Conductometric and spectroscopic methods were used to examine the interactions among the cationic surfactants, tetradecyltrimethylammonium bromide (TTAB) and cetylpyridinium chloride (CPC), and the anionic azo dye metanil yellow (MY) in an aqueous solution. The standard Gibb’s energy (ΔGm0), enthalpy (ΔHm0), and entropy (ΔSm0) of micellization were determined with the help of the equilibrium model. With temperature rise, the critical micelle concentration (cmc) increases because of the interruption of the organized water (WR) molecules enclosing the surfactant’s hydrophobic groups. As the total carbon atoms of the hydrophobic group are more in CPC than TTAB, a considerable fall in cmc value was observed. The presence of MY caused a higher degree of ionization (α) of micelles of TTAB and CPC. The negative values of ΔGm0 and ΔHm0 for both the surfactants in WR and aqueous MY solution (WR-MY) show that the micellization process is spontaneous and exothermic. As indicated by the -TΔSm0 values, which were found to be greater than ΔHm0 values, the entropy gain is typically what regulates the micellization process and the micellization was found to have a negative heat capacity (ΔCp,m0). UV–Visible spectra show that CPC has a higher binding constant (Kb) value as compared to TTAB implying that CPC has a comparatively greater binding affinity with MY dye in aqueous media (WR). The decreasing value of ΔGb for CPC indicates that the chance for the MY–CPC complex formation is more than that of the MY–TTAB complex. As shown by the rise in absorbance values as surfactant concentrations increase, a large number of the MY molecules are attracted to TTAB and CPC micelles.
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