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).

This screencast shows how to quickly visualize Pxy phase diagrams for nonideal systems using Excel (5min, uakron.edu). These sample calculations for methanol+benzene apply the simplest nonideal solution model: ΔH_mix = 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?

You can customize Kcalc.xlsx (uakron.edu, 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?

Bubble Temperature (2:43) (msu.edu)

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.