Effect of Pressure on the Rate of Alkaline Fading of Triphenylmethane Dyes in Cationic Micelles

Article abstract of DOI:10.1021/ja00361a002

The rates of alkaline fading of triphenylmethane dyes in cationic micelles have been measured at pressures up to about 2 kbar and at 25 deg C in 0.1 M Tris buffer solution.These rates follow the kinetics of the Michaelis-Menten type.The volume changes for the incorporation of dyes in the micellar phase are 14-15 cm³/mol for ethyl violet and brilliant green and 3-4 cm³/mol for crystal violet and malachite green.It was confirmed that these differences are due to the hydrophobicity of dyes.The activation volumes for the fading reaction in micellar phases are positive except in the case of the crystal violet-cetyltrimethylammonium bromide micellar system.However, the activation volumes in nonmicellar aqueous solutions are negative.The differences of the activation volumes between micellar and nonmicellar systems are discussed from the point of view of the general base catalysis, which contains both the water and hydroxide ion pathways.It was clear that micelles change the water control into hydroxide ion control.