title: Micellization behavior of aromatic moiety bearing hybrid fluorocarbon sulfonate surfactants.
abstract: Aggregation behavior and thermodynamic properties of two novel homologous aromatic moiety bearing hybrid fluorocarbon surfactants, sodium 2-(2-(4-ethylphenyl)-1,1,2,2-tetrafluoroethoxy)-1,1,2,2-tetrafluoroethanesulfonate (1) and sodium 2-(1,1,2,2-tetrafluoro-2-(4-vinylphenyl)ethoxy)-1,1,2,2-tetrafluoroethanesulfonate (2) were studied using surface tension measurements and isothermal titration calorimetry (ITC) in dilute aqueous solutions at room temperature. Because of the aromatic group in the hydrophobic tail, both surfactants are soluble at room temperature unlike their starting precursor, 5-iodooctafluoro-3-oxapentanesulfonate as well as several other fluorocarbon sulfonic acid salts. Moreover, the surfactant 2 has the ability that it can be polymerized once microemulsions are formed with it. The ionic conductivity measurements of 1 at five different temperatures from 288 to 313 K were carried out to study the effect of temperature on the micellization and its thermodynamics. The pseudophase separation model was applied to estimate thermodynamic quantities from conductivity data. The Gibbs energy of micellization versus temperature exhibited the characteristic U-shaped behavior with a minimum at 306 K. The micellization process was found to be largely entropy driven. Because of its hybrid structure, the entropy change of micellization for 1 was larger than what is common for hydrocarbon surfactants like SDS but less than for fully fluorinated surfactants like NaPFO. The micellization process was found to be following the entropy-enthalpy compensation phenomena.
authors.affiliation: Nano-Structured Materials, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628BL Delft, The Netherlands.
authors.forename: Mohan N
authors.initials: MN
authors.lastname: Wadekar
authors.forename: Job
authors.initials: J
authors.lastname: Boekhoven
authors.forename: Wolter F
authors.initials: WF
authors.lastname: Jager
authors.forename: Ger J M
authors.initials: GJ
authors.lastname: Koper
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Picken