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10.07 - Nonideal Systems Click here. 100 1

Nonideal Mixtures (4:58) (

Raoult's law is an easy way to calculate VLE, but it is inaccurate for most detailed VLE calculations. This screencast provides an overview of the problems, and introduces the concept of an azeotrope. The VLE K-ratio is shown to be less than one or greater than one dependenting on the overall system concentration relative to the azeotrope composition where K=1. The concept of positive and negative deviations is introduced.

10.06 - Relating VLE to Distillation Click here. 100 1

Distillation is the primary choice for separations in the petrochemical industry. Because the majority of chemical processing involves separations/purifications, that makes distillation the biggest economic driver in all of chemical production. Therefore, it is very important for chemical engineers to understand how distillation works (21min, and how VLE plays the major role. This video is a bit long, but it puts into context how phase diagrams and thermodynamic properties relate to very important practical applications. You may find it helpful to reinforce the conceptual video with some sample calculations.(12min) At the end of the video, you should be able to answer the following:

Consider the acetone+ethanol system. Use SCVP (Eqn 2.47) to answer the following.

  1. Sketch a Txy diagram for acetone+ethanol at 1 bar with accurate Tsat's. Label completely.
  2. Which component pertaining to #1 would have enhanced concentration in the distillate?
  3. Accurately sketch the yx diagram pertaining to #1
  4. Use Raoult's Law to estimate αLH pertaining to #1.
  5. Use your sketch from 3 to estimate Nmin  to go from x1=0.1 to 0.9.
  6. Use the Fenske equation to estimate Nmin  with splits of 0.9 and 0.1.
04.09 Turbine calculations Click here. 100 2

Entropy Balances: Solving for Turbine Efficiency Sample Calculation. (, 10min) Steam turbines are very common in power generation cycles. Knowing how to compute the actual work, reversible work, and compare them is an elementary part of any engineering thermodynamics course.

Comprehension Questions:

1. An adiabatic turbine is supplied with steam at 2.0 MPa and 600°C and it exhausts at 98% quality and 24°C. (a) Compute the work output per kg of steam.(b) Compute the efficiency of the turbine.

2. A Rankine cycle operates on steam exiting the boiler at 7 MPa and 550°C and expanding to 60°C and 98% quality. Compute the efficiency of the turbine.

08.07 - Implementation of Departure Functions Click here. 100 1

Helmholtz Departure - PR EOS (, 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).

10.08 - Concepts for Generalized Phase Equilibria Click here. 100 1

When expressing the derivative of the total Gibbs energy by chain rule, there is one particular partial derivative that relates to each component in the mixture: the "chemical potential." By adapting the derivation from Chapter 9 of the equilibrium constraint for pure fluids, we can show that the equilibrium constraint for mixtures is that the chemical potential of each component in each phase must be equal. That is fine mathematically but it is not very intuitive. By translating the chemical potential into a rigorous definition of fugacity of a component in a mixture, we recognize that an equivalent equilibrium constraint is that the fugacity of each component in each phase must be equal. (8min, Live, This offers the intuitive perspective of, say, molecules from the liquid escaping to the vapor and molecules from the vapor escaping to the liquid; when the "escaping tendencies" are equal, the phases experience no net change and we call that equilibrium. 

