UNIVERSITY OF NIGERIA, NSUKKA

DEPARTMENT OF MECHANICAL ENGINEERING

ME 561 – Thermodynamics III

Lecture Notes on
Thermodynamic Relations
for 2018/2019 Session
(Part II)

Lecturer:
Howard O. NJOKU PhD

April 3, 2019
Contents
0.1 Real gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
0.2 Principle or Law of corresponding states . . . . . . . . . . . . . . . . . . . 3
0.3 Generalized enthalpy chart for real gases . . . . . . . . . . . . . . . . . . . 4
0.4 Generalized entropy chart for real gases . . . . . . . . . . . . . . . . . . . . 5
0.5 Virial equation of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1
0.1 Real gases
The P - v - T relationship of a real gas can be defined using compressibility factor by

Pv
Z= (1)
RT

For an ideal gas, Z is obviously unity under all conditions. For a real gas, the value of Z
may be less or greater than unity. Thus, Z gives the deviation from ideal gas behaviour.
Expressing Z as a continuous function of T and P ,

Z = f (T, P ) (2)

This equation is the basis of compressibility factor chart (Fig. 1) in which Z is plotted
against P for various values of T .

Figure 1: The compressibility chart. Z = 1.0 corresponds to ideal gas operation. vR =

v/vc ; PR = P/Pc ; TR = T /Tc .

In order to use the chart, given P , T , Tc , Pc and M (molecular weight) to find Z and
v, for example, from curves, at P/Pc and T /Tc , Z is obtained on the ordinate of the chart.

2
 Pv Ro
Noting then that Z = , where R = ,
RT M
8.3143
R=
M

Hence, v, the specific volume can be obtained.

0.2 Principle or Law of corresponding states

This was first proposed by Van der waals in 1881. This empirical principle states that all
substances obey the same equation of state expressed in terms of the reduced properties.
A reduced property is the actual value of the property divided by its value at the critical
point. Thus by definition, the reduced pressure PR , the reduced temperature, TR and the
reduced volume vR are given as

P
PR = (3)
Pc
T
TR = (4)
Tc
v
vR = (5)
vc
It is found experimentally that for many gases, the compressibility factor, Z may be
approximated by the relation
Z = f (PR , TR ) (6)

This is the basis of the generalized compressibility chart in which Z versus PR is given
for various values of TR . Let us substitute equation (3), (4) and (5) into equation (1)

PR vR Pc vc PR vR
Z= = Zc (7)
TR RTc TR

Zc is the compressibility factor at the critical point. Zc is not constant but varies widely
from gas to gas. If Z is a function of TR and PR , the quality vR Zc , known as the ideal
reduced volume or the pseudo-reduced volume, must also be a function of TR and PR . The
pseudo-reduced volume vr is given by

TR v
vr = vR Zc = Z = Tc (8)
PR R Pc

Since vr is a function of TR and PR

P Vo = ZRo T

3
0.3 Generalized enthalpy chart for real gases
Since all substances obey the same equation of state expressed in terms of the reduced
properties, according to the principle of corresponding states, we wish to find expressions
for the specific enthalpy of real gases h in terms of the reduced properties TR and PR . We
recall from Eqn (1) that
Pv
Z= (1)
RT
from which we obtain upon re-arranging that

R
v= TZ
P

or
v RZ
= (9)
T P
For a constant pressure change
     
∂v R ∂Z
= Z +T (10)
∂T P P ∂T P
 
v RT ∂Z
= + (11)
T P ∂T P

According to equation ??, the enthalpy change of any gas at a fixed temperature is
   
∂V
dhT = V − T dP (12)
∂T P

RT
But v = Z
P    
RT ∂v
∴ dhT = Z −T dP (13)
P ∂T P
 
∂v
Substituting for from equation (11),
∂T P

    
RT v RT ∂Z
dhT = Z −T + dP (14)
P T P ∂T P
RT Z RT Z RT 2 ∂Z
   
= − − dP (15)
P P P ∂T P
RT 2 ∂Z
 
= − dP (16)
P ∂T P

Integrating equation (16) from zero pressure to any pressure P , for an isothermal
process, Z P 
∗ 2 ∂Z dP
h − h = −RT (17)
0 ∂T P P

