Chapter 3

August 20,
PROBLEMS ZAID YAHYA 11-CH-74

2013
Chapter 3
Problems
Problem 3.1:
Express the volume expansivity and isothermal compressibility as functions of density and its partial
6
derivatives. The isothermal compressibility coefficient () of water at 50 oC and 1 bar is 44.1810
bar-1. To what pressure must water be compressed at 50 oC to change its density by 1%? Assume that is
independent of P.
Given Data:
1 V
Volume expansivity== ( )
V T P
Or
1 dV
= ( ) (1)
V dT P
1 V
Isothermal Compressibilty==
V P( ) T
Or
1 dV
= ( ) ( 2)
V dP T
Temperature=T =50 0
C

1 kg kg kg
Pressure=P1=1 Density of water =1=1 2=( 1+1 ) 2=1.01
=44.18106 m3 m3 m3
P2=?
Solution:
(a)
We know that
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August 20,
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1 1
= V=
V
Put in (1) & (2)
d
= ( dTd 1 ) P
=
dT
2 ( ) P
=
1 d
dT( ) Proved
P
Now,
d 1 d 1 d
= ( dP )
T
= ( )
2 dP T
= ( ) Proved
dP T
(b)
As
1 d d
= ( )
dP T
dP=

Integrating on both sides

P2 2
d P2 2 2
dP= |P|P =|ln | ( P2 P 1 )=( ln 2ln 1 ) ( P2 P 1 )=ln
P1 1
1 1
1
Putting values
( P21 )= ln1.01
1 44.1810
6
P2=( 225.22+1 ) P2=226.22
44.1810 6 Answer
P21=0.00995

Problem 3.2:
Generally, volume expansivity and isothermal compressibility depend on T and P. Prove that
( P ) =( T )
T P
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August 20,
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Solution:
We know that
1 V
V T P
Since is very small
1 V 1 V
V= ( ) (1)
T P
Isothermal Compressibilty== ( )
V P T
Since is very small
1 V 1 V V 1 1 1
V=
P( )T
( ) =1
T ( P)
P T
( ) V =1
T (P)
P
V
T
( T ) =( P )
P T
( P ) =( T ) Proved
T P
Problem 3.3:
The Tait equation for liquids is written for an isotherm as:

AP
(
V =V 0 1
B+ P )
Where V is specific or molar volume, Vo is the hypothetical molar or specific volume at P = 0 and A & B
are positive constant. Find an expression for the isothermal compressibility consistent with this equation.
Solution:
We Know That,
1 V
Isothermal Compressibilty== ( ) (1)
V P T
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August 20,
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Given that
AP
(
V =V 0 1
B+ P )
Where
V0 = Hypothetical molar/specific volume at zero pressure, so it is constant
V = Molar/specific volume
Now,
AP
V =V o V
B+ P o
AP V V o AP
V V o = V =
B+ P o Vo B+ P
Differentiate w.r.t Pressure

1
V o P
AP
(
( V V o ) = P B + P ) 1 V
(
V o P )
0 =
[
A ( B+ P ) AP ( 1 )
( B+ P )2 ]
1 V AB+ AP AP 1 V AB
Vo P( )
=
( B+ P )2 ( ) =
V o P ( B+ P )2
Since, Temperature is constant

Therefore,
1 V AB
( )=
V o P T ( B+P )2
Or, From (1)
AB
= Proved
( B+ P )2
Problem 3.4:
For liquid water the isothermal compressibility is given by:

c
=
V ( P+b )
Where c & b are functions of temperature only if 1 kg of water is compressed isothermally & reversibly
from 1 bar to 500 bars at 60 oC, how much work is required?
At 60 oC, b=2700 bars and c = 0.125 cm3 g-1
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Given Data:
c
Isothermal compressibility== Mass of water=m=1 kg Pressure=P1=1
V ( P+ b )
P2=500 bars
Temperature=T =60 0
C
b=2700 bars c=0.125 cm3 / g Work=W =? Solution:
We know that
W = PdV (1)
c
= (2)
V ( P+b )
Also
1 dV
= ( ) ( 3)
V dP T
Comparing (2) & (3)
1 dV c c dP
= dV =
V dP V ( P+b ) P+b
Put in (1)
P2 P2 P2 P2
c dP P P+bb P+b b
W =P W =c dP W =c dP W =c dPc dP
P+b P
P+b
1 P
1
P+ b P1
P+b P
P+ b 1
P2 P2
1 P2 P2
W =c ( P2 P 1) bc [ ln ( P2 +b ) ln ( P1 +b ) ]
W =c dPb c dP W =c|P|P bc|ln (P+b)|P
P1 P1
P+b 1 1
W =c ( P2 P 1) bc ln
[ P2 +b
P1 +b ]
Putting values
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August 20,
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3
cm
3
3 3 g cm
cm ( 0.125 cm ln 500+ 2700 3
W =0.125 5001 )2700
cm g
g g 1+2700 57.216
g W =5.16
W =62.375
3
cm
1 m3
g
101325 N
1003 cm 3 W =0.516
J
Answer
J
1.01325 m2 g
Nm
W =5.16
Problem 3.5:
Calculate the reversible work done in compressing 1 ft 3 of mercury at a constant temperature of 32F from
1(atm) to 3,000(atm). The isothermal compressibility of mercury at 32F is:
/(atm)-1 = 3.9 x 10-6 - 0.1 x10-9P(atm)
Given Data:
Work done=W =? Volume=V =1 ft 3 Temperature=T =32 F Pressure=P1=1 atm
Pressure=P2=3000 atm /atm1=3.91060.1109 P (atm)
Where
Term, 3.9*10-6 has unit of atm-1 & 0.1*10-9 has units of atm-2
Solution:
We know that, work done for a reversible process is
W = PdV (1)
Also
1 dV
= ( )
V dP T
dV =VdP
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August 20,
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Put in (1),
P2
W = P (Vdp ) W =V P dP
P1
P2 P2 P2
2
W =V ( 3.910 0.110 P ) P dP W =V 3.910 P dPV 0.110 P dP
6 9 6 9
P1 P1 P1
3000 3000
W =3.910 V 6
P dP0.110 V 9
P2 dP
1 1
3000 3000
W =3.910 V
P2
6
2 || 1
9
0 .110 V
P3
3 || 1
1.951061 ft 3 ( 3.33310111 ft 3 (
W= 3000212 ) atm2 2
3000313 ) atm3
atm atm
W = (17.550.8991 ) atmft 3 W =16.65atmft 3 Answer
Problem 3.6:
Five kilograms of liquid carbon tetrachloride undergo a mechanically reversible, isobaric change of state
at 1 bar during which the temperature change from 0 oC to 20oC. Determine Vt, W, Q, and Ut. The
properties for liquid carbon tetrachloride at 1 bar & 0 oC may be assumed independent of temperature: =
1.2 x 10-3 K-1 Cp = 0.84 kJ kg-1 K-1, = 1590 kg m-3
Given Data:
Mass=m=5 kg Pressure=P=1
Temperature=T 1=0 0
C
T 1 =273.15 K
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August 20,
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Temperature=T 2=20 0
C
kJ kg
T 2 =( 20+273.15 ) K T 2 =293.15 K =1.210 K
3 1
C P=0.84 =1590 t
V =? W =?
kgK m3
t
Q=? U =?
Solution:
As
1 1 1 m3
V= V 1= V 1=
1 1590 kg
Also,
we know that
1 dV 1
V dT P
dT =
V
dV
Integrating on both sides,

T2 V2
dV T2 V2 V2
dT = |T |T =|lnV |V ( T 2T 1 )=( lnV 2ln V 1 ) ( T 2T 1 )=ln
T1 V1
V 1 1
V1
Putting values
1.024
1.210
3
V 1590 kg V 21590 kg m3
( 293.15273.15 ) K =ln 2 0.024
e = 1590
K m3 m3 V 2=
kg
m3
V 2=0.000644
kg
Now,
1 m3 m
3
V =V 2V 1 (
V = 0.000644 )
1590 kg
V =15.28106
kg
Now, for total volume,
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August 20,
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m3
V t = V m V t =( 15.281065 ) kg V t =7.638105 m3 Answer
kg
Now,
We know that for a reversible process,
m3101325 N
J
1.01325 m2
Work done=W =P V t 1 kJ W =7.638103 kJ Answer
Nm
W =1 7.638105
1000 J
Now,
For a reversible process at constant pressure,we have
kJ
Q= H Q=m C P T Q=5 kg0.84 ( 293.15273.15 ) K Q=84 kJ Answer
kgK
Now,
According to first law of thermodynamics,
U t =Q+W U t =( 847.368103 ) kJ U t =83.99 kJ Answer
Problem 3.7:
A substance for which k is a constant undergoes an isothermal, mechanically reversible process from
initial state (P1, V1) to (P2, V2), where V is a molar volume.
a) Starting with the definition of k, show that the path of the process is described by
V = A ( T ) exp (P)
b) Determine an exact expression which gives the isothermal work done on 1 mol of this constant-k
substance.
Solution:
(a)
We know that
1 dV dV
Isothermal compressibilty == ( )
V dP T V
=dP
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August 20,
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dV
V
= dP
lnV =P+lnA ( T )
Where ln A (T) is constant of integration & A depends on T only

lnV lnAT =P
V
ln =P
A (T )
Taking anti log on both sides,
V
=eP V = A ( T ) eP
AT
Or
V = A ( T ) exp (P ) Proved
(b)
Work done=W=?
For a mechanically reversible process, we have,
dW =PdV ( 1 )
Using,
d ( PV ) =PdV +VdP PdV =VdP d ( PV )
Put in (1)
dW =VdPd ( PV ) ( 2 )
We know that
1 dV
Isothermal compressibilty == ( )
V dP T
dV

=VdP
Put in (2)
dV
dW = d ( PV )

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August 20,
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1
dW = dV d ( PV )
1
W= V ( PV )

Since volume changes from V1 to V2 & pressure changes from P1 to P2 ,
Therefore,
W=
1 ( V 1V 2 )

( V 2V 1 ) ( P2 V 2P1 V 1 ) W= + P1 V 1P2 V 2 Proved

Problem 3.8:
One mole of an ideal gas with C V = 5/2 R, CP = 7/2 R expands from P 1 = 8 bars & T1= 600 K to P2 = 1 bar
by each of the following path:
a) Constant volume
b) Constant temperature
c) Adiabatically
Assuming mechanical reversibility, calculate W, Q, U, and H for each of the three processes.
Sketch each path in a single PV diagram.
Given Data:
5 7
CV = R C P= R P1=8 T 1 =600 K P2=1 W =? Q=? U =? H=?
2 2
Solution:
(a)
According to first law of thermodynamics,
U =Q+W (1)
For a constant volume process,

