The Effect of Electrolytes

Fig. VI-5. The effect of electrolyte concentration on the interaction potential energy between two spheres where K is k in cm". (From Ref. 44.)...

Stem layer adsorption was involved in the discussion of the effect of ions on f potentials (Section V-6), electrocapillary behavior (Section V-7), and electrode potentials (Section V-8) and enters into the effect of electrolytes on charged monolayers (Section XV-6). More speciflcally, this type of behavior occurs in the adsorption of electrolytes by ionic crystals. A large amount of wotk of this type has been done, partly because of the importance of such effects on the purity of precipitates of analytical interest and partly because of the role of such adsorption in coagulation and other colloid chemical processes. Early studies include those by Weiser [157], by Paneth, Hahn, and Fajans [158], and by Kolthoff and co-workers [159], A recent calorimetric study of proton adsorption by Lyklema and co-workers [160] supports a new thermodynamic analysis of double-layer formation. A recent example of this is found in a study... 

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 force between two adjacent surfaces can be measured directly with the surface force apparatus (SEA), as described in section BT20 [96]. The SEA can be employed in solution to provide an in situ detennination of the forces. Although this instmment does not directly involve an atomically resolved measurement, it has provided considerable msight mto the microscopic origins of surface friction and the effects of electrolytes and lubricants [97]. 

We shall be interested in determining the effect of electrolytes of low molecular weight on the osmotic properties of these polymer solutions. To further simplify the discussion, we shall not attempt to formulate the relationships of this section in general terms for electrolytes of different charge types-2 l, 2 2, 3 1, 3 2, and so on-but shall consider the added electrolyte to be of the 1 1 type. We also assume that these electrolytes have no effect on the state of charge of the polymer itself that is, for a polymer such as, say, poly (vinyl pyridine) in aqueous HCl or NaOH, the state of charge would depend on the pH through the water equilibrium and the reaction... 

Table II also shows the effect of electrolyte concentration on Rf and kj. Both effects reflect the fact that at the higher ionic strengths particle/substrate repulsion is decreased, thus effectively increasing the available pore volume at a given particle size. These results are illustrated in Figure 3. Included in this figure are data from work by Nagy (14) with a column set similar in configuration to that employed here.

U. Huetz and P. Englezos. Measurement of structure h hydrate phase equilibrium and the effect of electrolytes. Fluid Phase Equilibria, 117(1-2) 178-185,1995. 

These results have been initially considered as evidence for specific ion adsorption at ITIES [71,72]. Its origin was ascribed to extensive ion pair formation between ions in the aqueous phase and ions in the organic phase [71] [cf. Eq. (20)], or to a penetration into the interfacial region [72]. The former model, which has been considered in this context earlier [60], allows one to interpret the enhanced capacity in terms of Eq. (22). Pereira et al. (74) presented more experimental data demonstrating the effect of electrolytes and proposed a simple model, which is based on the lattice-gas model of the liquid liquid interface [23]. Theoretical calculations showed that ion pairing can lead to an increase in the stored... 

Figure 9 (C) and (B) show interfacial potential of the two-phase system in the presence of SDS and inorganic and organic electrolytes in the aqueous phase and tetra-butylammonium chloride in the octanol phase, iiD,sDS> and interfacial potential in the absence of SDS, iJc.sDS respectively. The potential of the octanol phase was measured in reference to the aqueous phase. The effects of electrolytes on c,sds and i D,sDS were the same for the most part as those on a,sds and iJs.sDS respectively, and differences between Eqsds and Tsdsds were essentially as much as those between a,sds and...

The effects of electrolytes on the interfacial potential of the two-phase system with CTAB, Fd ctaB) markedly differed from the case without CTAB, Fc,ctab [Fig. 11(B) and (C)]. The effects of electrolytes on F ctab Fj) ctab were basically those on Fa,ctab and Fb,ctaB) respectively and differences between Fc,ctab and F ctab were essentially as much as those between Fa,ctab and Fb ctab-... 

Craig VSJ, Ninham BW, Pashley RM (1993) The effect of electrolytes on bubble coalescence in water. J Phys Chem 97 10192-10197... 

Electrolytes are used to promote the exhaustion of direct or reactive dyes on cellulosic fibres they may also be similarly used with vat or sulphur dyes in their leuco forms. In the case of anionic dyes on wool or nylon, however, their role is different as they are used to facilitate levelling rather than exhaustion. In these cases, addition of electrolyte decreases dye uptake due to the competitive absorption of inorganic anions by the fibre and a decrease in ionic attraction between dye and fibre. In most discussions of the effect of electrolyte on dye sorption, attention is given only to the ionic aspects of interaction. In most cases, this does not create a problem and so most adsorption isotherms of water-soluble dyes are interpreted on the basis of Langmuir or Donnan ionic interactions only. There are, however, some observed cases of apparently anomalous behaviour of dyes with respect to electrolytes that cannot be explained by ionic interactions alone. 

