The partitioning coefficient of a surfactant between oil and water is related to the free energy of transfer
from one phase to the other. The influence of temperature on the partition coefficient of octylphenol ethoxylate
oligomers between oil and water is reported. The variation of the partition coefficient with formulation
variables can be used as a yardstick for the concept of generalized formulation expression.
Static and dynamic tensiometries show that a newly prepared water/asphaltenated cyclohexane interface behaves as expected: the mean area occupied per asphaltene molecule is 2 nm2, and variations of interfacial tension and dilatational elastic modulus with time indicate that equilibrium is reached more slowly than that for usual surfactants. The use of the time/temperature superposition principle allows a detailed rheological study of a 2 day old interface of the same type which has reached equilibrium. It is found that the two-dimensional asphaltene network exhibits a glass transition zone, behaves as a gel near its gelation point, and is built by a universal process of aggregation.
The gradient theory of fluid interfaces is for the first time applied, without any lumping, to complex mixtures of more than three components, here made up of hydrocarbons and of a high proportion of carbon dioxide, nitrogen, or methane. It is combined with the volume-corrected Peng-Robinson equation of state. No adjustable parameters are used in the influence parameters mixing rule, which allows use of the gradient theory in a predictive manner. It gives very good estimates of the surface tension of the complex mixtures studied. In any case, it is found to be much superior to the traditional parachor method. The gradient theory is also used to compute the density profiles of the mixture components in the interface; it confirms that the low interfacial tensions of the systems studied are principally induced by a local accumulation of carbon dioxide, nitrogen, or methane in the interface.
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