392 ENGINEERING THERMODYNAMICS

Carbon dioxide 44 0.840 0.650 0.190 1.3 0.274

Water 18 — — 0.462 — 0.230
Methane 16 2.22 1.70 0.520 1.3 —
Sulphur dioxide 64 0.796 0.67 0.126 1.19 0.268
Ammonia 17 — — 0.488 — —

8.11. LAW OF CORRESPONDING STATES

If any two gases have equal values of reduced pressure and reduced temperature, then
they have same values of reduced volume ; i.e., vR = f(Tr , pr) for all gases and the function is the
same.
This law is most accurate in the vicinity of the critical point.

8.12. COMPRESSIBILITY CHART

The compressibility factor (Z) of any gas is a function of only two properties, usually tem-
perature and pressure, so that Z = f(Tr, pr) except near the critical point. The value of Z for any real
gas may be less or more than unity, depending on pressure and temperature conditions of the gas.
The general compressibility chart is plotted with Z versus pr for various values of Tr. This
is constructed by plotting the known data of one or more gases and can be used for any gas. Such
a chart is shown in Fig. 8.10. This chart gives best results for the regions well removed from the
critical state for all gases.

1.2 3.0
5.0
2.0
1.0 1.6
1.4
Z = pv/RT

0.8
1.2
0.6

0.4 Tr = 1.0

0.2

0 1 2 3 4 5 6 7 8 9 10
Reduced pressure p r

Fig. 8.10. Generalised compressibility chart.

IDEAL GASES
Example 8.1. The volume of a high altitude chamber is 40 m3. It is put into operation by
reducing pressure from 1 bar to 0.4 bar and temperature from 25°C to 5°C.
How many kg of air must be removed from the chamber during the process ? Express this
mass as a volume measured at 1 bar and 25°C.
Take R = 287 J/kg K for air.
Solution. V1 = 40 m3 V2 = 40 m3
p1 = 1 bar p2 = 0.4 bar
T1 = 25 + 273 = 298 K T2 = 5 + 273 = 278 K
kg of air to be removed :
Assuming nitrogen to be a perfect gas,

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IDEAL AND REAL GASES 393

FG or m IJ
p1V1
p1V1 = m1RT1
H 1 =
K
RT1
FG or m pV I
p2V2 = m2RT2
H 2 =
RT K
J
2 2
2
Mass of air removed during the process = (m1–m2) kg
p1V1 p2V2
(m1–m2) = −
RT1 RT2

1 FpV p2V2 I= 1 LM (1 × 10 ) × 40 − ( 0.4 × 10 ) × 40 OP

5 5
=
R
GH T1 1
1
−
T2
JK 287 MN 298 278 PQ
= 26.71 kg. (Ans.)
Volume of this mass of gas at 1 bar and 25°C is given by
mRT 26.71 × 287 × 298
V= = = 22.84 m3. (Ans.)
p 1 × 105
Example 8.2. A steel flask of 0.04 m3 capacity is to be used to store nitrogen at 120 bar,
20°C. The flask is to be protected against excessive pressure by a fusible plug which will melt and
allow the gas to escape if the temperature rises too high.
(i) How many kg of nitrogen will the flask hold at the designed conditions ?
(ii) At what temperature must the fusible plug melt in order to limit the pressure of a full
flask to a maximum of 150 bar ?
Solution. Capacity of the steel flask, V = 0.04 m3
Pressure, p = 120 bar
Temperature, T = 20 + 273 = 293 K
(i) kg of nitrogen the flask can hold :
Now, R for nitrogen (molecular weight, M = 28)
R0 8314
= = = 296.9 J/kg K
M 28
Assuming nitrogen to be a perfect gas, we get
Mass of nitrogen in the flask at designed condition
pV 120 × 105 × 0.04
=m= = = 5.51 kg. (Ans.)
RT 296.9 × 293
(ii) Temperature at which fusible plug should melt, t :
When the fusible plug is about to melt
p = 150 bar ; V = 0.04 m3 ; m = 5.51 kg
Therefore, temperature t at which fusible plug must melt is given by
pV 150 × 105 × 0.04
T= = = 366.7 K
mR 5.51 × 296.9
∴ t = 366.7 – 273 = 93.7°C. (Ans.)
Example 8.3. A balloon of spherical shape 6 m in diameter is filled with hydrogen gas at
a pressure of 1 bar abs. and 20°C. At a later time, the pressure of gas is 94 per cent of its original
pressure at the same temperature :

