Revealing the Effects of Weak Surfactants on the Dynamics of Surface Fluctuations by Surface Light Scattering.

Abstract

Surfactant monolayers at liquid interfaces induce a viscoelastic behavior that influences the dynamics of surface fluctuations probed by surface light scattering (SLS). Recent thermophysical property research on viscosity and interfacial tension of liquid organic hydrogen carrier (LOHC) systems based on diphenylmethane suggested that such viscoelastic effects may also be present here, although not being expected a priori. To prove the hypothesis that the LOHC intermediate cyclohexylphenylmethane (H6-DPM) can induce a surfactant-like behavior, binary mixtures of diphenylmethane (H0-DPM) or dicyclohexylmethane (H12-DPM) with small amounts of H6-DPM were studied by SLS in combination with conventional viscometry and tensiometry and molecular dynamics simulations between (303 and 473) K. Only in mixtures with H0-DPM which has a slightly larger surface tension than H6-DPM, the presence of the latter compound causes a significant effect on the dynamics of surface fluctuations, especially on their damping. In analogy to the concentration-dependent behavior observed for a monolayer of a highly amphiphilic ionic surfactant on the surface of water at ambient temperature, the orientation of H6-DPM molecules with respect to the surface appears to change from a preferentially perpendicular to a parallel alignment with increasing temperature. This demonstrates that viscoelastic effects including accompanied surface orientation effects can be resolved by SLS even for weakly asymmetric surface-active molecules such as H6-DPM in its diluted mixtures with very similar species.