P340: Thermodynamics and Statistical Physics, Exam#2

Any answer without showing your work will be counted as zero

1. (15 points) The equation of state for the Van der Waals gas (n = 1 mole) is
a
 
p + 2 (V − b) = RT.
V
(a) Find (∂CV /∂V )T
(b) Find Cp − CV as a function of T and V .
(c) Assuming that CV is independent of T , express the entropy as a function of CV ,
T and V .
2. (15 points) A room is to be kept at an indoor temperature of TH = 294 K. The
outdoor temperature is TL . Heat, that leak through the windows and doors at a rate
of |Q̇leak | = a|∆T |, must be replenished by a room heater at the same rate.

(a) We assume that the electric radiator convert electric power Ẇel into heat with
100% efficiency. Find Ẇel as a function of a, TH , and TL .
(b) Now we consider the case of heating the room with an ideal electric heat pump
that uses Ẇsup of electric power to extract heat at a rate of Q̇L at the outdoor
temperature TL and convert it into heat at a rate of |Q̇H | = |Q̇L | + Ẇhp at the
indoor temperature. In general the heat derived from heat pump is given by
Ẇhp = (1 − b)Ẇsup , where the coefficient b represents the mechanical power in-
efficiency of the heat pump. Express power Ẇsup as a function of a, b, TH , and
TL .
(c) Determine the outdoor temperature range where the heat pump is more econom-
ical than the electric radiator for fixed TH = 294 K, and b = 0.75 (75% loss).

3. (20 points) The equation of state and the internal energy (Stefan’s law) for the black
body radiation are given by p = 13 aT 4 , U(T, V ) = aT 4 V, where a = 8π 5 k 4 /(15h3 c3 ) =
7.55 × 10−16 Jm−3 K−4 is a constant, T is the temperature, V is the volume, and p is
the pressure.

(a) Show that the equation of state for an adiabatic process is pV 4/3 = K, where K
is a constant.
(b) Describe the 4-steps (isothermal, adiabatic, isothermal, and adiabatic) Carnot
engine for the black-body radiation in the (p − V ) plane (use T2 = 104 K, T1 =
5 × 103 K), and calculate the efficiency of the black-body Carnot engine.
(c) Find Cv and κS .
(d) Determine the entropy and other thermodynamics potentials, i.e. S(T, V ), U(S, V ),
H(S, p), F (T, V ), and G(T, p).

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4. (10 points) A Diesel cycle for an ideal gas with γ = Cp /Cv operating between V1 , V2
and V3 , where V1 /V2 and V3 /V2 are respectively called the compression ratio and the
cut-off ratio. Find the efficiency of the engine in terms of γ, compression ratio, and
cut-off ratio.
5. (10 points) An ideal mixing corresponds to mixing of molecules having the same size,
same interactions. It is applicable to mixings of ideal gases, liquids, etc. Consider NA
blue and NB green marbles of the same size and weight. They are mixed in a box.
What is the entropy of mixing? Please expressed it in terms of x = NA /(NA + NB ).
6. (10 points) Using the Table of thermodynamics parameters at temperature T0 = 298
K and p0 = 1 bar below. Find the Gibbs free energy per mole (or chemical potential)
for water and steam as a function of temperature T . Evaluate the chemical potentials
at T = 350 K and T = 400 K, at a constant pressure p0 = 1 bar. Here, we can assume
constant Cp for both steam and liquid. See Table 1.
7. (10 points) In a hydrogen fuel cell, the steps of the chemical reactions are

at − electrode : H2 + 2OH − → 2H2 O + 2e− ,

at + electrode : 12 O2 + H2 O + 2e− → 2OH − .

Calculate the voltage of the fuel cell between these two electrodes. See Table 1.
8. (10 points) A biological cell is a water solution of sugar, amino acids, and other
molecules. Typically, it contains 200 water molecules for each molecule of something
else. Sea water has a salinity of 3.5%, i.e. if you boil away a kilogram of seawater you
will find 35 g of NaCl left in the pot. Each mole of NaCl is 58.44 g. If you drop a
biological cell into sea water, what will be the osmotic pressure when the equilibrium
is reached at T = 300 K? We assume that the cell wall is semipermeable that only
water molecules can pass through the cell wall.