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394 ENGINEERING THERMODYNAMICS

(i) What mass of original gas must have escaped if the dimensions of the balloon is not
changed ?
(ii) Find the amount of heat to be removed to cause the same drop in pressure at constant
volume.
Solution. Diameter of the spherical balloon = 6 m
Pressure of hydrogen gas, p1 = 1 bar abs.
Temperature of hydrogen gas, T1 = 20°C or 293 K
At a later time pressure of the gas, p2 = 0.94p1 at 293 K.
(i) Mass of original gas escaped :
∆m = m1 – m2
[where m1 and m2 are the initial and final masses of the gas]
p1V1 p2V2 V1
= = = (p1 – p2) [ 3 V1 = V2, T1 = T2 and p2 = 0.94p1]
RT1 RT2 RT1
V1 pV
= (p1 – 0.94p1) = 1 1 (1 – 0.94)
RT1 RT1
∆m
∴ %age mass escaped = × 100
m1
p1V1
(1 − 0.94 )
RT1
= = 6%. (Ans.)
p1V1
RT1
(ii) Amount of heat to be removed :
Using the gas equation,
p1V1 p2V2
=
T1 T2

p1 0.94 p1
or = (3 V1 = V2 and p2 = 0.94p1)
T1 T2
∴ T2 = 0.94T1 = 0.94 × 293 = 275.4 K or 2.42°C
The heat to be removed is given by
Q = mcv(T1 – T2)
LM 3 OP
MR = 8314

p1V1 1 × 105 ×
4
3
π × 33
MM∴ R= PP
8314
where m=
RT1
=
8314
× 293
= 9.28 kg
MNas M for H 2 = 2
2
PQ
2
cv = 10400 J/kg K for H2
∴ Q (heat to be removed) = 9.28 × 10400 (293 – 275.4) = 1.69 MJ. (Ans.)
Example 8.4. A vessel of capacity 3 m3 contains 1 kg mole of N2 at 90°C.
(i) Calculate pressure and the specific volume of the gas.
(ii) If the ratio of specific heats is 1.4, evaluate the values of cp and cv.
(iii) Subsequently, the gas cools to the atmospheric temperature of 20°C ; evaluate the final
pressure of gas.

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IDEAL AND REAL GASES 395

(iv) Evaluate the increase in specific internal energy, the increase in specific enthalpy, increase
in specific entropy and magnitude and sign of heat transfer.
Solution. Mass of N2, m = 1 kg mole i.e., 28 kg
Capacity of the vessel, V1 = 3 m3
Temperature, T1 = 90 + 273 = 363 K
(i) Pressure (p1) and specific volume (v1) of the gas :
Using the relation
p1V1 = mRT1
FG 8314 IJ LM3 R0 8314 OP
p1 × 3 = 28 × H 28 K × 363
N R=
M
=
28 Q
∴ p1 = 1005994 J/m2 or 10.06 bar. (Ans.)
V1 3
Specific volume, v1 = = = 0.107 m3/kg. (Ans.)
m 28
(ii) cp = ?, cv = ?
cp
= 1.4 (given) ...(i)
cv
8314
But cp – cv = R = ...(ii)
28
Solving for cp and cv between (i) and (ii)
cp = 1.039 kJ/kg K ; cv = 0.742 kJ/kg K. (Ans.)
(iii) Final pressure of the gas after cooling to 20°C :
Initially After cooling
p1 = 10.06 bar p2 = ?
V1 = 3 m3 V2 = 3 m3
T1 = 363 K T2 = 20 + 273 = 293 K
p1V1 pV
Now, = 2 2
T1 T2
p1 p
or = 2 (as V1 = V2)
T1 T2
p1T2 10.06 × 293
∴ p2 = = = 8.12 bar. (Ans.)
T1 363
(iv) ∆u, ∆h, ∆s, Q :
For a perfect gas,
Increase in specific internal energy
∆u = cv(T2 – T1) = 0.742(293 – 363) = – 51.94 kJ/kg. (Ans.)
Increase in specific enthalpy,
∆h = cp(T2 – T1) = 1.039(293 – 363) = – 72.73 kJ/kg. (Ans.)
Increase in specific entropy,
FT I FG v IJ
∆s = cv loge GH T JK
2
1
+ R loge
2
Hv K
1

