Chapter 3

August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Chapter 3
Problems
Problem 3.1:
Express the volume expansivity and isothermal compressibility as functions of density and its partial
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:
Volume expansivity==
1 V
V T
( )
Or
=
1 dV
V dT
( ) (1)
P
Isothermal Compressibilty==
1 V
V P
( )
Or
=
1 dV
V dP
( ) ( 2)
T
Temperature=T =50
Pressure=P1=1
=44.18106
1
(a)
We know that
Density of water =1=1

P2=?
Solution:
kg
m3
2=( 1+1 )
kg
m3
2=1.01
kg
m3
August 20,
2013
1
V
PROBLEMS
V=
ZAID YAHYA
11-CH-74
Put in (1) & (2)
( dTd 1 )
=
P
d
2
dT
( )
1 d
dT
( ) Proved
P
Now,
=
d 1
dP
d
2 dP
( )
1 d
dP
( ) Proved
T
(b)
As
=
1 d
dP
( )
dP=
Integrating on both sides

P2
dP=
P1
P2
|P|P =|ln |
( P2 P 1 )=( ln 2ln 1 )
( P2 P 1 )=ln
2
1
Putting values
( P21 )= ln1.01
1
6
44.1810
6
44.1810
P21=0.00995
P2=( 225.22+1 )
P2=226.22
Answer
Problem 3.2:
Generally, volume expansivity and isothermal compressibility depend on T and P. Prove that
( P ) =( T )
T
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Solution:
We know that
Since
1 V
V T
( )
is very small
V=
1 V
T
( ) (1)
1 V
V P
( )
Since is very small

V=
1 V
P
1 V
T
V
( ) =1
( P)
( )
1 1
T
1
V
( ) V =1
(P)
( T ) =( P )
( P ) =( T ) Proved
T
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
V P
( ) (1)
T
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Given that
V =V 0 1
AP
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
V V o =
AP
V
B+ P o
V V o AP
=
Vo
B+ P
Differentiate w.r.t Pressure

1
AP
( V V o ) = P B + P
V o P
1 V
AB+ AP AP
=
Vo P
( B+ P )2
( )
A ( B+ P ) AP ( 1 )
1 V
0 =
V o P
( B+ P )2
1 V
AB
=
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
4
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Given Data:
Isothermal compressibility==
c
V ( P+ b )
Pressure=P1=1
Mass of water=m=1 kg
P2=500 bars
Temperature=T =60
c=0.125 cm3 / g
b=2700 bars
Work=W =?
Solution:
We know that
W = PdV (1)
c
(2)
V ( P+b )
Also
=
1 dV
V dP
( ) ( 3)
T
Comparing (2) & (3)

