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17.06 Determining the Spontaneity of Reactions Click here. 100 1

Which way will a reaction go? (3:40) (msu.edu)

When both reactants and products are present in a reactng mixture, the direction the reaction will proceed is not necessarily indicated by the sign of ΔGo or Ka. Rather, it is determined by ΔG. This screencasts provides guidance for understanding this concept.

Comprehension Questions: (Hint: review Example 17.1 before answering.)

1. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 32%, will the reaction go forwards towards product or back to reactants?
2. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of CO is 52%, will the reaction go forwards towards product or back to reactants?
3. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 42%, will the reaction go forwards towards product or back to reactants?
4. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 42%, will the reaction go forwards towards product or back to reactants?

17.05 - Effect of Pressure, Inerts, Feed Ratios Click here. 100 1

How to push, pull, persuade a reaction (3:32) (msu.edu)

Pressure can be used to influence conversion for reactions where gas phase species are present. Feed ratios, inerts, or simultaneous reactions can also be used.

Comprehension Questions:

1. The principle by which a change in temperature, pressure, or concentration leads to a counteracting change in equilibrium is known as:_____.
2. For the reaction: CO + 2H2 = CH3OH, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
2. For the reaction: CH4 + H2O = CO + 3H2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (FYI: this reaction, known as "steam reforming" is an important step in making chemicals from natural gas.)
3. For the reaction: CO + 2H2 = CH3OH, adding an inert component will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
4. We discuss temperature effects in detail later, but for now you should be able to make predictions based on ____ principle (cf. #1 above). An exothermic reaction gives off heat. Therefore, adding heat to an exothermic reaction (ie. raising the temperature) will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
5. For the reaction: H2O + CO = H2 + CO2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (As a first approximation, you may neglect deviations from ideal gas behavior, but then discuss the effect these deviations would have if you did take them into account. Which component's fugacity would be most affected by these deviations and how do these deviations change with pressure?)
6. For the reaction: coal + H2O = CO + H2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (Hint: carbon in the form of coal is solid and does not exist in the vapor phase. cf. section 17.14. It might be helpful to think of the reverse reaction, known as coking, where the solid carbon precipitates from the gas. This is a very simple example of simultaneous reaction and phase equilibrium.)
7. For the reaction: CO + 2H2 = CH3OH, adding an inert liquid to the reactor through which all products are removed will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (Hint: this is a bit more sophisticated example of simultaneous reaction and phase equilibrium. How will the inert liquid alter the concentrations in the vapor? Remember that the fugacities are proportional to the gaseous partial pressures.)


09.05 - Fugacity and Fugacity Coefficient Click here. 100 1

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.)

07.11 - The molecular basis of equations of state: analytical theories Click here. 100 1

Nature of Molecular Parking Lots - RDFs(20min, uakron.edu) Molecules occupy space and they move around until they find their equilibrium pressure at a given density and temperature. Cars in a parking lot behave in a similar fashion except the parking lot is in 2D vs. 3D. Despite this exception, we can understand a lot about molecular distributions by thinking about how repulsive and attractive forces affect car parking. For example, one important consideration is that you should not expect to see two cars parked in the same space at the same time! That's entirely analogous for molecular parking. Simple ideas like this lead to an intuitive understanding of the number of molecules distributed at each distance around a central molecule. From there, it is straightforward to multiply the energy at a given distance (ie. u(r) ) by the number of molecules at that distance (aka. g(r) ), and integrate to obtain the total energy. A similar integral over intermolecular forces leads to the pressure. And, voila! we have a new conceptual route to developing engineering equations of state.
Comprehension questions:
1. Sketch u(r)/epsilon and g(r) vs. r/sigma for square well spheres at a very low density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.
2. Sketch u(r)/epsilon and g(r) vs. r/sigma for hard spheres at a high density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.
3. Sketch u(r)/epsilon and g(r) vs. r/sigma for square well spheres at a high density. Use a solid line for g(r) and a dashed line for u(r)/epsilon.