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396 ENGINEERING THERMODYNAMICS

But v1 = v2
FG T IJ FG 293 IJ = – 0.1589 kJ/kg K.
H 363 K
2
∴ ∆s = cv loge
HT K 1
= 0.742 loge (Ans.)

Now, Q = ∆u + W
Here W = 0 as change in volume is zero
∴ Q = ∆u
∴ Heat transfer, Q = – 51.94 kJ/kg = – 51.94 × 28 = – 1454.32 kJ. (Ans.)
Example 8.5. (a) 1 kg of air at a pressure of 8 bar and a temperature of 100°C undergoes
a reversible polytropic process following the law pv1.2 = constant. If the final pressure is 1.8 bar
determine :
(i) The final specific volume, temperature and increase in entropy ;
(ii) The work done and the heat transfer.
Assume R = 0.287 kJ/kg K and γ = 1.4.
(b) Repeat (a) assuming the process to be irreversible and adiabatic between end states.
Solution. (a) Mass of air, m = 1 kg
Pressure, p1 = 8 bar
Temperature, T1 = 100 + 273 = 373 K
The law followed : pv1.2 = constant
Final pressure, p2 = 1.8 bar
Characteristic gas constant, R = 0.287 kJ/kg K
Ratio of specific heats, γ = 1.4
(i) v2, T2 and ∆s :
Assuming air to be a perfect gas,
p1v1 = RT1
RT1 ( 0.287 × 1000) × 373
∴ v1 = = = 0.1338 m3/kg
p1 8 × 105
Also, p1v11.2 = p2v21.2

v2 FG p IJ 1
1/1.2

or v1 = Hp K 2

= v G J
Fp I 1/1.2
FG 8 IJ 1/1.2

H 1.8 K
1
or v2 1 Hp K 2
= 0.1338 = 0.4637 m3/kg

i.e., Final specific volume, v2 = 0.4637 m3/kg. (Ans.)

Again, p2v2 = RT2
p2v2 1.8 × 105 × 0.4637
T2 = = = 290.8 K
R ( 0.287 × 1000)
i.e., Final temperature, t2 = 290.8 – 273 = 17.8°C. (Ans.)
Increase in entropy ∆s is given by,
FG T IJ Fv I
∆s = cv loge 2
HT K
1
+ R loge GH v JK
2
1

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IDEAL AND REAL GASES 397

cp
But γ= = 1.4 (given) ...(i)
cv
and cp – cv = R (= 0.287 kJ/kg K for air) ...(ii)
Solving for cv between (i) and (ii),
cv = 0.717 kJ/kg K
FG 290.8 IJ FG 0.4637 IJ
∴ ∆s = 0.717 loge
H 373 K + 0.287 loge
H 01338
. K
= – 0.1785 + 0.3567 = 0.1782 kJ/kg K
i.e., Increase in entropy, ∆s = 0.1782 kJ/kg K. (Ans.)
(ii) Work done and heat transfer :
The work done in a polytropic process is given by,
p1v1 − p2v2 R(T1 − T2 )
W= =
n −1 n −1

0.287 (373 − 290.8 )