1 dV
c
=
V dP V ( P+b )
dV =
c dP
P+b
Put in (1)
c dP
W =P
P+b
P2
P2
W =c dPb c
P1
P1
P2
P
W =c
dP
P+b
P
1
dP
P+b
P2
P+bb
W =c
dP
P+ b
P
P2
P2
W =c ( P2 P 1) bc ln
Putting values
5
P2
P+b
b
W =c
dPc
dP
P+b
P+ b
P
P
W =c|P|P bc|ln (P+b)|P
P2
W =c ( P2 P 1) bc [ ln ( P2 +b ) ln ( P1 +b ) ]
P2 +b
P1 +b
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
3
cm
g
3
cm
57.216
g
W =62.375
cm (
0.125 cm ln 500+ 2700
W =0.125
5001 )2700
g
g
1+2700
cm
g
W =5.16
cm
1 m3
g
101325 N
1003 cm 3
J
1.01325 m2
Nm
W =5.16
W =0.516
J
Answer
g
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
Pressure=P2=3000 atm
Temperature=T =32 F
Pressure=P1=1 atm
/atm1=3.91060.1109 P (atm)
Where
Term,
3.9*10-6
has
unit
of
atm-1
&
Solution:
We know that, work done for a reversible process is
W = PdV (1)
Also
=
1 dV
V dP
( )
dV =VdP
0.1*10-9
has
units
of
atm-2
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Put in (1),
P2
W = P (Vdp )
W =V P dP
P1
P2
P2
6
9
W =V ( 3.910 0.110 P ) P dP
3000
W =3.910 V
P dP0.110 V
P1
P2 dP
3000
||
P2
W =3.910 V
2
W=
P1
3000
9
W =V 3.910 P dPV 0.110 P dP
P1
P2
6
3000
||
P3
0 .110 V
3
9
1.951061 ft 3 (
3.33310111 ft 3 (
3000212 ) atm2
3000313 ) atm3
2
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
T 1 =273.15 K
Temperature=T 1=0
August 20,
2013
PROBLEMS
ZAID YAHYA
Temperature=T 2=20
T 2 =( 20+273.15 ) K
T 2 =293.15 K
=1.210 K
C P=0.84
11-CH-74
kJ
kgK
=1590
kg
m3
Q=?
U =?
Solution:
As
V=
V 1=
1
1
1 m3
V 1=
1590 kg
Also,
we know that
1 dV
V dT
( )
dT =
1
dV
V
Integrating on both sides,

T2
V2
dT =
T1
V1
dV
V
T2
V2
|T |T =|lnV |V
( T 2T 1 )=( lnV 2ln V 1 )
( T 2T 1 )=ln
V2
V1
Putting values
V 1590 kg
1.210
( 293.15273.15 ) K =ln 2
K
m3
3
V 2=0.000644
0.024
V 21590 kg
m3
m3
kg
Now,
V =V 2V 1
V = 0.000644
Now, for total volume,
1 m3
1590 kg
V =15.28106
m
kg
V =?
1.024
m3
1590
V 2=
kg
W =?
August 20,
2013
PROBLEMS
V t = V m
ZAID YAHYA
V t =( 15.281065 )
m3
kg
kg
11-CH-74
V t =7.638105 m3 Answer
Now,
We know that for a reversible process,
Work done=W =P V t
W =1 7.638105
m3101325 N
J
1.01325 m2
1 kJ
Nm
1000 J
W =7.638103 kJ Answer
Now,
For a reversible process at constant pressure,we have
Q= H
Q=m C P T
Q=5 kg0.84
kJ
( 293.15273.15 ) K
kgK
Q=84 kJ Answer
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
Isothermal compressibilty ==
1 dV
V dP
( )
dV
=dP
V
August 20,
2013
PROBLEMS
ZAID YAHYA
dV
= dP
V
lnV =P+lnA ( T )
Where ln A (T) is constant of integration & A depends on T only
lnV lnAT =P
ln
V
=P
A (T )
Taking anti log on both sides,
V
=eP
AT
V = A ( T ) eP
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
Isothermal compressibilty ==
Put in (2)
dW =
dV
d ( PV )
10
1 dV
V dP
( )
dV
=VdP
11-CH-74
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
dW = dV d ( PV )
W=
1
V ( PV )
Since volume changes from V1 to V2 & pressure changes from P1 to P2 ,