W =0 U =CV T
Put in (1)
Q=U =C V T Q=U =C V ( T 2 T 1 ) (2)
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August 20,
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For T2 , We know that for an ideal gas
T1 T 2 T1 8 1
= T2= P 600 K T 2 =75 K
P1 P2 P1 2 T2=
Put in (2),
5 5 J J
Q=U = R ( 75600 ) K Q=U = 8.314 525 K Q=U =10912
2 2 molK mol
kJ
Q=U =10.912 Answer
mol
Also
For a mechanically reversible process we have,
7 7 J J
H=C P T H= R ( T 2T 1 ) H= 8.314 ( 75600 ) K H=15277
2 2 molK mol
kJ
H=15.277 Answer
mol
(b)
For a constant temperature process,

U =0 H=0
We know that at constant temperature, work done is

P2
W =R T 1 ln
P1
J 1 J kJ
W =8.314 600 Kln W =10373 W =10.373 Answer
molK 8 mol mol
Now, according to first law of thermodynamics,
U =Q+W 0=Q+ W Q=W
Or
kJ
Q=10.373 Answer
mol
(c)
We know that for an adiabatic process
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August 20,
2013
Q=0
Now, according to first law of thermodynamics,
U =Q+W U =W (1)
U =CV T
Put in (1)
W = U=C V T W = U=C V ( T 2T 1 ) (2)
For T2 , We know that for an adiabatic process

( 1 )
P1 ( 11.4 )
( ) 8
()
( 1 ) ( 1 )
T1 P
=T 2 P T 2 =T 1
T 2 =600 K 1.4 T 2 =331.23 K
1 2 P2 1
Put in (2)
5 5 J J
W = U= R( 331.23600 ) K W = U= 8.314 268.77 K W = U=5586.4
2 2 molK mol
J
W = U=5.5864 Answer
mol
For a mechanically reversible adiabatic process we have
7 7 J
H=C P T H= R ( T 2T 1 ) H= 8.314 ( 331.23600 ) K
2 2 molK
J
H=7.821 Answer
mol
Problem 3.9:
An ideal gas initially at 600k and 10 bar undergoes a four-step mechanically reversible cycle in a closed
system. In step 12, pressure decreases isothermally to 3 bars; in step 23, pressure decreases at constant
volume to 2 bars; in step 34, volume decreases at constant pressure; and in step 41, the gas returns
adiabatically to its initial state. Take CP = (7/2) R and CV = (5/2) R.
a) Sketch the cycle on a PV diagram.
b) Determine (where unknown) both T and P for states 1, 2, 3, and 4.
c) Calculate Q, W, U, and H for each step of the cycle.
Given Data:
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August 20,
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7 5
Initial Temperature=T 1=600 K Initial Pressure=P1=10 C P= R CV = R
2 2
Solution:
(b)
Step 12, an Isothermal process,

Since
For an isothermal process, temperature is constant
Therefore,
T 2 =T 1=600 K P2=3
We know that, for an ideal gas
2

1.01325 m
Nm
RT 2 101325 N m
3
P2 V 2 =R T 2 V 2= molK3 V 2=0.0166
P2 J mol
8.314J600 K
V 2=

Step 23, an Isochoric process,

Since
For an isochoric process, Volume is constant
Therefore,
m3 P3=2
V 3=V 2=0.0166
mol
2 0.0166 m 3molK
J
P3 V 3 mol8.314 J
P3 V 3 =RT 3 T3= 101325 N T 3 =400 K
R Nm
T3=
1.01325 m2
Step 34, an Isobaric process,

Since
For an isobaric process, pressure is constant
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August 20,
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Therefore,
P4 =P 3=2
For T4 , we will use an adiabatic relation of temperature and pressure

As
R R
T 4 P4 P4 2R
T1
=
( )
P1
CP
T 4=T 1
( )
P1
CP
T 4=600 K
2
( )
10
7R T 4=378.83 K
2
1.01325
m
Nm
RT4 101325 N m
3
P4 V 4 =RT 4 V 4= molK2 V 4 =0.0157
P4 J mol
8.314 J378.83 K
V 4=

Step 41, an adiabatic process,

Since
Gas returns to its initial state adiabatically
Therefore,
T 1 =600 K P1=10
1.01325 m2
Nm
RT 1 101325 N m
3
P1 V 1=R T 1 V 1= molK10 V 1=4.988103
P1 J mol
8.314 J600 K
V 1=

(c)
Step 12, an Isothermal process,

Since
For an isothermal process, temperature is constant
Therefore
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August 20,
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U 12 =0 H 12=0
For an isothermal process, we have
P2 J 3 J J
Q=R T 1 ln Q=8.314 600 Kln Q=6006 Q=6.006103 Answer
P1 molK 10 mol mol
According to first law of thermodynamics
J
U 12=Q12 +W 12 0=Q12+W 12 W 12=Q12 W 12=6.006103 Answer
mol
Step 23, an Isochoric process,

Since
For an isochoric process, Volume is constant
Therefore,
W 23=0
At constant volume we have

5
Q23= U 23=CV T Q23= U 23=CV ( T 3T 2 ) Q23= U 23= R ( 400600 ) K
2
5
8.314 J J J
2 Q23= U 23=4157 Q23= U 23=4.15710 3 Answer
Q23= U 23= (200 ) K mol mol
molK
We know that
7 7 J
H 23=C P T H 23=C P ( T 3T 2 ) H 23= R ( 400600 ) K H 23= 8.314 (200 ) K
2 2 molK
J J
H 23=5820 H 23=5.82103 Answer
mol mol
Step 34, an Isobaric process,

Since
For an isobaric process, pressure is constant
Therefore, at constant pressure we have,
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August 20,
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7 7 J
Q34= H 34 =C P T Q34= H 34 = R ( T 4T 3 ) Q34= H 34 = 8.314 ( 378.83400 ) K
2 2 molK
J
Q34= H 34 =616 Answer
mol
For an Isobaric process we have
J J
W 34=R T W 34=R ( T 4T 3 ) W 34=8.314 ( 378.83400 ) K W 34=176 Answer
molK mol
We know that,
5 5 J
U 34 =CV T U 34 = R ( T 4 T 3 ) U 34 = 8.314 ( 378.83400 ) K
2 2 molK
J
U 34 =440 Answer
mol
Step 41, an adiabatic process,

Since
For an adiabatic process there is no exchange of heat
Therefore,
Q41=0
We know that,
5 5 J J
U 41=C V T U 41= R ( T 1T 4 ) U 41= 8.314 ( 600378.83 ) K U 41=4597
2 2 molK mol
J
U 41=4.597103 Answer
mol
We know that
7 7 J J
H 41=C P T H 41= R ( T 1T 4 ) H 41= 8.314 ( 600378.83 ) K H 41=6435.8
2 2 molK mol
J
H 41=6.4358103 Answer
mol
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August 20,
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3 J
U 41=Q 41+W 41 U 41=W 41 W 41=4.59710 Answer
mol
Problem 3.10:
t
An ideal gas, CP= (5/2) R and CV= (3/2) R is changed from P1 = 1bar and V 1 = 12m3 to P2 = 12 bar and
t
V 2 = 1 m3 by the following mechanically reversible processes:
a) Isothermal compression
b) Adiabatic compression followed by cooling at constant pressure.
c) Adiabatic compression followed by cooling at constant volume.
d) Heating at constant volume followed by cooling at constant pressure.
e) Cooling at constant pressure followed by heating at constant volume.
Calculate Q, W, change in U, and change in H for each of these processes, and sketch the paths of all
processes on a single PV diagram.
Given Data:
5 3 t 3
C P= R CV = R Initial pressure=P1=1 V 1=12 m Final pressure=P 2=12
2 2
V t2=1 m3 Q=? W =? H=? U =?
Solution:
Since
Temperature=constant
Therefore, for all parts of the problem,
H=0 U =0
(a)
Isothermal compression,
For an isothermal process, we have
P2
Q=R T 1 ln
P1
Since
For an ideal gas, we have
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August 20,
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P1 V 1=R T 1
Therefore,
12
101325 N
1
P2 2
J
Q=P1 V 1 ln 1.01325 m Q=2981.88 kJ Answer
P1 1 kJ
3 Nm
Q=1 12 m ln
1000 J
U =Q+W 0=Q+ W W =Q W 12=2981.88 kJ Answer
(b)
Adiabatic compression followed by cooling at constant pressure

Since
For an adiabatic process, there is no exchange of heat
Therefore,
Q=0 Answer
The process completes in two steps

First step, an adiabatic compression to final pressure P 2 , intermediate volume can be given as
1
P1
'
P2 ( V ) =P 1 V 1 V ' =V 1
( )
P2

For mono atomic gas, we have
=1.67
1
1
V ' =12 m3 ( )
12
1.67
V ' =2.71 m3
We know that,
'
P V P 1 V 1
W 1= 2
1
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( 122.71112 ) m3
101325 N
1.671
J
1.01325 m2 W 1=3063 kJ (1)
1 kJ
Nm
W 1=
1000 J
Second step, cooling at constant pressure P2

We know that, for a mechanically reversible process
m3101325 N
J
W 2=P2 ( V 2V ' ) 1.01325 m2 W 2=2052 kJ ( 2)
1 kJ
Nm
W 2=12 ( 12.71 )
1000 J
Now
W =W 1+ W 2 W = ( 3063+ 2052 ) kJ W =5115kJ Answer
(c)
Adiabatic compression followed by cooling at constant volume

Since
For an adiabatic process, there is no exchange of heat
Therefore,
Q=0 Answer
First step, an adiabatic compression to volume V2 , intermediate pressure can be given as

V
'
P V 2 =P1 V 1 P =P1 1
'
V2( )
For mono atomic gas, we have
=1.67
12
1.67
P' =1 ( )
1
P' =63.42
We know that,
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August 20,
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( 63.421112 ) m3
101325 N
' 1.671
P V 2P 1 V 1 J
W 1= 1.01325 m 2 W 1=7674.76 kJ
1 1 kJ
Nm
W 1=
1000 J
Second step, cooling at constant Volume,

Therefore, No work will be done
W 2=0
Now
W =W 1+ W 2 W = (7674.76+ 0 ) kJ W =7674.76 kJ Answer
(d)
Heating at constant volume followed by cooling at constant pressure

Step 1, Heating at constant volume to P2
Therefore no work will be done
W 1=0
Step 2, Cooling at constant pressure P2 To V2

