Chemistry 60 - Problem Set 2 Due before lecture - Tuesday, September 27th Assigned problems are in boldface

1. Q contains information regarding all macroscopic thermodynamic properties In class, we derived the relation between the partition function and the average energy of the system: ln Q E = kB T 2 (1.1) T 1 Its possible to express this another equivalent way. Remembering that kB T = , we can express the partition function as: (1.2) 1.1. demonstrate that:
ln Q

Q=
i

eEi
i

= E =

Ei eEi Q

ln ln 1.2. using the chain rule of dierentiation, demonstrate that: Q = kB T 2 TQ Its also possible to derive other thermodynamic quantities from the partition function. In fact, you can determine ALL macroscopic thermodynamic properties from the partition function (expect more awesome questions regarding this in future problem sets).

2. The ideal 2D gas equation of state An equation of state is an equation in which state variables are related to one another. The state function is a very forgetful function. It has no memory of how it got to be what it was, only that it is what it is. In less confusing terms, the state is not path-specic1. In class, we derived the relation between P and Q. We found that: ln Q (2.1) P = kb T V In a horrifying analogy to bring home the number of particles of an ideal gas at STP that exist in a 1 mL volume, J. H. de Boer posed the following hypothetical situation2. : . . . imagine a magnied picture, using an enormous magnifying factor, for which we choose 32 million. When we magnify all our linear dimensions 32 million times, then the length of 1 cm becomes 320 kilometers which is roughly 200 miles. If we then imagine a cube with a height of 200 miles in the air, then we had the equivalent of 1 cm3 . In the same magnied scale an oxygen molecule has now attained the size of a bee. If we now imagine an articial gas of bees then we have
1McQuarrie and Simon; Your Textbook. pp. 189 2de Boer, J.H.; The Number n. The Dynamical Character of Adsorption, edition 2; Oxford University Press:

London, 1968; pp 13
1

Figure 1. An ideal 2D bee-gas pressure sensor to enclose 20 trillion bees in this cube in order to get a picture of 1 cm3 of gas at room temperature and atmospheric pressure.. . . Recall the previous problem set, where we found the average energy of a 2D ideal gas (problem 3, for those of you with short memories). Now imagine our gas of superbees swarming over our 200 mile square surface. Now imagine yourself on this surface; the bees y back and forth performing a random-walk sampling of the surface (except that there are no potential energy interaction terms, so no sampling is actually occurring in our ideal model) occasionally hitting you, transferring kinetic energy to your body.

Calm down! Remember that this is an ideal gas, so the bees wont sting you (to do so would require inelastic transfer of energy to the pressure sensor - i.e., leaving venom in your body). Okay, now zoom out. These bees are again ideal 2D gas atoms in a 1cm2 area. (2.2) Q(N, A, T ) = 1 N! 2mkB T h2
N

AN

2.1. What is the 2D pressure, F , in terms of the canonical partition function, Q?3

3The 2D pressure, F, is a hard concept to understand intuitively, but it isnt an abstraction; in 1890, Ms. Agnes Pockels (not to be confused with her brother Friedrich), who was denied university education on account of her gender, invented a technique to measure surface tension while cleaning her households dishes. She sent her ndings to Lord Rayleigh, who forwarded the letter to the journal Nature. After her initial publication in Nature, she proceeded to publish many more articles on the subject. She was later awarded an honorary doctorate for her contribution to science. I often wonder how more advanced science would be today if gender discrimination hadnt existed in the universities! For more information, see: Pockels, A. Surface Tension. Nature 1891, 41, 437-439.

2.2. Derive the 2D corollary to the Boyle-Gay Lussac law (the ideal gas equation) In a 3D ideal gas, the molar volume at 273K and 1 atmosphere is 22.4 liters. 2.3. If we choose 273K and the (seemingly) arbitrary pressure of 0.338 dyne/cm (1 dyne = 105 newtons) what is the molar area of the 2D ideal gas? Wow, this is an absurdly large area! The pressure chosen gives us the same intermolecular spacing as in a 3D ideal gas. This example illustrates some of the problems faced by chemists and physicists in surface science: the detection and characterization of about 1 millionth of a mole of surface species on a 1 cm2 substrate. 3. The Zeroth Law of Thermodynamics In thermodynamics, energy scaling is important. The interface between two systems in thermal contact is called the adhesive layer. The total energy of two systems in contact is: (3.1) Etot = Ea + Eb + Eab

where Eab is an energy coupling term arising from the thermal contact of the two systems.

