A generalization is presented of a method for the determination of equ
ilibrium constants for binary mixtures. It is shown that titrations in
volving several components can be quantitatively characterized in term
s of component concentrations and spectral responses, even when none o
f the component spectra is known and the components cannot be obtained
in pure form. The method is efficient even if the component spectra o
verlap extensively. It is applicable to all spectroscopic techniques t
hat provide a linear response, opening up new possibilities to analyze
complex chemical systems. The approach is illustrated by determining
the absorption spectra and protolytic constants for the fluorescein pr
otolytic equilibria.