Transfer number values

Divalent cation salt-PEO complexes display a wide variation in cationic transference number values. While some polymeric systems with salts of Mg2+,i7.ii4 Co + are essentially pure anion conductors (with... 

ZnCF species contribute to an increase in cationic transference number values, while ZnCF" and ZnCF " species are responsible for a decrease. 

For a fully dissociated salt, all techniques should give the same values of transport number, t. Transference number measurements are appropriate for electrolytes containing associated species and any technique within one of the three groups will give a similar response, but values of 7] across the groups may vary. 

As the cell is discharged, Zn2+ ions are produced at the anode while Cu2+ ions are used up at the cathode. To maintain electrical neutrality, SO4- ions must migrate through the porous membrane,dd which serves to keep the two solutions from mixing. The result of this migration is a potential difference across the membrane. This junction potential works in opposition to the cell voltage E and affects the value obtained. Junction potentials are usually small, and in some cases, corrections can be made to E if the transference numbers of the ions are known as a function of concentration.ee It is difficult to accurately make these corrections, and, if possible, cells with transference should be avoided when using cell measurements to obtain thermodynamic data. 

Units in SI system Si Stanton number h/Cf,pu Dimensions depend ort order of reaction. Suffixes 0 Value in bulk of phase 1 Phase 1 2 Phase 2 A Component A B Component B AB Of A in B b Bottom of column equilibrium with bulk of other phase G Gas phase / Interface value. L Liquid phase u Overall value (for height and number of transfer units) value in bulk of phase i Top of column Dimensions in in M. N, 1. T. 

So far, the data mentioned were measured at 25° C as is usual in electrochemical practice. However, it should not be forgotten that the ion mobilities increase considerably with temperature (see the Smithsonian table of equivalent conductivities as different temperatures in the Handbook of Chemistry and Physics, 61st ed.), although with the same trends for the various ions therefore, the change in transference numbers remains small and shows a tendency to approach a value of 0.5 at higher temperatures. 

The final dimensionless group to be evaluated is the interfacial heat-transfer number, and therefore the interfacial heat-transfer coefficient and the interfacial area must be determined. The interface is easily described for this regime, and, with a knowledge of the holdup and the tube geometry, the interfacial area can be calculated. The interfacial heat trasfer coefficient is not readily evaluated, since experimental values for U are not available. A conservative estimate for U is found by treating the interface as a stationary wall and calculating U from the relationship... 

The lithium transference number (t+) of a polymer bearing PEO550 side chain/LiCF3S03 was found to be 0.38 at 30°C. This value implies that anions were effectively trapped by organoboron units, similar to linear organoboron polymer electrolytes. 

Initially, a small current, called residual current, flows and continues till the decomposition potential of reducible ionic species is reached. A further increase in applied potential increases the current linearly and reaches to a maximum value called limiting current. Three factors effect the current that during the electrolysis are (i) migration or an electrical effect which depends upon the charge and transference number of the electroactive species, (ii) diffusion of all charged and uncharged species in solution between the... 

To minimize the effects of viscosity for purposes of comparing data between solvents, plots areoften made using the product of the ion mobility and the viscosity (Walden product) in place of mobility alone. A plot of the Walden product against the reciprocal of the crystallographic radii for several solvents is shown in Fig. 6. Arbitrary curves have been drawn to indicate general trends. Values in solvents for which precise transference numbers and conductance data are available, such as acetonitrile and nitromethane, give smooth curves. 

A comparison of equations 6.63 and 6.69 shows that similar forms of equations describe the processes of heat and mass transfer. The values of the coefficients are however different in the two cases, largely to the fact that the average value for the Prandtl number, Pr, in the heat transfer work was lower than the value of the Schmidt number, Sc, in the mass transfer tests. 

Calculate the value of the transfer number for silicon combustion in air. Show all the stoichiometric relationships in the calculation. 

The nanostructured Au and AuPt catalysts were found to exhibit electrocatalytic activity for ORR reaction. The cyclic voltammetric (CV) curves at Au/C catalyst reveal an oxidation-reduction wave of gold oxide at +200 mV in the alkaline (0.5 M KOH) electrolyte but little redox current in the acidic (0.5 M H2SO4) electrolyte. Under saturated with O2, the appearance of the cathodic wave is observed at -190 mV in the alkaline electrolyte and at +50 mV in the acidic electrolyte. This finding indicates that the Au catalyst is active toward O2 reduction in both electrolytes. From the Levich plots of the limiting current vs. rotating speed data, one can derive the electron transfer number (w). We obtained n = 3.1 for ORR in 0.5 M KOH electrolyte, and 2.9 for ORR in 0.5 M H2SO4 electrolyte. The intermittent n-value between 2 and 4 indicates that the electrocatalytic ORR at the Au/Ccatalyst likely involved mixed 2e and 4e reduction processes. 

The limiting current fraction is the maximum fraction of the initial current which may be maintained at steady state in the absence of interfacial resistances. In specific circumstances this parameter may be equal to the transport or transference number of particular species, but without a priori knowledge of the species present in an electrolyte it is preferable that values are referred to, rather than t+ or T+ values. For polyether electrolytes containing LiClO values of 0.2-0.3 are often observed. 

This value is discussed in terms of two-electron transfer when Zn + is reduced to free zinc on Pt(lll) surface with a true electron transfer number of = 2. Also, induced adsorption of OH ions takes place to give OHads in an oxidative process. 

From formula (8) it is seen that also uncharged molecules, e.g. the molecules of the solvent, may have a transference number with a positive value. 

The rate parameters of importance in the multicomponent rate model are the mass transfer coefficients and surface diffusion coefficients for each solute species. For accurate description of the multicomponent rate kinetics, it is necessary that accurate values are used for these parameters. It was shown by Mathews and Weber (14), that a deviation of 20% in mass transfer coefficients can have significant effects on the predicted adsorption rate profiles. Several mass transfer correlation studies were examined for estimating the mass transfer coefficients (15, jL6,17,18,19). The correlation of Calderbank and Moo-Young (16) based on Kolmogaroff s theory of local isotropic turbulence has a standard deviation of 66%. The slip velocity method of Harriott (17) provides correlation with an average deviation of 39%. Brian and Hales (15) could not obtain super-imposable curves from heat and mass transfer studies, and the mass transfer data was not in agreement with that of Harriott for high Schmidt number values. 

This equation provides a means of determining the transference number of the negative ions from measurement of the emf of the cell with the conditions that all of the assumptions made in obtaining the equation are valid and that the values of the mean activity coefficients in the solutions are known. An equation can be derived by use of the same methods for the case in which the solutions contain several solutes. When the electrodes are reversible with respect to the M+ ion, the equation is... 

The Hatta-number represents the ratio of maximal possible reaction and mass transfer rates and helps to specify different absorption regimes. Depending on the Hatta-number value, it is possible to discriminate between very fast, fast, average and slow chemical reactions, in respect to physical mass transport [19, 20]. 

Other criteria can be used to establish the extinction condition and that are partially equivalent to the critical Damkohler number. Such criteria are a critical mass transfer numbers (BCI) [21,32], critical mass flux of fuel [2,6,28] or critical temperatures (Ta) [2,5,29-31], The critical mass transfer number has a direct influence over the flame temperature, and thus, represents the link between the condensed phase (i.e., production of fuel) and the chemical time. The critical mass flux operates under the same principle, but assumes a consistent heat input. Combustion reactions generally have high activation energy, therefore, the reaction can be assumed to abruptly cease when the temperature reaches a critical value (Tcr). 

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