Viscosity of heptane-toluene mixtures. Comparison of molecular dynamics and group contribution methods.

Three methods of molecular dynamics simulation [Green-Kubo (G-K), non-equilibrium molecular dynamics (NEMD) and reversed non-equilibrium molecular dynamics (RNEMD)], and two group contribution methods [UNIFAC-VISCO and Grunberg-Nissan (G-N)] were used to calculate the viscosity of mixtures of n-heptane and toluene (known as heptol). The results obtained for the viscosity and density of heptol were compared with reported experimental data, and the advantages and disadvantages of each method are discussed. Overall, the five methods showed good agreement between calculated and experimental viscosities. In all cases, the deviation was lower than 9%. It was found that, as the concentration of toluene increases, the deviation of the density of the mixture (as calculated with molecular dynamics methods) also increases, which directly affects the viscosity result obtained. Among the molecular simulation techniques evaluated here, G-K produced the best results, and represents the optimal balance between quality of result and time required for simulation. The NEMD method produced acceptable results for the viscosity of the system but required more simulation time as well as the determination of an appropriate shear rate. The RNEMD method was fast and eliminated the need to determine a set of values for shear rate, but introduced large fluctuations in measurements of shear rate and viscosity. The two group contribution methods were accurate and fast when used to calculate viscosity, but require knowledge of the viscosity of the pure compounds, which is a serious limitation for applications in complex multicomponent systems. [ABSTRACT FROM AUTHOR]