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Selected topics in the statistical mechanics of fluids.

Davies, Lowri A (1997) Selected topics in the statistical mechanics of fluids. PhD thesis, University of Sheffield.

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The phase behaviour and thermodynamic properties of simple model mixtures are examined using the statistical associating fluid theory as extended to chain molecules interacting with potentials of variable range (SAFT-VR), and by computer simulation. The SAFT-VR approach is based on an accurate and compact representation of the free energy of chain molecules. We present the SA FT -VR methodology as applied to mixtures of non-conformal molecules. A series of mixing rules are presented, beginning with the van der Waals one-fluid prescription and including more complex treatments. The vapour-liquid equilibria of a mixture consisting of hard spheres and square-well monomers is examined with the SAFT-VR equation of state, together with the liquid-liquid equilibria of a symmetrical square-well mixture with no unlike interactions. Additionally, we examine the vapour-liquid equilibria of a square-well monomer-dimer mixture, composed of equal-sized segments, both with the SAFT-VR approach and by Gibbs ensemble Monte Carlo simulation. The simulation data are used to determine the vapourliquid critical line of the mixture. An extension of the SAFT-VR approach to describe the phase behaviour of chain molecules interacting with a soft repulsive potential and an attractive well of variable range is presented. We focus on the vapour-liquid properties of Lennard-Jones chains using a simple recipe for the evaluation of the chain free energy. We also perform a case study for a specific class of phase equilibria exhibited by binary mixtures, where systems are seen to posses a region of closed-loop immiscibility in their phase diagrams. We examine the nature of this type of pl1ase behaviour using the SA FT· VR equation of state and Gibbs ensemble simulation for a simple model system with an anisotropic bonding site, which is seen to be the governing factor in the appearance of the region of low-temperature miscibility for this system. The model is chosen in order to mimic the physical features of real systems which exhibit this type of re-entrant phase behaviour. The critical regions of this model are examined using a finite-size scaling analysis performed in the semigrand canonical ensemble.

Item Type: Thesis (PhD)
Keywords: Fluid mechanics
Academic Units: The University of Sheffield > Faculty of Science (Sheffield) > Chemistry (Sheffield)
Identification Number/EthosID: uk.bl.ethos.266008
Depositing User: EThOS Import Sheffield
Date Deposited: 14 Dec 2016 15:57
Last Modified: 14 Dec 2016 15:57
URI: http://etheses.whiterose.ac.uk/id/eprint/14744

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