Therefore,
W=
1
( V 2V 1 ) ( P2 V 2P1 V 1 )
W=
( V 1V 2 )
+ 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
CV = R
2
7
C P= R
2
P1=8
T 1 =600 K
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
11
Q=U =C V ( T 2 T 1 ) (2)
P2=1
W =?
Q=?
U =?
H=?
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
For T2 , We know that for an ideal gas
T1 T 2
=
P1 P2
T2=
T1
P
P1 2
8 1
600 K
T2=
T 2 =75 K
Put in (2),
5
Q=U = R ( 75600 ) K
2
Q=U =
5
J
8.314
525 K
2
molK
Q=U =10.912
Q=U =10912
kJ
Answer
mol
Also
For a mechanically reversible process we have,
H=C P T
7
H= R ( T 2T 1 )
2
7
J
H= 8.314
( 75600 ) K
2
molK
H=15.277
H=15277
kJ
Answer
mol
(b)
For a constant temperature process,
U =0
H=0
We know that at constant temperature, work done is
W =R T 1 ln
W =8.314
J
1
600 Kln
molK
8
0=Q+ W
Q=W
Or
Q=10.373
kJ
Answer
mol
(c)
12
We know that for an adiabatic process
P2
P1
W =10373
Now, according to first law of thermodynamics,
U =Q+W
J
mol
J
mol
W =10.373
kJ
Answer
mol
J
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
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
T1 P
( 1 )
=T 2 P
( 1 )
T 2 =T 1
P1
P2
( )
( 1 )
T 2 =600 K
8
1
()
( 11.4 )
1.4
T 2 =331.23 K
Put in (2)
5
W = U= R( 331.23600 ) K
2
W = U=
5
J
8.314
268.77 K
2
molK
W = U=5.5864
W = U=5586.4
J
mol
J
Answer
mol
For a mechanically reversible adiabatic process we have
7
H= R ( T 2T 1 )
2
H=C P T
H=7.821
7
J
H= 8.314
( 331.23600 ) K
2
molK
J
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:
13
August 20,
2013
PROBLEMS
ZAID YAHYA
Initial Temperature=T 1=600 K
Initial Pressure=P1=10
11-CH-74
7
C P= R
2
5
CV = R
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
P2 V 2 =R T 2
V 2=
RT 2
P2
1.01325
m
Nm
101325 N
molK3
J
8.314J600 K
V 2=
V 2=0.0166
m
mol
Step 23, an Isochoric process,

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

Since
For an isobaric process, pressure is constant
14
T 3 =400 K
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Therefore,
P4 =P 3=2
For T4 , we will use an adiabatic relation of temperature and pressure
As
T 4 P4
=
T1
P1
( )
R
CP
T 4=T 1
P4
P1
( )
R
CP
2
10
( )
T 4=600 K
2R
7R
T 4=378.83 K
P4 V 4 =RT 4
V 4=
2
1.01325
m
Nm
101325 N
molK2
J
8.314 J378.83 K
V 4=
RT4
P4
V 4 =0.0157
m
mol
Step 41, an adiabatic process,

Since
Gas returns to its initial state adiabatically
Therefore,
T 1 =600 K
P1=10
P1 V 1=R T 1
V 1=
RT 1
P1
1.01325 m2
Nm
101325 N
molK10
J
8.314 J600 K
V 1=
(c)
Step 12, an Isothermal process,

Since
For an isothermal process, temperature is constant
Therefore
15
V 1=4.988103
m
mol
August 20,
2013
U 12 =0
PROBLEMS
11-CH-74
H 12=0
For an isothermal process, we have
Q=R T 1 ln
ZAID YAHYA
P2
P1
Q=8.314
J
3
600 Kln
molK
10
Q=6006
J
mol
Q=6.006103
J
Answer
mol
According to first law of thermodynamics
U 12=Q12 +W 12
0=Q12+W 12
W 12=Q12
W 12=6.006103
J
Answer
mol
Step 23, an Isochoric process,

Since
For an isochoric process, Volume is constant
Therefore,
W 23=0
At constant volume we have
Q23= U 23=CV T
Q23= U 23=CV ( T 3T 2 )
5
8.314 J
2
Q23= U 23=
(200 ) K
molK
5
Q23= U 23= R ( 400600 ) K
2
Q23= U 23=4157
J
mol
Q23= U 23=4.15710 3
J
Answer
mol
We know that
H 23=C P T
H 23=C P ( T 3T 2 )
H 23=5820
Step 34, an Isobaric process,