= = 117.96 kJ/kg
(1.2 − 1)
i.e., Work done = 117.96 kJ/kg. (Ans.)
Heat transfer, Q = ∆u + W
where ∆u = cv(T2 – T1)
= 0.717 (290.8 – 373) = – 58.94 kJ/kg
∴ Q = – 58.94 + 117.96 = 59.02 kJ/kg
Hence heat transfer = 59.02 kJ/kg. (Ans.)
(b) (i) Though the process is assumed now to be irreversible and adiabatic, the end states are
given to be the same as in (a). Therefore, all the properties at the end of the process are the
same as in (a). (Ans.)
(ii) As the process is adiabatic, Q (heat transfer) = 0. (Ans.)
∆u = ∆u in (a)
Applying first law for this process
Q = ∆u + W
0 = ∆u + W
or W = – ∆u
= – (– 58.94) = 58.94
∴ Work done = 58.94 kJ/kg. (Ans.)
Example 8.6. Two spheres each 2.5 m in diameter are connected to each other by a pipe
with a valve as shown in Fig. 8.11. One sphere contains 16 kg of air and other 8 kg of air when the
valve is closed. The temperature of air in both sphere is 25°C. The valve is opened and the whole
system is allowed to come to equilibrium conditions. Assuming there is no loss or gain of energy,
determine the pressure in the spheres when the system attains equilibrium.
Neglect the volume of the pipe.

4 4 FG 2.5 IJ 3
Solution. Volume of each sphere =
3
πR3 =
3
π×
H 2K = 8.18 m3

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398 ENGINEERING THERMODYNAMICS

Spheres

1 2

2.5 m 2.5 m

Fig. 8.11

The temperature in both spheres is same (25°C)

i.e., T1 = T2 = 25 + 273 = 298 K
As no energy exchange occurs, the temperature reached after equilibrium is 298 K.
Mass of air in sphere 1, m1 = 16 kg
Mass of air in sphere 2, m2 = 8 kg
After opening the valve
Total volume, V = 8.18 + 8.18 = 16.36 m3
Total mass, m = m1 + m2 = 16 + 8 = 24 kg
Now using characteristic gas equation
pV = mRT
mRT 24 × 287 × 298
∴ p= = = 1.255 × 105 N/m2 or 1.255 bar
V 16.36
Hence pressure in the spheres when the system attains equilibrium
= 1.255 bar. (Ans.)
Example 8.7. CO2 flows at a pressure of 10 bar and 180°C into a turbine, located in a
chemical plant, and there it expands reversibly and adibatically to a final pressure of 1.05 bar.
Calculate the final specific volume, temperature and increase in entropy. Neglect changes in
velocity and elevation.
If the mass flow rate is 6.5 kg/min. evaluate the heat transfer rate from the gas and the
power delivered by the turbine.
Assume CO2 to be a perfect gas and cv = 0.837 kJ/kg K.
Solution. At entry to turbine At exit of turbine
Pressure, p1 = 10 bar Pressure, p2 = 1.05 bar
Temperature, T1 = 180 + 273 = 453 K
Since the expansion is reversible and adiabatic, therefore, the equation pvγ = constant is
applicable.
∴ p1v1γ = p2v2γ ...(i)
Eliminating v1 and v2 using the perfect gas equation
RT
v=
p
We can write equation (i) as

T1 FG p IJ
1
( γ − 1 )/ γ

T2
=
Hp K
2

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IDEAL AND REAL GASES 399

453 FG 10 IJ ( γ − 1)/ γ
∴
T2
=
H 1.05 K
cv = 0.837 kJ/kg K (given)
R0 8.314
R= = (Molecular weight of CO2 = 44)
M 44
= 0.1889 kJ/kg K
Also cp – cv = R
∴ cp – 0.837 = 0.1889
cp = 1.0259 kJ/kg K
cp 1.0259
∴ γ= = = 1.23
cv 0.837
Substituting for γ in equation (ii)
453 FG 10 IJ (1.23 − 1)/1.23

