Ion dissociation

The concept of ion pairs in nucleophilic substitution is now generally accepted. Presumably, the barriers separating the intimate, solvent-separated, and dissociated ion pairs are quite small. The potential energy diagram in Fig. 5.4 depicts the three ion-pair species as being roughly equivalent in energy and separated by small barriers. 

Studies of the stereochemical course of rmcleophilic substitution reactions are a powerful tool for investigation of the mechanisms of these reactions. Bimolecular direct displacement reactions by the limSj.j2 meohanism are expected to result in 100% inversion of configuration. The stereochemical outcome of the lirnSj l ionization mechanism is less predictable because it depends on whether reaction occurs via one of the ion-pair intermediates or through a completely dissociated ion. Borderline mechanisms may also show variable stereochemistry, depending upon the lifetime of the intermediates and the extent of internal return. It is important to dissect the overall stereochemical outcome into the various steps of such reactions. 

Complex formation reactions. These depend upon the combination of ions, other than hydrogen or hydroxide ions, to form a soluble, slightly dissociated ion or compound, as in the titration of a solution of a cyanide with silver nitrate... 

The evidence presented so far excludes the formation of dissociated ions as the principal precursor to sulfone, since such a mechanism would yield a mixture of two isomeric sulfones. Similarly, in the case of optically active ester a racemic product should be formed. The observed data are consistent with either an ion-pair mechanism or a more concerted cyclic intramolecular mechanism involving little change between the polarity of the ground state and transition state. Support for the second alternative was found from measurements of the substituent and solvent effects on the rate of reaction. 

Jorgensen et al. [84] studied how solvent effects could influence the course of Diels-Alder reactions catalyzed by copper(II)-bisoxazoline. They assumed that the use of polar solvents (generally nitroalkanes) improved the activity and selectivity of the cationic copper-Lewis acid used in the hetero Diels-Alder reaction of alkylglyoxylates with dienes (Scheme 31, reaction 1). The explanation, close to that given by Evans regarding the crucial role of the counterion, is a stabilization of the dissociated ion, leading to a more defined complex conformation. They also used this reaction for the synthesis of a precursor for highly valuable sesquiterpene lactones with an enantiomeric excess superior to 99%. 

Principles and Characteristics Analytical multistage mass spectrometry (MSn) relies on the ability to activate and dissociate ions generated in the ion source in order to identify or obtain structural information about an unknown compound and to analyse mixtures by exploiting two or more mass-separating steps. A basic instrument for the currently most used form, tandem mass spectrometry (MS/MS), consists of a combination of two mass analysers with a reaction region between them. While a variety of instrument set-ups can be used in MS/MS, there is a single basic concept involved the measurement of the m/z of ions before and after a reaction in the mass spectrometer the reaction involves a change in mass and can be represented as ... 

Table 2. Concentration, dissociation, ion size and other parameters of aqueous alkaline silicate solutions... 

Kf is the stability constant which is the negative logarithm of the dissociation constant, Ki. The dissociation constant is the product of the concentrations of the dissociated ions divided by the concentration of the parent molecule. 

Precursor Ion Ion that reacts to form particular product ions. The reaction can be unimolecular dissociation, ion/molecule reaction, isomerization, or change in charge state. The term parent ion is deprecated (but still very much in use). 

For the consideration of the ionizing properties of a solvent it is therefore imperative to consider both the coordinating and the dielectric properties 101. An illustrative example is given in Table 8, in which three different donor solvents Dj.Da and D3 are considered. Dt and D3 are assumed to have the same dielectric constant while Dj and D2 are assumed to have the same coordinating properties. The values for e and A Ion have arbitrarily been selected. From Aion and ATdiss the sum of associated and dissociated ions can readily be calculated and the result shows that in D3 the overall process of ionization is progressing further than in D2, which has a much higher dielectric constant, but has somewhat smaller coordinating properties than D3. 

The acidic or basic property of an aqueous solution of a salt results from reactions between water and the dissociated ions of the salt. Some ions do not react with water. They are neutral in solution. Ions that do react with water produce a solution with an excess of HsO iaq) or OH (aq). The extent of the reaction determines the pH of the solution. As you will see, the reaction between an ion and water is really just another acid-base reaction. 

As more ions enter the solution, the rate of the reverse change, recrystallisation, increases. Eventually, the rate of recrystallisation becomes equal to the rate of dissolving. As you know, when the forward rate and the backward rate of a process are equal, the system is at equilibrium. Because the reactants and the products are in different phases, the reaction is said to have reached heterogeneous equilibrium. For solubility systems of sparingly soluble ionic compounds, equilibrium exists between the solid ionic compound and its dissociated ions in solution. 

Solid ionic compound Dissociated ions in solution... 

When solvated ions migrate within the electrolyte, the drag force applied by the surrounding solvent molecules is measured by solvent viscosity rj. Thus, in a solvent of lower viscosity, the solvated ions would move more easily in response to an applied electric field, as expressed by the Einstein—Stokes relation (eq 3). Solvents of low viscosity have always been considered the ideal candidates for electrolyte application however, their actual use was restricted because most of these solvents have low dielectric constants (Tables 1 and 2) and cannot dissociate ions effectively enough to prevent ion pairing. 

A common sitnation is that the electrolyte is completely dissociated in the aqueons phase and incompletely, or hardly at all, in the organic phase of a ternary solvent extraction system (cf. Chapter 3), since solvents that are practically immiscible with water tend to have low valnes for their relative permittivities e. At low solnte concentrations, at which nearly ideal mixing is to be expected for the completely dissociated ions in the aqneons phase and the undissociated electrolyte in the organic phase (i.e., the activity coefficients in each phase are approximately nnity), the distribntion constant is given by... 

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