01.2 Molecular Nature of Temperature, Pressure, and Energy

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Molecular Nature of Energy and Temperature (msu.edu) (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.

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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. 

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Molecular Nature of Internal Energy: Configurational Energy. (uakron.edu, 19min) Making the connection between "u" and "U" requires the concept configuring the molecules such that their potentials overlap. Then it is a simple matter (conceptually) to count the number of overlaps that occur and multiply by the energy of the overlap to get the "configurational energy." Adding the configurational energy to the translational (and vibrational) energy (Uig, discussed above), gives the total "U."

Comprehension Questions:

For 1-4, assume 100 molecules are held in a cylinder with solid walls. A piston in the cylinder can move to adjust the density.
1. Suppose the range of the potential (λ) was increased. Would the configurational energy increase, decrease, or stay the same?
2. Suppose the density was decreased. Would the configurational energy increase, decrease, or stay the same?
3. Suppose the temperature was increased at constant density. Would the configurational energy increase, decrease, or stay the same?
4. Suppose the temperature was increased at constant density. Would the configurational energy characterized by (U-Uig)/RT  increase, decrease, or stay the same?
5. 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.)
6. 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?

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Molecular Nature of Energy, Temperature, and Pressure By Etomica(uakron.edu, 17min). We can use a free website (Etomica.org) 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.

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 etomica.org 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.)

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Intermolecular Potential Energy (msu.edu) (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?

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