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Resummed thermodynamic perturbation theory for central force associating potential: One-patch model
Y V Kalyuzhnyi1, H Docherty, P T Cummings
1Institute for Condensed Matter Physics, Svientsitskoho 1, 79011 Lviv, Ukraine. yukal@icmp.lviv.ua
The Journal of Chemical Physics
|August 7, 2010
Summary
This study introduces a new thermodynamic perturbation theory for associating fluids, accounting for particle bonding restrictions. The theory accurately predicts fluid properties, outperforming previous models, especially at lower temperatures.
Area of Science:
- Thermodynamics
- Statistical Mechanics
- Physical Chemistry
Background:
- Associating fluids exhibit complex behaviors due to directional interactions.
- Existing theories often neglect or inaccurately model the 'blocking effect' in multiply bonding systems.
Purpose of the Study:
- To develop a resummed thermodynamic perturbation theory for associating fluids with multiply bondable potentials.
- To accurately model the blocking effects in particle bonding.
- To provide analytical expressions for thermodynamic properties of a one-patch model.
Main Methods:
- Proposed a resummed thermodynamic perturbation theory.
- Utilized a hard-sphere model with circular attractive patches.
- Derived closed-form analytical expressions for thermodynamic properties.
- Validated results using Monte Carlo computer simulations.
Main Results:
- Developed analytical expressions for Helmholtz free energy, pressure, internal energy, and chemical potential.
- The theory accurately predicts thermodynamic properties and the fraction of multiply bonded particles.
- The refined theory shows very good agreement with Monte Carlo simulations, especially when corrected for ring formation.
Conclusions:
- The proposed resummed theory offers improved accuracy for thermodynamic properties of associating fluids compared to original theories and Wertheim's theory.
- The theory is particularly effective at lower temperatures and with larger attractive patch sizes.
- Accounting for blocking effects and ring formation is crucial for accurate predictions in multiply bonding systems.
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