Engineering Tripos Part IIA THIRD YEAR

Module 3A5 : Thermodynamics and Power Generation

THERMODYNAMICS

Solutions to Examples Paper 2

(J.B. Young, October 2007)

1. α−phase Total volume of system is V = Vα + Vβ

β−phase System enclosed in rigid container so dV = 0.

At equilibrium, Tα = Tβ = T and pα = pβ = p.
HEAT RESERVOIR Heat reservoir maintains T constant so dT = 0.
Temperature T

(a) From fi = ui − Tsi and Tdsi = dui + pdvi (and also dT = 0) :

df i = dui − Tdsi − si dT = − pdvi − si dT = − pdvi (1)

If there is a small transfer of mass from one phase to the other, T and V stay the same
but Vα and Vβ (and hence the pressure) all change a little. The specific volumes vi also
change (because they depend on T and p via the equation of state for each phase).

(b) The Helmholtz function of the whole system is F = mαfα + mβfβ. With T and V
constant, equilibrium corresponds to a minimum value of F so,
dF = mα dfα + fα dmα + mβ df β + f β dmβ = 0
Using eq. (1),
dF = − pmα dvα + fα dmα − pmβ dv β + f β dmβ = 0 (2)

The total volume V = mαvα + mβvβ is constant. Hence,

dV = mα dvα + vα dmα + mβ dvβ + vβ dmβ = 0 (3)

Multiplying eq. (3) by p and adding to eq. (2) gives,

dF = ( fα + pvα )dmα + ( f β + pv β )dmβ = 0
Noting that fi + pvi = gi = µi we have,
dF = µα dmα + µ β dmβ = 0

For an interphase transfer of mass keeping the total mass constant, dmβ = −dmα. Thus,
dF = ( µα − µ β )dmα = 0

There is no restriction on dmα so µα = µβ at equilibrium.

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2. The Clausius-Clapeyron equation is,

dpS h fg
=
dT v fg T

We make the approximations vg >> vf and pSvg = RT which are reasonable if the
temperature is much less than the critical temperature. Hence,

dpS pS h fg
≅
dT RT 2

Integrating between states 1 and 2 on the saturation line assuming hfg is constant gives,

pS2 h fg 1 1
ln ≅ −
pS1 R T1 T2

For saturated steam with T1 = 40 oC = 313.15 K and T2 = 100 oC = 373.15 K, taking hfg =
2333.0 kJ/kg at 70 oC and R = 8.3143/18 = 0.462 kJ/kg K,
pS2
≅ 13.37 (Exact value is 13.73 from Steam Tables in the Data Book)
pS1

2
3(a) From f = u − Ts and Tds = du + pdv, we have,
df = du − Tds − sdT = − pdv − sdT
Hence,

∂f ∂f
= −p = −s
∂v T ∂T v

∂2 f ∂p ∂2 f ∂s
= − = −
∂v∂T ∂T v ∂T∂v ∂v T

∂p ∂s
=
∂T v ∂v T

(b) Applying du = −pdv + Tds to changes along an isothermal,

∂u ∂s
= −p + T
∂v T ∂v T

Using the Maxwell relation,

∂u ∂p
= −p + T
∂v T ∂T v

This is a completely general thermodynamic relation which relates the volume

dependence of the internal energy to the p-v-T equation of state. For an ideal gas, we
have pv = RT and hence,

∂p R
=
∂T v v
Thus,

∂u RT
= −p + = 0
∂v T v

So u = u(T) for an ideal gas. By definition,

∂u
cv =
∂T v

and hence cv = cv(T) for an ideal gas. A special case of this is cv = constant.

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 T v −b 1 1
4(a) f = c(T − T0 ) − cT ln − RT ln − a −
T0 v0 − b v v0

From the differential relationship df = −pdv − sdT we have,

∂f − RT a
−p = = + 2
∂v T (v − b ) v
This is the van der Waals equation,

p+
a
(v − b ) = RT
v2

(b) The specific entropy is given by,

∂f T cT v −b
−s = = c − c ln − − R ln
∂T v T0 T v0 − b

Hence,
T v −b
s = c ln + R ln
T0 v0 − b

The specific internal energy is given by,

1 1
u = f + Ts = c(T − T0 ) − a −
v v0

The specific heat capacity at constant volume is given by,

∂u
cv = = c
∂T v

For a van der Waals fluid, cv is a constant but u varies with v as well as T. Evidently,
u = 0 and s = 0 when T = T0 and v = v0. Hence (T0, v0) is the arbitrary datum state for
u and s. It then follows that f = 0 at (T0, v0).

