Fluorescence Probe Studies of Ionic Micelles in Concentrated Salt Solutions

Abstract

AbstractWe have investigated the effect of salt concentration and temperature on the average aggregation number and micro‐polarity of the interior of micelles of sodium dodecyl sulfate (SDS). sodium tetradecyl sulfate (STDS) and lithium dodecyl sulfate (LiDS). The transient fluorescence decay of micelle‐solubilized pyrene has been measured and analyzed. An exponent weighted average aggregation number <n>e was obtained by this technique. For SDS and STDS in NaCl solution, <n>e increases as the temperature is lowered or salt concentration is increased <n>e increased from ∼ 50 to ∼ 250 over [NaCl] = 0 to 0.8 M. Due to the strong counterion binding of lithium in the micellar solution, the LiDS micelle is much, smaller and does not increase appreciabily even at [LiCl] =0.8 M. From the fluorescence spectrum fine structure of pyrene and the fluorescence decay of the monomer and excimer, we can understand the local polarity and the water penetration to the interior of the micelle upon addition of salts and with changing temperature. The interior of the micelle becomes more nonpolar as the salt concentration is increased and the temperature is lowered. A complete kinetic analysis of the time–dependence of the fluorescence is given. The kinetic analysis is in agreement with the results reached by fluorescence spectral analysis.