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08.02 - The Internal Energy Departure Function Click here. 80 4

The Internal Energy Departure Function (11min, Deriving departure functions for a variety of equations of state is simplified by transforming to dimensionless units and using density instead of volume. This also leads to an extra simplification for the internal energy departure function.

Comprehension Questions:

1. What is the value of T(∂P/∂T)V - P for an ideal gas?
2. What is the value of (∂U/∂V)T for an ideal gas and how can you explain this result at the molecular scale?
3. The Redlich-Kwong (RK) EOS is: P=RT/(V-b) -a/(V2RT1.5). Use Eqn. 8.13 to solve for (U-Uig)/RT of the RK EOS.
4. The RK EOS can be written as: Z = 1/(1-) - /(RT1.5). Use Eqn. 8.14 to solve for (U-Uig)/RT of the RK EOS.

10.10 - Mixture Properties for Ideal Solutions Click here. 80 1

10.9 - 10.12 Mixture Properties Overview (6:53) (

This section of the text is thick with lots of equations. It may help to filter out the most important equations and results so that you have the perspective of the overall objectives of this section. There are a lot of equations in this section to show that the component fugacity in an ideal solution is simply the mole fraction multiplied by the pure component fugacity. In a liquid mixture, this is approximated as the mole fraction times the vapor pressure! This screencast goes on to preview the most important results of the next section to help you see the overall story.

07.05 Cubic Equations of State Click here. 80 1

Intro to the vdW EOS. (, 5min) Provides a brief overview of the van der Waals (vdW) 1873 equation of state (EOS), which served as a prototype for EOS development for over 100 years. Note: the vdW EOS is just one conjecture of how equations of state for real fluids may be formulated. In reality, each fluid has its own unique EOS. The vdW model conjectures that the pressure is altered relative to the ideal gas by the presence of attractive forces and repulsive forces.

Comprehension Questions:

1. Of the two parameters a and b, which is related to attractive forces and which is related to attractive forces?
2. How are the parameters a and b typically characterized/computed? ie. To what experimental constants are they related in order to compute them?
3. Is the vdW EOS an example of a 2-parameter EOS or 3-parameter EOS?
4. When writing the term (V-b) we subtract b because the molecules occupy volume and when V=b, all the "free volume" is gone. Can you explain the term (P+a/V2) in a similar manner?
5. In the presented example of CO2 at 0.2L and 269K, how does the pressure compare when computed by the ideal gas law vs. the vdW model? (Give both values.)
6. In the presented example of CO2 at 0.0L and 269K, how does the pressure compare when computed by the ideal gas law vs. the vdW model? (Give both values.)

08.05 - Summary of Density Dependent Formulas Click here. 80 1

Enthalpy Departure Function for the vdW Fluid (5min) ( This short video shows the application of Eqn. 8.24 and the van der Waals equation of state. This is a simple equation of state and the derivation is easy, so it is a good place to start in order to understand the process.

01.2 Molecular Nature of Temperature, Pressure, and Energy Click here. 77.6 75

Molecular Nature of Energy and Temperature ( (3:34)
This introduction shows the connection with temperature and kinetic energy.  When applying Eqn. 1.1, you must be careful to keep your units straight, as illustrated in this sample calculation of the molecular temperature for xenon (Mw=131). (uakron, 5min).

Comprehension Questions:

1. A 1m3 vessel contains 0.5m3 of saturated liquid in equilibrium with 0.5 m3 of saturated vapor. Which molecules are moving slower? (a) the vapor (b) the liquid (c) they are all the same.

2. A glass of ice water is sitting in your freezer, set to 0C and fully equilibrated. Which molecules are moving slower? (a) the gas (b) the liquid (c) the solid (d) they are all the same.

3. You walk into the kitchen in the morning to get some breakfast. The ceiling fan is on. You forgot your slippers. Which one is "hotter?" (a) the floor (b) the ceiling (c) the granite counter top (d) the air in the room (e) they are all the same.

12.01 - The van der Waals Perspective for Mixtures Click here. 76.6667 6

Mixing Rules (7:23) (

How should energy depend on composition? Should it be linear or non-linear? What does the van der Waals approach tell us about composition dependence? This screencasts shows that the mixing rule for 'a' in a random mixture should be quadratic. A linear mixing rule is usually used for the van der Waals size parameter.

01.2 Molecular Nature of Temperature, Pressure, and Energy Click here. 75.7143 14

Molecular Nature of Energy, Temperature, and Pressure By Etomica(, 17min). We can use a free website ( to visualize the ways that molecules interact, resulting in the average properties that we see at the macroscopic level. The oversimplified nature of the ideal gas model becomes really obvious and the improvement of the hard sphere model is easily understood. Including both attractive and repulsive forces, as in the square well potential model, leads to more surprising behavior. The two effects may cancel and make the Z factor (Z=PV/RT) look like an ideal gas even though it is not. Also, the adiabatic transformation between potential energy and kinetic energy leads to spikes in temperature as molecules enter each other's attractive wells. In certain cases, you might see molecules get stuck in each others' wells. This is effectively "bonding." This bonding is limited at very low density because it requires a third interaction to occur during the collision in order to stay bonded. This requirement lies at the fundamental basis of what is known as "unimolecular reaction," a fairly advanced concept that is easily understood by watching the video. Note: if the etomica applet causes problems with your browser, check the instructions in section 7.10 to download all the apps and run locally. We use the apps for homework in Chapter 7, so it's money in the bank.