4
Where h∗ is the enthalpy of the gas at zero pressure and a given temperature. Since
all gases behave like an ideal gas at zero pressure, h∗ is the ideal gas value at a given
temperature. Thus the right hand side of equation (17) represents the enthalpy departure
from ideal gas behaviour. By definition, T = Tc TR and P = Pc PR . Hence, dT = Tc dTR
and dP = Pc dPR . Equation (17) is now expressed in terms of the reduced properties as
  Z PR
∗ 1 ∂Z Pc dPR
h−h = −R Tc2 TR2 (18)
0 Tc ∂TR PR Pc PR
Z PR  
2 ∂Z dPR
= −R Tc TR (19)
0 ∂TR PR PR
∗ Z PR  
h −h ∂Z dPR
= TR2 (20)
RTc 0 ∂TR PR PR

The right hand side of Eqn. (20) is a function of TR and PR only and consequently the
integration may be performed by making use of the generalized compressibility data. In
order to integrate the RHS
 graphically,
 the Z-PR -TR chart is used to construct, for given
∂Z 1
values of TR , curves of versus PR . The integral of the RHS of Eqn. (20) is
∂TR PR
∗
gotten from the curves graphically to obtain values of the departure function (h −h)/RTc .
These values have been plotted a presented in a generalized enthalpy chart.
To use the chart for a particular gas, all we need to know are Pc and Tc of the gas.
Making use of this chart, the change of enthalpy between the two states may be obtained
as  
∗ ∗
! !
h −h h −h  ∗ ∗

h2 − h1 = Tc  −  + hT2 ,P2 − hT1 ,P1 (21)
Tc Tc
T1 ,P1 T2 ,P2

  Z T2
∗ ∗
where hT2 ,P2 − hT1 ,P1 = c∗p dT is the enthalpy change due to ideal gas behaviour
T1
which requires data of the ideal gas constant pressure specific heat cp ∗ as a function of
temperature.

0.4 Generalized entropy chart for real gases

The change in entropy for a simple gas had been obtained earlier as
 
dT ∂v
ds = cP − dP (22)
T ∂T P

and, that for a constant pressure change in a real gas,

     
∂v R ∂Z
= Z +T (23)
∂T P P ∂T P

5
For a fixed temperature equation (22) becomes
 
∂v
ds = − dP (24)
∂T P

Integrating Eqn. 24, from zero pressure to any pressure, P for an ideal gas, we have at a
fixed temperature Z P  Z P
∗ ∗ ∂v R
sp − s0 = − dP − dP (25)
0 ∂T P 0 P

In terms of reduced properties, Eqn. (25) becomes

Z PR
dPR
s∗p − s∗0 = −R (26)
0 PR

Integrating Eqn. (24) from zero pressure to any pressure for a real gas, we have
Z P  
∂v
sP − s∗0 =− dP (27)
0 ∂T P

or Z P    
R ∂Z
sP − s∗0 =− Z +T dP (28)
0 P ∂T P
In terms of reduced properties, Eqn. (28) becomes
"  #
Z PR 
∂Z dPR
sP − s∗0 = −R Z + TR (29)
0 ∂TR PR PR

Subtracting Eqn. (26) from Eqn. 29, we have

"  #
Z PR 
∂Z dPR
sP − s∗P = −R (Z − 1) + TR (30)
0 ∂TR PR PR

or "  #
PR
s∗P − sP
Z 
∂Z dPR
= (Z − 1) + TR (31)
R 0 ∂TR PR PR

The right hand side of Eqn. (32) is a function of TR and PR only. The integration may
be performed by making use of the generalised compressibility factor data. Equation (32)
is the basis of the generalised entropy chart, from which the change in entropy between
two states may be obtained as

s2 − s1 = (s∗P − sP )T1 ,P1 − (s∗P − sP )T2 ,P2 + s∗T2 ,P2 − s∗T1 ,P1 (32)
R T2
Where s∗T2 ,P2 −s∗T1 ,P1 = T1
c∗p dT
T
−R ln PP21 is the entropy change due to ideal gas behaviour.