3.1. What happens to the Zeroth Law of Thermodynamics as the size of the systems under investigation become very, very small? While looking for the stairwell leading to the back cupola in the Mallinckrodt attic, you nd a wooden shipping container holding 3 boxes of thermodynamically-closed systems of ideal gases. The rst box is labeled 13 Liters volume, Pressure: 2 atmospheres in scotch tape. You always carry a spectrometer in your utility belt and its just a bit of mental math for you to gure out that the temperature of the box was 273K by relating the doppler eect to the second moment of the Maxwell-Boltzmann velocity distribution. The second box posed you more of a problem. You wistfully and regretfully think back to the year you graduated high school; while traipsing through the desert during your gap year, you found an old, rusty oil lamp. When you picked it up, a genie appeared and granted you the ability to immediately know the number of molecules in any closed system of ideal gases; unfortunately, the genie also stole your fancy elephant-tusk ruler. Youll have to gure out some way to nd the volume of that box. Thankfully, Box C is labeled with a piece of scotch tape reading 13 litres and a pressure gauge sticking out the side reads 2atm. You guess that the 13 litres refers to the volume of the system, but you dont know for sure, as you dont speak British English. Because you also suer from a compulsion disorder that dictates you completely understand the words on every piece of scotch tape you encounter, you devise an experiment to gure out what the devil 13 litres actually means.:

Box A B C

P 2 atm 1.5 atm 2 atm

V N 13L 1mol dont know - genie stole my ruler 1 mol 13 litres? 0.25 mol

T 273K 273K 1092K

3.2. Is Box A in thermal equilibrium with Box B? 3.3. If 13 litres meant 13 liters, would Box B be in thermal equilibrium with Box C? 3.4. If the answer to the above question was yes, assume that 13 litres is equal to 13 liters. Is Box A in thermal equilibrium with Box C? Content with your measurement, but perplexed as to why you were forced to actually carry it out, you continue on your journey to nd the cupola. After what must have been weeks of wandering through a dusty maze of abandoned oce furniture, chemicals, and analytical instruments, you nally nd it. Youre greeted at the base of the stairwell by two Securitas guards. They inform you that they are charged with enforcing the law The Zeroth Law. How, they ask, were you able to determine that a box with an apparent temperature 4 times that of the other boxes was or was not in thermal equilibrium with the other boxes? Strangely, your words materialize in the air in front of you as equations while you stammer on about joint probability distributions. 3.5. show that PA PC PA+C for a particle in a box at thermal equilibrium. 3.6. When Eab can be neglected, weve shown that Pa Pb Pa+b . What does the relationship look like if, for a particle in the box, Eab is 10% of the Ea = Eb energy?

Happy with your answer, the guards grant you permission to climb the stairs to the top of the cupola, on the condition that you do so in a thermodynamically reversible manner. Sadly, you realize that you wont know how to do this until Professor Gordon gives lecture 6 (nor do you realize that this would take an innite amount of time). You turn around dejectedly with tears in your eyes and head to Berryline to console yourself.

4. Energy levels and scaling Because the average energy is related to the logarithm of the partition function (which is a product of energy modes), the form of the energy expression itself is a sum of dierent modes. If the modes are not coupled, we call them separable.

In the Rigid Rotor-Harmonic Oscillator partition function from problem set 1, we nd four energetic modes: Translational - Etrans = 1 mv 2 Qtrans = 2 From the particle-in-a-box approximation Rotational - Erot = l(l+1) , l = 0, 1, 2, .. 2 2r0 From the rigid rotor approximation
2

2M kB T h2

Qrot =

T r ot

1 Vibrational - Evib = n + 2 , n = 0, 1, 2, .. From the harmonic oscillator approximation

Qvib =

evib /2T 1evib /T

Electronic - Eelec = De Qelec = gel eDe /kB T gel is the degeneracy and we assume that the electronic energy is in the ground state - no higher states are populated

Professor Gordon talked about the relative energies of these states in lecture. In general, one can make the following assumptions about the relative energy spacings of each mode:
1 Vibrational = 20 Electronic energy spacing 1 Rotational = 600 Vibrational energy spacing 1 Translational = 107 Rotational energy spacing

4.1. Please give an example of an analytical technique that can be used to characterize each energy mode