Theory of adsorption of ethoxylates at the water | oil and water | air interfaces. 1. Monolayers of single-component and Poisson distributed alkylphenol ethoxylates.

Currently, the bulk thermodynamic properties of an arbitrary liquid mixture of oligomers are accessible with reasonable accuracy through popular 3D statistical models (SAFT, Flory-Huggins) under a wide range of conditions. These models are implemented in widely available software suites used for process design. The hypothesis investigated here is that the same is, in principle, achievable with monolayers of mixed surfactants on liquid surfaces. A molecular thermodynamic theory of the adsorption of alkylphenoxypolyethoxyethanols, CHCH(OCH)OH, on fluid interfaces is presented. It covers homologues of m = 0-10; water|alkane and water|gas interfaces; single surfactants and surfactant mixtures. The adsorption behaviour has been predicted as a function of the structure of the ethoxylated surfactants and the model has been validated against tensiometric data for forty systems. All values of the adsorption parameters have been either predicted, independently determined, or at least compared to a theoretical estimate. The single surfactant parameters have been used to predict the properties of 'normal' Poisson distributed mixtures of ethoxylates, in good agreement with literature data. Partitioning between water and oil, micellization, solubility and surface phase transitions are also discussed.