6
0.5 Virial equation of state
The P -V -T relation of a real gas can be represented by an infinite series by expanding
the compressibility factor Z about P = 0 or ρ = 0:

Pv
Z= = 1 + B 0 P + C 0 P 2 D0 P 3 + ... (33)
RT

or
Z = 1 + Bρ + Cρ2 + Dρ3 + ... (34)

Equations (33) and (34) are known as virial equations of state. B 0 , C 0 and D0 are the
second, third and fourth virial coefficients in the pressure series, while B, C and D are
virial coefficients in the density series. All virial coefficients are functions of temperature
only for a pure gas. A comparison of the infinite series shows that

B
B0 =
RT

C − B2
C0 =
(RT )2
D + 2B − 3BL
D0 =
(RT )3
e.t.c. The virial equations of state may be truncated to

Z = 1 + B0P + C 0P 2 (35)
Z = 1 + Bρ + Cρ2 (36)

if the effects of three-body molecular interactions are neglected.

Examples
Example 1 Derive the expressions for (a) the change of internal energy and (b) the
change of entropy of a gas which obeys the Van der Walls equation of state. (P =
RT a
− 2 ).
v−b v
Solution:
RT a
P = − 2 (37)
v−b v

(a) The relation for internal energy was obtained as:

   
∂P
du = cv dT + T − P dv (38)
∂T v

7
  
∂P R
= (39)
∂T v v−b

   
R
∴ du = cv dT + T − P dv (40)
v−b
 
RT RT a
= cv dT + − + dv (41)
v − b v − b v2
a
du = cv dT + 2 dv (42)
Z 2 v Z
2
a
u2 − u1 = cv dT + 2
dv (43)
1 1 v
Z 2 h a i2
= cv dT + − (44)
v 1
Z1 2  
a a
u2 − u1 = cv dT + − (45)
1 v1 v2

(b) The relation for entropy was obtained as:

 
dT ∂P
ds = cv + dv (46)
T ∂T v

Substituting Eqn. (39)

dT R
ds = cv + dv (47)
T v−b
Z 2 Z 2
dT R
⇒ s2 − s1 = cv + dv (48)
1 T 1 v−b
Z 2  2
dT R
= cv + (49)
1 T v−b 1

Example 2 Derive an expression for the change of enthalpy of a gas using (a) ideal gas
equation of state; (b) the van der Walls equation of state. Hence for oxygen at
‰
27 being compressed from 1 to 100 atm, evaluate and compare the isothermal
enthalpy changes, (h2 − h1 )T , obtained on the bases of the ideal gas and van der
Waals equations.
Solution: (a) For ideal gas P v = RT
   
∂v
dh = cP dT + v − T dP (50)
∂T P
 
RT ∂v R
v= ;⇒ =
P ∂T P P

8
Thus
  
R
dh = cP dT + v − T dP (51)
P
 
RT RT
= cP dT + − dP (52)
P P
dh = cP dT (53)
Z 2
h2 − h1 = cP dT (54)
1

(b) For a van der Waals gas,

RT a
P = − 2 (55)
v−b v
Noting that h = u + P v, then h2 − h1 = u2 − u1 − P2 v2 + P1 v1 . We obtained earlier
that    
∂P
du = cv dT + T − P dv (56)
∂T v
 
∂P R
=
∂T v v−b

   
R
∴ du = cv dT + T − P dv (57)
v−b
 
RT RT a a
= cv dT + − + 2 dv = cv dT + 2 dv (58)
v−b v−b v v
Z 2 Z 2
a
⇒ u2 − u1 = cv dT + 2
dv (59)
1 1 v
Z 2 h a i2
= cv dT + − (60)
1 v 1
Z 2  
a a
Or u2 − u1 = cv dT + − (61)
1 v1 v2

From which we obtain

Z 2  
a a
h2 − h1 = cv dT + − + P2 v2 − P1 v1 (62)
1 v1 v2
Z 2  
a a RT2 v2 a RT1 v1 a
= cv dT + − + − − + (63)
1 v1 v2 v2 − b v2 v1 − b v1
Z 2  
a a T2 v1 v2 − T2 v2 b − T1 v1 v2 + T1 v1 b
= cv dT + 2 − +R (64)
1 v1 v2 (v2 − b)(v1 − b)

For oxygen at 27 ‰ being compressed isothermally, assuming ideal gas behaviour,

Z 2
h2 − h1 = cP dT = 0.
1

9
 Assuming a van der Waal behaviour, for an isothermal process
 
a a
(u2 − u1 )T = − (65)
v2 v1

From which we obtain

 
a a
(h2 − h1 )T = − + P2 v 2 − P1 v 1 (66)
v1 v1
 
a a RT v2 a RT v1 a
= − + − − + (67)
v v2 v − b v2 v1 − b v1
1  2
a a v1 − v2
= 2 − + RT b (68)
v1 v2 (v2 − b)(v1 − b)

