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The Khossravi-Connors-Skwierczynski step-wise competitive exchange model, which has previously led to successful descriptive expressions for solvent effects on solubility, surface tension and molecular complex formation, is modified to model fluorescence emission behavior of polycyclic aromatic hydrocarbon solutes dissolved in binary solvent mixtures. Expressions are derived for calculating numerical values of the various step-wise exchange equilibrium constants from measured emission intensity ratios in mixed solvents and from measured absolute emission intensities in both pure solvents. Computation procedure is illustrated using measured fluorescence properties of pyrene, benzo [e] pyrene, benzo [ghi] perylene, coronene, methylcoronene and 1,2-dimethylcoronene in n-heptane+ 1,4-dioxane and n-heptane + tetrahydrofuran mixtures. Also discussed are similarities and differences between the newly-derived expressions and ones based upon a recently published spectrofluorometric probe method, and the special conditions under which both models become mathematically equivalent.
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Acree et al. (1995) studied this question.
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