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Adsorption and solvation of ethanol at the water liquid-vapor interface: A molecular dynamics study

Journal Article · · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical
DOI:https://doi.org/10.1021/jp962629n· OSTI ID:501942
;  [1]
  1. NASA-Ames Research Center, Moffett Field, CA (United States)

The free energy profiles of methanol and ethanol at the water liquid-vapor interface at 310 K were calculated using molecular dynamics computer simulations. Both alcohols exhibit a pronounced free energy minimum at the interface and, therefore, have positive adsorption at this interface. The surface excess was computed from the Gibbs adsorption isotherm and was found to be in good agreement with experimental results. Neither compounds exhibits a free energy barrier between the bulk and the surface adsorbed state. Scattering calculations of ethanol molecules from a gas phase thermal distribution indicate that the mass accommodation coefficient is 0.98, and the molecules become thermalized within 10 ps of striking the interface. It was determined that the formation of the solvent structure around the ethanol molecule at the interface is not the rate-determining step in its uptake into water droplets. The motion of an ethanol molecule in a water lamella was followed for 30 ns. The time evolution of the probability distribution of finding an ethanol molecule that was initially located at the interface is very well described by the diffusion equation on the free energy surface. 37 refs., 6 figs.

OSTI ID:
501942
Journal Information:
Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 16 Vol. 101; ISSN 1089-5647; ISSN JPCBFK
Country of Publication:
United States
Language:
English

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