Electrolyte concentration layers

The repulsion between oil droplets will be more effective in preventing flocculation Ae greater the thickness of the diffuse layer and the greater the value of 0. the surface potential. These two quantities depend oppositely on the electrolyte concentration, however. The total surface potential should increase with electrolyte concentration, since the absolute excess of anions over cations in the oil phase should increase. On the other hand, the half-thickness of the double layer decreases with increasing electrolyte concentration. The plot of emulsion stability versus electrolyte concentration may thus go through a maximum. 

For example, van den Tempel [35] reports the results shown in Fig. XIV-9 on the effect of electrolyte concentration on flocculation rates of an O/W emulsion. Note that d ln)ldt (equal to k in the simple theory) increases rapidly with ionic strength, presumably due to the decrease in double-layer half-thickness and perhaps also due to some Stem layer adsorption of positive ions. The preexponential factor in Eq. XIV-7, ko = (8kr/3 ), should have the value of about 10 " cm, but at low electrolyte concentration, the values in the figure are smaller by tenfold or a hundredfold. This reduction may be qualitatively ascribed to charged repulsion. 

The theory has certain practical limitations. It is useful for o/w (od-in-water) emulsions but for w/o (water-in-oil) systems DLVO theory must be appHed with extreme caution (16). The essential use of the DLVO theory for emulsion technology Hes in its abdity to relate the stabdity of an o/w emulsion to the salt content of the continuous phase. In brief, the theory says that electric double-layer repulsion will stabdize an emulsion, when the electrolyte concentration in the continuous phase is less than a certain value. 

Density gradients to stabilize flow have been employed by Philpot IT> Yin.s. Faraday Soc., 36, 38 (1940)] and Mel [ j. Phys. Chem., 31,559 (1959)]. Mel s Staflo apparatus [J. Phys. Chem., 31, 559 (1959)] has liquid flow in the horizontal direction, with layers of increasing density downward produced by sucrose concentrations increasing to 7.5 percent. The solute mixture to be separated is introduced in one such layer. Operation at low electrolyte concentrations, low voltage gradients, and low flow rates presents no cooling problem. 

CNTs have been prepared recently by electrolysis and by electron irradiation of tube precursors. For example. Hsu e/ al. [30,31] have described the condensed-phase preparation of MWCNTs by an electrolytic method using a graphite rod (cathode) and carbon crucible (anode) (Fig. 6) in conjunction with molten LiCl as the electrolyte, maintained at 600°C under an Ar atmosphere. Application of a dc current (3-20 A, <20 V) for 2 min yielded MWCNTs (2-10 nm in diameter, >0.5 pm in length) consisting of 5-20 concentric layers with an interlayer... 

Figure 1-13 displays the experimental dependence of the double-layer capacitance upon the applied potential and electrolyte concentration. As expected for the parallel-plate model, the capacitance is nearly independent of the potential or concentration over several hundreds of millivolts. Nevertheless, a sharp dip in the capacitance is observed (around —0.5 V i.e., the Ep/C) with dilute solutions, reflecting the contribution of the diffuse layer. Comparison of the double layer witii die parallel-plate capacitor is dius most appropriate at high electrolyte concentrations (i.e., when C CH). 

Equation 46 suggests that, maintaining pi constant, q, must depend linearly on if only a first-order electroviscous effect exists, and an increase in the electrolyte concentration implies a decrease in the thickness, 1/k, of the electrical double layer. 

Non-situ and ex situ studies can provide important information for understanding the properties of metal/electrolyte interfaces. The applicability of these methods for fundamental studies of electrochemistry seems to be firmly established. The main differences between common electrochemical and UHV experiments are the temperature gap (ca. 300 vs. 150 K) and the difference in electrolyte concentration (very high concentrations in UHV experiments). In this respect, experimental research on double-layer properties in frozen electrolytes can be treated as a link between in situ experiments. The measurements of the work functions... 

The trends of behavior described above are found in solutions containing an excess of foreign electrolyte, which by definition is not involved in the electrode reaction. Without this excess of foreign electrolyte, additional effects arise that are most distinct in binary solutions. An appreciable diffusion potential q) arises in the diffusion layer because of the gradient of overall electrolyte concentration that is present there. Moreover, the conductivity of the solution will decrease and an additional ohmic potential drop will arise when an electrolyte ion is the reactant and the overall concentration decreases. Both of these potential differences are associated with the diffusion layer in the solution, and strictly speaking, are not a part of electrode polarization. But in polarization measurements, the potential of the electrode usually is defined relative to a point in the solution which, although not far from the electrode, is outside the diffusion layer. Hence, in addition to the true polarization AE, the overall potential drop across the diffusion layer, 9 = 9 + 9ohm is included in the measured value of polarization, AE. ... 

Some of the components of the EDL, such as a nonuniform electron distribution in the metal s surface layer and the layer of oriented dipolar solvent molecules in the solution surface layer adjacent to the electrode, depend on external parameters (potential, electrolyte concentration, etc.) to only a minor extent. Usually, the contribution of these layers is regarded as constant, and it is only in individual cases that we must take into account any change in these surface potentials, and which occurs as a result of changes in the experimental conditions. 

