Modeling of the Critical Micelle Concentration (CMC) of Nonionic Surfactants with an Extended Group-Contribution Method

A group-contribution (GC) property prediction model for estimating the critical micelle concentration (CMC) of nonionic surfactants in water at 25 °C is presented. The model is based on the Marrero and Gani GC method. A systematic analysis of the model performance against experimental data is carried out using data for a wide range of nonionic surfactants covering a wide range of molecular structures. As a result of this procedure, new third order groups based on the characteristic structures of nonionic surfactants are defined and are included in the Marrero and Gani GC model. In this way, those compounds that exhibit larger correlation errors (based only on first- and second-order groups) are assigned to more detailed molecular descriptions, so that better correlations of critical micelle concentrations are obtained. The group parameter estimation has been performed using a data set of 150 experimental measurements covering a large variety of nonionic surfactants including linear, branched, and phenyl alkyl ethoxylates; alkanediols; alkyl mono- and disaccharide ethers and esters; ethoxylated alkyl amines and amides; fluorinated linear ethoxylates and amides; polyglycerol esters; and carbohydrate derivate ethers, esters, and thiols. The model developed consists of linear group contributions, and the critical micelle concentration is estimated using the molecular structure of the nonionic surfactant alone. Compared to other models used for the prediction of the critical micelle concentration, and in particular, the quantitative structure–property relationship models, the developed GC model provides an accurate correlation and allows for an easier and faster application in computer-aided molecular design techniques facilitating chemical process and product design.