Since
For an isobaric process, pressure is constant
Therefore, at constant pressure we have,
16
7
H 23= R ( 400600 ) K
2
J
mol
H 23=5.82103
7
J
H 23= 8.314
(200 ) K
2
molK
J
Answer
mol
August 20,
2013
PROBLEMS
Q34= H 34 =C P T
ZAID YAHYA
7
Q34= H 34 = R ( T 4T 3 )
2
11-CH-74
7
J
Q34= H 34 = 8.314
( 378.83400 ) K
2
molK
Q34= H 34 =616
J
Answer
mol
For an Isobaric process we have
W 34=R T
W 34=R ( T 4T 3 )
W 34=8.314
J
( 378.83400 ) K
molK
W 34=176
J
Answer
mol
We know that,
U 34 =CV T
5
U 34 = R ( T 4 T 3 )
2
5
J
U 34 = 8.314
( 378.83400 ) K
2
molK
U 34 =440
J
Answer
mol
Step 41, an adiabatic process,

Since
For an adiabatic process there is no exchange of heat
Therefore,
Q41=0
We know that,
U 41=C V T
5
U 41= R ( T 1T 4 )
2
5
J
U 41= 8.314
( 600378.83 ) K
2
molK
U 41=4.597103
U 41=4597
J
mol
J
Answer
mol
We know that
H 41=C P T
7
H 41= R ( T 1T 4 )
2
7
J
H 41= 8.314
( 600378.83 ) K
2
molK
H 41=6.4358103
17
J
Answer
mol
H 41=6435.8
J
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
U 41=Q 41+W 41
U 41=W 41
11-CH-74
3
W 41=4.59710
J
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
C P= R
2
3
CV = R
2
V t2=1 m3
Q=?
Initial pressure=P1=1
W =?
H=?
Solution:
Since
Temperature=constant
Therefore, for all parts of the problem,
H=0
U =0
(a)
Isothermal compression,
For an isothermal process, we have
Q=R T 1 ln
P2
P1
Since
For an ideal gas, we have
18
U =?
V 1=12 m
Final pressure=P 2=12
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
P1 V 1=R T 1
Therefore,
Q=P1 V 1 ln
P2
P1
12
101325 N
1
J
2
1.01325 m
1 kJ
Nm
3
Q=1 12 m ln
1000 J
Q=2981.88 kJ Answer
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
'
P2 ( V ) =P 1 V 1
V ' =V 1
P1
P2
( )
For mono atomic gas, we have
=1.67
1
12
( )
V ' =12 m3
1
1.67
V ' =2.71 m3
We know that,
'
P V P 1 V 1
W 1= 2
1
19
August 20,
2013
PROBLEMS
ZAID YAHYA
( 122.71112 ) m3
101325 N
1.671
J
1.01325 m2
1 kJ
Nm
W 1=
1000 J
11-CH-74
W 1=3063 kJ (1)
Second step, cooling at constant pressure P2

We know that, for a mechanically reversible process
m3101325 N
J
1.01325 m2
1 kJ
Nm
W 2=12 ( 12.71 )
1000 J
W 2=P2 ( V 2V ' )
W 2=2052 kJ ( 2)
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
'
P V 2 =P1 V 1
V
P =P1 1
V2
'
( )
For mono atomic gas, we have
=1.67
P' =1
1.67
12
1
( )
We know that,
20
P' =63.42
August 20,
2013
PROBLEMS
'
W 1=
ZAID YAHYA
P V 2P 1 V 1
1
( 63.421112 ) m3
101325 N
1.671
J
1.01325 m 2
1 kJ
Nm
W 1=
1000 J
11-CH-74
W 1=7674.76 kJ
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
(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
W 2=P2 V
W 2=P2 ( V 2V 1 )
m3101325 N
J
1.01325 m2
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