We know that, for a mechanically reversible process
m3101325 N
J
W 2=P2 V W 2=P2 ( V 2V 1 ) 1.01325 m2 W 2=13200 kJ
1 kJ
Nm
W 2=12 ( 112 )
1000 J
Now
W =W 1+ W 2 W = ( 0+13200 ) kJ W =13200 kJ Answer
U =Q+W 0=Q+ W Q=W Q=13200 kJ Answer
(e)
Cooling at constant pressure followed by heating at constant volume

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Step 1, Cooling at constant Pressure P1 to V2
Therefore, for a mechanically reversible process
3
m 101325 N
2
J
W 1=P1 V W 1=P1 ( V 2V 1 ) 1.01325
m W 1=1100 kJ
1 kJ
Nm
W 1=1 ( 112 )
1000 J
Step 1, Heating at constant Volume V2 to pressure P2

Therefore no work will be done
W 2=0
Now
W =W 1+ W 2 W = (1100 +0 ) kJ W =1100 kJ Answer
U =Q+W 0=Q+ W Q=W Q=1100 kJ Answer
Problem 3.11:
dT
The environmental lapse rate dz characterizes the local variation of temperature with elevation in the
earth's atmosphere. Atmospheric pressure varies with elevation according to the hydrostatic formula,
dP
=M g
dz
Where M is a molar mass, is molar density and g is the local acceleration of gravity. Assume that the
atmosphere is an ideal gas, with T related to P by the polytropic formula equation (3.35 c). Develop an
expression for the environmental lapse rate in relation to M, g, R, and .
Solution:
Given that
dP
=M g ( 1 )
dz
The polytropic relation is
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August 20,
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1

TP =Constant
Or
1 1

TP =T o Po
Where
To =Temperature at sea level, so it is constant
Po = Pressure at sea level, so it is constant
T To 1
T P
P
1

=
P
1
o

=
( )
T o Po

T
P T Po
( )
To
1
=
Po
P=Po
To( ) 1
(a) P=
To

1
T 1
Differentiate w.r.t to Temperature on both sides
Po Po

1 1 1 1
dP T o 1
To 1
= T dP= T dT (2)
dT 1 1
P
=
RT
Where
R=Specific gas constant=R ' /M
Put (a) in above equation

1 T
=
RT
Po
To ( ) 1
Put in (1)
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dP g1 T g1 T
dz
=M
RT
Po
To ( ) 1
dP=M
RT
Po
( )
To
1
dz
Put (2) in above
1
M g

Po Po
R
T o 1
1 1 Po
To g1 T T 1
1
T 1
dT =M P
( )
RT o T o
1
dz
dT
=
To

1
dz 1
1
TT
1
M g

Po
R
T o 1
Po

T 1
1
dT To
=
dz
1
T

M g
dT 1
= Proved
dz R
Problem 3.12:
An evacuated tank is filled with gas from a constant pressure line. Develop an expression relating the
temperature of the gas in the tank to temperature T of the gas in line. Assume that gas is ideal with
constant heat capacities, and ignore heat transfer between the gas and the tank. Mass and energy balances
for this problem are treated in Ex. 2.13.
Solution:
Choose the tank as the control volume. There is no work, no heat transfer & kinetic & potential energy changes are
assumed negligible.
Therefore, applying energy balance
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August 20,
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d ( mU )tank d ( mU )tank
+ ( Hm )=0 + H ' ' m' ' H ' m' =0
dt dt
Since
Tank is filled with gas from an entrance line, but no gas is being escaped out,
Therefore,
d ( mU )tank d ( mU )tank
+0H ' m' =0 H ' m' =0(1)
dt dt
Where prime () denotes the entrance stream

Applying mass balance
d mtank
m' = ( 2)
dt
Combining equation (1) & (2)
d ( mU )tank ' d m tank

H =0
dt dt
1
dt
{d ( mU )tank H ' d mtank }=0 '
d ( mU )tank =H d mtank
Integrating on both sides
m2 m2
d ( mU )tank=H ' d mtank ( mU )tank =H ' ( m 2m 1 )

m1 m1
m 2 U 2 m1 U 1=H ' ( m 2m 1 )
Because mass in the tank initially is zero, therefore
m1=0
m2 U 2 =H ' m2
'
U 2=H (3)
We know that
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August 20,
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U=C V T U 2=C V T 2 ( a )
Also
H ' =C P T ' ( b )
Put (a) & (b) in (3)
CP '
CV T =C P T ' T= T
CV
Since heat capacities are constant, therefore
CP
= T = T ' Proved
CV
Problem 3.14:
A tank of 0.1-m3 volume contains air at 25 oC and 101.33 kPa. The tank is connected to a compressed-air
line which supplies air at the constant conditions of 45oC and 1,500 kPa. A valve in the line is cracked so
that air flows slowly into the tank until the pressure equals the line pressure. If the process occurs slowly
enough that the temperature in the tank remains at 25 oC, how much heat is lost from the tank? Assume
air to be an ideal gas for which CP = (7/2) R and CV = (5/2) R
Given Data:
Volume=V =0.1 m3 T 1 =25 o. C =298 K P1=101.33 kPa T 2 =45 o.C =318 K P2=1500 kPa
7 5
Heat lost =Q=? C P= R CV = R
2 2
Solution:
U =Q+W (1)
Since
H= U + ( PV ) U = H ( PV ) U = HP V V P ( a )
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August 20,
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Also, we know that
W =P V ( b )
Put (a) & (b) in (1)
HP V V P=QP V HV P=Q ( 2 )
Also, we have
H=nC P T H=nC P ( T 2T 1 )
Put in (2)
n C P ( T 2T 1 )V P=Q (3)
For n
We know that for an ideal gas,
PV =nRT
Initial number of moles of gas can be obtained as,
P1 V
P1 V =n1 R T 1 n1=
RT1
The final number of moles of gas at temperature T1 are
P2 V
P2 V =n2 R T 1 n2 =
RT 1
Now, Applying molar balance
n=n1n 2
P1 V P2 V ( P1P 2) V
n= n=
R T1 R T1 RT1
Put in (3)
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August 20,
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( P1P2 ) V
( P 1P2 ) V 7
C ( T 2T 1 )V P=Q RT1
R T1 P R( T 2T 1 )V P=Q
2
( P1P2 ) V
7
T1
( T 2 T 1 )V ( P2 P 1 )=Q
2
( 101.331500 ) kPa0.1 m3
7
298 K
( 318298 ) K 0.1 m3 ( 1500101.33 ) kPa=Q
2
kPa1 kN
2
1 kJ
3 1 kPam Q=172.717 kJ Answer
Q=172.717 m
1 kNm
Problem 3.17:
A rigid, no conducting tank with a volume of 4 m 3 is divided into two unequal parts by a thin membrane.
One side of the membrane, representing 1/3 of the tank, contains nitrogen gas at 6 bars and 100 oC, and
the other side, representing 2/3 of the tank, is evacuated. The membrane ruptures and the gas fills the
tank.
a) What is the final, temperature of the gas? How much work is done? Is the process reversible?
b) Describe a reversible process by which the gas can be returned to its initial state, How much work
is done
Assume nitrogen is an ideal gas for which CP = (7/2) R & CV = (5/2) R
Given Data:
3 V 11 4 3 o
Volume of thetank=V 1 =4 m V 2= = m Pressure=P2=6 Temperature=T 1=100 . C
3 3
V 12 8 3
V 3= = m
3 3 Solution:
(a)
Finaltemperature=T 2=?
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August 20,
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U =Q+W
Since
No work is done & no heat is transferred
Therefore
Q=W =0
U =0 mC V T =0 T =0 T 2 T 1=0 T 2 =T 1 T 2 =100 Answer
No, process is not reversible
(b)
Since
Therefore, the process is isothermal

For an isothermal process we have
V2
W =R T 2 ln
V1
As, for an ideal gas
V2 4 4 m 3101325 N kJ
P2 V 2 =R T 2 W =P2 V 2 ln W =6 m3 ln W =8.788 1
V1 3 34
1.01325 m 2
1000 Nm
W =878.8 kJ Answer
Problem 3.18:
An ideal gas initially at 30 0C and 100 kPa undergoes the following cyclic processes in a closed system:
a In mechanically reversible processes, it is first compressed adiabatically to 500 kPa then cooled at
a constant pressure of 500 kPa to 30 0C and finally expanded isothermally to its original state
b The cycle traverses exactly the same changes of state but each step is irreversible with an efficiency
of 80% compared with the corresponding mechanically reversible process NOTE: the initial step
can no longer be adiabatic
Find Q W U and H for each step of the process and for the cycle Take C = (7/2) R and C =
p V
(5/2) R
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August 20,
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Given Data:
7 5
T 1 =30 0.C T 1 =303.15 K P1=100 kPa Q=? W =? U =? H=? C P= R
2
CV = R
2 So
lution:
(a)
P2=500 kPa
1) Adiabatic Compression from point 1 to point 2

Q12=0
Now, from first law of thermodynamics,
U 12=Q12 +W 12 U 12 =W 12
5
W 12=U 12=CV T 12 W 12=U 12= R ( T 2T 1 ) ( 1 )
2
For T2
We know that
1 1
T 2 P2 P2 1.41
=
T 1 P1( )
T 2 =T 1
( )
P1

T 2 =303.15 K
500
( )
100
1.4 T 2 =480.13 K
Put in (1)
5 J kJ kJ
W 12=U 12= 8.314 ( 480.13303.15 ) K1 W 12= U 12=3.679
2 molK 1000 J mol
Also, we have
7 J kJ kJ
H 12=C P ( T 2T 1 ) H 12= 8.314 ( 480.13303.15 ) K1 H 12=5.15
2 molK 1000 J mol
2) Cooling at constant pressure from point 2 to point 3
Therefore at constant pressure we have,
7
Q23= H 23=C P T 23 Q23= H 23= R ( T 3T 2 )
2
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August 20,
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Here
T 3 =303.15 K
7 J kJ kJ
Q23= H 23= 8.314 ( 303.15480.13 ) K1 Q = H 23=5.15
2 molK 1000 J 23 mol
Also, we have
U 23 =C V ( T 3T 2)
5 J kJ
U 23 = 8.314 ( 303.15480.13 ) K1
2 molK 1000 J
kJ
U 23=3.679
mol
Now, from first law of thermodynamics,
kJ
U 23=Q23 +W 23 W 23= U 23Q23 W 23=3.679+5.15 W 23=1.471
mol
3) Isothermal expansion from point 3 to point 1

