# 07.05 Cubic Equations of State

### Intro to the vdW EOS (5min).

Intro to the vdW EOS. (LearnCheme.com, 5min) Provides a brief overview of the van der Waals (vdW) 1873 equation of state (EOS), which served as a prototype for EOS development for over 100 years. Note: the vdW EOS is just one conjecture of how equations of state for real fluids may be formulated. In reality, each fluid has its own unique EOS. The vdW model conjectures that the pressure is altered relative to the ideal gas by the presence of attractive forces and repulsive forces.

Comprehension Questions:

1. Of the two parameters a and b, which is related to attractive forces and which is related to attractive forces?
2. How are the parameters a and b typically characterized/computed? ie. To what experimental constants are they related in order to compute them?
3. Is the vdW EOS an example of a 2-parameter EOS or 3-parameter EOS?
4. When writing the term (V-b) we subtract b because the molecules occupy volume and when V=b, all the "free volume" is gone. Can you explain the term (P+a/V2) in a similar manner?
5. In the presented example of CO2 at 0.2L and 269K, how does the pressure compare when computed by the ideal gas law vs. the vdW model? (Give both values.)
6. In the presented example of CO2 at 0.0L and 269K, how does the pressure compare when computed by the ideal gas law vs. the vdW model? (Give both values.)

### Virial and Cubic EOS (11:18)

Virial and Cubic EOS (11:18) (msu.edu)
Discusses the strategy of the virial EOS and the cubic EOS and the strategy used to solve as a cubic in Z. Gives formulas for calculating the a and b parameters of both the vdW and Peng-Robinson EOS's, as well as the virial EOS. You might want to watch the video on "Visualizing the vdW EOS" if you want to understand where the equations for a and b come from or how to make quantitative plots of isotherms.

Comprehension Questions:

1. To what region of pressure is the virial EOS limited at a given temperature? Why?
2. Is the Pitzer EOS limited to the same conditions as the virial EOS?
3. Is the virial EOS a 2-parameter or 3-parameter EOS?
4. Is the Peng-Robinson (PR) EOS a 2-parameter or 3-parameter EOS?
5. What is the primary shortcoming of the vdW EOS, as described on slide 4 of this presentation?
6. Is the PR EOS limited to the same conditions as the virial EOS? Explain.
7. How does the "fugacity" help you to identify the stable root of a cubic EOS?
8. When there are 3 real roots to a cubic EOS, what do we do with the center root? Why?