T2
=
H 1.05 K
∴ T2 = 297 K
Final temperature = 297 – 273 = 24°C. (Ans.)
p2v2 = RT2
∴ 1.05 × 105 × v2 = (0.1889 × 1000) × 297
( 01889
. × 1000) × 297
∴ v2 = = 0.5343 m3/kg
1.05 × 105
i.e., Final specific volume = 0.5343 m3/kg. (Ans.)
As the process is reversible and adiabatic
∆s = 0
i.e., Increase in entropy = 0. (Ans.)
Since the process is adiabatic, therefore, heat transfer rate from turbine = 0. (Ans.)
Applying steady flow energy equation (S.F.E.E.) on unit time basis,
LM
 h1 +
m
C12 OP
+ Z1 + Q = m
C2 LM
 h2 + 2 + Z2 + W
OP
MN 2 PQ 2 MN PQ
By data changes in velocity and elevation are negligible, and Q = 0.
∴ S.F.E.E. reduces to
i.e.,  (h1 – h2)
W= m
LMas dh = c p , h1
OP
− h2 = c p (T1 − T2 )
 cp(T1 – T2)
= m
N dT Q
6.5
=
× 1.0259 (453 – 297) = 17.34 kW
60
Hence power delivered by the turbine = 17.34 kW. (Ans.)
Example 8.8. A certain quantity of air initially at a pressure of 8 bar and 280°C has a
volume of 0.035 m3. It undergoes the following processes in the following sequence in a cycle :
(a) Expands at constant pressure to 0.1 m3,

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400 ENGINEERING THERMODYNAMICS

(b) Follows polytropic process with n = 1.4, and

(c) A constant temperature process (which completes the cycle).
Evaluate the following :
(i) The heat received in the cycle ;
(ii) The heat rejected in the cycle ;
(iii) Efficiency of the cycle.
Solution. Fig. 8.12 shows the cycle on p-V and T-s planes.

p(Pressure) T(Temp.)

p = Constant 2
1 2
p = Const.
n
n
pV = Const.
pV = Const.

1 3
pV = Const. 3 T = Const.
V(Volume) s (Entropy)

Fig. 8.12

Pressure, p1 = 8 bar
Volume, V1 = 0.035 m3
Temperature, T1 = 280 + 273 = 553 K
Pressure, p2 = 8 bar (= p1)
Volume, V2 = 0.1 m3
Index, n = 1.4
To find mass of air, use the relation
p1V1 = mRT1
p1V1 8 × 105 × 0.035
∴ m= = = 0.1764 kg
RT1 287 × 553
From p2V2 = mRT2
p2V2 8 × 105 × 01
.
T2 = = = 1580 K
mR 01764
. × 287
Also, p2V21.4 = p3V31.4

T2 FG p IJ
2
(1.4 − 1 )/1.4

and
T3
=
Hp K
3
But T3 = T1 as 1 and 3 are on an isothermal line.

1580 FG 8 IJ 0.4 /1.4

∴
553
=
Hp K
3

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F8I 0.2857
2.857 = GH p JK 3

8 8
p3 = 1/ 0.2857 = = 0.2 bar
( 2.857) ( 2.857)3.5
Now, p3V3 = mRT3
∴ 0.2 × 105 × V3 = 0.1764 × 287 × 553
01764
. × 287 × 553
∴ V3 = = 1.399 m3
0.2 × 105
(i) The heat received in the cycle :
Applying first law to the constant pressure process 1-2,
Q = ∆U + W

W= z1
2

= p(V2 – V1)
pdV (as the process is reversible)

= 8 × 105 (0.1 – 0.035)

= 52000 J or 52 kJ (work done by air)
∴ Q = m × cv(T2 – T1) + 52
= 0.1764 × 0.71(1580 – 553) + 52 = 180.6 kJ
i.e., Heat received = 180.6 kJ
Applying first law to reversible polytropic process 2-3
Q = ∆U + W
p2V2 − p3V3 mR(T2 − T3 )
But W= =
n −1 n −1
01764
. × 0.287 (1580 − 553)
= = 129.98 kJ (work done by air)
1.4 − 1
∴ Q = mcv(T3 – T2) + 129.98
= 0.1764 × 0.71 (553 – 1580) + 129.98
= – 128.6 + 129.98 = 1.354 kJ (heat received)
∴ Total heat received in the cycle = 180.6 + 1.354 = 181.954 kJ. (Ans.)
(ii) The heat rejected in the cycle :
Applying first law to reversible isothermal process 3-1,
Q = ∆U + W
FG V IJ
1
W = p3V3 loge
HV K
3

