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Evidence of formation of dye–surfactant ion pair micelle in the anionic surfactant mediated alkaline fading of methyl violet carbocation
Author(s) -
Ghosh Dinesh C.,
Sen Pratik K.,
Pal Biswajit
Publication year - 2021
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21528
Subject(s) - chemistry , pulmonary surfactant , micelle , ion , carbocation , inorganic chemistry , counterion , critical micelle concentration , photochemistry , aqueous solution , organic chemistry , biochemistry
In the submicellar solution of anionic surfactants sodium dodecyl sulfate (SDS) and dioctyl sodium sulfosuccinate (AOT), the alkaline fading of methyl violet (MV + ) carbocation has been studied spectrophotometrically in the temperature range 293–308 K. The interaction behavior of the dye carbocation with the anionic surfactant and the observed submicellar rate retardation is consistent with the ion pair and subsequent ion‐pair micelle formation. The change in the spectral pattern along with a change in the peak intensity and shoulder intensity with increasing surfactant concentrations indicates the shifting of the equilibrium between the helical and distorted helical isomers of MV + owing to the existence of dye–surfactant ion pair, ion‐pair micelles, and dye‐embedded micelles. This dynamic dye–surfactant ion‐ion interaction has been corroborated by the tensiometric studies. The decrease in the fading rate and the change in the spectral pattern in the presence of anion, especially I – , support the existence of the dye–anion interaction. The premicellar rate inhibition and the corresponding interaction have been accounted for by the use of two kinetic models namely, Olson–Simonson and Piszkiewicz cooperativity models. The cooperativity index value suggested a 1:1 dye–surfactant association in both the surfactants. The ratio of the concentration of the premicellar complex and the free dye cation indicates appreciable binding. The kinetic and thermodynamic parameters associated with the dye–surfactant complex have been explained in terms of dye–surfactant, dye–water, and surfactant–water interactions.