Browsing by Author "White, Lee R."

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    On deviations from Young's equation
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (03), 1977) White, Lee R.
    Although Young's equation, γS=γSL+γL cos θC, is one of the oldest and most-used equations of classical physics and chemistry, it is in a rather delicate position scientifically, in that it is virtually impossible to prove experimentally. This is due, of course, to the uncertainties in the measurement of γS and γSL, the solid–air and solid–liquid surface tensions. Recently the validity of Young's equation has been questioned as the result of a theoretical analysis of the three-phase contact region where the liquid–air surface tension, γL, may be modified by interaction with the nearby substrate. The present paper argues that Young's equation is a “macroscopic” equation which does not concern itself with the microscopic shape of the liquid surface in the vicinity of the three-phase contact region. The concept of a microscopic contact angle θP is introduced. θP is the angle that the free liquid surface makes with the substrate when the liquid thickness is ≪∼ 10 Å, i.e., microscopically near the three-phase contact line. The contact angle θC given by Young's equation is shown to be the angle that the liquid surface makes with the substrate at microscopically large distances from the contact line where the modification of surface tensions by interaction is negligible (> 10 Å). The connection between θP and θC is established by making only very general statements about the nature of this interaction and does not impose the unphysical restrictions on the profile shape in the neighbourhood of the three-phase contact line which lead to the conclusions of Jameson and del Cerro.
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    Surface tension minimum in ionic surfactant systems
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Beunen, Joseph A.; Mitchell, D. John; White, Lee R.
    A theory is developed to explain the minimum in the surface tension of solutions of sparingly soluble ionic surfactants and its dependence on surfactant and its dependence on surfactant and electrolyte concentrations. The fundamental assumption is that at low pH, an acidic surfactant will be mostly undissolved and that this precipitate acts as a reservoir of surfactant molecules which enter the solution in the dissociated form as the pH is increased. This increase in solution concentration results in increased adsorption at the interface with a consequent lowering lowering of the surface tension. At the so-called solubility edge, the surfactant becomes completely soluble and the solution concentration of surfactant becomes constant. Thus there is no further tendency for γ to decrease as pH is increased. Indeed the conversion of neutral to charged surfactant species causes the monolayer to charge up. Thus, for pH values greater than the solubility edge the increasing electrostatic repulsion of negative surfactant from the interface causes γ to increase. A minimum in γ exists, therefore, at the solubility edge. In this model there is no necessity to postulate complexes of the surfactant species with peculiar surface activity to explain the observed γ(pH) behaviour as has been suggested by other authors. Quantitative comparison of the theory and experiment for the oleic acid system is presented.