21
W 2=13200 kJ
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74

Step 1, Cooling at constant Pressure P1 to V2
Therefore, for a mechanically reversible process
3
W 1=P1 V
W 1=P1 ( V 2V 1 )
m 101325 N
J
2
1.01325
m
1 kJ
Nm
W 1=1 ( 112 )
1000 J
W 1=1100 kJ
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:
The environmental lapse rate
dT
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
22
The polytropic relation is
August 20,
2013
TP
PROBLEMS
ZAID YAHYA
=Constant
Or
TP
=T o Po
Where
To =Temperature at sea level, so it is constant
Po = Pressure at sea level, so it is constant
T
P
T
To
( )
To
P
P
=
Po
T
P
=
T o Po
( )
T
P=Po
To
( )
(a)
P=
Po
To
T 1
Differentiate w.r.t to Temperature on both sides
Po
Po
dP T o
=
T
dT
1
1
1
1
To
1
dP=
T
dT (2)
1
P
RT
Where
R=Specific gas constant=R ' /M
Put (a) in above equation
Put in (1)
23
1
T
Po
RT
To
( )
11-CH-74
August 20,
2013
PROBLEMS
dP
g1
T
=M
Po
dz
RT
To
( )
ZAID YAHYA
dP=M
g1
T
Po
RT
To
( )
11-CH-74
dz
Put (2) in above
Po
1
M g
Po
R
T o 1
Po
To
1
1
1
dT =M
g1
T
P
RT o T o
( )
dz
1
M g
Po
R
T o 1
Po
dT
=
dz
To
To
dT
=
dz
TT
T 1
1
1
T 1
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:
24
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
August 20,
2013
PROBLEMS
d ( mU )tank
+ ( Hm )=0
dt
ZAID YAHYA
d ( mU )tank
+ H ' ' m' ' H ' m' =0
dt
Since
Tank is filled with gas from an entrance line, but no gas is being escaped out,
Therefore,
d ( mU )tank
+0H ' m' =0
dt
d ( mU )tank
H ' m' =0(1)
dt
Where prime () denotes the entrance stream

Applying mass balance
m' =
d mtank
( 2)
dt
Combining equation (1) & (2)
d ( mU )tank
' d m tank
H
=0
dt
dt
1
{d ( mU )tank H ' d mtank }=0
dt
'
d ( mU )tank =H d mtank
Integrating on both sides

