Ionic site

To an extent the surface charges are determined by the pH of the solution, and by the isoelectric point of the oxide, i.e. the pH at which the oxide surface is neutral. The surface is negative at pH values below the isoelectric point and positive above it. Obviously, the charged state of the surface enables one to bind catalyst precursors of opposite charge to the ionic sites of the support. 

The experimental results are presented by plotting A[H30+], the loss of protons from the pectic ionic sites, against the ratio [Me2+]t/Cp where [Me +Jt and Cp are the total cation concentration (equiv.l-i) and the pectin concentration (equiv. COO-.l- ), respectively. 

Only recently, we have shown experimentally for a selection of neutral ionophores and carefully purified, typical PVC plasticizers that in absence of ionic sites Nernstian EMF responses could not be obtained [55]. For plasticizers of low polarity no EMF responses were observed at all. Transient responses due to salt extraction even with the highly hydrophilic counterion chloride were observed in the case of the more polar nitrobenzene. Lasting primary ion-dependent charge separation at the liquid liquid interfaces of ISEs, resulting in a stable EMF response, seemed therefore only possible in the presence of ionic sites confined to the membrane phase. Because membranes free of impurity sites... 

To determine the influence of ionic sites on the charge separation at the membrane interface, we have measured in this study SHG with ionophore-free and ionophore-incorporated liquid membranes in absence and presence of ionic sites. The dependence of the SHG intensity on the activity of the primary ion in the aqueous solution is presented and compared to the corresponding EMF. 

C. Nitrobenzene Membranes with and Without ionic Sites... 

As in the 1,2-dichloroethane case too, transient EMF and SHG responses to KSCN were observed for the nitrobenzene membranes without ionic sites. This suggests that here too not only SCN but also K ions are transferred into the nitrobenzene phase. Salt extraction into the bulk of the organic phase, in analogy to similar observations previously reported for neutral ionophore-incorporated liquid membranes without ionic sites [55], was indeed independently confirmed by atomic absorption spectrometry. Figure 15 shows the concentration of K in nitrobenzene equilibrated at room temperature with a 10 M aqueous solution of KSCN as a function of equilibration time. The presence of the ion exchanger TDDMA-SCN efficiently suppresses KSCN extraction into the organic phase but in its absence a substantial amount of KSCN enters the nitrobenzene phase. The trends of the EMF and the SHG responses are therefore very similar in spite of the different polarities of the plasticizers. 

As stated in Section II, the SHG responses to primary cations of ISEs based on several crown ether ionophores could be correlated to the number of primary ion complexes at the phase boundary, which contributed to the membrane potential. We have now incorporated the K+ ionophore bis[(benzo-15-crown-5)-4-methyl]pimelate into 1,2-dichloroethane and nitrobenzene membranes and determined EMF and SHG responses to KCl in presence and absence of ionic sites. 

Figure 16(a) (O) shows the EMF responses of a 1,2-dichloroethane membrane containing anionic sites (KT/ C1PB). A Nernstian response was obtained. An SHG response to KCl was observed at activities of the latter above 10 M [Fig. 16(b), O]-These results can be interpreted in the same way as for ionophore-incorporated PVC liquid membranes, for which we have shown that the concentration of oriented cation complexes at the liquid-liquid interface can explain both the observed SHG signal and EMF response. The present SHG responses thus suggest primary ion concentration dependent charge separation at the interface of the 1,2-dichloroethane membranes incorporated with ionic sites. 

The EMF and SHG responses for nitrobenzene as solvent were qualitatively identical to those for l,k2-dichloroethane [Fig, 17(b)]. The only difference between the results for the two solvents was that the SHG response to KCl of nitrobenzene membranes with ionic sites was more sensitive than for 1,2-dichloroethane membranes with ionic sites, where an increase in the SHG intensity was observed at KCl activities above 10 " M KCl. 

Use of ionophore-incorporated membranes leads thus to the same conclusions as described above for the ionophore-free membranes. Here too, the SHG measurements suggest that a permanent, primary ion-dependent charge separation at the liquid-liquid interface, and therefore a potentiometric response, is only possible when the membrane contains ionic sites. 

The charge transport in a conjugated chain and the interchain hopping is explained in terms of conjugation defects (radical or ionic sites), called solitons and polarons. Several possible conjugation defects are demonstrated in Fig. 5.33 on the example of trans-polyacetylene. 

Lipophilic ion exchangers traditionally used for polymeric membrane preparation are the anionic tetraphenylborate derivatives and the cationic tetraalkylammonium salts. The charges on both lipophilic ions are localized on a single (boron or nitrogen) atom, but the steric inaccessibility of the charged center, due to bulky substituents, may inhibit ion-pair formation in the membrane and provide, when necessary, non-specific interactions between ionic sites and sample ions. 

The extent to which the ions compete with B for the charged sites (X) will determine their retention. In general, this type of chromatography may be used to separate ionic species, such as organic acids or bases, which can be ionized under certain pH conditions. Besides the reaction with ionic sites on the stationary phase, retention may also be affected by the partitioning of solutes between the mobile and stationary phases, as in reversed-phase chromatography. Thus, even nonionized solutes may be retained on ion-exchange columns. 

Blanks, left to right, starting upper left water, liquids or dissolved solids, size exclusion, porous polymer beads, any liquid type, polymer beads with ionic sites ions, gas, thin liquid film, thin layer, liquids or dissolved solids. 

The heat of formation of organic radicals and positive ions decreases with their size and even more important with their degree of branching at the radical or ionic site. A lower heat of formation is equivalent to a higher thermodynamic stability... 

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