The adsorption of tri-n-butylphosphate at the n-dodecane–water interface

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Abstract
The adsorption of tri-n-butylphosphate (TBP) from n-dodecane to the n-dodecane–water interface has been studied as a function of TBP mole fraction up to 2.7 × 10−4 in the n-dodecane, and as a function of temperature from 293.15 K to 308.15 K. Free energies of adsorption were calculated from the results at low TBP mole fractions, where the surface pressures were linear with mole fraction. They were in the range −36.1 to −35.6 kJ/mol. The enthalpy of adsorption, determined from the variation of the free energies of adsorption with temperature, was −45.4 kJ/mol.Several equations of state based on two-dimensional gas laws were applied to the results. The Schofield–Rideal equation described the results adequately but the simpler Volmer equation was inadequate especially at lower temperatures. Deviations from the Volmer equation were in the direction of higher surface pressure. A simple version of the two-dimensional solution model equation of state was not helpful.

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