Solubilization of octane in cationic surfactant–anionic polymer complexes: Effect of polymer concentration and temperature

Abstract

Polymers may alter the ability of oppositely charged surfactant micelles to solubilize hydrophobic molecules depending on surfactant–polymer interactions. This study was conducted to investigate the effects of polymer concentration and temperature on the solubilization thermodynamics of an octane oil-in-water emulsion in mixtures of an anionic polymer (carboxymethyl cellulose) and cationic cetyltrimethylammonium bromide (CTAB) surfactant micelles using isothermal titration calorimetry (ITC). Results showed that the CTAB binding capacity of carboxymethyl cellulose increased with increasing temperature from 301 to 323K, and correspondingly the thermodynamic behavior of octane solubilization in CTAB micelles, either in the absence or presence of polymer, was found to depend on temperature. The addition of carboxymethyl cellulose caused the solubilization in CTAB micelles to be less endothermic, and increased the solubilization capacity. Based on the phase separation model, the solubilization was suggested to be mainly driven by enthalpy gains. Results suggest that increasing concentrations of the anionic polymer gave rise to a larger Gibbs energy decrease and a larger unfavorable entropy increase for octane solubilization in cationic surfactant micelles.