08.07 - Implementation of Departure Functions

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Helmholtz Energy - Mother of All Departure Functions. (uakron.edu, 10min) This screencast begins with a brief perspective on energy and free energy as they relate to concepts from Chapter 1 and through to the end of the course. Then it focuses on how the Helmholtz departure function is one of the most powerful due to the relations that can be developed from it. The Helmholtz departure is relatively easy to develop from a density integral of the compressibility factor. Then the internal energy departure can be derived from a temperature derivative. Alternatively, if the internal energy departure is given, the Helmholtz energy can be inferred by integration, and the compressibility factor can be derived from a density derivative. 
Comprehension Questions: (Hint: some of the following may be answered in later videos below.)
1. Write an equation that takes you from the Helmholtz energy departure function to Z.
2. Write an equation that takes you from the Helmholtz energy departure function to (U-Uig)/RT.
3. Derive the internal energy departure function for the vdW EOS using Eqn. 8.22.
4. Derive the Helmholtz energy departure function for the vdW EOS using Eqn. 8.25.
5. Use the result of #4 to derive the internal energy departure function for the vdW EOS.

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Helmholtz Example - vdW EOS (uakron.edu, 18min) This video begins with a brief review of the connection of the Helmholtz departure with all other departures then shows four sample derivations assuming that Z is given by the vdW EOS: (1) the Helmholtz departure , (2) the internal energy departure from the Helmholtz departure. (3) the Helmholtz energy from the internal energy (4) the Z factor from the Helmholtz departure. The procedures illustrated here can be applied to any EOS starting with any part (U, A, or Z) as given to derive any other departure: ZUHAGS.
Comprehension Questions: The virial EOS for SW fluids can be written as: Z = 1 + Bρ/RT where B = 4b+[4b(λ^3-1)] [exp(βε)-1], b = πNAσ^3/6.
1. Derive an expression for the Helmholtz departure.
2. Use the result of #1 to derive the internal energy departure.
3. Use the result of #2 to derive the Helmholtz departure. What is the integration constant in this case?

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Helmholtz Example - Modified vdW EOS (uakron.edu, 13min) A sample derivation of the Helmholtz departure implicit in the Gibbs departure given Z = 1 + abρ/(1+)^3 - (9.5aρ/RT)/(1+aρ/RT). Note that the limits of integration matter for this EOS. The audio is inferior for this live video, but it responds to typical questions and confusion from students in the audience. Some students might find it helpful to hear the kinds of questions that students ask. The responses slow the derivation down so that no steps are skipped and key steps are reiterated multiple times. Just turn the volume up!
Comprehension questions:
1. Which part of this EOS is non-zero at the zero density limit of integration?
2. Is there a sign error on one of the terms in this video? Check the derivation independently.
3. Derive the Helmholtz departure given Z = 1 + 4bρ/(1-)2 - (9.5aρ/RT)/{1-a/bRT[1-4bρ+4(bρ)2]}.
4. Derive the Helmholtz departure given Z = 1 + 4bρ/(1-2) - (9.5aρ/RT){1+4/bRT[1-2(bρ)2]}/{1-a/bRT[1-4bρ+4(bρ)2]})/{1-a/bRT[1-4bρ+4(bρ)2]}

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Helmholtz Example - Scott+TPT EOS. (uakron.edu) A sample derivation (8min) for the compressibility factor given that (A-Aig)TV/RT = -2ln(1-2ηP) - 18.7ηPβε/[1+0.36βεexp(-5ηP)]. This equation of state is a little complicated, but the derivation is no problem if you just go slow and steady. The remainder of this screencast shows a sample calculation (21min) to solve the resulting equation of state at a given value of pressure and temperature following the methodology of "visualizing the vdW EOS." This problem was adapted from an actual test problem. This screencast is live so the audio is inferior, but it gives insight into questions that real students have. 
Comprehension Questions:
1. Derive an expression for the internal energy departure function of this EOS.
2. Is there a sign error on one of terms in this video? Check the derivation independently.
3. Derive the Z factor given (A-Aig)TV/RT = -2ln(1-2bρ) - (9.5aρ/RT)/{1-a/bRT[1-4bρ+4(bρ)2]}.

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Helmholtz Departure - PR EOS (uakron.edu, 11min) This lesson focuses first and foremost on deriving the Helmholtz departure function. It illustrates the application of integral tables from Apx. B and the importance of applying the limits of integration. It is the essential starting point for deriving properties involving entropy (S,A,G) of the PREOS, and it is a convenient starting point for deriving energetic properties (U,H).

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Internal Energy Departure - PR EOS starting from Helmholtz Departure (uakron.edu,9min) This sample derivation supplements what is in the textbook by starting from the Helmholtz departure function. It also includes a few intermediate steps to help clarify how the formal equations in the textbook were developed. Hopefully, seeing this content from slightly different perspectives will make it a little easier to comprehend. See also the derivation for (U-Uig).

Comprehension Questions: Starting from the Helmholtz Departure function and referring to the above results...

1. Derive the internal energy departure function for the "modified vdW" EOS.
2. Derive the entropy departure function for the "modified vdW" EOS. (Hint: A=U-TS)
3. Derive the internal energy departure function for the "Scott+TPT" EOS.

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Derive the internal energy departure function (uakron.edu, 20min) for the following EOS:
P = (RT(1+V1.5)/V1.5)*(1+sqrt(V)) - a/(V^2T^1.3)/(1+sqrt(V)) This sample derivation is more complicated than average, but the usual procedure still works. We begin by rearranging to obtain an expression for Z and finding the Helmholtz departure, then differentiating to get the internal energy.

Comprehension: Given (A-Aig)TV/RT = -2ln(1-ηP) - 16.49ηPβε/[1-βε(1-2ηP)/(1+2ηP)^2 ]

1. Derive the internal energy departure function.

2. Derive the expression for the compressibility factor.

3. Solve the EOS for Zc.

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