Polymer fluids first-order thermodynamic perturbation

The perturbed-hard-ehain (PHC) theory developed by Prausnitz and coworkers in the late 1970s was the first successful application of thermodynamic perturbation theory to polymer systems. Sinee Wertheim s perturbation theory of polymerization was formulated about 10 years later, PHC theory combines results fi om hard-sphere equations of simple liquids with the eoneept of density-dependent external degrees of fi eedom in the Prigogine-Flory-Patterson model for taking into account the chain character of real polymeric fluids. For the hard-sphere reference equation the result derived by Carnahan and Starling was applied, as this expression is a good approximation for low-molecular hard-sphere fluids. For the attractive perturbation term, a modified Alder s fourth-order perturbation result for square-well fluids was chosen. Its constants were refitted to the thermodynamic equilibrium data of pure methane. The final equation of state reads ... 

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