Effect of Temperature on the Critical Micelle Concentration and Micellization Thermodynamic of Nonionic Surfactants: Polyoxyethylene Sorbitan Fatty Acid Esters

Abstract

In this study, non‐ionic surfactants, polyoxyethylene sorbitan fatty acid esters (polysorbate) are chosen to examine the temperature effect on the CMC over a wide temperature range. The enthalpy and entropy of micelle formation are evaluated according to the phase separation model. The surface tension of solutions was determined by means of Du Nöuys ring. The CMC values were taken from the sharp breaks in the surface tension vs. logarithms of surfactant concentration plots. As the surfactants′ chain length increases the CMC at a constant temperature decreases, which is directly related to the decrease of hydrophilicity of the molecules. For each surfactant, as the system temperature increases, the CMC initially decreases and then increases, owing to the smaller probability of hydrogen bond formation at higher temperatures. The onset of micellization tends to occur at higher concentrations as the temperature increases. To evaluate the enthalpy of micellization, the CMCs are first correlated by a polynomial equation. It is found that ∆Gºm decreases monotonically as the temperature increases over the whole temperature range. Both ∆Hºm and ∆Sºm appear to be decrease monotonically with an increase in temperature. The compensation temperature was found to be 42 ºC by linear regression over the whole temperature range and for all three surfactant systems together.