The constants a and b are obtained for oxygen from the tables as 1.369 bar·m3 /kmol
≡ 1.369 × 105 Pa·m3 /kmol and 0.0315 m3 /kmol, respectively. With P1 = 1 atm ≡
1.01327 ×105 Pa, P2 = 100 atm ≡ 101.327 ×105 Pa, T = 27 ≡ 300 K, and ‰
using R̄ = 8.314 kJ/(kgmol.K), from Eqn. (55) we obtain v1 = 24.592 m3 /kg and
v2 = 0.226252 m3 /kg. Substituting these into Eqn. (68), we obtain

(h2 − h1 )T = −798.80 kJ/kmol (69)

We notice that whereas the ideal gas law predicts zero change in enthalpy, the van
der Waals law predicts a reduction in the specific enthalpy.

Example 3 The following information is obtained from the steam tables of the vapor-
ization process:
1378 kPa 467.7 K
1413 kPa 468.8 K
1448 kPa 469.9 K
At 1413 kPa, vf g = 0.1383 m3 /kg. Determine the latent heat of vaporization at 1413
kPa. Furthermore, use the Clapeyron relation to determine the change of enthalpy
of (a) steam at 300 psia; (b) ammonia at 100 F; and (f) Freon-12 at 60 F.
Solution: By the Clapeyron equation,
 
dP
hf g = vf g T (70)
dT

The differential can be approximated with a difference equation viz

   
∆P P2 − P1
hf g ≈ vf g T = vf g T (71)
∆T T2 − T1

10
Using pressure and temperature data on either side of the desired state,

1448 − 1378
hf g ≈ 0.1383 × 468.8 × (72)
469.9 − 467.7
= 2062.93 kJ/kg (73)

This is ∼ 5% higher than the value given by the steam tables.

(a) The state data in the neighbourhood of steam at 300 psia is given as follows

Pressure (psia) Temperature (R) vf g (ft3 /lbm)

250 860.71 1.8261
300 877.10 1.5253
350 891.49 1.3436

From which we obtain

350 − 250 144

hf g ≈ 1.5253 × 877.10 × × (74)
891.49 − 860.71 778
= 804.5 Btu/lbm (75)

Which is less than 1% different from the value given in the tables.
(b) The state data in the neighbourhood of ammonia at 100 F is given as follows

Pressure (psia) Temperature (R) vf g (ft3 /lbm)

210.0 559.1 1.4035
214.7 560.57 1.3725

From which we obtain by interpolation that vf g = 1.3915 ft3 /lbm at 100 F (559.67
R).

214.7 − 210 144

hf g ≈ 1.3915 × 559.67 × × (76)
560.57 − 559.1 778
= 460.9 Btu/lbm (77)

(c) The state data in the neighbourhood of Freon at 60 F is given as follows

Pressure (psia) Temperature (R) vf g (ft3 /lbm)

61.394 509.67 0.64362
72.433 519.67 0.54648
84.888 529.67 0.46609

11
 From which we obtain

84.888 − 61.394 144

hf g ≈ 0.54648 × 519.67 × × (78)
529.67 − 509.67 778
= 61.746 Btu/lbm (79)

Which is different from the value given in the tables by less than 1%.

Example 4 Determine the difference between cP and cv for a gas that obeys (a) the ideal
gas equation; (b) the Van der Waals equation of state.
Solution: Two entropy relations were obtained as
 
dT ∂v
ds = cP − dP (80)
T ∂T P
 
dT ∂P
ds = cv + dv (81)
T ∂T v

Equating both and solving,

   
dT ∂v dT ∂P
cP − dP = cv + dv (82)
T ∂T P T ∂T v
   
dT ∂P ∂v
(cP − cv ) = dv + dP (83)
T ∂T v ∂T P
T ∂P ∂v



∂T v
dv + ∂T P
dP
dT = (84)
cP − cv
T ∂P ∂v



∂T v
dv T ∂T P
dP
= + (85)
cP − cv cP − cv

For T = f (P, v),    

∂T ∂T
dT = dP + dv (86)
∂P v ∂v P

Equating the coefficients of the terms in Eqns. (85) and (86), we have for the terms
with dP ,
∂v