FG 0.035 IJ
= 0.2 × 105 × 1.399 × loge
H 1399
. K × 10–3

= – 103.19 kJ (work done on the air)

∴ Q = mcv(T1 – T3) + W
= 0 – 103.19 = – 103.19 kJ (3 T1 = T3)
Hence heat rejected in the cycle = 103.19 kJ. (Ans.)

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(ii) Efficiency of the cycle, ηcycle :

Heat received − Heat rejected
ηcycle =
Heat received
181.954 − 10319
.
= = 0.433 or 43.3%
181.954
i.e., Efficiency of the cycle = 43.3%. (Ans.)

REAL GASES
Example 8.9. One kg of CO2 has a volume of 1 m3 at 100°C. Compute the pressure by
(i) Van der Waals’ equation
(ii) Perfect gas equation.
Solution. (i) Using Van der Waals’ equation :
Molar specific volume, v = 1 × 44 = 44 m3/kg-mol (3 M for CO2 = 44)
Temperature, T = 100 + 273 = 373 K
The values of a and b for CO2 (from Table 8.1)
a = 362850 Nm4/(kg-mol)2
and b = 0.0423 m3/kg-mol
R0 = 8314 Nm/kg-mol K
Van der Waals’ equation is written as
FG p + a IJ
H vK 2 (v − b ) = R0T

FG R T − a IJ
0
or p=
Hv − b v K
2

Substituting the values in the above equation, we get

8314 × 373 362850
∴ p= –
44 − 0.0423 442
= 70548 – 187 = 70361 N/m2 or 0.7036 bar. (Ans.)
(ii) Using perfect gas equation :
p v = R0T
R0T 8314 × 373
∴ p= = = 70480 N/m2 or 0.7048 bar. (Ans.)
v 44
Example 8.10. A container of 3 m3 capacity contains 10 kg of CO2 at 27°C. Estimate the
pressure exerted by CO2 by using :
(i) Perfect gas equation
(ii) Van der Waals’ equation
(iii) Beattie Bridgeman equation.
Solution. Capacity of the container, V = 3 m3
Mass of CO2, m = 10 kg
Temperature of CO2, T = 27 + 273 = 300 K
Pressure exerted by CO2, p :

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IDEAL AND REAL GASES 403

(i) Using perfect gas equation :

R0 8314
Characteristic gas constant, R = = = 188.95 Nm/kg K (for CO2)
M 44
Using perfect gas equation
pV = mRT
mRT 10 × 188.95 × 300
∴ = p=
V 3
= 188950 N/m2 or 1.889 bar. (Ans.)
(ii) Using Van der Waals’ equation :
FG p + a IJ (v − b) = R0T
H vK 2

R0T a
p= – 2
v −b v
From Table 8.1
For CO2 : a = 362850 Nm4/(kg-mol)2
b = 0.0423 m3/(kg-mol)
3 × 44
v = Molar specific volume = = 13.2 m3/kg-mol
10
Now substituting the values in the above equation, we get
8314 × 300 362850
p= –
13.2 − 0.0423 (13.2)2
= 189562 – 2082.5 = 187479.5 N/m2 or 1.875 bar. (Ans.)
(iii) Using Beattie Bridgeman equation :
R0T (1 − e ) A
p= (v + B ) −
(v )2 v2

