Browsing by Author "Minkov I.L."

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    Measuring the Equilibrium Spreading Pressure—A Tale of Three Amphiphiles
    (2024-09-01) Peychev B.; Arabadzhieva D.; Minkov I.L.; Dimitrova I.M.; Mileva E.; Smoukov S.K.; Slavchov R.I.
    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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    The cause of accelerated desorption of sparingly soluble dodecanol monolayers: Convection or leakage?
    (2021-11-20) Minkov I.L.; Dimitrova I.M.; Arabadzhieva D.; Mileva E.; Slavchov R.I.
    The dissolution of sparingly soluble surfactants from spread monolayers is a complex multi-staged process. The desorption of dodecanol from the surface of water follows mixed barrier/diffusion kinetics only in the first stages of the dissolution. Significant acceleration of the desorption has been observed experimentally after this initial period, which has been hypothesized to be due to onset of convective diffusion; the source of convection, however, has never been identified. The goal of this work is to investigate the question through desorption experiments under controlled convection and respective modeling of the process under mixed barrier/convective diffusion control. Several hypotheses for the cause of the accelerated desorption have been tested. The analysis has shown that natural convection, Marangoni convection, convection due to the motion of the mechanical barrier of the Langmuir trough, and artificial convection caused by an electromagnetic stirrer cannot produce desorption rates of the observed magnitude. These findings convincingly prove for the first time that the convective diffusion has less of a role in the transport process than previously thought. The most likely reason for the acceleration is identified as leakage through the movable barrier. The rate of this leakage is estimated form the experimental data. Implications for the use of adsorption isobars to study desorption kinetics are discussed.