Ionic effects

Vlachy V 1999 Ionic effects beyond Poisson-Boltzmann theory Ann. Rev. Phys. Chem. 50 145... 

The most numerous cases of homogeneous catalysis are by certain ions or metal coordination compounds in aqueous solution and in biochemistry, where enzymes function catalyticaUy. Many ionic effects are known. The hydronium ion and the hydroxyl ion OH" cat-... 

Hastings, J. W., and Bode, V. C. (1961). Ionic effects upon bioluminescence in Gonyaulax extracts. In McElroy, W. D., and Glass, B. (eds.), Light and Life, pp. 294-306. Johns Hopkins Press, Baltimore. 

Referring to the ionic effects, measuring of swelling in solutions which closely model real ones can provide reliable estimates. The papers [58, 132] can serve as examples of such an approach. In choosing a type of SAH suitable for some particular soil it is necessary to take into account the acid-base properties of the gel and the soil because otherwise collapse phenomena are likely to result from common counterions and the sorption on solid surfaces. 

K = is the reciprocal Debye length and e, is the dielectric constant of the solvent. Through most of what follows we use the ideal conductor approximation, Eq. (66). Ionic effects will be considered in Section IV.D. 

A number of empirical methods exist for the adjustment of covalent bond lengths for ionic effects.34,35 These are based primarily on formulas that involve the sum of the covalent radii corrected by a factor that is dependent on the electronegativity difference between the atoms. In many instances, quite good agreement is obtained between the predicted and experimental values, as shown by the listing in Table I. 

These sense in which terms like conjugative interactions, nonbonded interactions, etc., are meant will become clear when we discuss each individual type of interaction or effect. Suffice to say that, in many instances, conjugative interactions as well as geminal interactions or bond ionicity effects contain implicitly the idea of nonbonded interactions. Thus, it should be emphasized that the labels of the basic types of interactions proposed here reflect the way in which the problem is formulated rather than different electronic principles. 

At the low ionic concentrations encountered in sour water strippers, the effect of dissolved ions is probably small. Thus at a 1% concentration of sodium acetate the volatility of ammonia only increases about 2.5% due to the salt. This is within the prediction accuracy of the ammonia volatility data and no correction is therefore required. However significant ionic effects could exist in the condenser where high concentrations of the ionic components could exist. 

Other models are based on electric breakdown of the oxide [Fo2, Chl2]. It is not clear whether this breakdown should be thought of in terms of an electronic or an ionic effect. However, in both cases breakdown may cause a degradation in the oxide morphology, which leads to an enhanced etch rate. An electric field strength in the order of 10 MV cm4, the observation of an electroluminescent burst associated with the current peak of the oscillation, and the presence of an electronic component in the interface current are in favor of this model [CalO, Chl2]. 

The fundamental principles of pK determination by CE rely upon measuring the ionic effective mobility of the solute as a function of pH. Consequently, the pK value is obtained by fitting an equilibrium equation to the effective mobility and pH data with a non-linear regression technique (Figure 1). Depending on the chemical character of the compound... 

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