FG a IJ FG
b IJ c
where p = pressure, A = A0 1 −
H v K
, B = B0 1 −
vH K
and e =
vT3
From Table 8.2 A0 = 507.2836, a = 0.07132
B0 = 0.10476, b = 0.07235
C = 66 × 104
FG1 − 0.07132 IJ = 504.5
∴ A = 507.2836
H 13.2 K
FG1 − 0.07235 IJ = 0.1042
B = 0.10476 H 13.2 K
66 × 104
C= = 0.001852
13.2 × ( 300 )3
Now substituting the various values in the above equation, we get
8314 × 300(1 − 0.001852) 504.5
p= (13.2 + 0.1042) –
(13.2)2 (13.2)2
_ 1.9 × 105 N/m2 = 1.9 bar. (Ans.)
= 190093 – 2.89 ~

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Example 8.11. One kg-mol of oxygen undergoes a reversible non-flow isothermal compres-
sion and the volume decreases from 0.2 m3/kg to 0.08 m3/kg and the initial temperature is 60°C.
If the gas obeys Van der Waals’ equation find :
(i) The work done during the process (ii) The final pressure.
Solution. The Van der Waals’ equation is written as
FG p + a IJ
H vK 2 (v − b) = R0T

where p = pressure of the gas ; a, b = constants ; v = molar volume ; R0 = universal gas constant
From Table 8.1
For O2 : a = 139250 Nm4/(kg-mol)2
b = 0.0314 m3/kg-mol
and R0 = 8314 Nm/kg-mol K
v1 = 0.2 × 32 = 6.4 m3/kg-mol
v2 = 0.08 × 32 = 2.56 m3/kg-mol.
(i) Work done during the process :
The work done per kg mole of O2 is given by

W=
z
1
2
p . dv = z LMMNFGH
IJ OP
2

K PQ
1
R0T
v −b
a
− 2 dv
v

L O LaO
= R T M log ( v − b)P + M P
v2 v2

MN0
PQ N v Q
e
v1 v1

L F v − b I OP + LMa F 1 − 1 I OP
= R T M log G
MN H v − b JK PQ MN GH v v JK PQ
2
0 e
1 2 1

L F 2.56 − 0.0314 I OP + LM139250 FG 1 − 1 IJ OP

= 8314 × (60 + 273) M log G
MN H 6.4 − 0.0314 JK PQ N
e
H 2.56 6.4 K Q
= – 2557359 + 32636 = – 2524723 Nm/kg-mol. (Ans.)
(ii) The final pressure, p2 :
R0T a
p2 = −
v2 − b v22
8314 × 333 139250
= − = 1073651 N/m2 or 10.73 bar. (Ans.)
2.56 − 0.0314 ( 2.56)2
Example 8.12. If the values for reduced pressure and compressibility factor for ethylene
are 20 and 1.25 respectively, compute the temperature.
Solution. Reduced pressure, pr = 20
Compressibility factor, Z = 1.25
Temperature, T=?
From the generalised compressibility chart on Z – pr co-ordinates corresponding to pr = 20
and Z = 1.25, Tr = 8.0.
Now, since T = Tc Tr
∴ T = 282.4 × 8.0 [From Table 8.3, Tc = 282.4 K]
= 2259.2 K. (Ans.)

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 IDEAL AND REAL GASES 405

Example 8.13. Calculate the density of N2 at 260 bar and 15°C by using the compressibility
chart.
~ Solution. Pressure, p = 260 bar
−
Temperature, T = 15 + 273 = 288 K
Density, ρ= ?
For N2 (from Table 8.3) : pc = 33.94 bar
Tc = 126.2 K
p 260
Now pr = = = 7.6
pc 33.94
T 288
and Tr = = = 2.28
Tc 126.2
From the compressibility chart for pr = 7.6 and Tr = 2.28, Z ~
− 1.08
pv p
Also Z= = , where ρ stands for density
RT ρRT

p 260 × 105
or ρ= = 8314 = 281.5 kg/m3. (Ans.)
ZRT 1.08 × × 288
28
Example 8.14. What should be the temperature of 1.3 kg of CO2 gas in a container
at a pressure of 200 bar to behave as an ideal ?
Solution. Pressure, p = 200 bar
Temperature, T=?
For CO2 (from Table 8.3) pc = 73.86 bar
Tc = 304.2 K
As the gas behaves like an ideal gas, Z = 1

