Bulk And Interfacial Properties Of Chain Fluids Pamies

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Cases in which bonding at one site is dependent of bonding at other sites on the same molecule can be accounted for with the extension of Wertheim’s theory to second order. Nevertheless, except for special cases [39], it is not of practical use due to the more structural information required, which is not always available. 2 SAFT equation of state As mentioned in the last section, Wertheim provided a relationship between the residual Helmholtz free energy due to association and the monomer density by means of expanding the Helmholtz energy in a series of integrals of molecular distribution functions and the association potential.

It is therefore expected that the more realistic LJ potential (as opposed to a hard potential) provides a better description of the output properties. The modified version of SAFT proposed by Ghonasgi and Chapman [63] and the EOS for LJ chains of Johnson et al. [53] also use a LJ potential and radial distribution function. Additionally, the LJ-SAFT equation of Kraska and Gubbins [64,65] considers dipole-dipole interactions. As already commented, in contrast to the hard-sphere potential, the use of a soft potential allows the association sites to be fully embedded inside the reference core.

On the other hand, it has been observed that normal alkanes show a great regularity in their behavior with respect to the carbon number. Therefore, the search of transferable parameters becomes an attractive route to obtain the thermodynamic properties of components otherwise hard to find. Recently, there has been some progress in the estimate of critical properties of n-alkanes. Anselme and co-workers [90] were able to measure the critical properties of the n-alkane series up to n-octadecane with a novel experimental technique.

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