Since for an isothermal process temperature remains constant
Therefore,
U 31= H 31=0
Here
P3=P2=500 kPa
For an Isothermal process we have
500
1 kJ
P3 J 100
W 31=R T 3 ln W 31=8.314 303.15 Kln
P1 molK 1000 J
kJ
W 31=4.056
mol
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August 20,
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U 31 =Q31 +W 31
kJ
0=Q31+W 31 Q31=W 31 Q31=4.056
mol
For the complete cycle,
kJ
Q=Q12 +Q23+ Q31 Q=05.15+ 4.056 Q=1.094 Answer
mol
W =W 12+W 23+W 31 W =3.679+ 1.4714.056
kJ
W =1.094 Answer
mol
kJ
H= H 12+ H 23+ H 31 H=5.155.15+0 H=0 Answer
mol
kJ
U = U 12 + U 23 + U 31 U =3.6793.679+0 U =0 Answer
mol
(b)
If each step that is 80% accomplishes the same change of state then values of U & H will remain same as
in part (a) but values of Q & W will change.
1. Adiabatic Compression from point 1 to point 2
W 12 3.679 kJ
W 12= W 12= W 12=4.598
0.8 0.8 mol

U 12 =Q12 +W 12
kJ kJ
3.679 =Q12+ 4.598
mol mol
kJ kJ kJ
Q12=3.679 4.598 Q12=0.92
mol mol mol
2. Cooling at constant pressure from point 2 to point 3
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W 23 1.471 kJ
W 23= W 23= W 23=1.839
0.8 0.8 mol
kJ kJ kJ kJ kJ
U 23=Q23 +W 23 3.679 =Q23 +1.839 Q23=3.679 1.839 Q23=5.518
mol mol mol mol mol
3. Isothermal expansion from point 3 to point 1

Since initial step can no longer be adiabatic , therefore
kJ kJ
W 31=W 310.8 W 31=4.056 0.8 W 31=3.245
mol mol
U 31 =Q31 +W 31 Q31=W 31+ 0
kJ
Q31=3.245
mol
kJ
Q=Q12 +Q 23+Q31 Q=0.925.518+ 3.245 Q=3.193 Answer
mol
kJ
W =W 12+W 23+W 31 W =4.598+1.8393.245 W =3.192 Answer
mol
Problem 3.19:
One cubic meter of an ideal gas at 600 K and 1,000 kPa expands to five times its initial volume as follows:
a) By a mechanically reversible, isothermal process
b) By a mechanically reversible adiabatic process
c) By adiabatic irreversible process in which expansion is against a restraining pressure of 100 kPa
For each case calculate the final temperature, pressure and the work done by the gas, Cp=21 J mol-1K-1.
Given Data:
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August 20,
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J
V 1=1 m3 T 1 =600 K P1=1000 kPa V 2=5 V 1 V 2=5 m3 C P=21 CV =? T 2 =? P2=?
mol K
W =?
Solution:
We know that,
J J
C PC V =R CV =C P R CV =( 218.314 ) CV =12.686
molK molK
As
CP
= =1.6554
CV
(a)
Since, for an isothermal process

Temperature remains constant, therefore
T 2 =T 1=600 K Answer
For an ideal gas we have
P1 V 1 1000 kPa1 m
3
P1 V 1 P 2 V 2 T 2 600 K
= T1 600 K P2=200 kPa Answer
T1 T2 P 2= P 2= 3
V2 5m
We know that, for an isothermal process
V2
W =R T 1 ln
V1
Since
P1 V 1=R T 1
Therefore,
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August 20,
2013
5
N
V 1
W =P1 V 1 ln 2 J W =1609.43 kJ Answer
V1 3 Pam2
W =1000 kPa1 m ln
Nm
(b)
We know that, for an adiabatic process

V 1.6554

P1 V 1 =P2 V 2

P2=P1 1
V2( ) P2=1000 kPa
1
()
5
P2=69.65 kPa Answer

P1 V 1 P2 V 2 P V 69.65 kPa5 m3
= T 2 = 2 2 T 1 T2= 600 K T 2 =208.95 K Answer
T1 T2 P1 V 1 1000 kPa1 m3
For an adiabatic process work done is
N
P V P1 V 1 J
W= 2 2 3
( 69.65510001 ) kPam Pam 2 W =994.43 kJ Answer
1 W=
1.65541 Nm
(c)
Pr=100 kPa
Since, for an adiabatic process
Q=0
U =Q+W U =W U =W =Pr dV U =W =Pr ( V 2V 1)
3
kPam N
J
Pam
2
U =400 kJ n CV T =400 kJ n CV ( T 2T 1 )=400 kJ
U =W =100 ( 51 )
Nm
400 kJ
T2= + T 1 ( 1)
n CV
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August 20,
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For an ideal gas we have,
3
1000 kPa1 m molK
P1 V 1 kN
8.314 J600 K
P1 V 1=nR T 1 n= kJ n=0.2005 mol
RT1 kPam2
n=
kNm
Put in (1)
400 kJmolK
1000 J
0.2005 mol12.686 J T 2 =157.26 K +600 K T 2 =442.74 K Answer
T2= +600 K
1 kJ
P1 V 1 1000 kPa1 m
3
P1 V 1 P2 V 2 T 2 442.74 K
= T1 600 K P2=147.58 kPa Answe r
T1 T2 P2= P2= 3
V2 5m
Problem 3.20:
One mole of air, initially at 150 0C and 8 bars undergoes the following mechanically reversible changes. It
expands isothermally to a pressure such that when it is cooled at constant volume to 50 0C its final
pressure is 3 bars. Assuming air is an ideal gas for which C P = (7/2) R and CV = (5/2) R, calculate W, Q,
U , and H
Given Data:
0
Mole of air=n=1mol Initial Temperature=T 1=150 .C =423.15 K Initial pressure=P1=8
7 5
Finaltemperature=T 3=50 0.C =323.15 K Final pressure=P 3=3 C P= R CV = R
2 2
Solution:
Since process is reversible
Two different steps are used in this case to reach final state of the air.
Step 12:
For step 12 temperatures is constant,
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August 20,
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T 1 =T 2
Therefore
U 12= H 12=0

V1
W 12=R T 1 ln
V2
As
V1
V 2=V 3 W 12=R T 1 ln (1)
V3
We know that
P1 V 1 P 3 V 3 V 1 P3 T 1 P T 8.314 J423.15 K
1 kJ
= = W 12=R T 1 ln 1 3 molK 3423.15
T1 T3 V 3 T 3P1 T 1P3 W 12= ln
1000 J 8323.15
kJ
W 12=2.502
mol
kJ
U 12=Q12 +W 12 0=Q12+W 12 Q12=W 12 Q12=2.502
mol
Step 23:
For step 23 volume is constant,
Therefore,
W 23=0
U 23=Q23 +W 23 U 23=Q23 +0 Q23= U 23 Q23= U 23=CV T Q23= U 23=CV ( T 3T 2 )
5
Q23= U 23= R ( 323.15423.15 ) K
2
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August 20,
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8.314

() K

2.0785

W e know that
J
1 kJ
H 23=C P T H 23=C P ( T 3T 2 ) 7 molK
H 23= 8.314 ( 423.15323.15 ) K
2 1000 J
kJ
H 23=2.91
mol
kJ kJ
Work=W =W 12 +W 23 W = (2.502+0 ) W =2.502 Answe r
mol mol
kJ kJ
Q=Q 12 +Q23 Q=( 2.5022.0785 ) Q=0.424 Answer
mol mol
kJ kJ
U = U 12 + U 23 U =( 02.0785 ) U =2.0785 Answe r
mol mol
kJ kJ
H= H 12+ H 23 H= ( 02.91 ) H=2.91 Answe r
mol mol
Problem 3.21:
An ideal gas flows through a horizontal tube at steady state. No heat is added and no shaft work is done.
The cross-sectional area of the tube changes with length, and this causes the velocity to change. Derive an
equation relating the temperature to the velocity of the gas. If nitrogen at 150 0C flows past one section of
the tube with a velocity of 2.5 m/s, what is the temperature at another section where its velocity is 50 m/s?
Let CP = (7/2) R
Given Data:
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August 20,
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0 m m 7
Temperature=T 1=150 .C =423.15 K Velocity=u 1=2.5 T 2 =? u2=50 C P= R
sec sec 2
g
Molecualr weight of Nitrogen=28
mol
Solution:
Applying energy balance for steady state flow process
u2
H+ + g z=Q+W S
2
Since
z=W S=Q=0
Therefore,
u
2
u
2
u22u12 u22u12
H+ =0 CP T = C P ( T 2 T 1 )= T2= + T1
2 2 2 2C P
( 50 22.52 )2m2molK
28 g Nitrogen
278.314 Jsec 2
J
1 mol Nitrogen T 2 =1.199 K + 423.15 K
Nsec 2
Nm
1 kg
kgm
T2= + 423.15 K
1000 g
0 0
T 2 =421.95 K T 2 =( 421.95273.15 ) .C T 2 =148.8 .C Answe r
Problem 3.22:
One mole of an ideal gas, initially at 30 0C and 1 bar, is changed to 130 0C and 10 bars by three different
mechanically reversible processes:
a) The gas is first heated at constant volume until its temperature is 130 0C; then it is compressed
isothermally until its pressure is 10 bar
b) The gas is first heated at constant pressure until its temperature is 130 0C; then it is compressed
isothermally to 10 bar
c) The gas is first compressed isothermally to 10 bar; then it is heated at constant pressure to 130 0C
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August 20,
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Calculate Q, W, U H in each case. Take CP = (7/2) R and CV = (5/2) R. alternatively, take CP =

(5/2) R and CV = (3/2) R
Given Data:
T 1 =30 0.C T 1 =( 30+273.15 ) K T 1 =303.15 K P1=1 T 2 =130 0.C T 3 =( 130+273.15 ) K
T 3 =403.15 K P3=10 Q=? W =? U =? H=?
Solution:
7 5
C P= R CV = R
2 2
Each part consist of two steps, 12 & 23

For the overall processes
5
U = U 12=U 23=CV T U = U 12=U 23= R ( T 3T 1 )
2
5 J K1 kJ
U = U 12=U 23= 8.314 ( 403.15303.15 )
2 molK 1000 J
kJ
U = U 12=U 23=2.079 (a) Answe r
mol
Now
H= H 12= H 23=C P T
7
H= H 12= H 23= R ( T 2T 1)
2
7 J kJ
H= H 12= H 23= 8.314 ( 403.15303.15 ) K1
2 molK 1000 J
kJ
H= H 12= H 23=2.91 ( b ) Answe r
mol
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August 20,
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(a)
Step 12:
For step 12 volume is constant
Therefore
W 12=0
Here
T 2 =T 3
kJ
U 12=Q12 +W 12 U 12=Q12 Q12= U 12=C V T Q12= U 12=2.079
mol
[ ( a ) ]
Also we have

kJ
H 12=2.91 [ ( b)]
mol
Step 23:
Since for step 23 process is isothermal
Therefore
U 23 = H 23=0
Here
T 2 =T 3
Now, intermediate pressure can be calculated as

