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2012

1. Compressibility of a system is dened to be the ratio of the fractional change of volume of a system to the applied pressure which causes that change. It is dened as Y = 1 V V P (1)

Y,N

where Y is the quantity held xed during the application of the pressure and N is the number of particles. For example, Y can be temperature, in which case we obtain the isothermal compressibility or if it is entropy, this means isoentropic or adiabatic compressibility. The coecient of thermal expansion, P is dened to be the fractional change of volume per unit change of temperature, i. e., P = (a) Show that, for an ideal gas T = 1 ; P P = 1 T (3) 1 V V T (2)

P,N

2 = T V P +

P T

(4)

P

(c) Use the above expression and the ideal gas equation of state, show that CP =0 (5) P T,N 2. Using the denition of specic heat capacities: CV = U T ; CP =

V,N

H T

(6)

P,N

(b) CP CV =

2 T V P T

2 T V P CP

(7)

3. As was discussed in the class, entropy is maximum for a system in thermal equilibrium. Entropy and internal energy satisfy the following conditions: d2 S 0 ; d2 U 0 (8)

These are called stability conditions for a system to be in equilibrium. The above condition is called concavity (convexity) property of entropy (internal energy). The above condition on internal energy leads to T S (dS)2 + 2

V

T V

dS dV

S

P V

(dV )2 0

S

(9)

Use this condition to show that (a) CV 0 (b) S 0, T 0 (c) CP CV 4. The van der Waals equation of state is given by P+ a (v b) = kB T v2 (10)

where v = V /N . Show that this equation violates the stability condition T 0 for some values of (P, V ). 5. Gibbs-Dunhem relation Using Euler relation U = T S P V + N and the rst-law of thermodynamics dU = T dS P dV + dN (a) obtain the following Gibbs-Dunhem relations S dT V dP + N d = 0 1 P Ud +V d Nd T T T 2 (13) =0 (14) (12) (11)

(b) Using the equations of state of the ideal gas and relation (14) P V = N kB T show that the entropy of ideal gas is S = N kB ln U 3/2 V N 5/2 + constant (16) 3 U = N kB T 2 (15)

6. A Carnot engine uses a paramagnetic substance as its working substance. The equation of state is M = nDH/T , where M is the magnetization, H is the magnetic eld, n is the number of moles, D is a constant determined by the type of the substance, and T is the temperature. (a) Show that the internal energy U if interpreted as a function of temperature T and magnetization M can only depend on the temperature and not on the magnetization. (b) Let us assume for the rest of the problem that the internal energy is simply U = C T with some constant C. Sketch a typical Carnot cycle in the M H plane (you may ignore the vector character of the quantities and concentrate on their absolute values only.) (c) Compute the total heat absorbed and the total work done by the Carnot engine. (d) d) Compute the eciency of the Carnot engine. Hint: Use the Maxwell relation S X =

T,Nj

Y T

X,Nj

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