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10.03 - Binary VLE using Raoult's Law Click here. 60 4

Raoult's Law Calculation Procedures (11:45) (msu.edu)
Details on how to implement bubble, dew, and flash calculations for Raoult's Law. This screencast shows sample calculations for the bubble pressure and dew pressure of methanol+ethanol.

Comprehension Questions: Assume the ideal solution SCVP model (Eqns. 2.47 and 10.8).

1. Estimate the bubble pressure (bars) of 30% acetone + 70% benzene at 333K.
2. Estimate the dew temperature (K) of 30% acetone + 70% benzene at 1 bar.
3. Estimate the fraction vapor and phase compositions ethylamine+ethanol at 298K, 400mmHg and a feed of 60%amine.

09.10 - Saturation Conditions from an Equation of State Click here. 60 2

Solving for the saturation pressure using PREOS.xls simply involves setting the temperature and guessing pressure until the fugacities in vapor and liquid are equal. (5min, learncheme.com) It is not shown, but it would also be easy to set the pressure and guess temperature until the fugacities were equal in order to solve for saturation temperature. One added suggestion would be to type in the shortcut vapor pressure (SCVP) equation to give an initial estimate of the pressure. Rearranging the SCVP can also give an initial guess for Tsat when given P. This presentation illustrates a sample calculation for toluene to explore when the vapor is the stable, when the liquid is the stable phase, and when the phases are roughly in equilibrium.

Comprehension Questions:

1. Estimate the vapor pressure (MPa) of n-pentane at 450K according to the PREOS. Compare your result to the value from Eq. 2.47 (SCVP) and to the Antoine equation using the coefficients given in Appendix E. What do you think explains the observations that you make?
2. Estimate the saturation temperature (K) of n-pentane at 3.3 MPa according to the PREOS. Compare your result to the value from Eq. 2.47 (SCVP) and to the Antoine equation using the coefficients given in Appendix E. What do you think explains the observations that you make?
3. Estimate the vapor pressure (MPa) of n-pentane at 223K according to the PREOS. Compare your result to the value from Eq. 2.47 (SCVP) and to the Antoine equation using the coefficients given in Appendix E. What do you think explains the observations that you make?
4. Estimate the saturation temperature (K) of n-pentane at 3.3 kPa according to the PREOS. Compare your result to the value from Eq. 2.47 (SCVP) and to the Antoine equation using the coefficients given in Appendix E. What do you think explains the observations that you make?

14.04 LLE Using Activities Click here. 60 2

Txy Phase Diagram Showing LLE and VLE Simultaneously (9min,uakron.edu)

The binary Txy phase diagram of methanol+benzene is visualized with sample calculations of the SSCED model with several values of the nonideality (kij) parameter. The calculations show the liquid-liquid equilibrium (LLE) phase boundary as well as the vapor-liquid equilibrium (VLE) boundary. As the estimated nonideality (kij) increases, the LLE boundary crashes into the VLE. It is so exciting that it makes a thermo nerd wax poetic about the "valley of Gibbs."

Comprehension Questions:

1. The LLE phase boundary moves up as the nonideality increases. Which way does the VLE contribution move? Explain how this relates to the molecules' escaping tendencies.
2. How would this phase diagram change if the pressure was increased to, say, 10 bars?
3. What value of kij is required to make the LLE binodal barely touch the VLE at 1 bar?
4. What value of kij is required to make the LLE binodal barely touch the VLE at 10 bars?

09.10 - Saturation Conditions from an Equation of State Click here. 60 1

We can combine the definition of fugacity in terms of the Gibbs Energy Departure Function with the procedure of visualizing an equation of state to visualize the fugacity as characterized by the PR EOS. (21min, uakron.edu) This amounts to plotting Z vs. density, similar to visualizing the vdW EOS. Then we simply type in the departure function formula. Since the PR EOS describes both vapors and liquids, we can calculate fugacity for both gases and liquids. Taking the reciprocal of the dimensionless density ( V/b=1/(bρ) ) gives a dimensionless volume. When the dimensionless pressure (bP/RT) is plotted vs. the dimensionless volume, the equal area rule indicates the pressure where equilibrium occurs and this can be checked by comparing the ln(f/P) values for the liquid and vapor roots. When the pressure is not exactly saturated, we may still be in the 3-root region. Then you need to check the fugacity to determine which phase is stable.