P1 P2 P 1 403.15 K
= P2= 1T 2 303.15 K P2=1.329 b ar
T1 T 2 T1 P2=

P3 J K1 kJ 10
W 23=R T 2 ln W 23=8.314 403.15 ln
P2 molK 1000 J 1.329
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August 20,
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kJ
W 23=6.764
mol
kJ
U 23=Q23 +W 23 0=Q23+W 23 Q23=W 23 Q23=6.764
mol
kJ kJ
Work=W =W 12 +W 23 W = ( 0+6.764 ) W =6.764 Answe r
mol mol
kJ kJ
Q=Q12 +Q23 Q=( 2.0796.764 ) Q=4.685 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 2.079+0 ) U =2.079 Answe r
mol mol
kJ kJ
H= H 12+ H 23 H= ( 2.91+ 0 ) H=2.91 Answe r
mol mol
(b)
Step 12:
Therefore, at constant pressure we have
kJ
Q12 H 12=2.91
mol
[ (b)]
Also,
kJ
U 12 =2.079
mol
[ (a)]
kJ kJ
U 12=Q12 +W 12 W 12=U 12Q12 W 12=( 2.0792.91 ) W 12=0.831
mol mol
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August 20,
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Step 23:
Since for step 23 process is isothermal ( T = Constant)
Therefore
U 23 = H 23=0
Here
T 2 =T 3P 1=P2

P3 J K1 kJ 10
W 23=R T 2 ln W 23=8.314 403.15 ln
P2 molK 1000 J 1
kJ
W 23=7.718
mol
kJ
U 23 =Q23 +W 23 0=Q23+W 23 Q23=W 23 Q23=7.718
mol
kJ kJ
Work=W =W 12 +W 23 W = (0.831+7.718 ) W =6.887 Answer
mol mol
kJ kJ
Q=Q12 +Q23 Q=( 2.917.718 ) Q=4.808 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 2.079+0 ) U =2.079 Answe r
mol mol
kJ kJ
H= H 12+ H 23 H= ( 2.91+ 0 ) H=2.91 Answe r
mol mol
(c)

Therefore
U 12= H 12=0
Here
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August 20,
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P2=P3

P2 J K1 kJ 10
W 12=R T 1 ln W 12=8.314 303.15 ln
P1 molK 1000 J 1
kJ
W 12=5.8034
mol
kJ
U 12=Q12 +W 12 0=Q12+W 12 Q12=W 12 Q12=5.8034
mol
Step 23:
kJ
Q23= H 23=2.91 [ (b)]
mol
Here
T 2 =T 3
Now
kJ
U 23=2.079 [ (a)]
mol
kJ kJ
U 23=Q23 +W 23 W 23= U 23Q23 W 23=( 2.0792.91 ) W 23=0.831
mol mol
kJ kJ
Work=W =W 12 +W 23 W = (5.80340.831 ) W =4.972 Answer
mol mol
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August 20,
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kJ kJ
Q=Q 12 +Q23 Q=(5.8034+2.91 ) Q=2.894 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 0+2.079 ) U =2.079 Answe r
mol mol
kJ kJ
H= H 12+ H 23 H= ( 0+2.91 ) H=2.91 Answe r
mol mol
Solution:
5 3
C P= R CV = R
2 2
Each part consist of two steps, 12 & 23

For the overall processes
3
U = U 12=U 23=CV T U = U 12=U 23= R ( T 3 T 1 )
2
3 J K1 kJ
U = U 12=U 23= 8.314 ( 403.15303.15 )
2 molK 1000 J
kJ
U = U 12=U 23=1.247 (a) Answe r
mol
Now
H= H 12= H 23=C P T
5
H= H 12= H 23= R ( T 2T 1 )
2
5 J kJ
H= H 12= H 23= 8.314 ( 403.15303.15 ) K1
2 molK 1000 J
kJ
H= H 12= H 23=2.079 ( b ) Answer
mol
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August 20,
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(a)
Step 12:
Therefore
W 12=0
Here
T 2 =T 3
kJ
U 12 =Q12 +W 12 U 12 =Q12 Q12= U 12=C V T Q12= U 12=1.247
mol
[ ( a) ]
Also we have
kJ
H 12=2.079 [ ( b)]
mol
Step 23:
Since for step 23 process is isothermal
Therefore
U 23 = H 23=0
Here
T 2 =T 3

P1 P2 P 1 403.15 K
= P2= 1T 2 303.15 K P2=1.329 b ar
T1 T 2 T1 P2=
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August 20,
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P3 J K1 kJ 10
W 23=R T 2 ln W 23=8.314 403.15 ln
P2 molK 1000 J 1.329
kJ
W 23=6.764
mol
kJ
U 23=Q23 +W 23 0=Q23+W 23 Q23=W 23 Q23=6.764
mol
kJ kJ
Work=W =W 12 +W 23 W = ( 0+6.764 ) W =6.764 Answe r
mol mol
kJ kJ
Q=Q 12 +Q23 Q=( 1.2476.764 ) Q=5.516 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 1.247+0 ) U =1.247 Answer
mol mol
kJ kJ
H= H 12+ H 23 H= ( 2.079+ 0 ) H=2.079 Answe r
mol mol
(b)
Step 12:
kJ
Q12 H 12=2.079
mol
[ (b)]
Also,
kJ
U 12 =1.247
mol
[ (a)]
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August 20,
2013
kJ kJ
U 12 =Q12 +W 12 W 12=U 12Q12 W 12=( 1.2472.079 ) W 12=0.832
mol mol
Step 23:
Therefore
U 23 = H 23=0
Here
T 2 =T 3P 1=P2

P3 J K1 kJ 10
W 23=R T 2 ln W 23=8.314 403.15 ln
P2 molK 1000 J 1
kJ
W 23=7.718
mol
kJ
U 23 =Q23 +W 23 0=Q23+W 23 Q23=W 23 Q23=7.718
mol
kJ kJ
Work=W =W 12 +W 23 W = (0.832+7.718 ) W =6.886 Answer
mol mol
kJ kJ
Q=Q12 +Q23 Q=( 2.0797.718 ) Q=5.639 Answer
mol mol
kJ kJ
U = U 12 + U 23 U =( 1.247+0 ) U =1.247 Answer
mol mol
kJ kJ
H= H 12+ H 23 H= ( 2.079+ 0 ) H=2.079 Answe r
mol mol
(c)
Step 12:
48
August 20,
2013

Therefore
U 12= H 12=0
Here
P2=P3

P2 J K1 kJ 10
W 12=R T 1 ln W 12=8.314 303.15 ln
P1 molK 1000 J 1
kJ
W 12=5.8034
mol
kJ
U 12=Q12 +W 12 0=Q12+W 12 Q12=W 12 Q12=5.8034
mol
Step 23:
kJ
Q23= H 23=2.079 [ (b)]
mol
Here
T 2 =T 3
Now
kJ
U 23=1.247 [ (a)]
mol
kJ kJ
U 23=Q23 +W 23 W 23= U 23Q23 W 23=( 1.2472.079 ) W 23=0.832
mol mol
49
August 20,
2013
kJ kJ
Work=W =W 12 +W 23 W = (5.80340.832 ) W =4.9714 Answe r
mol mol
kJ kJ
Q=Q 12 +Q23 Q=(5.8034+2.079 ) Q=3.724 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 0+1.247 ) U =1.247 Answer
mol mol
kJ kJ
H= H 12+ H 23 H= ( 0+2.079 ) H=2.079 Answe r
mol mol
Problem 3.23:
One mole of an ideal gas, initially at 30 and 1 bars, undergoes the following mechanically
reversible changes. It is compressed isothermally to point such that when it is heated at constant volume to
120 its final pressure is 12 bars. Calculate Q, W, U H for the process. Take C (7/2) R and P=
CV = (5/2) R.
Given Data:
T 1 =30 T 1 =( 30+273.15 ) K T 1 =303.15 K P1=1 T 3 =120 T 3 =( 120+273.15 ) K
7 5
T 3 =393.15 K P3=12 Q=? W =? U =? H=? C P= R CV = R
2 2
Solution:
The process consist of two steps, 12 & 23
Step 12:
Therefore
U 12= H 12=0
50
August 20,
2013

P2 P P 12 303.15 K
3 P2= 3 T 2 393.15 K P2=9.25 b ar
T2 T3 T3 P2=

P2 J K1 kJ 9.25
W 12=R T 1 ln W 12=8.314 303.15 .15 ln
P1 molK 1000 J 1
kJ
W 12=5.607
mol
kJ
U 12=Q12 +W 12 0=Q12+W 12 Q12=W 12 Q12=5.607
mol
Step 23:
Since for step 23 volume is constant
Therefore
W 23=0
U 23 =Q23 +W 23 U 23=Q23
5
Q23= U 23=CV T Q23= U 23= R ( T 3T 1 )
2
5 J K1 kJ kJ
Q23= U 23= 8.314 ( 393.15303.15 ) Q23= U 23=1.871
2 molK 1000 J mol
Now
H 23=C P T
7 7 J kJ kJ
H 23= R ( T 2T 1 ) H 23= 8.314 (393.15303.15 ) K1 H 23=2.619
2 2 molK 1000 J mol
51
August 20,
2013
kJ kJ
Work=W =W 12 +W 23 W = (5.607 +0 ) W =5.607 Answe r
mol mol
kJ kJ
Q=Q 12 +Q23 Q=(5.607+1.871 ) Q=3.736 Answe r
mol mol
kJ kJ
U = U 12 + U 23 U =( 0+1.871 ) U =1.871 Answe r
mol mol
kJ kJ
H= H 12+ H 23 H= ( 0+2.691 ) H=2.691 Answe r
mol mol
Problem 3.24:
A process consists of two steps: (1) One mole of air at T = 800 K and P = 4 bars are cooled at constant
volume to T = 350 K. (2) The air is then heated air constant pressure until its temperature reaches 800 K.
If this two step process is replaced by a single isothermal expansion of the air from 800 K and 4 bar to
some final pressure P, what is the value of P that makes the work of two step processes the same? Assume
mechanical reversibility and treat air as an ideal gas with CP = (7/2) R and CV = (5/2) T.
Given Data:
T 1 =800 K P1=4 T 2 =350 K P=?
Solution:
For the first step volume is constant
Therefore,
W 12=0
For the work done is
W =W 23=P 2 V (1)
For one mole of an ideal gas we have,
P V =R T P2 V =R T
52
August 20,
2013
Put in (1)
W =R T W =R ( T 3T 2 )
Since
T 3 =T 1
Therefore
W =R ( T 1T 2) (2)
P
W =R T 1 ln (3)
P1
Compare (2) and (3)
P
P P T 2T 1 P 4 4
R ( T 1T 2 )=R T 1 ln T 2 T 1=T 1 ln =ln P
P1 P1 T1 P1 ( 350800 ) K e0.5625=
=ln
800 K
4 0.5698=P
P=2.279 Answer
Problem 3.25:
A scheme for finding the internal volume V tB of the gas cylinder consists of the following steps. The
cylinder is filled with a gas to low pressure P 1, and connected through a small line and valve to an
t
evacuated reference tank of known volume V A . The valve is opened, and the gas flows through the line
into the reference tank. After the system returns to its initial temperature, a sensitive pressure transducer
t
provides a valve for the pressure change P in the cylinder. Determine the cylinder volume VB
from the following data:

t 3
a) V A =256 cm
b)
P/ P1=0.0639
Given Data:
53
August 20,
2013
P
V tB =? V tA =256 cm3 =0.0639
P1
Solution:
P P2 P 1 P2 P2 P2
=0.0639 =0.0639 1=0.0639 =0.0639+1 =0.9361 (1)
P1 P1 P1 P1 P1
Assume that gas is ideal & P2 is the pressure of the tank

t t
When gas flows through the line into the tank then tanks total volume becomes V A +V B
Now, by applying condition for an ideal gas
P2 Vt
t
P1 V =P2 ( V +V
B
t
A
t
B ) = t B t
P1 V A +V B
Put in (1)
V tB
=0.9361 V tB =0.9361 ( V tA +V tB ) V tB =0.9361V tA +0.9361V tB V tB 0.9361V tB=0.9361V tA
V tA +V tB
t 239.6461 3
V tB ( 10.9361 ) =0.9361V tA 0.0639 V tB =256 cm 30.9361 V B= cm V tB =3750.26 cm 3 Answe r
0.0639
Problem 3.26:
A closed, non-conducting, horizontal cylinder is fitted with non-conducting, frictionless, floating piston
which divides the cylinder in two Sections A & B. The two sections contains equal masses of air, initially at
the same conditions, T1 = 300 K and
P1 = 1 atm. An electrical heating element in section A is activated, and the air temperature slowly
increases: TA in section A because of heat transfer, and T B in section B because of adiabatic compression
by slowly moving piston. Treat air as an ideal gas with C P = (7/2) R and let nA be the number of moles of
air in section A. For the process as described, evaluate one of the following sets of quantities:
a) TA, TB, and Q/ nA, if P (final) = 1.25 atm
b) TB, Q/ nA, and P (final), if TA = 425 K
c) TA, Q/nA, and P (final), if TB = 325 K
d) TA, TB, and P (final), if Q/nA = 3 kJ mol-1.
Given Data:
54
August 20,
2013
7
T 1 =300 K P1=1 atm C P= R
2
Solution:
According to ideal gas equation,
PV =nRT
Applying ideal gas equation for initial conditions

On section A
nART1
P1 V A =n A R T 1 V A=
P1
On section B
P1 V B=n B RT 1
Since
n A =n B
Therefore,
n A RT 1
P1 V B=n A R T 1 V B=
P1
Total initial volume can be given as
nA R T1 nA R T1 n A RT 1
V i=V A + V B V i= + V i=2.
P1 P1 P1
Let P2 be the final pressure & TA & TB are the final temperatures of section A & section B
respectively
Applying ideal gas equation for final conditions
On section A
P2 V A =n A R T A
nART A
V A=
P2
On section B
n A RT B
P2 V B=n A R T B V B=
P2
Total Final volume can be given as
55
August 20,
2013
nA R T A nA R T B nA R (T A+ T B)
V f =V A +V B Vf= + Vf=
P2 P2 P2
Since the total volume is constant, therefore
V i=V f
n A R T 1 n A R ( T A +T B ) 2. T 1 ( T A +T B )
2. = = (1)
P1 P2 P1 P2
(a)
P2=1.25 atm
Since the process occurring in section B is reversible adiabatic compression

Therefore, for an adiabatic compression we have
1

1 1 T 1 ( P1 )
T 1 ( P1 )
=T B ( P2 ) T B= 1

( P 2)
1
P2
T B=T 1
( )
P1

(2)
We know that,
7 7 R2 R 5
C PC V =R CV =C P R CV = RR CV = CV = R
2 2 2
As
CP 7R2
= = =1.4
CV 25R
Put in (2)
1.4 1
1.25
T B=300 K ( ) 1
1.4 T B=300 K1.0658
T B=319.74 K Answe r
56
August 20,
2013
Put in (1)
2300 K ( T A +319.74 K )
=
1 atm 1.25 atm
600 K1.25=T A +319.74 K T A =750 K319.74 K T A =430.26 K Answe r
U =Q+W
Since volume is constant, therefore
U =Q( a)
For section A & B

U = U A + U B
Put in (a)
Q=U A + U B Q=n A CV T +n A C V T Q=n A CV ( T AT 1 ) +n A C V ( T B T 1 ) Q=n A CV [ T AT 1 +T BT 1 ]
Q Q 5
Q=n A CV [ T A +T B2T 1 ] =C V [ T A +T B 2 T 1 ] (3) = R ( 430.26+ 319.742300 ) K
nA nA 2
Q 5 J K1 kJ Q kJ
= 8.314 150.02 =3.118 Answe r
nA 2 molK 1000 J nA mol
(b)
T A =425 K
From equation (1)
2. T 1 ( T A +T B ) P2 ( T A +T B )
= =
P1 P2 P1 2.T 1
Put in (2)
57
August 20,
2013
1
T A +T B
T B=T 1
( 2. T 1 )
Assume T B=319 K
1.41
425+ 319
T B=300 K (
2300 ) 1.4
T B=300 K( 1.0634 ) T B=319.02 K
Since 319 319.02 , therefore
T B=319.02 K Answe r
Put in (1)
2300 K ( 425+319.02 ) K 744.02

= P2= atm P2=1.24 atm Answe r
1 atm P2 600
From equation (3)
Q
=C V [ T A +T B 2 T 1 ]
nA
Q 5
= R ( 425+319.022300 ) K
nA 2
Q 5 J K1 kJ Q kJ
= 8.314 144.02 =2.993 Answer
nA 2 molK 1000 J n A mol
(c)
T B=325 K
Put in (2)
58
August 20,
2013
1 1 1
P2
P2 1.4
T B=T 1
( )
P1

325 K=300 K
P2
1 atm( ) 325
=
P2
( )
300 1 atm
325
( )
300
1
=
1 atm
P2=( ) 325
300
1.41
atm
P2=1.323 atm Answe r
Put in (1)
2. T 1 ( T A +T B ) 2300 K T A +325 K
= = T A +325 K =600 K1.323 T A =793.9 K325 K
P1 P2 1 atm 1.323 atm
T A =468.9 K Answe r
From equation (3)
Q
=C V [ T A +T B 2 T 1 ]
nA
Q 5
= R ( 468.9+3252300 ) K
nA 2
Q 5 J K1 kJ Q kJ
= 8.314 193.9 =4.0302 Answe r
nA 2 molK 1000 J n A mol
(d)
Q kJ
=3
nA mol
From equation (1)
2. T 1 ( T A +T B ) 2.T 1P2
= T A +T B= (b )
P1 P2 P1
From equation (3)
Q Q Q
=C V [ T A +T B 2 T 1 ] T A +T B2 T 1 = T A +T B= + 2T 1 (c )
nA n AC V n AC V
Comparing (b) and (c)
59
August 20,
2013
2. T 1P2 Q
= +2 T 1
P1 n ACV
[ ]
P1 6 kJmolK
P 2=
[ Q
2.T 1 n AC V
+2 T 1
] P 2=
1 atm
[23 kJ
2300 K 5 Rmol
+2300 K ] P 2=
1 atm 5mol8.314 J
600 K 1 kJ
1000 J
+600 K
1 atm
P 2= [ 144.335+ 600 ] K P2=1.2406 atm Answe r
600 K
Put in (2)
1
P2
T B=T 1
( )
P1

1.4 1
1.2406
T B=300 K ( 1 ) 1.4 T B=300 K1.0635
T B=319.06 K Answer
Put in (1)
2. T 1 ( T A +T B )
=
P1 P2
2300 K ( T A + 319.06 K )
=
1 atm 1.2406 atm
600 K1.2406=T A +319.06 K T A =744.36 K319.06 K T A =425.3 K Answe r
Problem 3.27:
One mole of an ideal gas with constant heat capacities undergoes an arbitrary mechanically reversible
process. Show that:
1
U= ( PV )
1
60
August 20,
2013
Given Data:
Number of moles=n=1
Solution:
We know that
U =nCV T U =1.C V T U =CV ( T 2T 1 ) (1)
For an ideal gas we have,

