Characterization of Mixed Micelles of SDS and a Sugar-Based Nonionic Surfactant as a Variable Reaction Medium

• Published in: The journal of physical chemistry. B 2001-08, Vol.105 (31), p.7465-7473
• Main Authors: Bales, Barney L, Ranganathan, Radha, Griffiths, P. C
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp010941d

Time-resolved fluorescence quenching (TRFQ), electron paramagnetic resonance (EPR), and small-angle neutron scattering (SANS) are employed to characterize mixed micelles of sodium dodecyl sulfate (SDS) and the nonionic sugar-based surfactant dodecylmalono-bis-N-methylglucamide (DBNMG) as a reaction medium. Interpretation of the results from the three methods are constrained to fit the classical model of a hydrocarbon core surrounded by a polar shell. As measured by TRFQ, at 45 °C, the aggregation numbers increase from 48 for pure SDS to a maximum of 63 at 36 mole percent DBNMG and decrease again to 49 for pure DBNMG. The aggregation numbers of the pure DBNMG increase from 33 at 21 °C to 49 at 45 °C. SANS results of the pure DBNMG are interpreted by fixing the aggregation number at 49 (from TRFQ) and allowing the polar shell thickness to vary as a fitting parameter, yielding a value of 5.8 Å at 45 °C. EPR, utilizing a hydrophobic spin probe, is used to measure the nonempirical polarity index, H(25 °C), of the polar shell. H(25 °C) is defined to be the ratio of molar concentration of OH dipoles in a solvent or solvent mixture to that in water at 25 °C; thus, both water and the sugar headgroups contribute. By fixing the volume in the polar shell inaccessible to water due to the presence of SDS (127 Å3) and DBNMG (580 Å3), theoretical values of H(25 °C) are computed, the result depending only on the number of OH bonds in DBNMG available to interact with the spin probe. A constant average value of 7.4 OH bonds out of a maximum possible number of 10 reproduces the measured values over the full range of mixed micelle compositions. At 45 °C, the microviscosity of the polar shell, as deduced from the rotational correlation time of the spin probe, varies from 2.79 ± 0.05 cP for pure SDS to 13.1 ± 0.2 cP for pure DBNMG departing only slightly from a linear dependence on the mole fraction of DBNMG. The uncertainties in the viscosity are the standard deviations in 10 measurements and therefore represent the uncertainty in the relative values of the viscosity. The viscosity decreases from 32 ± 4 cP at 21 °C to 13.1 ± 0.2 cP at 45 °C for pure DBNMG micelles. These viscosities are used to show that the quenching rate constant of pyrene by dimethyl benzophenone, measured by TRFQ, follows the Stokes−Einstein−Smolukhovsky equation with a quenching probability of P = 0.5 whether the mixed micelle composition is changed at constant temperature or if the temperature is varied i