m2
m2
d ( mU )tank=H ' d mtank

m1
( mU )tank =H ' ( m 2m 1 )
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
25
11-CH-74
August 20,
2013
PROBLEMS
U=C V T
ZAID YAHYA
11-CH-74
U 2=C V T 2 ( a )
Also
H ' =C P T ' ( b )
Put (a) & (b) in (3)
CV T =C P T '
T=
CP '
T
CV
Since heat capacities are constant, therefore
CP
CV
T = T ' Proved
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
Heat lost =Q=?
T 1 =25 o. C =298 K
7
C P= R
2
P1=101.33 kPa
T 2 =45 o.C =318 K
5
CV = R
2
Solution:
U =Q+W (1)
Since
H= U + ( PV )
26
U = H ( PV )
U = HP V V P ( a )
P2=1500 kPa
August 20,
2013
PROBLEMS
ZAID YAHYA
Also, we know that
W =P V ( b )
Put (a) & (b) in (1)
HP V V P=QP V
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 =n1 R T 1
n1=
P1 V
RT1
The final number of moles of gas at temperature T1 are
P2 V =n2 R T 1
n2 =
P2 V
RT 1
Now, Applying molar balance
n=n1n 2
Put in (3)
27
n=
P1 V P2 V
R T1 R T1
n=
( P1P 2) V
RT1
HV P=Q ( 2 )
11-CH-74
August 20,
2013
PROBLEMS
ZAID YAHYA
( P 1P2 ) V
R T1
( P1P2 ) V
C ( T 2T 1 )V P=Q
P
( P1P2 ) V
T1
2
RT1
2
11-CH-74
7
R( T 2T 1 )V P=Q
7
( T 2 T 1 )V ( P2 P 1 )=Q
( 101.331500 ) kPa0.1 m3
7
298 K
( 318298 ) K 0.1 m3 ( 1500101.33 ) kPa=Q
2
kPa1 kN
1 kJ
2
3 1 kPam
Q=172.717 m
1 kNm
Q=172.717 kJ Answer
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:
Volume of thetank=V 1 =4 m
V 3=
V 12 8 3
= m
3
3
Solution:
(a)
Finaltemperature=T 2=?
28
V 2=
V 11 4 3
= m
3
3
Pressure=P2=6
Temperature=T 1=100 . C
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
U =Q+W
Since
No work is done & no heat is transferred
Therefore
Q=W =0
mC V T =0
U =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
W =R T 2 ln
V2
V1
As, for an ideal gas
P2 V 2 =R T 2
W =P2 V 2 ln
V2
V1
4
4
W =6 m3 ln
3
34
W =8.788
m 3101325 N
kJ
1
2
1000
Nm
1.01325 m
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
(5/2) R
29
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Given Data:
T 1 =30 0.C
T 1 =303.15 K
P1=100 kPa
Q=?
W =?
U =?
H=?
7
C P= R
2
5
CV = R
2
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
W 12=U 12=CV T 12
5
W 12=U 12= R ( T 2T 1 ) ( 1 )
2
For T2
We know that
T 2 P2
=
T 1 P1
( )
T 2 =T 1
P2
P1
( )
T 2 =303.15 K
500
100
( )
1.41
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
H 12=C P ( T 2T 1 )
7
J
kJ
H 12= 8.314
( 480.13303.15 ) K1
2
molK
1000 J
2) Cooling at constant pressure from point 2 to point 3

Therefore at constant pressure we have,
Q23= H 23=C P T 23
30
7
Q23= H 23= R ( T 3T 2 )
2
H 12=5.15
kJ
mol
So
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
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
U 23=3.679
kJ
mol
Now, from first law of thermodynamics,
U 23=Q23 +W 23
W 23= U 23Q23
W 23=3.679+5.15
W 23=1.471
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
W 31=4.056
31
kJ
mol
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
U 31 =Q31 +W 31
0=Q31+W 31
Q31=W 31
Q31=4.056
kJ
mol
For the complete cycle,
Q=Q12 +Q23+ Q31
Q=05.15+ 4.056
W =W 12+W 23+W 31
U = U 12 + U 23 + U 31
kJ
Answer
mol
W =3.679+ 1.4714.056
W =1.094
H= H 12+ H 23+ H 31
Q=1.094
kJ
Answer
mol
H=5.155.15+0
H=0
kJ
Answer
mol
U =3.6793.679+0
U =0
kJ
Answer
mol
(b)
If each step that is 80% accomplishes the same change of state then values of
in part (a) but values of Q & W will change.

1. Adiabatic Compression from point 1 to point 2
W 12=
W 12
0.8
W 12=
3.679
0.8
W 12=4.598
kJ
mol
U 12 =Q12 +W 12
3.679
kJ
kJ
=Q12+ 4.598
mol
mol
Q12=3.679
kJ
kJ
4.598
mol
mol
2. Cooling at constant pressure from point 2 to point 3

32
Q12=0.92
kJ
mol
&
will remain same as
August 20,
2013
PROBLEMS
ZAID YAHYA
W 23=
W 23
0.8
W 23=
1.471
0.8
11-CH-74
W 23=1.839
kJ
mol
U 23=Q23 +W 23
3.679
kJ
kJ
=Q23 +1.839
mol
mol
Q23=3.679
kJ
kJ
1.839
mol
mol
kJ
0.8
mol
W 31=3.245
Q23=5.518
kJ
mol
3. Isothermal expansion from point 3 to point 1