C P CV R CP R
C PC V =R = 1=
C V CV C V CV CV
Since
CP
=
CV
Therefore,
R R
1= CV =
CV 1
Put in (1)
R 1
U= ( T T ) U= ( R T 2R T 1 ) ( 2)
1 2 1 1
For one mole of an ideal gas we have
P1 V 1=R T 1 ( a) P2 V 2 =R T 2 ( b)
Put (a) & (b) in (2)
1 1
U= ( P V P1 V 1 ) U= ( PV ) Proved
1 2 2 1
Problem 3.28:
61
August 20,
2013
Derive an equation for the work of a mechanically reversible, isothermal compression of 1 mole of a gas
from an initial pressure p1 to a final pressure p2 when the equation of state is the virial expansion
truncated to:
Z =1+ B ' P
How does the result compare with the corresponding equation for an ideal gas?
Solution:
V2
W = PdV (1)
V1
Given that
Z =1+ B ' P
Also
PV
Z=
RT
Therefore,
PV RT
RT
'
=1+ B P V=
P
( 1+ B' P ) V =RT ( P1 + B' )
Differentiate both sides w.r.t to pressure
dV
dP
1
(
=RT 2 +0
P ) dV =
RT
P2
dP
Put in (1)
V2 P2 P2
RT 1 P2
W = PdV W = P 2 dP W =RT dP W =RT |ln P|P W =RT ( ln P 2ln P1 )
V1 P P
1 P1
P 1
P2
W =RT ln Proved
P1
62
August 20,
2013
Problem 3.30:
For methyl chloride at 100 the second and third virial coefficients are:
B=242.5 cm3 mol1 ; C=25 200 cm 6 mol2 .
Calculate the work of mechanically reversible, isothermal compression of 1 mol of methyl chloride 1 bar
to 55 bars at 100 . Base calculations on the following forms of virial equations
B C
Z =1+ + 2
a) V V
b) Z =1+ B' P+C ' P2
' B ' CB 2
B= C =
Where RT ( RT )2
Why dont both equations give exactly the same result?
Given Data:
Temperature=T =100 T =( 100+273.15 ) K T =373.15 K B=242.5 cm3 mol1
B ' CB2
C=25200 cm mol 6 2
P1=1 P2=55
B '= C= W =?
RT ( RT )2
Solution:
As
B
B'=
RT
1 m3
m21.01325
100 3 cm3
242.5 cm3molK 1
J '
B =7.817103
mol8.314 J373.15 K
101325 N
' Nm
B=
Now,
63
August 20,
2013
21 m6
m41.013252
1006 cm 6
' CB
2
[ 25200(242.5 )2 ] cm6K 2mol 2 J 2 2
C= 1
( RT )2 mol28.3142 J 2373.152 K 2 C' =3.492105
2 2
101325 N
2 2
N m
C' =
(a)
B C PV B C RT B C
Z =1+ +
V V2 RT
=1+ + 2
V V
P=
V ( V V )
1+ + 2 (1)
V2
W = PdV (2)
V1
Put (1) in (2)
V2 V2
RT B C B C 1
W =
V
V
1+ + 2 dV
1
V V ( ) W =RT 1+
V1
( +
V V2 V )
dV (3)
Again using
RT B C
V 1=
P1 ( )
1+ + 2 ( 4 )
V1 V1
Assume that
3
cm
V 1=30780 (a)
mol
Nm
1.01325 m2
J
1003cm 3
101325 N RT cm3
molK1 =31023.6 (b)
1 m3 P1 mol
RT 8.314 J373.15 K
=
P1
64
August 20,
2013
Put (a) and (b) in (4)
cm3 cm3 242.5 25200

30780
mol
=31023.6
mol (
1 +
30780 307802 )
cm3 cm3 ( cm3 cm3
30780 =31023.6 10.007878+ 0.000026598 ) 30780 =31023.60.99215
mol mol mol mol
cm3 cm3
30780 =30780
mol mol
Since
L. H . S=R . H . S
Therefore
3
cm
Initial volume=V 1=30780
mol
Again using
RT B C
V 2=
P2 (
1+ + 2 (5 )
V2 V2 )
Assume that
cm3
V 2=241.33 ( c)
mol
Nm
1.01325 m2
J
100 3cm3
101325 N RT cm 3
molK55 =564.067 (d )
1 m3 P2 mol
RT 8.314 J373.15 K
=
P2
Put (c) and (d) in (4)
65
August 20,
2013
3 3 3 3
cm cm 242.5 25200
241.33
mol
=564.067
mol
1 (
+
241.33 241.332 ) 241.33
cm
mol
=564.067
cm (
mol
11.0048+ 0.4327 )
cm3 cm3 cm3 cm3

241.33 =564.0670.4278 241.33 =241.33
mol mol mol mol
Since
L. H . S=R . H . S
Therefore
cm 3
Finalvolume=V 2=241.33
mol
Now from equation (3)
[ ]
V2 V2 V2 V2
B C 1
W =RT ( 1+ + 2
V V V
dV ) W =RT V1 dV + B V12 dV +C V13 dV
V1 V 1 V 1V 1
[ | |] [ )]
V2 V2
1 1 1 1 1
W =RT |ln V|V B
V2
1 ||
1
V V1
1 1
C 2
2 V V1
W =RT ( ln V 2ln V 1 )B
(
) (
C 2
V2 V1 2 V2 V1
2
W =RT ln
[ V2
V1
B
1

(1 1
C
1

1
) (
V 2 V 1 2 V 22 V 12 )]
8.314J373.15 K
1 kJ
W=
molK
1000 J
ln
241.33
30780
+242.5
[ 1

1
241.33 30780

25200
2
1
2 (

1
241.33 30780
2 ) ( )]
kJ kJ
W =3.102 [ 4.848+0.9960.2163 ] W =12.62 Answer
mol mol
(b)
PV RT
Z =1+ B' P+C' P 2
RT
=1+ B' P+C ' P2 V=
P
( 1+ B' P+ C' P2 ) V =RT ( P1 + B +C ' P)
'
Differentiate w.r.t to pressure on both sides
66
August 20,
2013
dV
dP
1
=RT 2 +0+C '
P ( ) dV =RT
( P1 +C ' ) dP
2
Put in (2)
[ ]
P2 P2 P2
1 1
W = PRT 2 +C ' dP
P 1
P ( ) W =RT dP+C ' PdP
P P 1P 1
[ ]
'
C P2 P2
W =RT |lnP|P + |P2|P
1
2 1
2
2 ( 55 21 )
55 3.492105 1
[
W =RT ln
P2
P1
+C' ( P22P12 )
] ln
1
8.314J373.15 K
2
1 k J
W=
3.102 kJ
mol
( 3.9545 )
molK
W=
1000 J
kJ
W =12.268 Answer
mol
The answers for part (a) and (b) differ because the relations between the two sets of
parameters are exact only for infinite series
Problem 3.32:
Calculate Z and V for ethylene at 25 oC and 12 bars by the following equations:

a) The truncated virial equation [Eq. (3.40)] with the following experimental values of virial
coefficients:
B=140 cm 3 mol1 C=7200 cm 6 mol2
b) The truncated virial equation [Eq.(3.38)], with a value of B from the generalized Pitzer
correlations [Eq. (3.63)]
c) The Redlich/Kwong equation
d) The Soave/Redlich/Kwong equation
e) The Peng/Robinson equation.
Given Data:
67
August 20,
2013
Temperature=T =25 T =( 25+273.15 ) K T =298.15 K
Pressure=P=12
Solution:
(a)
3 1 6 2
B=140 cm mol C=7200 cm mol
Given equation is
B C
Z =1+ +
V V2
molK12Nm
1.01325 m2
J
1003cm 3
PV B C RT B C 101325 N
RT
=1+ + 2
V V
V=
P( V V )
1+ + 2 ( 1 )
1 m3
RT 8.314J298.15 K
=
P
RT cm3
=2065.68
V mol
Put in (1)
3
cm B C
V =2065.68
mol
1+ + 2
V V ( )
Assume
cm3
V =1919
mol
Therefore
3 3 3 3 3 3
cm cm 140 7200
1919
mol
=2065.68
mol (
1 +
1919 19192 ) 1919
cm
mol
=2065.68
cm (
mol
0.9290 ) 1919
cm
mol
=1919
cm
mol
Since
68
August 20,
2013
L. H . S=R . H . S
Therefore
cm3
V =1919 Answer
mol
We know that
12 1919cm3molK
J
8.314J298.15Kmol
PV 101325 N
Z= Nm Z =0.929 Answer
RT 2
1m 3

1.01325 m
Z=
1003 cm3
(b)
Given equation 3.38 is
BP
Z =1+ ( 2)
RT
We know that
T P
Reduced temperature=T r = T =T r T c ( a ) Reduced Pressure=Pr = P=Pr Pc (b)
Tc Pc
B Pr Pc
Z =1+
R T r Tc
Since
^ B Pc
Reduced second virial coefficient =B=
R Tc
Therefore
^B P r
Z =1+ (3)
Tr
Also
69
August 20,
2013
^
B=B O
+ B1
Put in (3)
Pr
Z =1+ ( B O + B1 ) ( 4)
Tr
For ethylene (From Table B.1 Appendix B)
T 298.15 K
=0.087 (i) Critical temperature=T c =282.3 K Tr= = =1.056(ii)
T c 282.3 K
50.40 =0.238 (iii)

12
Critical pressure=Pc =50.40

P
Pr = =
Pc
Also we have
0.422 0.422 0.172

B o=0.083 B o=0.083 B o=0.304 ( iv ) B 1=0.139
T r1.6 1.056
1.6
1.056
4.2
B 1=2.183103 ( v)
Put (i), (ii), (iii), (iv) & (v) in (4)
0.238
Z =1+ (0.304+0.0872.183103 ) Z =0.931 Answer
1.056
We know that
Nm
1.01325 m2
J 3 3
100 cm
Z=
PV
V=
ZRT 101325 N cm3
molK12 V =1923. Answer
RT P 1m3 mol
0.9318.314 J298.15 K
V=

(c)
The Redlich/Kwong equation is
70
August 20,
2013
Z
Z =1+ q ( 5)
( Z + ) ( Z + )
Where
Pr
=
Tr
From table 3.1
1
2
=1, =0.08664, =0,=0.42748, ( T r )=T r
Now
0.086640.238
= =0.0195 (i ' )
1.056
Also
1
( T r )
q= 0.427481.056 2 q=4.547 (i i' )
T r q=
0.086641.056
Put (i) and (ii) in (5)
Z
Z =1+ 0.01954.5470.0195
( Z + ) ( Z + )
Assume
0.9280.0195
Z =0.928 0.928=1.01950.08866 0.928=1.01950.088661.033 0.928=0.928
0.928 ( 0.928+ 0.0195 )
Since
L. H . S=R . H . S
Therefore,
Z =0.928 Answer
We know that
71
August 20,
2013

Nm 2
1.01325
m
J
1003 cm3 3
PV ZRT 101325 N cm
Z= V= molK12 V =1916.8 Answer
RT P 1m3 mol
0.9288.314 J298.15 K
V=

(d)
From table 3.1
=1, =0.08664, =0,=0.42748, ( T r )= SRK ( T r ; )
[ {
SRK ( T r ; )= 1+ ( 0.480+ 1.574 0.176 2 ) 1T r (
1
2
)}]
2
[ {
SRK ( T r ; )= 1+ ( 0.480+1.5740.0870.1760.087 ) 11.056 2
(
1
2 ) }] 2
SRK ( T r ; )=[ 0.9828 ]
SRK ( T r ; )=0.966 (ii i ' )
Now
( T r ) 0.427480.966 '
q= q= q=4.515 (ii i )
T r 0.086641.056
Put (i) and (iii) in (5)
Z
Z =1+ 0.01954.5150.0195
( Z + )( Z + )
Assume
0.9280.0195
Z =0.928 0.928=1.01950.08803 0.928=1.01950.23831.36 0.928=0.928
0.9 ( 0.9+ 0.0195 )
Since
L. H . S=R . H . S
72
August 20,
2013
Therefore,
Z =0.928 Answer
We know that