Provided that Ag

P2 are constant, and Tjjx is proportional to (c "). The observed nonlinearity at higher electrolyte concentrations [2] is probably due to a change in the inner-layer potential difference A"y>, with the surface excess charge density. The inner-layer potential difference (< 50 mV) was evaluated from the linear part of the Tjj vs. plot, and was found to depend on the nature of the... 

The same system has been studied previously by Boguslavsky et al. [29], who also used the drop weight method. While qualitatively the same behavior was observed over the broad concentration range up to the solubility limit, the data were fitted to a Frumkin isotherm, i.e., the ions were supposed to be specifically adsorbed as the interfacial ion pair [29]. The equation of the Frumkin-type isotherm was derived by Krylov et al. [31], on assuming that the electrolyte concentration in each phase is high, so that the potential difference across the diffuse double layer can be neglected. 

It is assumed that the quantity Cc is not a function of the electrolyte concentration c, and changes only with the charge cr, while Cd depends both on o and on c, according to the diffuse layer theory (see below). The validity of this relationship is a necessary condition for the case where the adsorption of ions in the double layer is purely electrostatic in nature. Experiments have demonstrated that the concept of the electrical double layer without specific adsorption is applicable to a very limited number of systems. Specific adsorption apparently does not occur in LiF, NaF and KF solutions (except at high concentrations, where anomalous phenomena occur). At potentials that are appropriately more negative than Epzc, where adsorption of anions is absent, no specific adsorption occurs for the salts of... 

According to Eq. (4.3.13) the differential capacity of the diffuse layer Cd has a minimum at 2 = 0, i.e. at E = Epzc. It follows from Eq. (4.3.1) and Fig. 4.5 that the differential capacity of the diffuse layer Cd has a significant effect on the value of the total differential capacity C at low electrolyte concentrations. Under these conditions, a capacity minimum appears on the experimentally measured C-E curve at E — Epzc. The value of Epzc can thus be determined from the minimum of C at low electrolyte concentrations (millimolar or lower). 

This theory of the diffuse layer is satisfactory up to a symmetrical electrolyte concentration of 0.1 mol dm-3, as the Poisson-Boltzmann equation is valid only for dilute solutions. Similarly to the theory of strong electrolytes, the Gouy-Chapman theory of the diffuse layer is more readily applicable to symmetrical rather than unsymmetrical electrolytes. 

If the effect of the electrical double layer is neglected (e.g. at higher indifferent electrolyte concentrations), the rate constant of the cathodic reaction is approximately given by the equation... 

The Gouy-Chapman theory relates electrolyte concentration, cation valence, and dielectric constant to the thickness of this double layer (see Equation 26.2). This theory was originally developed for dilute suspensions of solids in a liquid. However, experience confirms that the principles can be applied qualitatively to soil, even compacted soil that is not in suspension.5... 

Mobility of The Anion-Free Water. It is well known that water in the electrical double layer is under a field strength of 10 -10 V/cm and that the water has low dielectric constants (36). Since anion-free water is thought to be the water in the electrical double layer between the clay and the bulk solution, at high electrolyte concentrations, the double layer is compressed therefore, the water inside is likely quite immobile. At low electrolyte concentrations, the electrical double layer is more diffuse, the anion-free water is expected to be less immobile. Since the evaluation of the shaly formation properties requires the knowledge of the immobile water, experiments were conducted to find out the conditions for the anion-free water to become mobile. 

Calculations of the capacitance of the mercury/aqueous electrolyte interface near the point of zero charge were performed103 with all hard-sphere diameters taken as 3 A. The results, for various electrolyte concentrations, agreed well with measured capacitances as shown in Table 3. They are a great improvement over what one gets104 when the metal is represented as ideal, i.e., a perfectly conducting hard wall. The temperature dependence of the compact-layer capacitance was also reproduced by these calculations. 

The calculations were subsequently extended to moderate surface charges and electrolyte concentrations.8 The compact-layer capacitance, in this approach, clearly depends on the nature of the solvent, the nature of the metal electrode, and the interaction between solvent and metal. The work8,109 describing the electrodesolvent system with the use of nonlocal dielectric functions e(x, x ) is reviewed and discussed by Vorotyntsev, Kornyshev, and coworkers.6,77 With several assumptions for e(x,x ), related to the Thomas-Fermi model, an explicit expression6 for the compact-layer capacitance could be derived ... 

At high electrolyte concentrations of the soil solution, the double layer is compressed so that clay remains flocculated. A decrease in ion concentration, e.g. as a result of dilution by percolating rain water, can result in dispersion of clay and collapse of aggregates. If the exchange complex is dominated by polyvalent ions, the double layer may remain narrow even at low electrolyte concentrations and consequently aggregates remain intact (FAO, 2001). 

The distribution of potential in TC is practically the same as that near the flat surface if the electrolyte concentration is about 1 mol/1 [2], So the discharge of TC may be considered as that of a double electric layer formed at the flat electrode surface/electrolyte solution interface, and hence, an equivalent circuit for the TC discharge may be presented as an RC circuit, where C is the double layer capacitance and R is the electrolyte resistance. 

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