07.11 - The molecular basis of equations of state: analytical theories Click here. 100 1

Nature of Molecular Energy - Example Calculation(8min, uakron.edu) Given an estimate for the radial distribution function (RDF) integrate to obtain an estimate of the internal energy. The result provides an alternative to the attractive term of the vdW EOS.

17.07 - Temperature Dependence of Ka Click here. 100 2

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?

17.07 - Temperature Dependence of Ka Click here. 100 2

Example 17.4 and 17.5 solved using Kcalc.xlsx (6:01) (msu.edu)

The full form of the temperature dependence of Ka is implemented in Kcalc.xlsx and Kcalc.m. This screecast covers the use of Kcalc.xlsx for Example 17.4 and Example 17.5 of the textbook.

Comprehension Questions:

1. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔGRº and ΔHRº.
2. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔGRº and ΔHRº.
3. CO and H2 are fed in a 1:1 ratio to a reactor at 600K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔGRº and ΔHRº.
4. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔGTº and ΔHTº. Check your answer for ΔGTº using the value given for Ka in Example 17.1.
5. CO and H2 are fed in a 1:1 ratio to a reactor at 600K and 10 bars with a catalyst that favors only CH3OH as its product. Calculate Ka, ΔGTº and ΔHTº.
6. CH3OH is fed to a reactor at 200ºC and 1 bar with a catalyst that produces CO and H2. Calculate Ka, ΔGTº and ΔHTº for this reaction and compare to the literature values given in Example 17.6 of Section 17.10.
7. CH3OH is fed to a reactor at 300ºC and 1 bar with a catalyst that produces CO and H2. Calculate Ka for this reaction and compare to the value given in Example 17.6 of Section 17.10. Give two reasons why the two estimates are not identical.




03.3 - Introduction to Mixture Properties Click here. 100 1

Props.xlsx has a lot of data, but usually we are only interested in a few components at a time. Adding a few lines at the top and applying the VLookup function makes it easy to tabulate the properties you need. (8min, uakron.edu)

Comprehension questions

1. Download the latest version of Props.xlsx from sourceforge. Add lines to support 8 components of interest and cells to compute Psat given T as input and Tsat given P as input by appropriately arranging Eqn. 2.47. Add a column for computing Hvap at Tsat for each component by Eqn. 2.45.

2. Insert a sheet(tab) called Hrxn in Props.xlsx. Types the names for components in the reaction CO+0.5O2=CO2. Use VLookup to tabulate the Hf values for each component. To the left of the name column, insert cells to represent the stoichiometric coefficients. Then calculate the heat of reaction by using the sumproduct() function applied to the stoichiometric coefficients and Hf values. Check your result with a hand calculation.

3. Download the latest versions of PREOS.xls and Props.xlsx from sourceforge. Update the Props tab appropriately. Then implement the VLookup function on the ThermoProps tab of PREOS so all you need to do is type the name of the compound of interest in order to update the ThermoProps sheet to all properties of interest. We discuss how to use PREOS.xls to solve problems in Unit II.

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.

02.01 Expansion/Contraction Work Click here. 100 2

Vocabulary in Sections 2.1-2.3: Forms of "Work." (uakron.edu, 11 min) Making cookies is hard work. In discussing work, we develop several shorthand terms to refer to specific common situations: expansion-contraction work, shaft work, flow work, stirring work, "lost" work. These terms comprise the headings of sections 2.1-2.3, but it is convenient to discuss them all at once. The important thing to remember is that work is really just force times distance, pure and simple. The shorthand terms are not intended to complicate the discussion, but to expedite the analysis of the energy balance. Developing some familiarity with the terms related to common daily experiences may help you to assimilate this new vocabulary. Sample calculations (13min) illustrate a remarkable difference when one is faced with gas compression vs. liquid pump work. 

Comprehension Questions:
1. How is "expansion-contraction" work related to force times distance?
2. What is the expression for "flow" work? Explain how it relates to force times distance for fluid flowing in a pipe.
3. What expression can we use for calculating "shaft" work, as in a pump or turbine? What is the technique of calculus to which it is related?

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