In this study, we aim to systematically investigate the surface, micellization, and thermodynamic properties of Cetyl Trimethyl Ammonium Bromide (CTAB) in Sodium Polystyrene Sulfonate (NaPSS) solutions with and without methyl red (MR) dye in water–ethanol mixed solvent media (0, 0.1, 0.2, and 0.3 vol fraction of ethanol at 298.15 ± 0.2 K, 308.15 ± 0.2 K, and 318.15 ± 0.2 K. By employing surface tension measurements, we seek to uncover the effects of solvent composition, temperature, polyelectrolyte presence, and dye addition on the Critical Micelle Concentration (CMC) and other key surface and thermodynamic parameters. The CMC, slope (dγdlnC), and γCMC values determined from γ versus ln [CTAB] for the CTAB + NaPSS + MR diminish in contrast to the CTAB + NaPSS in the chosen solvent and the temperature range studied. However, with a rising temperature and ethanol volume fraction, the CMC value rises while the obtained γCMC values fall. Various surface and thermodynamic parameters like γCMC,Amin,Γmax, ΠCMC, adsorption efficiency (PC20), packing parameter (P), aggregation number (Nagg), micellization Gibbs’ energy (ΔGm0), adsorption of Gibbs’ energy (ΔGads0), effective Gibbs’ energy (ΔGeff0), minimum Gibbs’ energy (ΔGmin), and many other parameters have been determined, comparatively discussed, and analyzed for CTAB + NaPSS and CTAB + NaPSS + MR systems. This research provides a deeper understanding of the fundamental behaviors of these complex systems, their stability, and their feasibility, with potential implications for their practical applications in fields such as drug delivery, wastewater treatment, and the formulation of personal care products.
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