Measuring the Equilibrium Spreading Pressure—A Tale of Three Amphiphiles

TL;DR

This paper explores methods to measure the equilibrium spreading pressure of three different amphiphiles, addressing challenges in experimental protocols and offering practical solutions.

Contribution

The paper introduces practical experimental techniques to measure equilibrium spreading pressure for challenging amphiphiles.

Findings

Using a temporary mechanical barrier reduces disturbances during the spreading of n-dodecanol.

Presaturating the subphase improves measurement accuracy and speeds up equilibration.

A volatile solvent aids in overcoming mass transfer barriers for nonspreading amphiphiles like DPPC.

Abstract

A surfactant’s equilibrium spreading pressure (ESP) is the maximum decrease in surface tension achievable at equilibrium below the Krafft point. Difficulties in measuring the ESP have been noted previously but no well-established experimental protocols to overcome them exist. We present a case study of three solid amphiphiles with different propensities to spread on the air–water interface. Starting with the partially water soluble n-dodecanol (C12H25OH), which spreads instantaneously. The strong Marangoni flows associated with the spreading result in the dislocating of the Wilhelmy plate or crystals attaching to it. A temporary mechanical barrier in front of the spreading crystals mitigates the flows disturbing the plate. Presaturating the subphase with the amphiphile prevents the establishment of dynamic steady states, reduces the standard error by a factor of three and causes faster equilibration. The perfluoroalkylated analog of dodecanol (11:1 fluorotelomer alcohol, C11F23CH2OH) is slow spreading. With surfactant crystals on the interface, the surface pressure reaches a pre-equilibrium plateau within an hour, followed by equilibration on day-long timescales. We show that it is better to estimate the ESP by averaging the values of multiple pre-equilibrium plateaus rather than waiting for equilibrium to be established. Finally, the nonspreading amphiphile DPPC exhibits a large barrier for the mass transfer from the DPPC crystal to the aqueous surface. This was overcome by introducing a volatile, water-immiscible solvent deposited on the surface next to the crystals to facilitate the spreading process and leave behind a monolayer.

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