Spectrophotometric study of the sodium dodecyl sulfate in the presence of methylene blue in the methanol–water mixed solvent system

Abstract

The methylene blue (MB) dye is very sensitive to changes in the polarity of its surroundings. The interaction of MB with sodium dodecyl sulfate (SDS) was studied spectrophotometrically in 0.1, 0.2, 0.3 and 0.4 vol fractions of methanol in an aqueous medium. The dielectric constant value decreases with the addition of methanol in the water and hence there is the lower stabilization of the lowest unoccupied molecular orbital which results in the hypsochromic shift in the monomeric form of methylene blue. In a 0.1 vol fraction of methanol, the peaks are seen at 665 and 612 nm, which are monomeric and dimeric MB peaks, respectively. The dimerization of MB is reduced with the increasing volume fraction of methanol in the solvent and ceases at/above 0.3 vol fraction of methanol. In the 0.4 vol fraction of methanol, the turbidity appears with the addition of SDS and there were no significant changes in the absorbance. In the presence of methanol, MB prefers to stay with the sulfate groups of SDS at the peripheral regions of the premicelle and micelle. At very low surfactant concentrations, far below their critical micelle concentration (CMC), the formation of MB-MB dimers and/or MB-SDS ion pairs or clusters occurs, and a corresponding shift in absorption and decrease in absorbance is observed. On increasing the concentration of SDS, micellization occurs, which disrupts the MB-MB dimers and MB-SDS ion pairs are incorporated with the micelles. On further addition of SDS, lone MB monomers become associated with these micelles and the absorbance increases slightly higher than those of the original dye in the solvent. This is the case of dye solubilization where monomers are completely incorporated or bounded by micelles. The CMC of SDS decreases in the presence of dye suggesting the strong interaction between the oppositely charged dye-surfactant ion pairs. The value of binding constant and partition coefficient decreased with the increasing volume fraction of methanol. The negative value of ΔGb indicates that the interaction between SDS and MB is spontaneous but the negative values of ΔGb decreased with the increasing volume fraction of methanol.