Low density shear viscosity of Lennard-Jones chains of variable rigidities.

The zero-density shear viscosity of different types of short Lennard-Jones chains, up to the hexa-decamer, has been evaluated using a non-equilibrium molecular dynamics scheme. Simulations have been performed on chains of variable rigidities going from the fully flexible to the fully rigid chains. Very interestingly, it is found that there exists a universal relation (a power law) between the zero-density viscosity of the Lennard-Jones chains and their radius of gyration whatever the rigidity of the chain and for all tested temperatures (ranging from 2.5 to 6 in reduced units). Furthermore, for the studied range of temperature, it is shown that the zero-density viscosity of both fully flexible chains and fully rigid chains models can be obtained with an accuracy of a few percents knowing only the dimer viscosity and the length of the chain.

Simultaneous free-volume modeling of the self-diffusion coefficient and dynamic viscosity at high pressure.

In this work, a simultaneous modeling of the self-diffusion coefficient and the dynamic viscosity is presented. In the microstructural theory these two quantities are governed by the same friction coefficient related to the mobility of the molecule. A recent free-volume model, already successfully applied to dynamic viscosity, has been considered and generalized. In this generalized model the compound is characterized by only four parameters. But if the quadratic length is known, the number of adjustable parameters is three. The compounds considered in this work are benzene, carbon tetrachloride, chlorotrifluoromethane, cyclohexane, methylcyclohexane, and tetramethylsilane. For these pure compounds we have found in the literature several data for both the self-diffusion and the dynamic viscosity in large viscosity, diffusion, temperature, and pressure intervals (up to around 500 MPa for methylcyclohexane and tetramethylsilane). The average absolute deviation obtained by the modeling is generally less than 3% for the viscosity and 5% for the self-diffusion.

Free-volume viscosity model for fluids in the dense and gaseous states.

A free-volume and friction viscosity model is presented versus pressure and temperature, valid for both gaseous and dense fluids. This model involves only three adjustable parameters for each pure compound. It is able to represent the gas-liquid transition and the behavior in the supercritical conditions. The model has been successfully applied to methane (885 data points for 0.01< or =P< or =200 MPa and 90.7< or =T< or =600 K) and to propane (1085 data points for 0.01< or =P< or =200 MPa and 90< or =T< or =600 K) in the gaseous and dense states (average absolute deviation is 2.59% for methane and 2.50% for propane, with maximum deviation of 14.8% for methane and 9.19% for propane). It has also been applied to hexane, octane, dodecane, benzene, trans-decaline, and 2,2-dimethylpropane (903 data points) in a large pressure range (up to 505.5 MPa). Considering these compounds the maximum deviation is 19.5% (for octane) and the average deviation is 3.51% in the worst case (dodecane, which has data points up to 501.6 MPa).