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05.2 - The Rankine cycle Click here. 100 1

Rankine Cycle Introduction (, 4min) The Carnot cycle becomes impractical for common large scale application, primarily because H2O is the most convenient working fluid for such a process. When working with H2O, an isentropic turbine could easily take you from a superheated region to a low quality steam condition, essentially forming large rain drops. To understand how this might be undesirable, imagine yourself riding through a heavy rain storm at 60 mph with your head outside the window. Now imagine doing it 24/7/365 for 10 years; that's how long a high-precision, maximally efficient turbine should operate to recover its price of investment. Next you might ask why not use a different working fluid that does not condense, like air or CO2. The main problem is that the heat transfer coefficients of gases like these are about 40 times smaller that those for boiling and condensing H2O. That means that the heat exchangers would need to be roughly 40 times larger. As it is now, the cooling tower of a nuclear power plant is the main thing that you see on the horizon when approaching from far away. If that heat exchanger was 40 times larger... that would be large. And then we would need a similar one for the nuclear core. Power cycles based on heating gases do exist, but they are for relatively small power generators.
     With this background, it may be helpful to review the relation between the Carnot and Rankine cycles. (, 6min) The Carnot cycle is an idealized conceptual process in the sense that it provides the maximum possible fractional conversion of heat into work (aka. thermal efficiency, ηθ).
Comprehension Questions:
1. Why is the Carnot cycle impractical when it comes to running steam through a turbine? How does the Rankine cycle solve this problem?
2. Why is the Carnot cycle impractical when it comes to running steam through a pump? How does the Rankine cycle solve this problem?
3. It is obvious which temperatures are the "high" and "low" temperatures in the Carnot cycle, but not so much in the Rankine cycle. The "boiler" in a Rankine cycle actually consists of "simple boiling" where the saturated liquid is converted to saturated vapor, and superheating where the saturated vapor is raised to the temperature entering the turbine. When comparing the thermal efficiency of a Rankine cycle to the Carnot efficiency, should we substitute the temperature during "simple" boiling, or the temperature entering the turbine into the formula for the Carnot efficiency? Explain.

08.07 - Implementation of Departure Functions Click here. 100 1

Helmholtz Departure - PR EOS (, 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).

08.02 - The Internal Energy Departure Function Click here. 100 1

Departure Function Derivation Principles (8:03) (
This screencast covers sections 8.2 - 8.8. Concepts of using the equation of state to evaluate departure functions. The screencasts also discusses the choice of density integrals or pressure integrals. The use of a reference state is discussed.

10.07 - Nonideal Systems Click here. 100 1

This screencast shows how to quickly visualize Pxy phase diagrams for nonideal systems using Excel (5min, These sample calculations for methanol+benzene apply the simplest nonideal solution model: ΔHmix = A12*x1*x2. Rigors of this model are discussed in Chapter 11. Nevertheless, its basic elements are simple enough that they can be understood in Chapter 10. When x1=0 or x2=0, a pure fluid is indicated, corresponding to no mixing and zero heat of mixing. When A12=0, the ideal solution approximation is recovered. When A12>0, the model indicates an endothermic interaction (like 2-propanol+water, Fig. 10.8c), giving rise to "positive deviations from Raoult's Law." When A12<0, the model indicates an exothermic interaction (like acetone+chloroform, Fig. 10.9c), giving rise to "negative deviations from Raoult's Law." With this spreadsheet, you can quickly change your components and A12 values to see how the phase diagram changes and gain "hands-on" familiarity with the principles discussed in Section 10.7. 

Note: This is a companion file in a series. You may wish to choose your own order for viewing them. For example, you should implement the first three videos before implementing this one. Also, you might like to see how to quickly visualize the Txy analog of the Pxy phase diagram. If you see a phase diagram like the ones in section 11.8, you might want to learn about LLE phase diagrams. The links on the software tutorial present a summary of the techniques to be implemented throughout Unit3 in a quick access format that is more compact than what is presented elsewhere. Some students may find it helpful to refer to this compact list when they find themselves "not being able to find the forest because of all the trees."

