The semi-empirical spectrophotometric (SESp) method, for the indirect determination of ion exchange constants (K
XBr) of ion exchange processes occurring between counterions (X
– and Br
–) at the cationic micellar surface, is described in this article. The method uses an anionic spectrophotometric probe molecule,
N-(2-methoxyphenyl)phthalamate ion (1
–), which measures the effects of varying concentrations of inert inorganic or organic salt (Na
vX, v = 1, 2) on absorbance, (A
ob) at 310 nm, of samples containing constant concentrations of 1
–, NaOH and cationic micelles. The observed data fit satisfactorily to an empirical equation which gives the values of two empirical constants. These empirical constants lead to the determination of K
XBr (= K
X/K
Br with K
X and K
Br representing cationic micellar binding constants of counterions X and Br
–). This method gives values of K
XBr for both moderately hydrophobic and hydrophilic X
–. The values of K
XBr, obtained by using this method, are comparable with the corresponding values of K
XBr, obtained by the use of semi-empirical kinetic (SEK) method, for different moderately hydrophobic X. The values of K
XBr for X = Cl
– and 2,6-Cl
2C
6H
3CO
2–, obtained by the use of SESp and SEK methods, are similar to those obtained by the use of other different conventional methods.
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