Table 1: Thermodynamic Properties of some substances at T0 = 298K and p0 = 1 bar

Substance ∆G (kJ) S (J/K) Cp (J/K)

H2 O (l) −237.13 69.91 75.29
H2 O (g) −228.57 188.83 33.58
H2 (g) 0 130.68 28.82
O2 (g) 0 205.14 29.38

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 P340: Thermodynamics and Statistical Physics, Exam#2, Solution

1. The equation of state for the Van der Waals gas (n = 1 mole) is
a
 
p+ (V − b) = RT.
V2
(a) Show that CV is independent of V , i.e. (∂CV /∂V )T = 0.
(b) Find Cp − CV as a function of p and V .
(c) Assuming that CV is independent of T , show that the entropy of the Van der
Waals gas is
S = CV ln T + R ln(V − b) + constant.

Answer:

! !
RT a ∂u ∂p a
p= − 2, =T −p=
v−b v ∂v T
∂T v
v2

Thus
! !
∂u ∂u a
du = dT + dv = Cv dT + dv
∂T v
∂v T
v2

(a) Since du is an exact differential, we find

∂(a/v 2 )
! !
∂Cv
= = 0,
∂V T
∂T v

i.e. Cv is a function of T only.

(b)
!
∂S
Cp = T ,
∂T p
 2
!2 !2 ! ∂p
T vβ 2 β ∂p ∂v ∂T
Cp − Cv = =T vκ = −T = −T  ∂p  V ,
κ κ ∂T V
∂p T ∂v T
" #" #−1
RT RT a
Cp − Cv = R −2 3 .
(v − b)2 (v − b) 2 v

In the limit that a → 0 and b → 0, we find Cp − Cv → R.

(c) To evaluate entropy, we begin with
" ! ! #
1 1 ∂U ∂U
dS = (dU + pdV ) = dT + dV + pdV .
T T ∂T V
∂V T

1
 We know (∂U/∂T )V = CV . Now we evaluate
! !
∂U ∂p RT a
=T −p = − p = 2.
∂V T
∂T V
V −b V

Substituting the result in the entropy equation, we find

CV R
dS = dT + dV.
T V −b
If CV is independent of T , we can integrate the equation to obtain

S = CV ln T + R ln(V − b) + S0 ,

where S0 is an integration constant.

2. A room is to be kept at an indoor temperature of TH = 294 K. The outdoor temperature

is TL . Heat, that leak through the windows and doors at a rate of |Q̇leak | = a|∆T |,
must be replenished by a room heater at the same rate.

(a) We assume that the electric radiator convert electric power Ẇel into heat with
100% efficiency. Find Ẇel as a function of a, TH , and TL .
(b) Now we consider the case of heating the room with an ideal electric heat pump
that uses Ẇsup of electric power to extract heat at a rate of Q̇L at the outdoor
temperature TL and convert it into heat at a rate of |Q̇H | = |Q̇L | + Ẇhp at the
indoor temperature. In general the heat derived from heat pump is given by
Ẇhp = (1 − b)Ẇsup , where the coefficient b represents the mechanical power in-
efficiency of the heat pump. Express power Ẇsup as a function of a, b, TH , and
TL .
(c) Determine the outdoor temperature range where the heat pump is more econom-
ical than the electric radiator for fixed TH = 294 K, and b = 0.75 (75% loss).

Answer:

(a) Ẇel = a∆T = a(TH − TL ).

(b) To supply constant temperature, we need Q̇H = a∆T = a(TH − TL . Since Q̇H =
Q̇L + Ẇhp = (cop + 1)Ẇhp = [TH /(TH − TL )]Ẇhp , we find

1 TH − TL (TH − TL )2
Ẇsup = Ẇhp = Q̇H = a .
1−b (1 − b)TH (1 − b)TH

(c) Setting Ẇsup ≤ Ẇel , we find TTHL ≥ b This means that TL ≥ bTH = 221 K or
above −52◦ C, the heat pump can provide more heat for heating the house than
an electric space heater.

