Complex interactions of phenol (PhOH), heptanol (HeOH) and heptanoic acid (HeOIC) with micellar aggregates of hexadecyltrimethylammonium bromide (HTAB) in aqueous solutions at surfactant concentrations close to the CMC, HeOH or HeOIC content of 0.5 mmol kg(-1), and phenol molality of 1, 5, or 10 mmol kg(-1) have been investigated at 303 K by means of (1)H NMR spectroscopy, titration calorimetry and solution conductimetry. The analysis of the composition-dependence of the (1)H chemical shifts assigned to selected protons in the surfactant and additive units revealed the location of PhOH both within the hydrophobic micelle core and in the vicinity of the quaternary ammonium groups, the phenol penetration being somewhat deeper in the presence of HeOIC. The phenomenon was globally more exothermic with increasing extent of PhOH solubilization and it was accompanied by a gradual decrease in the positive entropy of micellization. The solubilization was competitive for high phenol contents in the aqueous phase, with some HeOH and HeOIC units being displaced progressively towards the aqueous phase.
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