Abstract
In order to improve the precision of the determination of p K values by spectrophotometric methods, the ratios of absorbance values at two or more wavelengths can be used. It is shown that these ratios can be handled in exactly the same way as absorbance values, provided that a simple correction is applied to the p K value calculated from them. The method is illustrated for the determination of protonation equilibria of weak organic bases, using acidity functions, by visible-u.v. spectrophotometry. Data are given for the protonation of the sesquiterpene, α-santonin, and the advantages of the method are discussed: it eliminates experimental scatter caused by variations in concentrations and cell pathlengths. The method applies equally to the protonation of bases in acids defined by the pH scale, and to the deprotonation of acids.
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