Nm
m2
1.01325
J
1003 cm3
Z=
PV
V=
ZRT 101325 N cm3
molK12 V =1917 Answer
RT P 1m3 mol
0.9288.314 J298.15 K
V=

(e)
From table 3.1
=1+ 2=2.41, =0.07780, =1 2=0.414, =0.45724, ( T r )= SRK ( T r ; )
Now
Pr
=
Tr
0.077800.238
= =0.0175 (iv ' )
1.056
[ {
SRK ( T r ; )= 1+ ( 0.37464 +1.54226 0.26992 2 ) 1T r (
1
2
)}]
2
[ {
SRK ( T r ; )= 1+ ( 0.37464+ 1.542260.0870.269920.087 ) 11.056 2
(
1
2 ) }]
2
SRK ( T r ; )=[ 0.986 ] SRK ( T r ; )=0.9722
Now
( T r ) 0.427480.9722
q= q= q=4.542 (v ' )
T r 0.086641.056
73
August 20,
2013
Put (iv) and (v) in (5)
Z
Z =1+ 0.01754.5420.0175
( Z + )( Z+ )
Assume
0.920.0175
Z =0.92 0.92=1.01750.07949 0.92=1.01750.079491.027
( 0.920.4140.0175 ) ( 0.92+ 2.410.0175 )
0.92 0.93
Since
L. H . S R . H . S
Therefore,
Z =0.92 Answer
We know that
Nm
1.01325 m2
J
1003 cm3 3
PV ZRT 101325 N cm
RT P 1m3 mol
0.928.314 J298.15 K
V=

Problem 3.33:
Calculate Z and V for ethane at 50 oC and 15 bars by the following equations:

a) The truncated virial equation [Eq. (3.40)] with the following experimental values of virial
coefficients:
3 1 6 2
B=156.7 cm mol C=9650 cm mol
b) The truncated virial equation [Eq.(3.38)], with a value of B from the generalized Pitzer
correlations [Eq. (3.63)]
c) The Redlich/Kwong equation
d) The Soave/Redlich/Kwong equation
e) The Peng/Robinson equation.
Given Data:
74
August 20,
2013
Temperature=T =50 T =( 50+273.15 ) K T =323.15 K
Pressure=P=15
Solution:
(a)
3 1 6 2
B=156.7 cm mol C=9650 cm mol
Given equation is
B C
Z =1+ +
V V2
PV B C RT B C
RT
=1+ + 2
V V
V=
P( V V )
1+ + 2 ( 1 )
molK15Nm
1.01325 m2
J
1003cm 3
101325N RT cm3
=2065.68
1 m3 V mol
RT 8.314J323.15 K
=
P
Put in (1)
cm 3 B C
V =1791
mol (
1+ + 2
V V )
Assume
cm3
V =1625
mol
Therefore
cm3 cm3 156.7 9650 cm3 cm3 ( cm3 cm3

1625
mol
=1791
mol(1 +
1625 16252 ) 1625
mol
=1791
mol
0.9072 ) 1625
mol
=1625
mol
75
August 20,
2013
Since
L. H . S=R . H . S
Therefore
3
cm
V =1625 Answer
mol
We know that
15 1625cm3molK
J
8.314J323.15Kmol
PV 101325 N
Z= Nm Z =0.907 Answer
RT 2
1m3
1.01325 m
Z=
1003 cm3
(b)
Given equation 3.38 is
BP
Z =1+ ( 2)
RT
We know that
T P
Reduced temperature=T r = T =T r T c ( a ) Reduced Pressure=Pr = P=Pr Pc (b)
Tc Pc
B Pr Pc
Z =1+
R T r Tc
Since
^ B Pc
Reduced second virial coefficient =B=
R Tc
Therefore
76
August 20,
2013
^B P r
Z =1+ (3)
Tr
Also
^
B=B O
+ B1
Put in (3)
Pr
Z =1+ ( B O + B1 ) ( 4)
Tr
For ethylene (From Table B.1 Appendix B)
T 323.15 K
=0.1 (i) Critical temperature=T c =305.3 K Tr= = =1.058 (ii)
T c 305.3 K
48.72 =0.308 (iii )

15
Critical pressure=Pc =48.72
P
Pr = =
Pc
Also we have
o 0.422 0.422 0.172

B =0.083 B o=0.083 B o=0.303 ( iv ) B 1=0.139
T r1.6 1.058
1.6
1.058
4.2
B 1=3.266103 (v)
Put (i), (ii), (iii), (iv) & (v) in (4)
0.308
Z =1+ (0.303+ 0.13.266103 ) Z =0.912 Answer
1.058
We know that
Nm
1.01325 m2
J 3 3
100 cm
Z=
PV
V=
ZRT 101325 N cm3
molK15 V =1633.36 Answer
RT P 1 m3 mol
0.9128.314 J323.15 K
V=

77
August 20,
2013
(c)
The Redlich/Kwong equation is
Z
Z =1+ q ( 5)
( Z + ) ( Z + )
Where
Pr
=
Tr
From table 3.1
1
2
=1, =0.08664, =0,=0.42748, ( T r )=T r
Now
0.086640.308 '
= =0.0252 (i )
1.058
Also
1
( T r ) 2
q= 0.427481.058 q=4.533 (ii ' )
T r q=
0.086641.058
Put (i) and (ii) in (5)
Z
Z =1+ 0.02524.5330.0252
( Z+ )( Z+ )
Assume
0.9060.0252
Z =0.906 0.906=1.02520.114 0.906=1.02520.1141.044 0.906=0.906
0.906 ( 0.906+ 0.0252 )
Since
L. H . S=R . H . S
Therefore,
78
August 20,
2013
Z =0.906 Answer
We know that
Nm 2
1.01325 m
J 3 3
100 cm 3
PV ZRT 101325 N cm
RT P 1 m3 mol
0.9068.314 J323.15 K
V=

(d)
From table 3.1
=1, =0.08664, =0,=0.42748, ( T r )= SRK ( T r ; )
[ {
SRK ( T r ; )= 1+ 0.480+1.574 0.176 2 1T r (
1
2
)}]
2
[ {
SRK ( T r ; )= 1+ 0.480+1.5740.10.1760.1 11.058 2
(
1
2 ) }] 2
SRK ( T r ; )=[ 1+0.6374 ]
SRK ( T r ; )=2.681 (ii i' )
Now
( T r ) 0.427482.681 '
q= q= q=12.50 (iii )
T r 0.086641.058
Put (i) and (iii) in (5)
Z
Z =1+ 0.025212.500.0252
( Z + ) ( Z + )
Assume
0.9070.0252
Z =0.907 0.907=1.02520.315 0.907=1.02520.3151.0429 0.695=0.695
0.907 ( 0.907+0.0252 )
79
August 20,
2013
Since
L. H . S=R . H . S
Therefore,
Z =0.695 Answer
We know that
Nm 2
1.01325 m
J
1003 cm3 3
PV ZRT 101325 N cm
RT P 1m3 mol
0.6958.314 J298.15 K
V=

(e)
From table 3.1
=1, =0.07780, =0,=0.45724, ( T r )= SRK ( T r ; )
Now
Pr
=
Tr
0.077800.238
= =0.0175 (iv ' )
1.056
[ {
SRK ( T r ; )= 1+ 0.37464 +1.54226 0.26992 2 1T r (
1
2
)}]
2
SRK ( T r ; )=[ 1+ {0.37464+1.542260.0870.269920.087 ( 11.056 ) } ]
2 2
2
SRK ( T r ; )=[ 1+0.509 ] SRK ( T r ; )=2.277
Now
80
August 20,
2013
( T r ) 0.427482.277
q= q= q=10.64 ( v ' )
T r 0.086641.056
Put (iv) and (v) in (5)
Z
Z =1+ 0.017510.640.0175
( Z + )( Z+ )
Assume
0.7930.0175
Z =0.793 0.793=1.01750.1862 0.793=1.01750.18621.2066 0.793=0.793
0.793 ( 0.793+0.0175 )
Since
L. H . S=R . H . S
Therefore,
Z =0.793 Answer
We know that

Nm
m2
1.01325
J
1003 cm3
Z=
PV
V=
ZRT 101325 N cm 3
molK12 V =1638.1 Answer
RT P 1m3 mol
0.7938.314 J298.15 K
V=

81

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August 20,

PROBLEMS ZAID YAHYA 11-CH-74

Put in (1) & (2)

Integrating on both sides

Since is very small

Since is very small

The Tait equation for liquids is written for an isotherm as:

Differentiate w.r.t Pressure

Since, Temperature is constant

Or, From (1)

For liquid water the isothermal compressibility is given by:

b=2700 bars c=0.125 cm3 / g Work=W =? Solution:

Comparing (2) & (3)

Work done=W =? Volume=V =1 ft 3 Temperature=T =32 F Pressure=P1=1 atm

Pressure=P2=3000 atm /atm1=3.91060.1109 P (atm)

W = (17.550.8991 ) atmft 3 W =16.65atmft 3 Answer

Integrating on both sides,

Now, for total volume,

Integrating on both sides,

Where ln A (T) is constant of integration & A depends on T only

According to first law of thermodynamics,

For a constant volume process,

For T2 , We know that for an ideal gas

For a constant temperature process,

We know that at constant temperature, work done is

Now, according to first law of thermodynamics,

U =Q+W 0=Q+ W Q=W

We know that for an adiabatic process

For T2 , We know that for an adiabatic process

Step 12, an Isothermal process,

We know that, for an ideal gas

Step 23, an Isochoric process,

We know that, for an ideal gas

Step 34, an Isobaric process,

For T4 , we will use an adiabatic relation of temperature and pressure

We know that, for an ideal gas

Step 41, an adiabatic process,

We know that, for an ideal gas

Step 12, an Isothermal process,

For an isothermal process, we have

According to first law of thermodynamics

Step 23, an Isochoric process,

At constant volume we have

Step 34, an Isobaric process,

For an Isobaric process we have

Step 41, an adiabatic process,

According to first law of thermodynamics

V t2=1 m3 Q=? W =? H=? U =?

U =Q+W 0=Q+ W W =Q W 12=2981.88 kJ Answer

Adiabatic compression followed by cooling at constant pressure

The process completes in two steps

For mono atomic gas, we have

Second step, cooling at constant pressure P2

Adiabatic compression followed by cooling at constant volume

First step, an adiabatic compression to volume V2 , intermediate pressure can be given as

Second step, cooling at constant Volume,

Heating at constant volume followed by cooling at constant pressure

Step 2, Cooling at constant pressure P2 To V2

According to first law of thermodynamics

U =Q+W 0=Q+ W Q=W Q=13200 kJ Answer

Cooling at constant pressure followed by heating at constant volume

The process completes in two steps