05.4 - Refrigeration Click here. 100 2

Refrigeration Cycle Introduction (, 3min) explains each step in an ordinary vapor compression (OVC) refrigeration cycle and the energy balance for the step. You might also enjoy the more classical introduction (USAF, 11min) representing your tax dollars at work. The musical introduction is quite impressive and several common misconceptions are addressed near the end of the video.
Comprehension Questions: Assume zero subcooling and superheating in the condenser and evaporator.
1. An OVC operates with 43 C in the condenser and -33 C in the evaporator. Why is the condenser temperature higher than than the evaporator temperature? Shouldn't it be the other way around? Explain.
2. An OVC operates with 43 C in the condenser and -33 C in the evaporator. The operating fluid is R134a. Estimate the pressures in the condenser and evaporator using the table in Appendix E-12.
3. An OVC operates with 43 C in the condenser and -33 C in the evaporator. The operating fluid is R134a. Estimate the pressures in the condenser and evaporator using the chart in Appendix E-12.
4. An OVC operates with 43 C in the condenser and -33 C in the evaporator. The operating fluid is R134a. Estimate the pressures in the condenser and evaporator using Eqn 2.47.
5. An OVC operates with 43 C in the condenser and -33 C in the evaporator. Assume the compressor of the OVC cycle is adiabatic and reversible. What two variables (P,V,T,U,H,S) determine the state at the outlet of the compressor?

08.07 - Implementation of Departure Functions Click here. 100 1

Derive the internal energy departure function (, 20min) for the following EOS:
P = (RT(1+V1.5)/V1.5)*(1+sqrt(V)) - a/(V^2T^1.3)/(1+sqrt(V)) This sample derivation is more complicated than average, but the usual procedure still works. We begin by rearranging to obtain an expression for Z and finding the Helmholtz departure, then differentiating to get the internal energy.

Comprehension: Given (A-Aig)TV/RT = -2ln(1-ηP) - 16.49ηPβε/[1-βε(1-2ηP)/(1+2ηP)^2 ]

1. Derive the internal energy departure function.

2. Derive the expression for the compressibility factor.

3. Solve the EOS for Zc.

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.

10.08 - Concepts for Generalized Phase Equilibria Click here. 100 1

Concepts for General Phase Equilibria (12:33) (

The calculus used in Chapter 6 needs to be generalized to add composition dependence. Also, we introduce partial molar properties and composition derivatives that are not partial molar properties. We introduce chemical potential These concepts are used to show that the chemical potentials and component fugacities are used as criteria for phase equilibria.

05.2 - The Rankine cycle Click here. 100 1

Rankine Cycle Introduction (, 4min) The Carnot cycle becomes impractical for common large scale application, primarily because H2O is the most convenient working fluid for such a process. When working with H2O, an isentropic turbine could easily take you from a superheated region to a low quality steam condition, essentially forming large rain drops. To understand how this might be undesirable, imagine yourself riding through a heavy rain storm at 60 mph with your head outside the window. Now imagine doing it 24/7/365 for 10 years; that's how long a high-precision, maximally efficient turbine should operate to recover its price of investment. Next you might ask why not use a different working fluid that does not condense, like air or CO2. The main problem is that the heat transfer coefficients of gases like these are about 40 times smaller that those for boiling and condensing H2O. That means that the heat exchangers would need to be roughly 40 times larger. As it is now, the cooling tower of a nuclear power plant is the main thing that you see on the horizon when approaching from far away. If that heat exchanger was 40 times larger... that would be large. And then we would need a similar one for the nuclear core. Power cycles based on heating gases do exist, but they are for relatively small power generators.
     With this background, it may be helpful to review the relation between the Carnot and Rankine cycles. (, 6min) The Carnot cycle is an idealized conceptual process in the sense that it provides the maximum possible fractional conversion of heat into work (aka. thermal efficiency, ηθ).
Comprehension Questions:
1. Why is the Carnot cycle impractical when it comes to running steam through a turbine? How does the Rankine cycle solve this problem?
2. Why is the Carnot cycle impractical when it comes to running steam through a pump? How does the Rankine cycle solve this problem?
3. It is obvious which temperatures are the "high" and "low" temperatures in the Carnot cycle, but not so much in the Rankine cycle. The "boiler" in a Rankine cycle actually consists of "simple boiling" where the saturated liquid is converted to saturated vapor, and superheating where the saturated vapor is raised to the temperature entering the turbine. When comparing the thermal efficiency of a Rankine cycle to the Carnot efficiency, should we substitute the temperature during "simple" boiling, or the temperature entering the turbine into the formula for the Carnot efficiency? Explain.