Electrolytes, effect

Here (log cmc) is tire log cmc in tire absence of added electrolyte, is related to tire degree of counterion binding and electrostatic screening and c- is tire ionic strengtli (concentration) of inert electrolyte. Effects of added salt on cmc are illustrated in table C2.3.7. 

Insoluble corrosion prodiic ts may be completely impeivious to the corroding liquid and, therefore, completely protective or they may be quite permeable and allow local or general corrosion to proceed unhindered. Films that are nonuniform or discontinuous may tend to localize corrosion in particular areas or to induce accelerated corrosion at certain points by initiating electrolytic effects of the concentration-cell type. Films may tend to retain or absorb moisture and thus, by delaying the time of drying, increase the extent of corrosion resulting from exposure to the atmosphere or to corrosive vapors. 

For the determination of the molecular weight (Mw) by light scattering, the number of solvent systems is limited. The refractive index difference should be at least 0.1 and the solvent should not have an electrolytic effect. Useful solvents include formic acid containing KC1 salt and fluorinated alcohols. 

While the pzc of Hg in F solution has not changed by more than 1 mV for over 70 years, marginal variations are visible for Ga, Tl, In, Cd, Bi, Sn, and Sb that are related to electrolyte effects (weak specific adsorption or disturbance of the adsorbed water layer, as for Ga).847 Important variations can be seen, on the other hand, for polycrystalline Ag, Zn, Ni, Fe, and Cu. For all these metals a drop of the pzc to much more negative values has been recorded this is evidently related to an improvement in the preparation of the surface with more effective elimination of surface oxides. All these metals, with the exception of Ag, are naturally sensitive to atmospheric oxygen. Values of pzc for single-crystal faces first appeared in a 1974 compilation,23 in particular for the three main faces of Ag and for Au (110). Values for a number of other metals were reported in 1986.25 However, for sd-metals, an exhaustive, specific compilation of available experimental data was given by Hamelin etal. in 1983.24... 

Hsueh KL, Gonzalez ER, Srinivasan S. 1983. Electrolyte effects on oxygen reduction kinetics at platinum—A rotating-ring disk electrode analysis. Electrochim Acta 28 691-697. 

Neddermeyer, P. A. and Rogers, L. B., Column efficiency and electrolyte effects of inorganic salts in aqueous gel chromatography, Anal. Chem., 41, 94, 1969. 

In the following sections, synthesis of the anionic polymers, copolymer molecular weight, limiting viscosity number, electrolyte effects, solution shear thinning, screen factor, polymer radius of gyration, and solution aging will be discussed and data on the copolymers presented. 

Electrolyte Effect on Polymer Solution Rheology. As salt concentration in an aqueous poly(1-amidoethylene) solution increases, the resulting brine becomes a more Theta-solvent for the polymer and the polymer coil compresses(47) This effect is particularly pronounced for partially hydrolyzed poly(l-amidoethylene). The... 

Electrolyte effects on the cycling stability of lithium storage metals and alloys indicate the importance of SEI formation in this case, too. Very early measurements suggest that additives such as CO2 do not only improve the cycling stability of metallic lithium [41] and graphitic carbons (see above), but also that of lithium storage metals (Fig. 18), which may be related with the electrical properties of the SEI (Fig. 19) [13]. 

The electrolyte effect for the adsorption of anionic surfactants which leads to an enhancement of soil removal is valid only for low water hardness, i.e. low concentrations of calcium ions. High concentrations of calcium ions can lead to a precipitation of calcium surfactant salts and reduce the concentration of active molecules. Therefore, for many anionic surfactants the washing performance decreases with lower temperatures in the presence of calcium ions. This effect can be compensated by the addition of complexing agents or ion exchangers. 

For charged surfaces, complex stability may be enhanced (or reduced) by the poly electrolytic effect, if the pH is significantly different from the pH of zero charge, pHpzc, of the surface [106,146], In that case, the equilibrium constant, K, between the solute and a surface site, S, can be expressed as ... 

Table 4 Data and Results of Fit for Uni-univalent Electrolyte Effect on the Vapor Pressure of Methanol at 298.05°K... 

Ramette, R.W. and Spencer, J.B. Electrolyte effects on silver bromate solubility in protium and deuterium oxide solutions at 25 °. Evidence for association of silver and nitrate ions, J. Am. Chem. Soc., 67(4) 944-946, 1963. 

Although these effects are often collectively referred to as salt effects, lUPAC regards that term as too restrictive. If the effect observed is due solely to the influence of ionic strength on the activity coefficients of reactants and transition states, then the effect is referred to as a primary kinetic electrolyte effect or a primary salt effect. If the observed effect arises from the influence of ionic strength on pre-equilibrium concentrations of ionic species prior to any rate-determining step, then the effect is termed a secondary kinetic electrolyte effect or a secondary salt effect. An example of such a phenomenon would be the influence of ionic strength on the dissociation of weak acids and bases. See Ionic Strength... 

MICROTUBULE ASSEMBLY KINETICS KINETIC ELECTROLYTE EFFECT IONIC STRENGTH KINETIC EQUIVALENCE KINETIC AMBIGUITY KINETIC HALDANE RELATIONSHIPS HALDANE RELATIONSHIPS... 

The possibility of adverse electrolytic effects if the metal is subject to contact with a dissimilar metal. 

An illustration of the effect of micelle/nanoparticle volume fraction on contact line motion is found in [57]. They used 0.1 M NaCl solution to reduce the electrical double layer thickness surrounding the NaDS micelle. At a given number concentration of micelles, decreasing the size of each micelle decreases the volume fraction greatly, since the volume of each spherical micelle varies as the third power of the radius. Thus, the addition of electrolyte effectively reduced the micellar volume fraction in the aqueous medium. The authors found that the oil droplet that would otherwise become completely detached from the solid surface, came back to reattach itself to the solid when electrolyte was present. They rationalized this finding as being caused by the inability of the weakened structural disjoining forces to counteract the attraction of the oil drop to the solid surface. 

Lagrange, J., C. Pallares, G. Wenger, and P. Lagrange, "Electrolyte Effects on Aqueous Atmospheric Oxidation of Sulphur Dioxide by Hydrogen Peroxide, Atmos. Environ., 27A, 129-137 (1993). 

TRANSPORT IN THE ELECTROLYTE EFFECTS CHARGE TRANSFER AT THE INTERFACE... 

A re-investigation of the mechanism of the hydrolysis of acetic anhydrides in water was made by Bunton and Fendler4. They found that the hydrolysis of trimethylacetic anhydride follows an A-2 mechanism both in water and in aqueous dioxan and is slower than that of acetic anhydride. If acetic anhydride follows an A-l mechanism in water, both anhydrides should have the same mechanism and both should have similar reactivities in aqueous acids. If the A-2 mechanism is followed, steric effects should make trimethylacetic anhydride the less reactive compound. The entropy of activation of the hydrolysis catalysed by perchloric acid was re-estimated, taking into account the electrolyte effect of the perchlorate ions upon the rate of spontaneous hydrolysis, and a new value for A5 of—35 eu (for the spontaneous hydrolysis) and — 10 eu at 2 M HC104 for the acid-catalysed hydrolysis was obtained, compared with the value of + 2.2eu obtained previously. The new value is in the order of magnitude of A 5 for A-2 reactions but smaller than that observed for trimethylacetic anhydride under similar acidic conditions (— 26 eu). Plots... 

It may not be obvious exactly how the addition of excess supporting electrolyte effectively nullifies migration. This will be clearer after reading Sect. 4.6, in which the quantitative effect of additions of supporting electrolyte are assessed. 

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