Prediction of Micellar Thermodynamics of Nonionic Surfactants Based on the Square Gradient Theory.

A geometry-dependent contribution based on the square gradient theory of van der Waals is proposed as a predictive modification of the interfacial energy contribution for the micellar thermodynamic theory. The model has an analytic prediction for the spherical and cylindrical geometries. For ellipsoidal geometry, a simple yet physically meaningful approximation is proposed. The critical micelle concentration (CMC) and the surface tension isotherm under the new contribution are compared with the classical theory. The modified model describes qualitatively the available experimental data and the surface isotherm, showing an improvement in the predictions of the CMC.