T dP
 
∂T ∂T P
dP = (87)
∂P v cP − cv
∂v


T ∂T dP
   
P ∂v ∂P
⇒ cP − cv = ∂T

=T dP (88)
∂P v
dP ∂T P ∂T v

The cyclic relation applied to P , v and T gives,

     
∂v ∂T ∂P
= −1 (89)
∂T P ∂P v ∂v T

12
      
∂v ∂P ∂v
⇒ = − (90)
∂T P ∂T v ∂P T
     
∂P ∂v ∂P
∴ cP − cv = −T (91)
∂T v ∂P T ∂T v
 2  
∂P ∂v
= −T (92)
∂T v ∂P T

2
−T ∂P ∂T v
or cP − cv = ∂P

(93)
∂v T

(a) For ideal gas behavior

RT
P v = RT ; ⇒ P = (94)
v
   
∂P R ∂P RT
∴ = , and =− 2 (95)
∂T v v ∂v T v

−T (R/v)2
∴ cP − cv = (96)
−(RT /v 2 )
cP − cv = R (97)

(b) For a van der Waal’s gas,

RT a
− 2
P = (98)
v−b v
   
∂P R ∂P RT 2a
∴ = , and =− + (99)
∂T v v − b ∂v T (v − b)2 v 3

−T (R/(v − b))2 −R2 T /(v − b)2

∴ cP − cv = RT 2a
= (100)
− (v−b)2 + v3 (−RT v 3 + 2a(v − b)2 )/((v − b)2 v 3 )
−R2 T v 3
= (101)
−RT v 3 + 2a(v − b)2
−1   −1
−RT v 3 2a(v − b)2 2a(v − b)2

1
= − = 1− (102)
−R2 T v 3 −R2 T v 3 R −R2 T v 3
−1
2a(v − b)2

cP − cv = R 1− (103)
−R2 T v 3

Example 5 Calculate the coefficient of thermal expansion and the coefficient of isother-
mal compressibility for a gas that obeys (a) the ideal gas equation; (b) the Van der
Waals equation of state.

13
Solution: The coefficient of thermal expansion is expressed as
 
1 ∂v
β= (a)
v ∂T P

while the coefficient of isothermal compressibility is expressed as

 
1 ∂v
κ=− (b)
v ∂P T

(a) For an ideal gas,

RT
P v = RT, =⇒ v =
P
 
∂v R
=
∂T P P
Substituting this into Eqn. (a),

1 R R
β= · =
v P Pv

which upon comparing with Eqn. (a) gives

1
β=
T

 
∂v RT
=−
∂P T P2
Substituting this into Eqn. (b),

1 RT RT 1
κ=− ·− 2 ≡ ·
v P Pv P

which upon comparing with Eqn. (b) gives

1
κ=
P

(b) For the van der Waal gas,

RT a
P = − 2
v−b v
 a v−b
=⇒ T = P + 2
v R 
 a v b
= P+ 2 −
v R R
Pv Pb a ab
= − + −
R R Rv Rv 2

14
    −1
∂v 1 P a 2ab
= = − +
∂T P (∂T /∂v)P R Rv 2 Rv 3
Rv 3
=
P v 3 − av + 2ab

Substituting this into Eqn. (a),

1 Rv 3 Rv 2
β= · =
v P v 3 − av + 2ab P v 3 − av + 2ab

   −1
∂v 1 RT 2a
= = − +
∂P T (∂P/∂v)T (v − b)2 v 3
(v − b)2 v 3
=
2a(v − b)2 − RT v 3

Substituting this into Eqn. (b),

1 (v − b)2 v 3 (v − b)2 v 2
κ=− · =
v 2a(v − b)2 − RT v 3 RT v 3 − 2a(v − b)2

Example 6 Show that the Joule-Thomson coefficient equals µ = (v/cp )(T β − 1), and
‰
hence estimate µ ( /bar) for water at (a) 60 bars and 320 and (b) 100 bars and ‰
‰
400 .
Solution:  
∂T
µ= (a)
∂P h

