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THERMODYNAMICS
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)
For an interphase transfer of mass keeping the total mass constant, dmβ = −dmα. Thus,
dF = ( µα − µ β )dmα = 0
1
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
∂u ∂s
= −p + T
∂v T ∂v T
∂u ∂p
= −p + T
∂v T ∂T v
∂p R
=
∂T v v
Thus,
∂u RT
= −p + = 0
∂v T v
∂u
cv =
∂T v
and hence cv = cv(T) for an ideal gas. A special case of this is cv = constant.
3
T v −b 1 1
4(a) f = c(T − T0 ) − cT ln − RT ln − a −
T0 v0 − b v v0
p+
a
(v − b ) = RT
v2
Hence,
T v −b
s = c ln + R ln
T0 v0 − b
∂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).
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.
4
5. The van der Waals equation of state is,
p+
a
(v − b ) = R T
v2
∂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
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
5
6(a) The chemical equation is,
0.21 O2 + 0.79 N2 → a O2 + b N2 + c NO
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.
6
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)
where p0 = 1 bar (standard pressure) and T2 = 2600 K. From the Data Book,
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
7
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
Hence,
a = 1.0, b = 2.70752, c = 0.29248, d = 0.14624, n = 4.14624
(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
This is clearly very small and hence the approximate calculation is justified.
8
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
( p 2 p0 ) 0.5 ( p3 p0 ) 0.5
K (T ) =
( p1 p0 )
(a / 2) 0.5 (a 2) 0.5 2K
K = → a =
(1 − a) 2 K +1
2(h1 + K h2 + K h3 ) dK
(2 K +1) 2 dT
The isobaric molar heat capacities for the individual species are defined by,
9
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
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
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.
10