Some consequences of the free-group postulate

If it is accepted that there are significant concentrations of these free groups, it is worthwhile considering some consequences. If the results of titrations with 

1 Analogy with ionisation. Perhaps the best way to understand this point and, indeed, the potential importance of these free groups, is the link with the process of self-ionisation (3.7). 

There must be many bulk properties of water such as diffusion, viscosity, etc., that depend, in part, on the concentrations of (OH)f, and (LPjf units. Also, in my view, there are important chemical consequences [46, 47]. Just as OH and are often important reagents in chemical reactions, so also, I 

A second example is the hydrolysis of arylsulphonylmethyl perchlorates [50]. The first, and rate-determining, step is thought to be the ionisation (3.10). In this case the active agent is thought to be (LP)j , and catalysis should occur when additives induce an increase in the concentration of these groups. This is again found to occur in the predicted fashion. So far as I know, these concepts provide the simplest and most direct explanation for these quite disparate reactions. It seems a pity that this approach is not used in mechanistic studies. 

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