Ionic shapes

In an ionic crystal the structure adopted represents the most efficient packing of ions of opposite charge subject to the additional influence of thermal energy. Electrostatic forces are non-directional and the structure adopted is determined by three main controls (i) the relative numbers of cations and anions, (ii) the relative sizes of positive and negative ions and (iii) ionic shapes. Additional species, including hydrated or otherwise coordinated ions together with molecules of water... 

Draw Lewis structures and give the molecular or ionic shape 54 of each of the following compounds ... 

To predict molecular or ionic shapes, first draw Lewis structures for the molecules or ions using the methods discussed in Sections 4.6 and 4.7. Once you have drawn the Lewis structure... 

The shapes of many molecules and polyatomic ions can be predicted by using the valence-shell electron-pair repulsion theory (VSEPR). According to the VSEPR theory, electron pairs in the valence shell of the central atom of a molecule or ion repel one another and become arranged so as to maximize their separation distances. The resulting arrangement determines the molecular or ionic shape when one or all of the electron pairs involved form bonds between the central atom and other atoms. 

Since taking simply ionic or van der Waals radii is too crude an approximation, one often rises basis-set-dependent ab initio atomic radii and constnicts the cavity from a set of intersecting spheres centred on the atoms [18, 19], An alternative approach, which is comparatively easy to implement, consists of rising an electrical eqnipotential surface to define the solnte-solvent interface shape [20],... 

Ion-exchange isotherms assume different shapes depending on the selectivity factor and the variations in with the level of exchange The rational selectivity coefficient includes the ionic charge and is given by... 

In some cases, e.g., the Hg/NaF q interface, Q is charge dependent but concentration independent. Then it is said that there is no specific ionic adsorption. In order to interpret the charge dependence of Q a standard explanation consists in assuming that Q is related to the existence of a solvent monolayer in contact with the wall [16]. From a theoretical point of view this monolayer is postulated as a subsystem coupled with the metal and the solution via electrostatic and non-electrostatic interactions. The specific shape of Q versus a results from the competition between these interactions and the interactions between solvent molecules in the mono-layer. This description of the electrical double layer has been revisited by... 

For some nonionic, nonpolar polymers, such as polyethylene glycols, normal chromatograms can be obtained by using distilled water. Some more polar nonionic polymers exhibit abnormal peak shapes or minor peaks near the void volume when eluted with distilled water due to ionic interactions between the sample and the charged groups on the resin surface. To eliminate ionic interactions, a neutral salt, such as sodium nitrate or sodium sulfate, is added to the aqueous eluent. Generally, a salt concentration of 0.1-0.5 M is sufficient to overcome undesired ionic interactions. 

Ionic repulsion between anionic samples and the resin causes poor resolution. As shown in Fig. 4.17, the addition of only 0.01 M NaNO, results in normal elution and peak shape for an anionic polymer, sodium polyacrylate. 

Cationic samples can be adsorbed on the resin by electrostatic interaction. If the polymer is strongly cationic, a fairly high salt concentration is required to prevent ionic interactions. Figure 4.18 demonstrates the effect of increasing sodium nitrate concentration on peak shapes for a cationic polymer, DEAE-dextran. A mobile phase of 0.5 M acetic acid with 0.3 M Na2S04 can also be used. 

Three different types of columns packed with gels of different pore sizes are available. Columns should be selected that are suitable for the molecular weight range of specific samples, as each type has a different exclusion limit (Fig. 6.41, page 215). Bovine serum albumin (BSA), myoglobin, and lysozyme show good peak shapes using only 100 mM of sodium phosphate buffer as an eluent. There is no need to add any salt to the eluent to reduce the ionic interaction between protein and gel. 

Anionic and neutral polymers are usually analyzed successfully on Syn-Chropak GPC columns because they have minimal interaction with the appropriate mobile-phase selection however, cationic polymers adsorb to these columns, often irreversibly. Mobile-phase selection for hydrophilic polymers is similar to that for proteins but the solubilities are of primary importance. Organic solvents can be added to the mobile phase to increase solubility. In polymer analysis, ionic strength and pH can change the shape of the solute from mostly linear to globular therefore, it is very important to use the same conditions during calibration and analysis of unknowns (8). Many mobile phases have been used, but 0.05-0.2 M sodium sulfate or sodium nitrate is common. 

Mobile-phase selection for cationic polymers is similar to that for the other polymers in that ionic strength and pH can change the shape of the solute from linear to globular (9). Mobile phases are often low pH e.g., 0.1% trifluo-roacetic acid, including 0.2 M sodium chloride, has been used successfully for polyvinylpyridines. Sodium nitrate can be substituted for the chloride to avoid corrosive effects. Some salt must be included so that ion exclusion does not occur (3). 

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