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07.02 Corresponding States Click here. 100 1

Principles of Corresponding States (10:02) (
An overview of use of Tc and Pc and acentric factor to create corresponding states correlation. The relation between acentric factor and deviations from spherical fluids is highlighted.

Comprehension Questions:

1. What is the value of the reduced vapor pressure for Krypton at a reduced temperature of 0.7? How does this help us to characterize the vapor pressure curve?

2. Sketch the graph of vapor pressure vs. temperature as presented in this screencast for the compounds: Krypton and Ethanol. Be sure to label your axes completely and accurately. Draw a vertical line to indicate the condition that defines the acentric factor.

13.04 - UNIQUAC Click here. 100 2

Volumes and Areas from Group Contributions (3:04)

Group contributions are used widely in property prediction. The volumes and surface areas have been determined by x-ray data and high-temperature collision data. The UNIQUAC and UNIFAC activity coefficient methods use these quantities to calculation volume fractions and surface area fractions. The assignment of functional groups for a molecule must be done carefully to assure agreement with the groups used by the model developers.

Comprehension Questions:

1. Estimate R and Q for 1,4 dihydroxy benzene.

2. Estimate R and Q for n-propyl alcohol and compare them to the values for IPA.

3. Estimate R and Q for methyl-npropyl ketone.

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

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

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.)

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.

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

Partial pressures and reactor sizing are among the keys to chemical engineering calculations (, 7 min, review from Section 1.6). Partial pressures (, 7 min) also play an essential role in reaction equilibrium calculations. Partial pressure calculations basically involve straightforward mass balances, but specific vocabulary and a need for systematic precision can cause difficulty. The calculations involve six elements that must be carefully computed:

(1) Stoichiometry - the reaction equation must be stoichiometrically balanced such that the number of atoms of each element are the same on both sides of the equation. This balance is achieved by adjusting the stoichiometric coefficients. The change in the number of moles of each component must be in correct stoichiometric proportions relative to the "key component." Inert compounds (see below) are NOT included in the stoichiometric equation. For the example in this presentation, the objective of the reactor is to oxidize carbon monoxide (CO) in a catalytic converter by reacting it with oxygen (O2). So, CO + 0.5 O2 = CO2.
(2) Limiting reactant (aka. "key component") - It is common to feed an excess of one of the components in order to promote complete conversion of the other components. The limiting reactant is the component that is NOT in excess. For this example, O2 is fed in excess so that CO conversion can be promoted. CO becomes the limiting reactant in that case and conversion must be computed relative to CO, NOT O2. If you think about it, expressing the conversion with respect to the excess component would mean that 100% conversion could result in a negative mole number for the limiting reactant. Such an implication is obviously physically impossible (and potentially embarrassing if you appear not to know that).
(3) %Excess - The number of moles of an excess component in the feed is (1+Xs) times the stoichiometric amount relative to the key component, where the stoichiometric amount is the number of moles necessary to perfectly balance the key component, and Xs is the fractional form of the %excess. For this example,  the stoichiometric ratio of CO:O2 would be 1:0.5 and for 50% excess, Xs = 0.50, and the actual ratio would be 1:0.75.
(4) %Conversion - the %conversion is the fraction of the entering amount of the limiting reactant that is transformed into product(s). Note that this might be different from the "extent of reaction," ξ. For example, if 50 moles/h of CO enter the reactor and the conversion is 90%, then 5 moles of CO exit the reactor. If you express the number of moles of CO as 50-ξ, you might conclude that the moles of CO exiting the reactor is 49.1. Take a minute to think about what the words mean before you start to calculate, then make a mental estimate of what the results should be, then get out your calculator. Another common mistake is to apply the % conversion to all the components, wrongly including the excess component. For example, if 45 moles of CO react, then 22.5 moles of O2 react. With 50% excess O2 in the feed, the O2 exiting should be 37.5-22.5=15, NOT 3.75. This is what it means to be careful and systematic. You must compute the conversion of limiting reactant first, then compute the conversion of other components relative to the limiting reactant.
(5) Inerts - These are components that may enter the reactor by coincidence or convenience but do not participate in the reaction. Therefore, their number of moles exiting the reactor is simply equal to their number of moles entering the reactor. A common mistake is to apply the %conversion to all components entering the reactor, including the inerts. In this example, the source of O2 is air, with roughly 4:1 ratio of nitrogen (N2) to O2. The N2 is inert.
(6) Total Pressure - Once the mole numbers and mole fractions have been computed, don't forget to multiply the mole fractions by the total pressure to get the partial pressure. The partial pressure is equal to the mole fraction only in the case that the reactor operates at 1.00 bar.

Comprehension Questions:

1. What is the value of the total pressure (bar) applied in the presentation of this example?
2. What equation is used to compute the mole number of O2? What is the final overall equation used to compute PO2?
3. Suppose 100 moles/h of ammonia (NH3) at 100bars is to be produced from N2 and hydrogen (H2) with 10% excess N2. Methane (CH4) is included with the N2+H2 as a result of the synthesis process with a ratio of 1:10 CH4:H2. (a) Write a stoichiometrically balanced equation (b) Identify the limiting reactant (c) Calculate the number of moles and partial pressures of each component entering the reactor. (d) Calculate the number of moles and partial pressures of each component exiting the reactor assuming 25% conversion.

11.02 - Calculations with Activity Coefficients Click here. 96 5

Dew Temperature (7:57) (

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.

10.01 - Introduction to Phase Diagrams Click here. 96 5

Introduction to Phase Behavior (9:37) (
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?

14.10 Solid-liquid Equilibria Click here. 93.3333 3

SLE using Excel with the M1 model (7min,

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. 

07.06 Solving The Cubic EOS for Z Click here. 93.3333 3

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

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.

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). ( 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.