p 200
pr = = = 2.7
pc 73.86
From compressibility chart for Z = 1, pr = 2.7
Tr = 2.48
∴ T = Tr × Tc = 2.48 × 304.2 = 754.4 K. (Ans.)
Example 8.15. A spherical shaped balloon of 12 m diameter contains H2 at 30°C and
1.21 bar. Find the mass of H2 in the balloon using real gas equation.
Solution. Diameter of spherical balloon = 12 m
∴ Volume, V = 4/3 π × (6)3 = 904.78 m3
Temperature, T = 30 + 273 = 303 K
Pressure, p = 1.21 bar
Mass of H2 in the balloon, m :
For H2 (from Table 8.3) pc = 12.97 bar
Tc = 33.3 K
p 1.21
Now, pr = = = 0.093
pc 12.97
T 303
Tr = = = 9.1
Tc 33.3

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406 ENGINEERING THERMODYNAMICS

From compressibility charge, corresponding to pr = 0.093 and Tr = 9.1

− 1
Z ~
(This indicates that the gas having higher critical pressure and lower critical temperature
behaves like an ideal gas at normal pressure and temperature conditions.)
Also, pV = ZmRT
pV 1.21 × 105 × 904.78
or
ZRT
=
m=
8314 FG
= 86.9 kg. (Ans.)
IJ
1×
2
× 303
H K
Example 8.16. Determine the value of compressibility factor at critical point (Zcp) for the
Van der Waals’ gas.
Solution. Refer Fig. 8.13.

p
C.P. C.P. = Critical point
pcp

Isotherms

v
vcp

Fig. 8.13

From the isotherms plotted on p-v diagram in Fig. 8.13 it can be seen that the critical
isotherms has an inflection point, whose tangent is horizontal at the critical point.

FG ∂p IJ ∂2 p
H ∂v K
c
= 0 and ∂v2 =0
cp cp
The Van der Waal’s equation at the critical point is
R0 Tcp a
pcp = − ...(i)
vcp − b vcp 2

F ∂p I
As Tcp is constant GH ∂v JK = − (vR T− b) + v2a
cp

cp
0 cp
2 3
=0 ...(ii)
cp cp

F ∂ p I 2 R T 6a
2
GGH ∂v JJK =
cp
2 −
0 cp
3 4 =0 ...(iii)
cp (v − b)cp (v ) cp

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IDEAL AND REAL GASES 407

F3I
GH v JK
cp
× (ii) + (iii) gives

3 R0 T 2 R0 T
− + =0
vcp (vcp − b )2 (vcp − b)3
3 2
or =
vcp ( vcp − b)

or vcp = 3b
Substituting for b in (ii), we get
R0Tcp 2a
− + =0
[ vcp − (1 / 3) vcp ]2 ( vcp )3
9
∴ a= RT v
8 0 cp cp
Substituting for a and b in (i), we get
R0Tcp ( 9 / 8 ) R0 Tcp vcp
pcp = –
vcp − (1 / 3 ) vcp vcp 2

pcp vcp 1 ( 9 / 8)
∴ = –
R0 Tcp ( 2 / 3) 1
pcp vcp
But = Zcp
R0 Tcp
3 9 3
∴ Zcp = − = . (Ans.)
2 8 8

HIGHLIGHTS

1. An ‘ideal gas’ is defined as a gas having no forces of intermolecular attraction. It obeys the law pv = RT. The
specific heat capacities are not constant but are functions of temperature.
A ‘perfect gas’ obeys the law pv = RT and has constant specific heat capacities.
2. The relation between the independent properties, such as pressure, specific volume and temperature for a
pure substance is known as ‘equation of state’.
3. Each point on a p-v-T surface represents an equilibrium state and a line on the surface represents a
process.
4. Joule’s law states that the specific internal energy of a gas depends only on the temperature of the gas and
is independent of both pressure and volume.
5. Van der Waals’ equation may be written as

FG p + a IJ
H v2 K (v – b) = RT

where a and b are constants for the particular fluid and R is the gas constant.

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