Now by the cyclic relation,

     
∂T ∂P ∂h
= −1
∂P h ∂h T ∂T P

But  
∂h
= cP
∂T P
 
∂P
∴µ cP = −1 (b)
∂h T
Change in enthalpy is given by

dh = T ds + vdP

15
 and dividing through by dP while keeping temperature constant,
   
∂h ∂s
=T +v
∂P T ∂P T

   
∂s ∂v
But one of the Maxwell relations states that =−
∂P T ∂T P

   
∂h ∂v
∴ =v−T
∂P T ∂T P

Re-arranging Eqn. (b),    

1 ∂v
µ= T −v (c)
cP ∂T P
   
1 ∂v ∂v
But β = ,⇒ = βv Substituting in Eqn. (c), we obtain
v ∂T P ∂T P

1 v
µ= (T βv − v) ≡ (T β − 1)
cp cp

From Eqn. (a), the Joule-Thomson coefficient can be approximated by

     
∂T ∆T T2 − T1
µ= ≈ =
∂P h ∆P h P 2 − P1 h

This approximation can be evaluated as follows

i.) Determine h at the given T and P .

ii.) For a pressure P1 < P , determine, if necessary by interpolation, the value of
T1 corresponding to h.
iii.) For a pressure P2 > P , determine, if necessary by interpolation, the value of
T2 corresponding to h.
iv.) Compute µ using P1 , P2 , T1 and T2 .

‰
(a) For water at 60 bars and 320 , h = 2952.6 kJ/kg. At 40 bars and 80 bars, the
temperatures corresponding to h = 2952.6 kJ/kg are obtained by interpolation as
‰
297.89 and 341.15 , respectively.

(341.15 − 297.89)
µ= = 2.163 ◦ C/bar
80 − 60

Example 7 Determine the Joule-Thomson coefficient for a gas with the following equa-
tions of state: (a) P (v − b) = RT ; (b) (P + a/v 2 )(v − b) = RT .

16
Solution: In the previous problem, we obtained that
   
1 ∂v
µ=− v−T (a)
cP ∂T P

RT
(a) For P (v − b) = RT , v= + b.
P
 
∂v R
∴ =
∂T P P

Substituting in Eqn. (a),

 
1 RT R b
µ=− +b−T =−
cP P P cP

 a RT a
(b) For P + 2 (v − b) = RT , P = − 2.
v v−b v
The cyclic relation gives
     
∂v ∂T ∂P
= −1
∂T P ∂P v ∂v T

     
∂v ∂P ∂v
=⇒ =− (b)
∂T P ∂T v ∂P T
 
∂P R
= (c)
∂T v v−b
−RT v 3 + 2a(v − b)2
 
∂P RT 2a
=− + =
∂v T (v − b)2 v 3 (v − b)2 v 3
(v − b)2 v 3
 
∂v 1
= = (d)
∂P T (∂P /∂v)T 2a(v − b)2 − RT v 3
Substituting Eqns. (c) and (d) into Eqn. (b),

(v − b)2 v 3 R(v − b)v 3

 
∂v R
=− · = (e)
∂T P v − b 2a(v − b)2 − RT v 3 RT v 3 − 2a(v − b)2

Substituting Eqn. (e) into Eqn. (a),

RT (v − b)v 3
 
1
µ = − v−
cP RT v 3 − 2a(v − b)2
1 RT v 4 − 2av(v − b)2 − RT v 4 + RT bv 3
 
= −
cP RT v 3 − 2a(v − b)2
1 RT bv 3 − 2av(v − b)2
 
= −
cP RT v 3 − 2a(v − b)2

17
 ‰
Example 8 Refrigerant 134a is maintained at 60 and 14 bars. Determine the specific
volume (m3 /kg) based on (a) the ideal gas equation; (b) the principle of correspond-
ing states; (c) data in the superheat tables. What are the errors associated with
methods (a) and (b).
Solution: (a) By the ideal gas postulate,

R̄
P v = RT = T
M

‰
R̄ = 8.314 kJ/(kg K); T = 60 ≡ 333K; P = 14 bars ≡ 1.4 × 106 Pa; Molecular
mass for R134a, M = 102 kg/kmol. Hence

P R̄T 8.314 × 103 × 333

v= = = 0.0194 m3 /kg
M 102.03 × 1.4 × 106

(b) By the principle of corresponding states,

R̄
P v = ZRT ≡ Z T
M

Critical properties for R134a: Pc = 40.6 bars; Tc = 374.6K. Hence the reduced
properties are

Pr = P/Pc = 14/40.6 = 0.345 and Tr = T /Tc = 333/374 = 0.89

With these, we obtain from the charts, the compressibility factor, Z = 0.82. Hence,

R̄T Z 8.314 × 103 × 333 × 0.82

v= = = 0.0159 m3 /kg
MP 102.03 × 1.4 × 106

(c) From the superheat tables, v = 0.01495 m3 /kg.

