Binding electrolytes

Ion retardation is a process opposite in its result to ion exclusion. It is effected on special amphoteric snake-cage resins (cf., section 4.5.2.1). These ion exchangers will bind electrolytes but not non-electrolytes. One of the first typical examples described by Hatch et al. [146] is the chromatographic separation of glycerol (which leaves the column first) from sodium chloride using Retardion 11A8. The salt retained can be washed from the column by elution with water only. 

Either the same or different approximations may be used to treat the binding at r = L and the remaining electrical interactions between the ions. The excess energy of the sticky electrolyte is given by... 

The PY approximation for die binding leads to negative results for X the HNC approximation for this is satisfactory. Figure A2.3.18 shows the excess energy as a fiinction of the weak electrolyte concentration for the RPM and SEM for a 2-2 electrolyte. 

Figure A2.3.18 The excess energy in units of NkT as a fiinction of the concentration for the RPM and SEM 2-2 electrolyte. The curves and points are results of the EfNC/MS and HNC approximations, respectively, for the binding and the electrical interactions. The ion parameters are a = 4.2 A, and E = 73.4. The sticking coefficients = 1.6x10 and 2.44x 10 for L = all and a/3, respectively.

Protems can be physisorbed or covalently attached to mica. Another method is to innnobilise and orient them by specific binding to receptor-fiinctionalized planar lipid bilayers supported on the mica sheets [15]. These surfaces are then brought into contact in an aqueous electrolyte solution, while the pH and the ionic strength are varied. Corresponding variations in the force-versus-distance curve allow conclusions about protein confomiation and interaction to be drawn [99]. The local electrostatic potential of protein-covered surfaces can hence be detemiined with an accuracy of 5 mV. 

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. 

Poly(ethylene oxide) associates in solution with certain electrolytes (48—52). For example, high molecular weight species of poly(ethylene oxide) readily dissolve in methanol that contains 0.5 wt % KI, although the resin does not remain in methanol solution at room temperature. This salting-in effect has been attributed to ion binding, which prevents coagulation in the nonsolvent. Complexes with electrolytes, in particular lithium salts, have received widespread attention on account of the potential for using these materials in a polymeric battery. The performance of soHd electrolytes based on poly(ethylene oxide) in terms of ion transport and conductivity has been discussed (53—58). The use of complexes of poly(ethylene oxide) in analytical chemistry has also been reviewed (59). 

Eb,EL binding energy of core level electrons of species in the electrolyte kJ/mol... 

FIG. 9 Schematic illustration of adsorption of poly(styrenesulfonate) on an oppositely charged surface. For an amphiphile surface in pure water or in simple electrolyte solutions, dissociation of charged groups leads to buildup of a classical double layer, (a) In the initial stage of adsorption, the polymer forms stoichiometric ion pairs and the layer becomes electroneutral, (b) At higher polyion concentrations, a process of restructuring of the adsorbed polymer builds a new double layer by additional binding of the polymer. 

Not all ions are mobile within the ionic atmosphere of the polyion. A proportion are localized and site-bound-a concept apparently first suggested by Harris Rice (1954). Localized ion binding is equivalent to the formation of an ion-pair in simple electrolytes. Experimental evidence comes mainly from studies on monovalent counterions. 

---