Since initial step can no longer be adiabatic , therefore
W 31=W 310.8
W 31=4.056
kJ
mol
U 31 =Q31 +W 31
Q31=W 31+ 0
Q31=3.245
kJ
mol
Q=Q12 +Q 23+Q31
W =W 12+W 23+W 31
Q=0.925.518+ 3.245
W =4.598+1.8393.245
W =3.192
Q=3.193
kJ
Answer
mol
kJ
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:
33
August 20,
2013
V 1=1 m3
PROBLEMS
T 1 =600 K
ZAID YAHYA
P1=1000 kPa
V 2=5 V 1
V 2=5 m3
C P=21
11-CH-74
J
mol K
CV =?
T 2 =?
W =?
Solution:
We know that,
C PC V =R
CV =C P R
CV =( 218.314 )
J
molK
CV =12.686
J
molK
As
CP
CV
=1.6554
(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 P 2 V 2
=
T1
T2
P1 V 1
T 2
T1
P 2=
V2
1000 kPa1 m
600 K
600 K
P 2=
3
5m
We know that, for an isothermal process
W =R T 1 ln
Since
P1 V 1=R T 1
Therefore,
34
V2
V1
P2=200 kPa Answer
P2=?
August 20,
2013
PROBLEMS
ZAID YAHYA
5
N
1
J
Pam2
3
W =1000 kPa1 m ln
Nm
V
W =P1 V 1 ln 2
V1
11-CH-74
(b)
We know that, for an adiabatic process
P1 V 1 =P2 V 2
V
P2=P1 1
V2
1
5
1.6554
()
P2=1000 kPa
P2=69.65 kPa Answer
P1 V 1 P2 V 2
=
T1
T2
( )
P V
T 2 = 2 2 T 1
P1 V 1
69.65 kPa5 m3
T2=
600 K
1000 kPa1 m3
T 2 =208.95 K Answer
For an adiabatic process work done is
P V P1 V 1
W= 2 2
1
N
J
( 69.65510001 ) kPam Pam 2
W=
1.65541
Nm
3
W =994.43 kJ Answer
(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)
kPam N
J
2
Pam
U =W =100 ( 51 )
Nm
U =400 kJ
T2=
35
n CV T =400 kJ
400 kJ
+ T 1 ( 1)
n CV
n CV ( T 2T 1 )=400 kJ
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
For an ideal gas we have,