In a study of the effect of electrolyte concentration on gas holdup, Bly and Worden (1990) found a strong effect. A salt solution resulted in twice the gas holdup that distilled water did under otherwise identical operating conditions, because the salt solution suppressed bubble coalescence. Investigation of this phenomenon is important in biofluidization, because biological media commonly have high electrolyte concentrations. 

For homopolyelectrolyte, we first studied the ellipsometric measurement of the adsorption of sodium poly(acrylate) onto a platinum plate as a function of added sodium bromide concentration (5). We measured the effect of electrolyte on the thickness of the adsorbed layer and the adsorbances of the polyelectrolyte. It was assumed that the Donnan equilibrium existed between the adsorbed layer and the bulk phase. The thickness was larger and the adsorbance of the polyelectrolyte was lower for the lower salt concentration. However, the data on the molecular weight dependence of both the adsorbance and the thickness of the adsorbed polyelectrolyte have been lacking compared with the studies of adsorption of nonionic polymers onto metal surfaces (6-9). 

As a final topic in this section, we briefly consider the effect of electrolyte concentration on the solvent properties. The linearized Poisson-Boltzmann equation [31,121] can be used instead of (2) and (3) when the dielectric medium... 

The asymmetric reduction of C=N double bonds in prochiral oximes afforded a maximum of 18% ee [380, 384, 385]. Prochiral azomethines were reduced to the corresponding 1,2-diamines and secondary amines using 36 optically active supporting electrolytes. The dimers were optically inactive, while the monomers showed low optical inductions (<11% ee). The effect of electrolyte, substrate concentration, temperature, pH, and cathode potential on the induction was studied. It was proposed that the enantioselectivity... 

Cai Q, Paulose M, Varghese OK, Grimes CA (2005) The effect of electrolyte composition on the fabrication of self-organized titanium oxide nanotuhe arrays hy anodic oxidation. J Mater Res 20 230-236... 

Mukherjee has extended his hypothesis to a consideration of the effects of electrolytes on electric endosmose, utilising the data of Eiissafoff Zeit Phys. Ghem. Lxxix. 385,1912) (see p. 226). 

Kawamura etal. [421] have studied the effect of electrolytic conditions on the coverage of an Au(lll) electrode with underpotentially deposited layer of Cd. The Cd atomic layer was located on the Au(lll) surface similar to the reconstructed structure. Also, a layer of sulfate anions was positioned on the Cd atomic layer. Cd coverage was found to be dependent on the concentration of H 2 S O4. 

Other molecular thermodynamic models for protein-reverse micelle complexes have also emerged. Bratko et al. [171] presented a model for phase transfer of proteins in RMs. The shell and core model was combined with the Poisson-Boltzmann approximation for the protein-RM complex and for the protein-free RM. The increase in entropy of counterions released from RMs on solubilization of a protein was the main contribution to the decrease in free energy of com-plexation. Good agreement was found with SANS results of Sheu et al. [151] for cytochrome C solubilization and the effect of electrolytes on it. However, this model assumes that filled and empty RMs are of the same size, independent of salt strength and pH, which is not true according to experimental evidence available since then. 

Different surfactants are usually characterised by the solubility behaviour of their hydrophilic and hydrophobic molecule fraction in polar solvents, expressed by the HLB-value (hydrophilic-lipophilic-balance) of the surfactant. The HLB-value of a specific surfactant is often listed by the producer or can be easily calculated from listed increments [67]. If the water in a microemulsion contains electrolytes, the solubility of the surfactant in the water changes. It can be increased or decreased, depending on the kind of electrolyte [68,69]. The effect of electrolytes is explained by the HSAB principle (hard-soft-acid-base). For example, salts of hard acids and hard bases reduce the solubility of the surfactant in water. The solubility is increased by salts of soft acids and hard bases or by salts of hard acids and soft bases. Correspondingly, the solubility of the surfactant in water is increased by sodium alkyl sulfonates and decreased by sodium chloride or sodium sulfate. In the meantime, the physical interactions of the surfactant molecules and other components in microemulsions is well understood and the HSAB-principle was verified. The salts in water mainly influence the curvature of the surfactant film in a microemulsion. The curvature of the surfactant film can be expressed, analogous to the HLB-value, by the packing parameter Sp. The packing parameter is the ratio between the hydrophilic and lipophilic surfactant molecule part [70] ... 

Schulze and Hardy (1882-1900) studied the effects of electrolytes on colloid stability. 

The effect of electrolytes and drugs on the cloud point of hydroxypropylmethylcellulose gels and the dissolution of drugs from hydroxypropylmethylcellulose matrix tablets... 

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