Studies of thermodynamics of micellization and pattern of self-association of decyltrimethylammonium bromide in aqueous solutions at 298.15 K

• Published in: Journal of molecular liquids Vol. 341; p. 117413
• Main Authors: Tomar, Preeti A., Shaikh, Vasim R., Patil, Kesharsingh J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-11-2021
• Subjects: Aggregation number; Free energy and entropy changes due to micellization; Internal pressure of solutions; Number density of the species in solution; Rational Equilibrium constant; Free energy and entropy changes due to micellization; Aggregation number; Internal pressure of solutions; Rational Equilibrium constant; Number density of the species in solution
• ISSN: 0167-7322
• DOI: 10.1016/j.molliq.2021.117413

A micelle of decyltrimethylammonium bromide in water. The dashed lines indicate the excluded volumes for a solvent molecule with a diameter σs.
[Display omitted]
•Aggregation number variations with molality of C10TAB in water are studied.•Rational and stoichiometric equilibrium constants are estimated.•Standard free energy of aggregation goes through a maximum at cmc of surfactant.•Small positive magnitude and a break at cmc for ΔGmic0are observed.
Using recently reported density, thermal coefficient of expansion and internal pressure data along with the literature osmotic coefficient and enthalpy data and adopting Mass–action model, the properties of decyltrimethylammonium bromide (C10TAB) in water are studied at 298.15 K. The number density, aggregation number, equilibrium constant, standard free energy changes due to micellization, standard entropy changes due to micellization and mean ionic activity coefficient are calculated in pre–micellar and post–micellar regions of concentration assuming that the cationic surfactant C10TAB is fully dissociated in water. Characteristic pattern of association are examined through the models/concepts developed by Tanford, Mukerjee as well as by O. P. Ts’o and noted that hydrophobic interactions between the non–polar chains and water structural effects (in the form of ion–solvent and ion–ion interactions) govern the equilibrium properties of such solutions. The critical micelle concentration (cmc) value and aggregation number value agree with the literature data. It has been observed that aggregation number value decreases slightly, equilibrium constant value goes through a minimum, standard free energy changes due to micellization parameter go through a maximum while positive magnitude of entropy changes due to micellization are observed as a function of concentration of C10TAB. The variation of mean ionic activity coefficient of the salt ions with concentration indicates deviation from ideal–associative solution behaviour. All these results are interpreted on the basis of monomer–micelle equilibria existing in solution phase, affecting the solution properties through electrostatic, hydrophobic solvation and hydrophobic interaction effects.