Compared to the data from the superheat tables, errors of ∼ 30% and ∼ 6%, re-
spectively, are associated with the results of (a) and (b).

‰ ‰
Example 9 Ethane (C2 H6 ) is compressed from 30 and 15 bars to 124 and 98 bars
in a steady-flow process. The molar specific heat (kJ/kmol K) is given by c̄P,0 =
16.8 + 0.123T , where T is in kelvins. Determine the enthalpy change (kJ/kmol), if
(a) an ideal gas model is used and (b) a generalized chart is used.
‰
Solution: (a) T1 = 30 ≡ 303 K; T2 = 124 ‰ ≡ 397 K. At the average temperature
of (303 + 397) ÷ 2 = 305 , ‰
c̄P,0 = 16.8 + 0.123 × 350 = 59.85 kJ/(kmolK)

18
 For an ideal gas,

h̄∗2 − h̄∗1 = c̄P,0 (T2 − T1 )

= 59.85 × (397 − 303) = 5625.9 kJ/kmol

(b) P1 = 15 bars; P2 = 98 bars. Critical data for CH4 : Pc = 48.8 bars; Tc = 305.4
K. Hence the reduced properties are:

Pr1 = P1 /Pc = 0.307; Pr2 = P2 /Pc = 2.01; Tr1 = T1 /Tc = 0.99; Tr2 = T2 /Tc = 1.30

h̄∗ − h̄
 
From the enthalpy departure (generalize enthalpy) chart, ≈ 0.38, while
 ∗  R̄Tc 1
h̄ − h̄
≈ 1.5.
R̄Tc 2

h̄∗ − h̄
   ∗ 
h̄ − h̄
h̄2 − h̄1 = R̄Tc − + (h̄∗2 − h̄∗1 )
R̄Tc 1 R̄Tc 2
= 8.314 × 305.4(0.38 − 1.5) + 5625.9
= 2782.11 kJ/kmol

Example 10 Methane (CH4 ) is compressed in a steady flow process from 13.9 bars and
‰ ‰
51 to 186 bars and 108 . Using the generalized charts, determine (a) the change
in enthalpy (kJ/kmol), and (b) the change in entropy (kJ/kmol K).
Solution:
P1 = 13.9 bars; T1 = 51 ‰ = 324 K; P 2 = 186 bars; T2 = 108 ‰ = 381 K.
Critical data for Methane: Pc = 46.4 bars; Tc = 190.7 K.
Pr1 = P1 /Pc = 0.30; Tr1 = T1 /Tc = 1.70; Pr2 = P2 /Pc = 4.01; Tr2 = T2 /Tc = 2.00.
(a) c̄P = Ru (a + bT + cT 2 + dT 3 + eT 4 ), where a = , b = , c = , d = and e = .
At the average temperature of (324 + 381) ÷ 2 = 352.5 K, c̄P = 38.1 kJ/(kmol K).

h̄∗2 − h̄∗1 = c̄P (T2 − T1 ) = 38.1 × (381 − 324) = 2173.6 kJ/kmol

h̄∗ − h̄
 
From the enthalpy departure (generalize enthalpy) chart, ≈ 0.08, while
 ∗  R̄Tc 1
h̄ − h̄
≈ 0.86.
R̄Tc 2

h̄∗ − h̄
   ∗ 
h̄ − h̄
h̄2 − h̄1 = R̄Tc − + (h̄∗2 − h̄∗1 )
R̄Tc 1 R̄Tc 2
= 8.314 × 190.7(0.08 − 0.86) + 2173.6
= 936.9 kJ/kmol

19
 (b) The ideal gas change in entropy is

T2 P2 381 186
s̄∗2 − s̄∗1 = c̄P ln − R̄ ln = 31.8 ln − 8.314 ln = −16.41 kJ/(kmolK)
T1 P1 324 13.9

s̄∗ − s̄
 
From the entropy departure (generalize entropy) chart, ≈ 0.0, while
 ∗  R̄ 1
s̄ − s̄
≈ 0.37.
R̄ 2

s̄∗ − s̄
   ∗ 
s̄ − s̄
s̄2 − s̄1 = R̄ − + (s̄∗2 − s̄∗1 )
R̄ 1 R̄ 2
= 8.314(0.0 − 0.37) + (−16.41)
= −19.48 kJ/(kmolK)

Exercises
1. (a) Derive the relation (∂ 2 g/∂T 2 )P = −cp /T . (b) Methane gas in a close system
‰
is cooled at constant pressure of 55 bars from 100 to 300 . The equation for cp,0
may be found in property tables. Calculate the heat transferred, in kJ/kg, using
generalized data.

