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Winter, 2011
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.
Winter, 2011
(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)
Winter, 2011
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.
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 .
Winter, 2011
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?
Winter, 2010
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?
Winter, 2011
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
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)