Interaction between methyl red and cetyltrimethylammonium bromide under the influence of sodium polystyrene sulphonate in ethanol-water binary solvent systems: A spectrophotometric investigation

Abstract

This research aims to comprehensively investigate and analyze the UV–visible spectroscopic behavior of the methyl red (MR)-cetyltrimethylammonium bromide (CTAB) system under the influence of sodium polystyrene sulfonate (NaPSS) in aqueous and different volume fractions (v.f.) of ethanol (EtOH)–H2O (0.1, 0.2, and 0.3) at 298.15 ± 0.2 K. In EtOH–H2O solvent systems, the triple interactions of dyes-surfactants-polyelectrolyte (DSP) complex systems are entirely novel. MR interacts with CTAB in NaPSS in the binary solvent media (0.1, 0.2, and 0.3 v.f. of EtOH–H2O) resulting in the formation of ion-pairs at very low CTAB concentrations, far below their apparent critical micelle concentration (CMC*) reducing the absorbance, and the new complexes above the CMC* due to solubilization of the MR into CTAB micelles observed by distinct spectral shifts. The CMC* values obtained from spectroscopic data increase in the order: (CMC*)water< (CMC*)0.1< (CMC*)0.2< (CMC*)0.3. This is because of the reduced polarity or dielectric constant and increased degree of water structure disruption around the hydrophobic chains of CTAB, where micelle formation occurs at somewhat higher concentrations. The Gibbs energy of micellization (ΔGmo) increases in the order: (ΔGmo=−16.89)water <(ΔGmo=−16.17)0.1<(ΔGmo=−15.62)0.2<(ΔGmo=−15.38)0.3, which further supports the inhibitory effect of increasing ethanol content towards micellization. In the post-micellar region, the decrease in hydrophobic interactions and an increase in electrostatic interactions lead to a rise in the overall binding constant value. This means that, when NaPSS is present, the stronger electrostatic interactions in the post-micellar region contribute significantly to the increased binding of CTAB micelles with MR. The tautomeric activity of MR and the solvent composition played a prime role in affecting the interaction mechanism, as evidenced by the blue and red spectral shifts.