Monomer fraction data for water (and other compounds) can provide useful information about their structure and can be used in “advanced” equations of state, which account explicitly for association phenomena. Recent findings about the performance of association theories in representing the monomer fraction of water are reviewed. Three such theories are considered and all of them perform qualitatively similar. They can all represent phase equilibria for water solutions qualitatively well but with parameters which are not in good agreement with Luck’s famous monomer fraction data. While this could set the theoretical basis of these theories in doubt, we also show in this work that the findings with these association models are in agreement with a recently presented theory which links monomer fraction to dielectric constants. This new theory, like the three thermodynamic models, predicts more hydrogen bonding in water than Luck’s data (Angew. Chem. Int. Ed. Engl. 1980, vol. 19, pp. 28). Moreover, it appears that both the new theory and the three models provide evidence for the four-site association scheme for water and thus support that the tetrahedral structure of the water molecule is correct or at least that the tetrahedral structure is in agreement with several pure water physical properties, monomer fraction information and phase equilibria data in mixtures with alkanes.
- Monomer fractions
- Dielectric constant