Prediction of Transport Properties by Molecular Simulation: Methanol and Ethanol and their mixture

TL;DR

This study uses molecular dynamics simulations to accurately predict various transport properties of methanol, ethanol, and their mixture, showing good agreement with experimental data across a wide temperature range.

Contribution

The paper develops and applies molecular simulation models to predict transport properties of alcohols and their mixture, validating against experimental data.

Findings

Predicted diffusion coefficients and viscosity deviate less than 8% from experiments.

Thermal conductivity predictions are within 5% of experimental values.

Vapor-liquid equilibrium data agree well with experiments.

Abstract

Transport properties of liquid methanol and ethanol are predicted by molecular dynamics simulation. The molecular models for the alcohols are rigid, non-polarizable and of united-atom type. They were developed in preceding work using experimental vapor-liquid equilibrium data only. Self- and Maxwell-Stefan diffusion coefficients as well as the shear viscosity of methanol, ethanol and their binary mixture are determined using equilibrium molecular dynamics and the Green-Kubo formalism. Non-equilibrium molecular dynamics is used for predicting the thermal conductivity of the two pure substances. The transport properties of the fluids are calculated over a wide temperature range at ambient pressure and compared with experimental and simulation data from the literature. Overall, a very good agreement with the experiment is found. For instance, the self-diffusion coefficient and the shear viscosity are predicted with average deviations of less 8% for the pure alcohols and 12% for the mixture. The predicted thermal conductivity agrees in average within 5% with the experimental data. Additionally, some velocity and shear viscosity autocorrelation functions are presented and discussed. Radial distribution functions for ethanol are also presented. The predicted excess volume, excess enthalpy and the vapor-liquid equilibrium of the binary mixture methanol + ethanol are assessed and the vapor-liquid equilibrium agree well with experimental data.