2. (a) Derive the relation (∂ 2 a/∂T 2 )v = −cv /T . (b) The isothermal compressibility
of ethyl alcohol at 20 ‰
and 1 bar is 110 × 10−6 bar−1 and the specific gravity is
0.789. Find the work required to compress the fluid isothermally from 1 to 100 bars
at 20 ‰ if v is assumed constant.

3. (a) Prove that, for any homogeneous system, cp /cv = (∂P/∂v)s (∂P/∂v)T . (b) The
isothermal compressibility for liquid water at 50 ‰
is given by KT = 0.125 ×
−3 −1
10 /v(P + 2740), where KT is in bar , P is in bars, and v is in m3 /kg. A
mass of 2.5 kg of water is compressed isothermally and reversibly at 50 from 1 to ‰
600 bars. Determine (a) the work required and (b)the heat transfer, both answers
in kilojoules.

4. Oxygen initially at 40 bars and -41 ‰

is compressed adiabatically in a steady-flow
process to 100 bars. Determine the minimum work of compression, in kJ/kmol, if
(a) the generalized charts are used, and (b) the gas is assumed to be ideal.

5. Steam at 280 bars and 520 ‰

is expanded adiabatically and reversibly in a steady-
flow process to 100 bars. Determine the final temperature, in degrees Celsius, and
the change in enthalpy, in kJ/kg, using (a) generalized charts and (b) tabular su-
perheat data.

20
 6. (a) Derive the expression for isothermal change (a) of enthalpy and (b) of entropy
for a substance which fulfills the Berthelot equation of state, which is of the form
P = RT (v − b) − a/T v 2 . (c) Carbon dioxide is compressed in a reversible, adia-
‰
batic, steady-flow process from 10 bars, 30 , to 74 bars. Determine the work of
compression, in kJ/kg, using generalized charts.

7. Refrigerant 134a is throttled from 6 bars and 100 ‰to 4 bars. Determine the final
temperature based (a) on generalized charts and (b) on tabulated superheat data .
The value of cp,0 in this temperature range may be taken to be 0.85 kJ/kg.K

8. (a) Show that the change in volume of a substance can be related to β and KT such
that dv/v = βdT − KT dP . Calculate (b) the heat transfer (c) the work required, in
kJ/kg, when ethane is compressed reversibly and isothermally from 5 to 98 bars at
30 ‰ in a steady-flow process, using generalized charts.

9. Ethylene at 67 ‰ and 1 bar is compressed isothermally in a reversible, nonflow

process to 255 bars. On the basis of generalized charts determine (a) the change in
entropy, in kJ/kmol.K, (b) the work required, in kJ/kmol.

10. Nitrogen at 50 bars and 200 K is contained in a tank of 0.3 m3 . Heat is transferred
to the Nitrogen until the temperature is 300 K. Determine the heat transferred, in
kJ/kmol, and the final pressure, (a) using generalized charts, (b) assuming ideal-gas
behavior, and (c) using data from the superheat table.

11. At 800 K, the value of v for solid copper is 7.215 × 10−3 m3 /kmol (a) Determine
the value of cp − cv for copper, in kJ/kmol.K. (b) If cp is 28.48 kJ/kmol.K, find
the percentage error that would be made in cv if we assumed that cp = cv at this
temperature.

21
Figure 2: The generalized enthalpy chart. PR = P/Pc ; TR = T /Tc ; Tc = critical temper-
∗
ature, Pc = critical pressure, h = enthalpy of an ideal gas; h = enthalpy of an actual
gas. 22
Figure 3: The generalized entropy chart. PR = P/Pc ; TR = T /Tc ; Tc = critical tem-
∗
perature, Pc = critical pressure, h = entropy of an ideal gas; s = entropy of an actual
gas.
23