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3. The equation of state and the internal energy (Stefan’s law) for the black body radiation
are given by p = 13 aT 4 , U(T, V ) = aT 4 V, where a = 8π 5 k 4 /(15h3c3 ) = 7.55 × 10−16
Jm−3 K−4 is a constant, T is the temperature, V is the volume, and p is the pressure.

(a) Show that the equation of state for an adiabatic process is pV 4/3 = K, where K
is a constant.
(b) Describe the 4-steps (isothermal, adiabatic, isothermal, and adiabatic) Carnot en-
gine for the black-body radiation in the (p − V ) plane, and calculate the efficiency
of the black-body Carnot engine
(c) Find Cv and κS , and determine the entropy and other thermodynamics potentials,
i.e. S(T, V ), U(S, V ), H(S, p), F (T, V ), and G(T, p).

Answer:

(a) From the first law of thermodynamics, we find T dS = dU + P dV = (4aT 3 dT +

aT 4 dV ) + 13 aT 4 dV. For an adiabatic process, dS = 0, we find

dT dV
+ = d[ln(T V 1/3 )] = 0,
T 3V
or T V 1/3 = constant, or 31 aT 4 V 4/3 = pV 4/3 = constant.
(b) A cycle of a Carnot engine is divided into 4 processes:
i. isothermal: Q2 = dU + P dV = 34 aT24 (V2 − V1 )
R R

¯ = 0, T2 V21/3 = T1 V31/3
ii. adiabatic: dQ
iii. isothermal: Q1 = dU + P dV = 34 aT14 (V4 − V3 )
R R

¯ = 0, T1 V41/3 = T2 V11/3
iv. adiabatic: dQ

4
W = Q2 + Q1 = a(T2 − T1 )[T13 V3 − T23 V1 ],
3
W T2 − T1 T1
η= = =1− .
Q2 T2 T2

(c) Using definition of each physical quantities, we obtain:

! !
∂U 3 1 ∂V 3 4
CV = = 4aT V, κS = − = , S(T, V ) = aT 3 V,
∂T V
V ∂p S
4p 3
4/3
3S 34/3

4
U(S, V ) = aT V = a V =
4/3 1/3
S 4/3 V −1/3 ,
4aV 4 a
4 4 31/4
H(p, S) = U + pV = aT V = 1/4 p1/4 S,
3 a
1
F (T, V ) = U − T S = − aT 4 V,
3
G(T, p) = H − T S = 0

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 Figure 1: The Carnot cycle exam-
ple with T2 = 104 K, T1 = 5 × 103
K, V2 = 1 m3 , and V3 = 2 m3 is
shown in this example. For the pho-
ton gas, isothermal process is equiv-
alent to an isobaric process.

4. (10 points) A Diesel cycle for an ideal gas with γ = Cp /Cv operating between V1 , V2
and V3 , where V1 /V2 and V3 /V2 are respectively called the compression ratio and the
cut-off ratio. Find the efficiency of the engine in terms of γ, compression ratio, and
cut-off ratio.
Answer:

The Diesel cycle is described by 1 → 2 adiabatic, 2 → 3 isobaric, 3 → 4 adiabatic, and

4 → 1 constant volume. Thus

Qh = Cp (T3 − T2 ), Qc = Cv (T4 − T1 ),
Qc 1 T4 − T1 1 V1 (p4 − p1 )
e=1− =1− = 1− ,
Qh γ T3 − T2 γ p2 (V3 − V2 )
where we applied the ideal gas law in the last equation, and use γ = Cp /CV . Now, the
adiabatic processes provide the following identities:

p4 V1γ = p2 V3γ , p1 V1γ = p2 V2γ .

