ABSTRACT
It is well-known that methylene blue (MB),a cationic dye forms dimer and higher aggregates in aqueous solutions. For specific concentration range (1∙10−6–1∙10−4 M), a D⇌2M equilibria has been postulated and well characterized by visible electronic spectroscopy. The dye molecules can lead to formation of stacking (end on end and sandwich) type structures in solution phase stabilized by weak dispersion van der Waals forces and cation-anion-cation ion pairs and triplet interactions usually referred as hydrophobic interactions. Recent literature reports indicate that excess chemical potential of small hydrophobic particles and the strength of hydrophobic pair interactions appear to be linearly related. Our observations about precipitation of dye (MB) at higher concentrations of salt like sodium chloride (NaCl) made us to study the dimerization equilibria in detail since in the Corona health disaster;use of MB to diagnose the type of Covid variants helped Scientists in a great way. Salting-out of proteins is in general used to explain the specific protein aggregation behaviour observed in Huntington's disease. For model compound like tertiary butyl-alcohol, Geiger et al. reported enhancement of hydrophobic contacts which increase with increase in salt concentration. NaCl is an essential ingredient of biological fluids, of which concentration controls the various biological life governing processes. However, such information is non-existent for aqueous solutions of dyes. We therefore reported measured optical absorbance of aqueous solution containing NaCl (0.1–1.0 M) and dye at different concentrations (1∙10−6–1∙10−4 M) at 298 K spectrophotometrically, in the wavelength range of 550–700 nm. The spectrums are compared to those obtained for binary solutions of MB in water. Analysis of the spectral data yielded the dimer dissociation constant and individual characteristic monomer and dimer spectra. Further information about the geometry and twist angle between the dipoles of the MB molecules in the dimer species has been obtained. The results are analyzed for the monomer-dimer equilibria and salting-out effect as well applications of mass action model and exciton theories are discussed.