(c) By definition h = u + pv. Hence,

∂h ∂u ∂v a ∂v ∂v
cp = = + p = c + + p
∂T p ∂T p ∂T p v 2 ∂T p ∂T p

We now know that c = cv and so,

a ∂v RT ∂v
c p − cv = p+ =
v2 ∂T p (v − b) ∂T p

We can get (∂v ∂T ) p from the p-v-T equation of state but the algebra is rather messy
and the result is not very informative. However, note that cp − cv ≠ R for a van der
Waals fluid.

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5. The van der Waals equation of state is,

p+
a
(v − b ) = R T
v2

Differentiating to find the critical point conditions:

∂p RT 2a
= − + 3 = 0 at T = TC , v = v C .
∂v T (v − b ) 2
v

∂2 p 2R T 6a
= − 4 = 0 at T = TC , v = v C .
∂v 2 T
( v − b) 3
v

Solving these equations simultaneously gives,

9 vC R TC vC
a = b =
8 3
According to the van der Waals equation, the ‘excluded’ molar volume is one third of the
molar volume at the critical point. Substituting for a and b in the equation of state and
setting p = pC , T = TC and v = vC gives the value of the compressibility factor at the critical
point,
pC vC 3
ZC = =
R TC 8

Substituting the definitions of the reduced pressure, temperature and volume in the equation
of state gives,

p R pC +
a
(VR vC − b ) = R TRTC
VR2 vC2

Introducing the expressions for a, b and ZC then gives the ‘universal’ form,

pR +
3
(3VR − 1) = 8TR
VR2

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6(a) The chemical equation is,
0.21 O2 + 0.79 N2 → a O2 + b N2 + c NO

(b) Conservation of atomic O → 2a + c = 2 × 0.21 = 0.42 (i)

Conservation of atomic N → 2b + c = 2 × 0.79 = 1.58 (ii)
No. of moles of products → a + b + c = n
Partial pressures :
a b c
pO2 = p p N2 = p p NO = p
n n n
Reaction 4 in the Data Book is,
− 2 NO + O2 + N2 = 0
The equilibrium constant is therefore defined by,
−2 +1 +1
p NO pO2 p N2
K p (T ) =
p0 p0 p0

where p0 = 1 bar. From the Data Book at 2000 K, ln(Kp) = 7.824, giving Kp = 2599.9.
Hence,
(a / n) (b / n) ab
2499.9 = = (iii)
(c / n ) 2 c2

We now have three equations for the three unknowns a, b and c. Substituting (i) and
(ii) into (iii) gives,
(0.42 − c) (1.58 − c)
2499.9 c 2 =
2 2
Collecting terms,
9998.6 c 2 + 2 c − 0.6636 = 0
The solution is c = 0.0080. From (i) and (ii) a = 0.2060, b = 0.7860. Also, n = 1.0.
The mole fractions are, XNO = 0.0080, XO2 = 0.2060, XN2 = 0.7860

(c) If the pressure were raised to 5 bar, the mole fractions would remain the same. This is
because, in the reaction O2 + N2 ↔ 2NO, the total number of moles does not
change. Hence, there is no effect of pressure.

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7(a) With stoichiometric O2, the chemical reaction is,
3 CO + H2 + 2 O2 → a H2O + b CO2 + c CO + d O2
Conservation of atomic H → 1 = a (i)
Conservation of atomic C → 3 = b + c (ii)
Conservation of atomic O → 7 = a + 2b + c + 2d (iii)
No. of moles of products → n = a + b + c + d (iv)

If the pressure after combustion is p2, the partial pressures are :

a b c d
pH2O = p2 pCO2 = p2 pCO = p2 pO2 = p2
n n n n
Reaction 7 in the Data Book is : − CO − ½ O2 + CO2 = 0
The equilibrium constant is therefore given by,
−1 −1 / 2 +1
pCO pO2 pCO2
K p 7 (T2 ) =
p0 p0 p0

where p0 = 1 bar (standard pressure) and T2 = 2600 K. From the Data Book,

ln(Kp7) = 2.800 → Kp7 = 16.445

Hence,
(b / n)
16.445 =
(c / n) (d / n) 0.5 ( p2 / p0 ) 0.5

The combustion is at constant volume. If all species behave as ideal gases,

p1V = 6 R T1
p2V = nR T2

where p1 = 2 bar and T1 = 400 K are the initial pressure and temperature. Hence,
p2 n p1 T2 2 × 2600
= = n = 2.1667 n
p0 6 p0 T1 6 × 400

