 ratio gave a water-in-oil microemulsion and the 1 1 ratio a bicontinuous structure. No substantial difference in reaction rate could be seen between the different types of micro emulsions, indicating that the curvature of the oil-water interface was not decisive for the reaction kinetics. More recent studies on the kinetics of hydrolysis reactions in different types of microemulsions showed a considerable dependence of the reaction rate on the oil-water curvature of the micro emulsion, however [17]. This was interpreted as being due to differences in hydrolysis mechanisms for different types of microemulsions. 

Williams et al,92) have investigated the diffusion of the sodium ion in NMA solutions of NaCl at 40 °C. The values of the diffusion coefficient for the Na+ ion were found to be equal to approximately half the value of the self-diffusion coefficient for pure NMA. This suggests a solvation which is equivalent to three or four molecules of NMA coordinated to the sodium ion. 

Examinations of other physical properties of pyridazine include the ESR spectrum of pyridazine radical anion (obtained with pyridazine and sodium or potassium in dimethoxyethane or tetra-hydrofuran, the self-diffusion coefficient and activation energy, the half-wave potential (-2.16V), and magnetic susceptibility. Pyridazine was reported not to fluoresce and no luminiscence could be observed even under very long exposures. More recently, room-temperature fluorescence in solution is reported to be at 23,800 cm (max.), with a life time of 2.6 x 10 . ... 

The self-diffusion coefficients of CF and Na" in molten sodium chloride are, respectively, 33 x 10 exp(-8500// 7) and 8x10 exp(-4000// 7) cm s". (a) Use the Nernst-Einstein equation to calculate the equivalent conductivity of the molten liquid at 935°C. (b) Compare the value obtained with the value actually measured, 40% less. Insofar as the two values are significantly different, explain this by some kind of structural hypothesis. 

Interactions between oppositely charged micelles in aqueous solutions spontaneously form vesicles. The self-diffusion coefficient of water and 2H relaxation of 2H-labeled dodecyl trimethyl ammonium chloride of the dodecyl trimethyl ammonium chloride-sodium dodecyl benzenesulfonate systems show that in these mixtures there is limited growth of the micelles with changes in composition. The vesicles abruptly begin to form at a characteristic mixing ratio of the two surfactants. The transition is continuous.205 Transformation from micelle to vesicle in dodecyl trimethyl ammonium chloride-sodium perfluoro-nonanoate aqueous solution has been studied by self-diffusion coefficient measurements, and it was found that at a concentration of 35 wt% with a molar ratio of 1 1, the self-diffusion coefficient of the mixed micelles is far smaller than that of the two individual micelles.206 The characteristics of mixed surfactant... 

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