# 07.11 - The molecular basis of equations of state: analytical theories

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### Nature of Molecular Parking L

Nature of Molecular Parking Lots - RDFs(20min, uakron.edu) Molecules occupy space and they move around until they find their equilibrium pressure at a given density and temperature. Cars in a parking lot behave in a similar fashion except the parking lot is in 2D vs. 3D. Despite this exception, we can understand a lot about molecular distributions by thinking about how repulsive and attractive forces affect car parking. For example, one important consideration is that you should not expect to see two cars parked in the same space at the same time! That's entirely analogous for molecular parking. Simple ideas like this lead to an intuitive understanding of the number of molecules distributed at each distance around a central molecule. From there, it is straightforward to multiply the energy at a given distance (ie. u(r) ) by the number of molecules at that distance (aka. g(r) ), and integrate to obtain the total energy. A similar integral over intermolecular forces leads to the pressure. And, voila! we have a new conceptual route to developing engineering equations of state.
Comprehension questions:
1. Sketch u(r)/epsilon and g(r) vs. r/sigma for square well spheres at a very low density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.
2. Sketch u(r)/epsilon and g(r) vs. r/sigma for hard spheres at a high density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.
3. Sketch u(r)/epsilon and g(r) vs. r/sigma for square well spheres at a high density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.

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### Nature of Molecular Energy -

Nature of Molecular Energy - Example Calculation(8min, uakron.edu) Given an estimate for the radial distribution function (RDF) integrate to obtain an estimate of the internal energy. The result provides an alternative to the attractive term of the vdW EOS.

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### Nature of Molecular Pressure

Nature of Molecular Pressure - Example Calculation(11min, uakron.edu) Similar to integrating intermolecular energy to obtain the macroscopic internal energy, integrating the intermolecular force per unit area leads to the macroscopic force per unit area (aka. pressure).

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