Substituting into the equilibrium equation we obtain,

b
0.5
= 16.445 × (2.1667) 0.5 = 24.207 (v)
cd
It is just chance that n cancels out. We now have 5 equations for the 5 unknowns a, b,
c, d and n. The solution must be obtained iteratively and one strategy is as follows :

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 Combine (i), (ii) and (iii) to give,
c = 2d
b = 3 − 2d
Substitute for b and c in (v) to give,

48.414 d 3 / 2 = 3 − 2d

Starting with a value of d = 0 on the RHS, the iteration proceeds as follows :

d = 0.0 → d = 0.156591 → d = 0.145494 → d = 0.146294 → d = 0.146236
→ d = 0.146241 → d = 0.146240 → d = 0.146240

Hence,
a = 1.0, b = 2.70752, c = 0.29248, d = 0.14624, n = 4.14624

The mole fractions are :

XH2O = 0.2412, XCO2 = 0.6530, XCO = 0.0705, XO2 = 0.0353

The final pressure is : p2 = 2.1667 n p0 = 8.984 bar

(b) If the H2O dissociation is very small, the mole fractions of the major species will
hardly change. We therefore consider the chemical equation,
3 CO + H2 + 2 O2 → a H2O + b CO2 + c CO + d O2 + e H2
with a, b, c and d unchanged. Reaction 5 is : − H2 − ½ O2 + H2O = 0
The equilibrium constant is therefore given by,
−1 −1 / 2 +1
p H2 pO2 p H2O
K p 5 (T2 ) =
p0 p0 p0

where p0 = 1 bar and T2 = 2600 K. From the Data Book,

ln(Kp5) = 4.647 → Kp5 = 104.27
Hence,
( a / n)
104.27 =
(e / n) (d / n) 0.5 ( p 2 / p0 ) 0.5

As before, p2 p0 = 2.1667 n . Hence,

a e
e ≅ = 0.01697 → X H2 ≅ = 0.0041
104.7 × (2.1667) 0 .5
×d 0.5 n

This is clearly very small and hence the approximate calculation is justified.

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8(a) The dissociation of 1 mole of A1 is represented by,
a a
A1 → (1− a) A1 + A2 + A3
2 2
The total number of moles in the mixture = 1, and the partial pressures are given by,
a a
p1 = (1 − a) p , p2 = p, p3 = p
2 2
The dissociation reaction is,
−A1 + 1
A
2 2
+ 1
A
2 3
= 0

so the equilibrium constant is given by,

( p 2 p0 ) 0.5 ( p3 p0 ) 0.5
K (T ) =
( p1 p0 )

Substituting the expressions for the partial pressures,

(a / 2) 0.5 (a 2) 0.5 2K
K = → a =
(1 − a) 2 K +1

Hence, the mole fractions are,

1 K K
X1 = , X2 = , X3 =
2 K +1 2 K +1 2 K +1

The molar enthalpy of the mixture is,

3 h1 + K h2 + K h3
h = X i hi =
i =1 (2 K +1)

(b) The isobaric molar heat capacity is,

∂h 1 ∂h1 ∂h2 ∂h3 dK

cp = = + K + K + (h2 + h3 ) −
∂T p
(2 K +1) ∂T p
∂T p
∂T p
dT

2(h1 + K h2 + K h3 ) dK
(2 K +1) 2 dT

The isobaric molar heat capacities for the individual species are defined by,

∂h1 ∂h2 ∂h3

c p1 = c p2 = c p3 =
∂T p
∂T p
∂T p

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Hence,
c p1 + K c p 2 + K c p3 (2h1 − h2 − h3 ) dK
cp = −
(2 K +1) (2 K +1) 2 dT

We need to write this in terms of ∆H T which is the enthalpy change when 1 mole of
A1 dissociates completely at temperature T :
1 1
∆H T = − h1 + h2 + h3
2 2
Thus,
c p1 + K c p 2 + K c p 3 2 ∆H T dK
cp = +
(2 K +1) (2 K +1) 2
dT

Introducing van’t Hoff’s equation,

d (ln K ) 1 dK ∆H T
= =
dT K dT RT 2
We obtain finally,

c p1 + K c p 2 + K c p 3
2
2K R ∆H T
cp = +
(2 K +1) (2 K +1) 2 RT

The first term can be written,

c p1 + K c p 2 + K c p 3 3
= X i c pi
(2 K +1) i =1

This is the molar specific heat capacity of the mixture in the absence of any chemical
reaction. The second term represents the effect of the dissociation.
Because K > 0, the effect of the dissociation is always to increase c p and hence
decrease the final temperature.

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