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Thermodynamics and Statistical Physics

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about 2000 K, the pressure is is 8.0 × 105 Pa, and the volume is 100 cm3 . The piston

has cross sectional area of 80 cm2 . The gas then expand adiabatically as the piston

is pushed downward until its volume incrases by a factor of 10. The gasoline has

the parameter of γ = Cp /Cv = 1.4.

(a) How much work is done by the gas?

(b) Assuming the gas behaves as an ideal gas, what is the final temperature?

Answer:

(a)

Z V2 K1 −γ+1

W = pdV = V2 − V1−γ+1 = 120 J

V1 −γ + 1

.

(b)

T1 V1γ−1 = T2 V2γ−1

Thus T2 = 796 K.

2. (10 point) Let p be the pressure and V be the volume for a real gas of n moles.

If the equation of state is given by pV = φ(T ), where T is the temperature of

the system. The internal energy of the system U is also a function of T only,

i.e. (∂U/∂V )T = 0. Show that the function φ(T ) must be linear function of the

temperature, i.e. φ(T ) = cT , where c is a constant.

Answer:

∂U

Since ∂V = 0, we find

T

! !

∂U ∂U

dU = dT + dV = CV dT.

∂T V

∂V T

SincedU

is an exact differential, we find CV is a function of temperature only, i.e.

∂CV

∂V

= 0. Now, we candider the first law of thermodynamics:

T

T dS = dU + pdV = CV dT + pdV

CV φ(T )

dS = dT + dV

T VT

Since dS is an exact differential, we obtain

! !

∂(φ(T )/V T ) ∂(CV /T )

= =0

∂T V

∂V T

Thus φ(T )/T must be a constant, and we find φ(T ) = cT , where c is a constant.

1

3. (15 point) A room, filled with air (ideal gas) at STP condition (1 atm, 0◦ C), has

a dimension of (10m) × (10m) × (3m). [Properties of the air: ρ = 1.29 kg/m3 ,

CV = 707.4 J/(kg·K), γ = Cp /CV = 1.41].

(a) Find the amount heat ∆Q needed to raise the temperature of the room, with

insulated rigid walls, from 0◦ C to 20◦ C.

(b) Calculate the change of the internal energy of the air in this room.

(c) Calculate the change of entropy of the system.

Answer:

The total mass of the air is m = ρV = 1.29 × (10 × 10 × 3) = 387 kg.

(a) The amount of heat needed is

∆Q = mCV ∆T = 5.47 × 106 J

(c) The change of entropy is

T2 CV T2

Z

∆S = m dT = mCV ln = 1.94 × 104 J/K.

T1 T T1

4. (10 point) An ideal gas in a container with an initial condition of p1 = 1.0 × 105 Pa,

V1 = 1.0 m3 and T1 = 300 K. Calculate the change of the entropy of the system and

its environment in the following processes.

(a) The system is in thermal contact with a reservoir, so that the volume is in-

creased isothermally from 1.0 m3 to 2.0 m3 in a reversible process.

(b) The volume of the gas is free-expanded by the Gay-Lussac-Joule free expansion

process to a volume of 2.0 m3 .

Answer:

Using pV = nRT , we find nR = 333.3 J/K.

(a) When the system is isothermally expanded from V1 to V2 , the change of entropy

is Z V2

P V2

(∆S)system = dV = nR ln = nR ln 2 = 231 J/K.

V1 T V1

The change of the entropy for the environment is (∆S)environment = −Q/T =

−W/T (isothermal). We need to calculate the work done by the system!

V2 V2

Z

W = P dV = nRT ln = nRT ln 2.

V1 V1

Thus (∆S)environment = −231 J/K.

(∆S)universe = (∆S)system + (∆S)environment = 231 + (−231) = 0 J/K.

2

(b) For free expansion, the expansion occurs very fast. Gay-Lussac-Joule’s experi-

ment shows that (∂T /∂V )u = 0, i.e. the process occurs isothermally. Thus we

find

P V2

Z V2

(∆S)system = dV = nR ln = nR ln 2 = 231 J/K.

V1 T V1

Since the expansion is very fast, there is no change of entropy from the envi-

ronment, i.e. (∆S)environment = 0, and we find

5. (10 point) A vessel with insulating walls of negligible heat capacity contains 10 kg

of ice at −20 ◦ C. Now we pour 2 kg of water at +40 ◦ C into the vessel and seal

it. [Specific heat of ice: 2090 J/(kg·K); Specific heat of water: 4180 J/(kg·K); The

latent heat of ice-water is ℓ12 = 3.34 × 105 J/kg.]

