# Top-rated ScreenCasts

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In a contest for "the most hated word in Chemical Engineering," fugacity won by a landslide. This video (15min, uakron.edu) reviews how the term was developed and why it's not really as bad as all that. In fact, it's a nice word that sets the stage for all of phase and reaction equilibrium with a straightforward extension of the same conceptual basis to mixtures. On second thought, perhaps the power of that conceptual basis and all that it implies is what really intimidates new students. Many perspectives have been offered to help overcome the frustration that students feel toward fugacity. If you like a comic book perspective, even that is available.

Comprehension Questions:

1.What is the fugacity of a vapor phase component in a mixture according to Raoult's law?
2.What is the fugacity of a liquid phase component in a mixture according to Raoult's law?
3. What word is modern usage is closely related to the latin root "fuga-"?
4. Water is in VLE at 0.7 bars in a fixed volume vessel. Five cm3 of air are injected into the vessel and the temperature is allowed to return to its original value. Does the water in the vapor phase increase, decrease, or remain the same? (Learncheme.com, 2min) (Hint: you may assume that air does not dissolve in the liquid water and the pressure is sufficiently low that the vapor can be assumed to behave as an ideal gas.)

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.

The Flory and Flory-Huggins Models (7:05) (msu.edu)

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.

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: 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?

Introduction to Phase Behavior (9:37) (msu.edu)
Students tend to be distracted with the algorithms for bubble, dew, and flash, and often miss the important concepts of the relation of the calculations to the phase diagram. This screencast discusses the pure component endpoints, the trends in phase behavior at the bubble and dew conditions, and the qualitative relation between the P-x-y and T-x-y diagrams.

Comprehension Questions:

1. Referring to the Txy diagram on slide 3, estimate T, nature (ie. L,V, V+L, L+L), composition(s), and amount of the phase(s) for points: a, b. d, g.
2. Referring to the Txy diagram on slide 3, suppose we had T = 340K and zA = 0.40. Estimate T, nature (ie. L,V, V+L, L+L), composition(s), and amount of the phase(s) for that point.
3. Which component is more volatile, A or B?

Dew Temperature (7:57) (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 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. However, many applications require dew calculations, so they cannot be avoided. The dew calculations are more complicated than bubble calculations, because the liquid activity coefficients are not known until the unknown liquid mole fractions are found. This screencast describes the procedure and how to implement the method in Matlab or Excel.

SLE using Excel with the M1 model (7min, uakron.edu)

Similar to LLE in Excel, the iteration feature can be used to quickly solve for SLE at multiple temperatures.

Comprehension Questions:
1. Estimate the solubility of naphthalene in benzene at 25C. (a) Use the ideal solution model. (b) Use the MAB model. (ANS. a. 0.306, b. 0.302)
2. Estimate the solubility of biphenyl in nhexane at 25C. (a) Use the ideal solution model. (b) Use the MAB model.
3. Estimate the solubility of phenol in benzene at 25C. (a) Use the ideal solution model. (b) Use the MAB model.

07.09 -The Molecular Basis of Equations of State: Concepts and Notation Click here. 93.3333 3

Nature of Molecular Interactions - Macro To Nano(8min). (uakron.edu) Instead of matching the critical point, we can use experimental data for density vs. temperature from NIST as a means of characterizing the attractive energy and repulsive volume. A plot of compressibility factor vs. reciprocal temperature exhibits fairly linear behavior in the liquid region. Matching the slope and intercept of this line characterizes two parameters. This characterization may be even more useful than using the critical point if you are more interested in liquid densities than the critical point. In a similar manner, you could derive an EOS based on square-well (SW) simulations and use the SW EOS to match the NIST data(11min), as shown in this sample calculation of the ε and σ values for the SW potential. In this lesson, we learn how to characterize the forces between individual atoms, which may seem quite unreal or impractical when you first encounter it. On the other hand, "nanotechnology" is a scientific discipline that explores how the manipulation of nanostructure is now quite real with very significant practical implications. "The world's smallest movie" shows dancing molecules, (IBM, 2min) demonstrating the reality of molecular manipulation, and the accompanying text explains some of the practical implications. Along similar lines, researchers at LLNL and CalTech have developed 3D printers that can display "voxels" (the 3D analog of pixels) of ~1nm3. That's around 10-100 atoms per voxel. Since 2013-14, chemical/materials engineers have been building nanostructures (TEDX, 13min) in the same way that civil engineers build infrastructure.
Comprehension Questions:
1. What does the y-intercept represent in a plot of compressibility factor vs. reciprocal temperature?
2. What parameter does the y-intercept help to characterize, b or ε?
3. What does the x-intercept represent in a plot of compressibility factor vs. reciprocal temperature?
4. What parameter does the x-intercept help to characterize, b or ε?
5. Apply the SW EOS given in the second video to the isochore at 16.1 mol/L. Do you get the same values for ε/k and σ? Explain.

1. Peng-Robinson PVT Properties - Excel (3:30) (msu.edu)

Introduction to PVT calculations using the Peng-Robinson workbook Preos.xlsx. Includes hints on changing the fluid and determining stable roots.

Comprehension Questions:

1. At 180K, what value of pressure gives you the minimum value for Z of methane? Hint: don't call solver.

2. At 30 bar, what value of pressure gives Z=0.95 for methane?

3. Compute the molar volume(s) (cm3/mol) for argon at 100K for each of the following?
(a) 3.000 bars (b) 4.000 bars (c) 3.26903 bars.