Thus we find
p4 − p1 V3 γ V2 γ
   
= −
p2 V1 V1
1 V1 (p4 − p1 ) 1 V2 γ (V3 /V2 )γ − 1
 
e=1− =1−
γ p2 (V3 − V2 ) γ V1 (V3 /V2 ) − 1

5. (10 points) An ideal mixing corresponds to mixing of molecules having the same size,
same interactions. It is applicable to mixings of ideal gases, liquids, etc. Consider NA
blue and NB green marbles of the same size and weight. They are mixed in a box.
What is the entropy of mixing? Please expressed it in terms of x = NA /(NA + NB ).
Answer:

4
 The number of possible states for the mixing is
N!
Ω=
NA !NB !
Thus the mixing entropy is S = k ln Ω = −Nk(x ln(x) + (1 − x) ln(1 − x), where
x = NA /N.

6. (10 points) Using the Table of thermodynamics parameters at temperature T0 = 298

K and p0 = 1 bar below. Find the Gibbs free energy per mole (or chemical potential)
for water and steam as a function of temperature T . Evaluate the chemical potentials
at T = 350 K and T = 400 K, at a constant pressure p0 = 1 bar. Here, we can assume
constant Cp for both steam and liquid. See Table 1.
Answer:

The Gibbs free energy at constant pressure is given by

Z T
∆G(T ) = ∆G(T0 ) − S(T )dT
T0

where ∆G is the Gibbs free energy relative to the Gibbs free energy of H2 and 12 O2 at
T0 and p0 . The entropy is given by
T Cp (T ) T
Z
S(T ) = S(T0 ) + dT = S0 + Cp ln .
T0 T T0
Thus
T
 
∆G(T ) = ∆G0 − S0 (T − T0 ) − Cp T ln − (T − T0 )
T0
Using the Table 1, we can calculate the Gibbs free energy vs temperature. Figure 2
shows the Gibbs free energies of H2 O liquid and gas phases. They cross at the boiling
point. Their values are −241.1 kJ (l), −238.5 kJ (g) at T = 350 K, and −245.5 kJ (l),
−248.4 kJ (g) at T = 400 K respectively

7. (10 points) In a hydrogen fuel cell, the steps of the chemical reactions are

at − electrode : H2 + 2OH − → 2H2 O + 2e− ,

at + electrode : 21 O2 + H2 O + 2e− → 2OH − .

Calculate the voltage of the fuel cell between these two electrodes. See Table 1.
Answer:
The available Gibbs free energy in this reaction is 237.13 kJ (see Table 1). Each
reaction transports 2 electrons across the electrodes, and thus the voltage available is
∆G 237.13 × 103 J/mol
V = = = 1.23 Volts
Q 2 × (1.602 × 10−19 ) × (6.022 × 1023 )

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 Figure 2: The Gibbs free energy vs the
temperature at p0 = 1 bar. (Problem
#6). At the boiling point, the Gibbs
functions of water and steam are equal.

8. (10 points) A biological cell is a water solution of sugar, amino acids, and other
molecules. Typically, it contains 200 water molecules for each molecule of something
else. Sea water has a salinity of 3.5%, i.e. if you boil away a kilogram of seawater you
will find 35 g of NaCl left in the pot. Each mole of NaCl is 58.44 g. If you drop a
biological cell into sea water, what will be the osmotic pressure when the equilibrium
is reached at T = 300 K? We assume that the cell wall is semipermeable that only
water molecules can pass through the cell wall.
Answer:

The chemical potentials are equal for both solutions. Thus

NB1 kT NB2 kT
µ0 (T, p1 ) − = µ0 (T, p2 ) −
NA NA
nB2 − nB1
p2 − p1 = RT
V
Since NaCl is ionized, each molecule counts as two solutes, we find

nB2 3.5 × 104 g

=2× = 2 × 599 mol/m3
V 58.44 g/mol m3
nB1 1.0 mol
= 3
= 278 mol/m3 .
V 200 mol × 18 g/mol × 10 m /g
−6

Ths osmotic pressure is p2 − p1 = 22.9 bar.