Physics 212A Problem Set #1

Roya Zandi Due: Friday 14, 2011

1. Given that the eciency, R , of a reversible heat engine that works between two reservoirs at temperatures Th and Tc (Th > Tc ) can be written in the form b(Tc ) R = 1 b(Th ) do the following a) First, show that the eciency cannot be greater than one. b) Then, show that the function b(T ) must be either always positive or always negative. c) Finally, show that if b(T ) is chosen so that it is always positive, then b(T ) is a monotonically increasing function of T . 2. Suppose that a system with constant heat capacity C is taken from an initial temperature TA to a higher temperature TB by placing it in contact with n thermal reservoirs at n equally-spaced temperatures between TA and TB . That is, the temperature of the rst reservoir is equal to TA , the temperature of the second reservoir is TA + (TB TA )/(n 1), the temperature of the third reservoir is equal to TA + 2(TB TA )/(n 1), and so on. Thermal reservoirs have innite heat capacity. Now, suppose you return the system to its initial temperature by placing it in contact with the thermal reservoirs again, going in reverse. What is the net eect of this process? Show that as n , the process becomes one in which everything is back to its initial state. 3. Three systems have identical heat capacities, C. They are initially at temperatures T , 2T and 3T . With the use of innitesimal, reversible cycles they are brought to a common temperature, Tf .

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a) What is Tf ? b) How much work has been extracted in the process? The heat capacities are all temperature independent, and the systems perform no work during the process above. In addition, there is no heat exchange between the systems and any other entity.

B C F E D T1 V T2

4. Two isotherms of one mole of a substance that can undergo a gas-liquid phase transition are shown in the gure above, which is a P -V diagram. The absolute temperatures are T1 and T2 , respectively. The substance is made to go through one cycle of a cyclic reversible transformation, ABCDEF, as indicated in the gure. You are given the following information. (a) ABC and DEF are isothermal transformations. (b) FA and CD are adiabatic transformations. (c) In the gas phase (BCDE ) the substance is an ideal gas. at A the substance is a pure liquid. (d) The latent heat, L along AB is given by L = 200 cal/mole. Furthermore: T2 T1 VA VB VC = = = = = 300K 150K 0.5 liters 1 liter 2.71828 liters

Calculate the amount of work done by the substance over the course of this cycle. 5. Chapter 1, Problem 10 in Kardar.

Physics 212A Problem Set #2

Roya Zandi Due: Jan. 21, 2011
1. Consider a system in equilibrium with a thermal reservoir that keeps it at a temperature T . The system is also in mechanical contact with a pressure reservoir that maintains the pressure of the system at a constant value, P . Show that the maximum amount of work that can be extracted from this in taking it from one equilibrium state in contact with the two reservoirs to another equilibrium state, also in contact with the two reservoirs, is equal to the decrease in the Gibbs free energy of this system. 2. Find the Helmholtz free energy of the van der Waals liquid-vapor system, given the equation of state P +a N V
2

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(V N b) = N kB T

and the information that the heat capacity at constant volume of this system is equal to 3N kB /2 3. Find the heat capacity at constant pressure of the van der Waals liquidvapor system. 4. Given that the quantity CP is the heat capacity at constant pressure: (a) Derive the equation CP P = T
T

2V T 2

(b) Prove that CP of an ideal gas is a function of T only. (c) In the case of a gas obeying the equation of state P V = RT + BP N

where B is a function of T only, show that CP d2 B (0) = T P 2 + cP N dT where cP is the limit of the right hand side at very low temperatures.
(0)

Physics 212A Problem Set #3

Roya Zandi Due: Jan. 28, 2010
1 1. Derive a relationship between the isothermal compressibility, T = V (V /P )T , 1 and the adiabatic compressibility, S = V (V /P )S that allows you to demonstrate the inequality T > S .

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2. The equation of state of a magnetic system is M = N D tanh (H/kB T ) where D and are system-dependent constants. The heat capacity at zero magnetic eld of this system is given by CH |H=0 = N T n where is a constant, and the exponent n is greater than two. Does this system obey the third law of thermodynamics? That is, is its entropy at T = 0 unique? 3. Rewrite the following derivatives in terms of the second derivatives of the Gibbs free energy: cp , , and T . v |P s s |v F s |H v 4. Problem 8, chapter 1 in Kardar. 5. Problem 9, chapter 1 in Kardar.

Physics 212A Problem Set #4

R. Zandi Due: February 9, 2011
1. Chapter 2, Problem 8 in Kardar 2. Consider the container of gas shown in the gure below. Originally the

Winter, 2011

Moveable piston
Figure 1: The container of gas divided in two by a freely moveable partition. All walls are thermally insulating. Initially, as shown, the volume on each side of the piston is the same.

volume on each side of the movable piston is the same, V0 . The gases on each side are also at a common pressure, P0 and a common temperature, T0 . Clearly, in mechanical equilibrium the pressures must be the same, but as all walls are thermally insulating, as is the piston, there is no a priori reason for the temperatures to be the same. Nevertheless, they are, at the outset. The gas in both sides is a monatomic ideal gas. The gas in the left hand side of the container is now provided with heat, say by a heating coil inside the left-hand side of the container. The heat is transferred to the gas slowly until the pressure in the gas on each side is equal to 27P0 /8. 1