Comprehension Questions:
1. Make a Pxy diagram for cyclohexane+toluene at 80C and A12=200. What kind of system is this?
2. Make a Pxy diagram for cyclohexane+benzene at 80C and A12=200. What kind of system is this?
3. Why does the system's qualitative behavior change so much when the components and model parameters are changed so little?

10.08 - Concepts for Generalized Phase Equilibria Click here. 100 1

Concepts for General Phase Equilibria (12:33) (

The calculus used in Chapter 6 needs to be generalized to add composition dependence. Also, we introduce partial molar properties and composition derivatives that are not partial molar properties. We introduce chemical potential These concepts are used to show that the chemical potentials and component fugacities are used as criteria for phase equilibria.

17.07 - Temperature Dependence of Ka Click here. 100 2

You can customize Kcalc.xlsx (, 17min) to facilitate whatever calculations you may need to perform. This presentation shows how to implement VLOOKUP to automatically load the relevant Hf, Gf, and Cp values. It also shows how to automatically use the Cp/R value when a,b,c,d values for Cp are not available. Finally, it shows how a fairly general table of inlet flows, temperatures, and pressures can be used to set up the equilibrium conversion calculation. The initial set up is demonstrated for the dimethyl ether process, then revised to initiate solution of Example 17.9 for ammonia synthesis.

Comprehension Questions:

1. The video shows how the shortcut Van't Hof equation can be written as lnKa=A+B/T. What are the values of A and B for the dimethyl ether process when a reference temperature of 633K is used?
2. The video shows how the shortcut Van't Hof equation can be written as lnKa=A+B/T. What are the values of A and B for the ammonia synthesis process when a reference temperature of 600K is used?

12.04 - The Flory-Huggins Model Click here. 100 2

The Flory and Flory-Huggins Models (7:05) (

Flory recognized the importance of molecular size on entropy, and the Flory equation is an important building block for many equations in Chapter 13. Flory introduced the importance of free volume. The Flory-Huggins model combines the Flory equation with the Scatchard-Hildebrand model using the degree of polymerization and the parameter χ. The Flory-Huggins model is used widely in the polymer industry.

Comprehension Questions:

Assume δP=δS for polystyrene, where δS is the solubility parameter for styrene. Also, polystyrene typically has a molecular weight of about 15,000. Room temperature is 25°C.

1. Estimate the infinite dilution activity coefficient of styrene in polystyrene.
2. Estimate the infinite dilution activity coefficient of toluene in polystyrene.
3. Estimate the infinite dilution activity coefficient of acetone in polystyrene.
4. Which of the above would be the "best" solvent for polystyrene? Explain quantitatively.

11.02 - Calculations with Activity Coefficients Click here. 100 3

Bubble Temperature (2:43) (

The culmination of the activity coefficient method is application of the fitted activity coefficients to extrapolate from limited experiments in a Stage III calculation. The bubble temperature is the easiest after bubble pressure. The recommended order of study is 1) Bubble Pressure; 2) Bubble Temperature; 3) Dew Pressure; 4) Dew Temperature. Note that an entire Txy diagram can be generated with bubble temperature calculations; no dew calculations are required.

01.6 Summary Click here. 100 1

The objectives for Chapter 1 were:

1. Explain the definitions and relations between temperature, molecular kinetic energy,
molecular potential energy and macroscopic internal energy, including the role of intermolecular potential energy and how it is modeled. Explain why the ideal gas internal energy
depends only on temperature.
2. Explain the molecular origin of pressure.
3. Apply the vocabulary of thermodynamics with words such as the following: work, quality,
interpolation, sink/reservoir, absolute temperature, open/closed system, intensive/extensive
property, subcooled, saturated, superheated.
4. Explain the advantages and limitations of the ideal gas model.
5. Sketch and interpret paths on a P-Vdiagram.
6. Perform steam table computations like quality determination, double interpolation.

To these, we could add expressing and explaining the first and second laws. Make a quick list of these expressions and explanations in your own words, including cartoons or illustrations as you see fit,  starting with the first and second laws.

08.07 - Implementation of Departure Functions Click here. 100 1

Derive the internal energy departure function (, 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.