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The apparent thermodynamic parameters of ionisation and the association constants of the two forms of Methyl Orange were evaluated in the presence of different surfactants (TX‐100 as nonionic, CTAB as cationic and SDS as anionic). The enthalpy of ionisation of the dye in aqueous solution and at different surfactant concentrations is obtained from a novel thermochromic method and is found to decrease in aqueous medium in CTAB and TX‐100 micelles and to increase in the case of SDS micelles. The apparent ionisation constant of the dye is evaluated spectrophotometrically for each surfactant concentration and type. The apparent Gibbs free energy, entropy of ionisation and association constants are also calculated. The results are discussed in light of the stabilisation of the two forms of the dye in the micellar core of the different surfactants and their effect on properties of the bulk solution is examined.