On the cooperativity of association and reference energy scales in thermodynamic perturbation theory

Abstract

Equations of state for hydrogen bonding fluids are typically described by two energy scales. A short range highly directional hydrogen bond energy scale, as well as a reference energy scale which accounts for dispersion and orientationally averaged multi-pole attractions. These energy scales are always treated independently. In recent years, extensive first principles quantum mechanics calculations on small water clusters have shown that both hydrogen bond and reference energy scales depend on the number of incident hydrogen bonds of the water molecule. In this work we propose a new methodology to couple the reference energy scale to the degree of hydrogen bonding in the fluid. We demonstrate the utility of the new approach by showing that it gives improved predictions of water-hydrocarbon mutual solubilities.

References in corpus (4)

• Thermodynamic perturbation theory for associating fluids with small bond angles: Effects of steric hindrance, ring formation and double bonding
• Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids
• Thermodynamic perturbation theory for self assembling mixtures of multi - patch colloids and colloids with spherically symmetric attractions
• Resummed thermodynamic perturbation theory for bond cooperativity in associating fluids with small bond angles: Effects of steric hindrance and ring formation

Cited by in corpus (3)

• A second order thermodynamic perturbation theory for hydrogen bond cooperativity in water
• A perturbation theory for water with an associating reference fluid
• Nucleation Rates of Water Using Adjusted SAFT-0 EOS