Concept Questions:

1. What equation can we use to estimate the fugacity of a compressed liquid relative to its saturation value?
2. How accurate is that equation relative to the change in pressure when we are close to saturation?
3. The video shows a graph of ln(f/P) vs. P. Which phase gives the lower value of fugacity when you are to the right of the intersection point? (ie. vapor or liquid?)

03.6 - Energy Balance for Reacting Systems Click here. 60 1

Heat Removal from a Chemical Reactor (uakron, 8min) determines heat removal so that a chemical reactor is isothermal following the pathway of Figure 3.5b using the pathway of Figure 2.6c if a heat of vaporization is involved. The reaction is: N2 + 3H2 = 2NH3 at 350C and 1 bar. The pathway to go from products to the reference condition is to correct for any liquid formation at the conditions of the product stream then cool/heat the products to 25C (the reference temperature), then "unreact" them back to their elements of formation. Summing up the enthalpy changes over these steps gives the overall enthalpy of the reactor outlet stream. The same procedure applied to the reactor inlet gives the overall enthalpy of reactor inlet stream. Then the heat duty of the reactor is simply the difference between the two stream enthalpies.

Comprehension Questions:
1. Use this approach to compute the heat of reaction for 2 CH3OH = CH3OCH3 + H2O at 250C and 1 bar. Compare to your answer when using the pathway of Figure 3.5a. 
2. Methanol is a liquid at 45C and 2bars. Compute the enthalpy of a stream that is 100 mol/h of pure methanol at 45 C and 2 bars according to the method of Figure 3.5b. Hint: this is different from the pathway of Figure 2.6c because it includes the heat of formation.

07.08 Matching The Critical Point Click here. 60 2

Visualizing the vdW EOS (uakron.edu, 16min) Building on solving for density, describes plotting dimensionless isotherms of the vdW EOS for methane at 5 temperatures, two subcritical, two supercritical, and one at the critical condition. From these isotherms in dimensionless form, it is possible to identify the critical point as the location of the inflection point where the temperature first exits the 3-root region. This method can be adapted to any equation of state, whether it is cubic or not. The illustration was adapted from a sample test problem. This screencast also addresses the meaning of the region where the pressure goes negative, with a (possibly disturbing) story about a blood-sucking octopus.

Comprehension Questions:

1. What are the dimensions of the quantity (bP/RT)?
2. Starting with the expression for Z(ρ,T), rewrite the vdW EOS to solve for the quantity (bP/RT) in terms of () and (a/bRT).
3. Consider the following EOS: Z = 1 + 2/(1-2) - (a/bRT) /(1-)2. Estimate the value of bPc/(RTc) for this EOS.
4. Consider the following EOS: Z = 1 + 2/(1-2) - (a/bRT) /(1-)2. Estimate the value of (a/bRTc) for this EOS.
5. Compute the values of a(J-cm3/mol2) and b(cm3/mol) for methane according to this new EOS.

01.5 Real Fluids and Tabulated Properties Click here. 60 2

Steam Tables (LearnChemE.com) (5:59) calculate enthalpy of steam by interpolation

11.12 - Lewis-Randall Rule and Henry's Law Click here. 60 11

Introduction to Henry's Law (10:16) (msu.edu)

Fugacities are calculated relative to standard state values, and the relations developed earlier in the chapter use a pure fluid standard state. What if the pure fluid does not exist as a liquid when pure? One choice is to use Henry's law.

11.13 - Osmotic Pressure Click here. 60 8

Osmotic Pressure (7:23) (Learncheme.com)

A derivation of the relation for osmotic pressure, and an explanation of why the pressures are different on each side of the semi-permeable membrane.

07.06 Solving The Cubic EOS for Z Click here. 60 4

2. Solving the PR EOS for Z . (learncheme.com, 5min) Shows how to copy/paste from "Crit.Props" and "IG Cps" to "Props". Then compute some properties. Note: this video incorrectly uses a simple copy/paste instead of "paste special." Therefore, the color of the values on the "Props" tab changes from blue to black. Blue values should indicate values that you can change and black values should indicate cells that you should not alter. If you are having trouble finding a particular compound in the database, try searching for a piece of the name. e.g. if the compound is "nitrous oxide," search for "nitro."

Comprehension Questions:

1. What is the value for Zc of nitrous oxide? What is its "abbreviated name?"

2. What is the value of Tc for R1234yf?

3. Estimate the entropy of vaporization of toluene at 383.4K according to the Peng-Robinson EOS.

4. Estimate the entropy of vaporization of ethanol at 0.1MPa according to the Peng-Robinson EOS. Compare to the value you infer from Appendix E.

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