Comprehension Questions:
1. What is the average temperature (K) illustrated in the screencast? Is it higher or lower than the initial temperature? Explain.
2. What is the average pressure (bar) illustrated in the screencast?
3. Go to the website and perform your own simulation with the piston-cylinder applet starting with 100 molecules and assuming the square well poential model. You can run the simulation in fast mode, but let the molecules collide for 2500 ps. Then report the average value of T,P,U,Z. (Hint: compute Z from its definition, and be careful with units.)

01.2 Molecular Nature of Temperature, Pressure, and Energy Click here. 75.7143 14

Intermolecular Potential Energy ( (7:11)

The intermolecular potential energy is distinct from the gravitational potential energy of the center of mass. Further, understanding of the potential energy relation with intermolecular force is important.

Comprehension Questions:

1. Molecules A and B can be represented by the square-well potential. For molecule A, σ = 0.2 nm and ε = 30e-22 J. For molecule B, σ = 0.35 nm and ε = 20e-22 J.  Sketch the potential models for the two molecules on the same pair of axes clearly indicating σ's and ε's of each species. Start your x-axis at zero and scale your drawing properly.  Make molecule A a solid line and B a dashed line. Which molecule would you expect to have the higher boiling temperature? (Hint: check out Figure 1.2.)

2. The potential, u(r), represents the work of bringing two molecules together from infinite distance to distance r. So, what is the force law between two molecules according to the Lennard-Jones potential model? Hint: W=∫F*dx

3. Sketch the potential and the force between two molecules vs. dimensionless distance, r/σ, according to the Lennard-Jones potential. Considering the value of r/σ when the force is equal to zero, is it greater, equal, or less than unity?

01.2 Molecular Nature of Temperature, Pressure, and Energy Click here. 74.8148 27

Molecular Nature of Internal Energy: Thermal Energy
This introduction to "thermal energy" elaborates on the ideal gas definition of temperature, which derives from the way that PV is related to kinetic energy. This PV relation can be easily understood in terms of an ultrasimplified model of ideal gas pressure. (uakron, 6min). Noting empirically from the ideal gas law that PV=nRT, we are led to the derivation of Eqn. 1.1 (uakron, 5min, same as above). This result suggests counter-intuitive implications about the the ways that solid, liquid, and gas molecular velocities must be related. When applying Eqn. 1.1, you must be careful to keep your units straight, as illustrated in this sample calculation of molecular temperature for Xenon (Mw=131g/mol) (uakron, 5min). On a closely related note, we could perform a sample calculation of molecular pressure for Xenon using Eqn. 1.21.

Comprehension Questions:
1. If two phases are in equilibrium (e.g. a vapor with a solid), then their temperatures are equal and the rate at which molecules leave the solid equals the rate at which molecules enter the solid. Which molecules are moving faster, solid or vapor? For simplicity, assume that the vapor is xenon and the solid is xenon. Hint: think about the exchange of momentum when the vapor molecules collide with the solid.
2. Compute the average (root mean square) velocity (m/s) of molecules at room temperature and pressure and compare to their speeds of sound. You can search the internet to find the speed of sound.
a. Argon
b. Xenon
3. Three xenon atoms are moving with (x,y,z) velocities in m/s of (300,-450,100), (-100,300,-50), (-200,-150,-50). Estimate the temperature (K) of this fluid.
4. Estimate the pressure of the xenon atoms in Q3 above in a vessel that is 4nm3 in size. 

12.03 - Scatchard-Hildebrand Theory Click here. 74.5455 11

Scatchard-Hildebrand Theory (6:53) (

Have you ever heard 'Like dissolves like'? Here we see that numerically. The Scatchard-Hildebrand model builds on the van Laar equation by using pure component information. Scatchard and Hildebrand replaced the energy departure with the experimental energy of vaporization. Because this is related to the 'a' parameter in the van Laar theory, they developed a parameter called the 'solubility parameter', but based it on the energy of vaporization. Interestingly, the model reduces to the one parameter Margules equation when the molar volumes are the same.

Comprehension Questions:

1. Based on the Scatchard-Hildebrand  model, arrange the following mixtures from  most compatible to least compatible.  (a) Pentane+hexane,   (b) decane+decalin,  (c) 1-hexene+dodecanol,   (d) pyridine+methanol,
Most compatible                                                                     Least compatible

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