(a) How much ice (in kg) will remain in the vessel when the system is in thermal

equilibrium again?

(b) Find the entropy change that takes place inside the insulated vessel.

Answer:

The net heat content of 40◦ C water and −20◦ C ice relative to 0◦ C is

Q = 2(kg)×4180(J/kg·K)×40(K)+10(kg)×2090(J/kg·K)×(−20K) = −8.36×104 J.

The negative sign in the amount of heat shows that some water will become ice.

The amount is mfreeze = |Q|/ℓ12 = 0.25 kg.

(a) The amount of ice is the vessel is 10 + 0.25 = 10.25 kg, and amount of water

is 2 − 0.25 = 1.75 kg.

(b) The change of entropy is

dT T2

Z Z

∆S = dS = CV = CV ln

T T1

273 273

∆S = (2kg)(4180J/(kg · K)) ln( ) + (10kg)(2090J/(kg · K)) ln( )

313 253

ℓ12

−(0.25kg) × = 141 J/K.

273

6. (10√points) Show that the heat conduction coefficient of an ideal gas is proportional

to T , where T is the temperature.

Answer:

3

Let the radius of each gas molecule be r. The cross-section of the the collision is

π(2r)2 . Thus the mean free path ℓ is related to the average volume occupied by

each molecule V /N by

V V 1 kT

π(2r)2 ℓ = , ℓ= = .

N 2

4πr N 4πr 2 p

Consider two adjacent slabs of length ℓ and area A with temperature T1 and T2

respectively. Molecules in each slab can move from the slab #1 to the slab #2 in

one mean free path. The amount of heat exchange is

1 1 1 dT

∆Q = (U1 − U2 ) = − Cv (T2 − T1 ) = − Cv ℓ ,

2 2 2 dx

∆Q Cv ℓ dT

=− A .

∆t 2∆tA dx

By definition, the heat conduction coefficient is

s

Cv ℓ Cv ℓ Cv ℓv̄ k 3kT

kt = = = =f ,

2A∆t 2A(ℓ/v̄) 2V 16πr 2 m

volume V at the temperature T . Let the total energy of the gas be E, i.e.

1 X 2

E= (p + p2iy + p2iz ).

2m i ix

√

We define the amplitude of the momentum as p = 2mE.

(a) Find the available√phase space states, Σ(P ), for the particle to occupy from

p = 0 to P (E) = 2mE.

(b) Find the integral

dΣ(P ) dP −E/kT

Z ∞

Z(T, V ) = e dE.

0 dP dE

(d) Use the Tetrode-Sackur Equation to evaluate U −T S, and compare with ln(Z).

Answer:

4

(a) The volume of 3N dimensional sphere of radius p and the number of available

states are

π 3N/2

Vp (p) = p3N

Γ( 3N

2

+ 1)

1

Σ(p) = V N Vp (p)

N! h3N

√

where p = 2mE, V is the volume in the coordinate space, h is the Planck

constant, and Γ is the gamma-function.

(b) Carrying out the integration, we obtain

dΣ dp

∞

Z

Z(T, V ) = exp −E/kT dE

0 dp dE

1

= V N (2πmkT )3N/2

N! h3N

(c) Using the stirling formula, we find

!3/2

V 2πmkT

ln(Z) = N ln +1 .

N h2

F ≡ U − T S = −kT ln(Z).

8. (15 points) Consider an Einstein solid of N oscillators and q quanta, where the

energy of the system is U = qǫ.

(b) Find the U as a function of the temperature T .

(c) Find the heat capacity as a function of T .

(d) Find the chemical potential. Plot your chemical potential vs Temperature.

Answer:

(N + q)!

Ω(N, q) = ,

N! q!

S = k ln Ω = k[(N + q) ln(N + q) − N ln N − q ln q].

5

(b)

!

1 ∂S k N

= = ln 1 +

T ∂U ǫ q

Nǫ

U = ǫ/kT .

e −1

(c)

eǫ/kT

2

∂U ǫ

C= = Nk .

∂T kT (eǫ/kT − 1)2

(d)

∂S

µ = −T = kT ln(1 − e−ǫ/kT ).

∂N

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