An equation of state for the isotropic phase of linear, partially flexible and fully flexible tangent hard-sphere chain fluids

作者：van Westen Thijs; Oyarzun Bernardo; Vlugt Thijs J H; Gross Joachim^*

来源：Molecular Physics, 2014, 112(7): 919-928.

DOI：10.1080/00268976.2013.812257

A new equation of state is developed that accurately describes the isotropic phase behaviour of linear, partially flexible and fully flexible tangent hard-sphere chain fluids and their mixtures. The equation of state is based on the equation of state of Liu and Hu [H. Liu and Y. Hu, Fluid Phase Equilibr. 122, 75 (1996)] for fully flexible chain fluids. The effect of molecular flexibility is described by a pure-component parameter that is introduced in the theory at the level of the cavity correlation function of next-to-nearest neighbour segments in a chain molecule. The equation of state contains a total of three adjustable model constants. The extension to partially flexible- and linear chain fluids is based on a refitting of the first model constant to numerical data of the second virial coefficient of partially flexible and linear tangent hard-sphere chain fluids. The numerical data were obtained from an analytical approximation for the pair-excluded volume. The other two parameters were adjusted to molecular simulation data for the pressure of linear tangent hard-sphere chain fluids. For both, pure component systems and mixtures of chains of variable flexibility, the pressure and second virial coefficient obtained from the equation of state, are in excellent agreement with the results from Monte Carlo simulations. A significant improvement to TPT1, TPT2, generalised Flory-dimer theory and scaled particle theory is observed.

• 出版日期2014-4-3