Journal article
Intramolecular Association within the SAFT Framework
CERE – Center for Energy Ressources Engineering, Department of Chemical and Biochemical Engineering, Technical University of Denmark1
Department of Chemical and Biochemical Engineering, Technical University of Denmark2
Rice University3
Center for Energy Resources Engineering, Centers, Technical University of Denmark4
A general theory for modelling intramolecular association within the SAFT framework is proposed. Sear and Jackson [Phys. Rev. E. 50 (1), 386 (1994)] and Ghonasgi and Chapman [J. Chem. Phys. 102 (6), 2585 (1995)] have previously extended SAFT to include intramolecular association for chains with two sites.
We show that the resulting equations from the two approaches are equivalent, and use their work as a basis for developing a new general theory. The approach used by Ghonasgi and Chapman is based on mass balances and an infinite dilution result and provides the equations needed to determine the contribution to the Helmholtz free energy from association (inter- as well as intramolecularly) at equilibrium.
Sear and Jackson rederived the contribution to the Helmholtz free energy from association from the theory by Wertheim [J. Stat. Phys. 42 (3–4), 459 (1986)] with inclusion of intramolecular association, and using this approach we obtain an expression for the Helmholtz free energy that is valid also at non-equilibrium states (with respect to hydrogen bonds), which is very useful when calculating derivatives.
| Language: | English |
|---|---|
| Publisher: | Taylor & Francis Group |
| Year: | 2011 |
| Pages: | 1759-1769 |
| Journal subtitle: | An International Journal at the Interface Between Chemistry and Physics |
| ISSN: | 13623028 and 00268976 |
| Types: | Journal article |
| DOI: | 10.1080/00268976.2011.589990 |
| ORCIDs: | Kontogeorgis, Georgios |