(a) What is the nal right-hand volume? (b) What is the nal right-hand temperature? (c) What is the nal left-hand temperature? (d) How much heat has been supplied to the gas on the left? (e) How much work has been done to the gas on the right? (f) What is the entropy change in the gas on the left? (g) What is the entropy change in the gas on the right? 3. Consider the case of a box with total volume V divided into two unequal parts by an imaginary partition. Let the volume of the rst part be V1 , where V1 /V = p = 1/2. The volume of the second part is, then, V2 , where V2 /V = 1 p. Assume that the total number of molecules in an ideal gas contained in this box is N , where N 1. (a) What is the probability that N1 of the molecules are in the rst part of the box and N2 = N N1 are in the second part of the box? (b) For what value of N1 is this probability a maximum? (c) Call the answer to the above question Nmax . Making use of Stirlings formula, nd an expression for the probability that Nmax + molecules are in the rst part of the box and N1 Nmax molecules are in the second part of the box, under the assumption that << N . 4. There is another way to do the above problem. You can show, given your answer to part (a) of problem 4 that the function f (x) = (px + 1 p)N (1)

generates the probabilities that there are N1 molecules in the rst portion of the box and N2 = N N1 molecules in the second portion. If we call the probability of such a distribution PN1 , then
N

f (x) =
N1 =0

PN1 xN1

(2)

(a) Use the two equations above to show that the probabilities add up to 1: N1 =0 PN1 = 1. N (b) Use those two equations to show that the expectation value of the number of molecules in the rst portion of the box is equal to pN : N1 = N1 =0 N1 PN1 = pN . N (c) Use those two equations to obtain a simple, closed form expression for (N1 N1 )2 .

Physics 212A Problem Set #5

Roya Zandi Due: February 18, 2011
1. Problem 7, chapter 4 in Kardar. 2. Consider a system that can exchange energy and volume with a large reservoir. a) Show that the entropy of this combined system (system & reservoir) is maximized when the temperature of the system is equal to the temperature of the reservoir and the pressure of the system is equal to the pressure of the reservoir. b) Assume that the reservoir is much larger than the system. Expand to second order in the energy and volume of the system. Show that two inequalities must be satised in order that the entropy of the combined system is a maximum at the extremum point. c) Show that when you sum over all ways in which the system shares energy and volume with the reservoir and then take the log, you generate the Gibbs free energy of the system. 3. Consider, again a system that shares energy and volume with a reservoir. Calculate the relevant partition function in the case that the system is a monatomic ideal gas. From this, obtain the Gibbs free energy of the monatomic ideal gas. 4. Consider a set of N noninteracting molecules in a container that consists of two portions. One portion of the container has a volume V1 and the other has a volume V2 . The potential energy of a molecule in the rst portion of the container is equal to 1 , and the potential energy of a molecule in the second portion of the container is equal to 2 . a) Calculate the partition function of this system.

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b) Use this result to nd the pressure in each portion of the container at a temperature T . Are the two values of the pressure that you obtain the same?

Physics 212A Problem Set #6

Roya Zandi Due: March 2, 2011
1. Find the contribution of the diagram shown below to the virial expansion for the grand partition function of an interacting classical gas. See Fig. 1.
k j

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Figure 1: A second-order contribution to the virial expansion of the interacting gas.

Now, nd the correction to the equation of state for the pressure. How does the correction depend on the density of the gas? To nd the correction, stay at the lowest possible order in the virial expansion. 2. Here, I want you to try to work out another approximation for the grand potential of the interacting gas. You will make use of the linked cluster expansion, and you will calculate the diagrammatic sum shown in Fig. 2 for the grand potential. The sum that you will end up doing is an innite one, but it will also be a sum that is possible to perform. Write down your result for the grand potential. 3. Consider the case of a system that shares both volume and energy with a bath. Find the mean square deviation of the volume occupied by the system about the optimal volume. Show that this is simply related to the appropriately dened compressibility. Which compressibility is it, and what 1

+ + ...
Figure 2: The diagrammatic sum for the contributions of interactions to the grand potential of the interacting gas.

is the relationship?

Physics 212A Problem Set #7

R. Zandi Due: March 11, 2011
1. The two equations of state of the monatomic ideal gas can be written in the form PV 2 U 3 3 U = N kB T 2 = (1) (2)

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The above equations of state have also been derived for the classical ideal gas. I would like you to show that the equation of state (1) holds for the quantum mechanical monatomic ideal gas, whether its statistics are Fermi-Dirac or Bose-Einstein. 2. Problem 11 Chapter 7 in Kardar 3. Problem 16 Chapter 7 in Kardar

Physics 212A Midterm Exam

Roya Zandi Winter, 2011

Solutions
1. Given the ideal gas equations of state P V = N kB T U = N BT 3 where B is a positive constant, a) What is the Helmholtz free energy of this system, up to terms independent of V and T ? b) What is the relationship between temperature and volume in an adiabatic expansion or compression of this ideal gas? c) What is the heat capacity at constant pressure of this gas? The Helmholtz free energy of this system is obtained by integrating up the two equations above. We end up with the result F = N kB T ln V T3 NB + DN T N 2 (1)

Ive inserted the N in the log to keep the free energy properly extensive. If you forgot the factor, you will not be docked any points. Here, the constant D cannot be obtained on the basis of the information given. I got the second term on the right hand side of Eq. (1) by making use of the equality U = T 2 T F T (2)

To nd the relationship between the volume and the temperature in an adiabatic compression or expansion of this gas, take the derivative of the

Helmholtz free energy with respect to temperature, which is minus the entropy, and demand that it be a constant. This translates into the relation kB ln V 3 + BT 2 = a constant N 2 (3)

As the volume increases, the temperature decreases. Finally, the heat capacity at constant pressure can be obtained from the second derivative of the Gibbs free energy, or by other means. Performing a Legendre transformation on the Helmholtz free energy, we nd G(T, P, N ) = N kB T ln Making use of the relationship CP = T we nd CP = 3N BT 2 + N kB (6) 2 G(T, P, N ) T 2 (5)
P,N

kB T P

NB

T3 + DN T + N kB T 2

(4)