3
P1 V 1=nR T 1
n=
P1 V 1
RT1
1000 kPa1 m molK

kN
8.314 J600 K
kJ
kPam2
n=
kNm
Put in (1)
400 kJmolK
1000 J
0.2005 mol12.686 J
T2=
+600 K
1 kJ
n=0.2005 mol
T 2 =157.26 K +600 K
T 2 =442.74 K Answer
P1 V 1 P2 V 2
=
T1
T2
P1 V 1
T 2
T1
P2=
V2
1000 kPa1 m
442.74 K
600 K
P2=
3
5m
P2=147.58 kPa Answe r
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:
Mole of air=n=1mol
Initial Temperature=T 1=150 .C =423.15 K
Finaltemperature=T 3=50 0.C =323.15 K
Final pressure=P 3=3
Initial pressure=P1=8
7
C P= R
2
5
CV = R
2
Solution:
Since process is reversible
Two different steps are used in this case to reach final state of the air.
Step 12:
36
For step 12 temperatures is constant,
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
T 1 =T 2
Therefore
U 12= H 12=0
W 12=R T 1 ln
V1
V2
As
V 2=V 3
W 12=R T 1 ln
V1
(1)
V3
We know that
P1 V 1 P 3 V 3
=
T1
T3
V 1 P3 T 1
=
V 3 T 3P1
8.314 J423.15 K
1 kJ
molK
3423.15
W 12=
ln
1000 J
8323.15
P T
W 12=R T 1 ln 1 3
T 1P3
W 12=2.502
kJ
mol
U 12=Q12 +W 12
0=Q12+W 12
Q12=W 12
Q12=2.502
kJ
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
5
Q23= U 23= R ( 323.15423.15 ) K
2
37
Q23= U 23=CV ( T 3T 2 )
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
()
8.314
2.0785
W e know that
H 23=C P T
H 23=C P ( T 3T 2 )
J
1 kJ
7
molK
H 23= 8.314
( 423.15323.15 ) K
2
1000 J
H 23=2.91
kJ
mol
Work=W =W 12 +W 23
Q=Q 12 +Q23
W = (2.502+0 )
Q=( 2.5022.0785 )
U = U 12 + U 23
H= H 12+ H 23
kJ
mol
kJ
mol
W =2.502
Q=0.424
kJ
Answe r
mol
kJ
Answer
mol
U =( 02.0785 )
kJ
mol
U =2.0785
H= ( 02.91 )
kJ
mol
H=2.91
kJ
Answe r
mol
kJ
Answe r
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:
38
August 20,
2013
PROBLEMS
ZAID YAHYA
0
Velocity=u 1=2.5
Temperature=T 1=150 .C =423.15 K
m
sec
Molecualr weight of Nitrogen=28
11-CH-74
T 2 =?
u2=50
m
sec
7
C P= R
2
g
mol
Solution:
Applying energy balance for steady state flow process
H+
u2
+ g z=Q+W S
2
Since
z=W S=Q=0
Therefore,
2
u
H+
=0
2
u
CP T =
2
u22u12
T2=
+ T1
2C P
u22u12
C P ( T 2 T 1 )=
2
( 50 22.52 )2m2molK
28 g Nitrogen
278.314 Jsec 2
J
1 mol Nitrogen
Nsec 2
Nm
1 kg
kgm
T2=
+ 423.15 K
1000 g
T 2 =421.95 K
T 2 =( 421.95273.15 ) .C
T 2 =148.8 .C
T 2 =1.199 K + 423.15 K
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
39
August 20,
2013
PROBLEMS
Calculate Q, W,
ZAID YAHYA
U H
11-CH-74
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 3 =403.15 K
P1=1
T 1 =303.15 K
P3=10
Q=?
W =?
T 2 =130 0.C
U =?
T 3 =( 130+273.15 ) K
H=?
Solution:
7
C P= R
2
5
CV = R
2
Each part consist of two steps, 12 & 23

For the overall processes
U = U 12=U 23=CV T
5
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
U = U 12=U 23=2.079
kJ
(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
H= H 12= H 23=2.91
40
kJ
( b ) Answe r
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
(a)
Step 12:
For step 12 volume is constant
Therefore
W 12=0
Here
T 2 =T 3
U 12=Q12 +W 12
U 12=Q12
Q12= U 12=C V T
Q12= U 12=2.079
kJ
[ ( a ) ]
mol
Also we have
H 12=2.91
kJ
[ ( 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
=
T1 T 2
P
P2= 1T 2
T1
403.15 K
303.15 K
P2=
P2=1.329 b ar
W 23=R T 2 ln
41
P3
P2
W 23=8.314
J
K1 kJ
10
403.15
ln
molK
1000 J
1.329
August 20,
2013
PROBLEMS
ZAID YAHYA
W 23=6.764
11-CH-74
kJ
mol
U 23=Q23 +W 23
0=Q23+W 23
Q23=W 23
Q23=6.764
kJ
mol
Work=W =W 12 +W 23
Q=Q12 +Q23
W = ( 0+6.764 )
Q=( 2.0796.764 )
U = U 12 + U 23
kJ
mol
kJ
mol
W =6.764
Q=4.685
kJ
Answe r
mol
U =( 2.079+0 )
kJ
mol
U =2.079
H= ( 2.91+ 0 )
kJ
mol
H=2.91
H= H 12+ H 23
kJ
Answe r
mol
kJ
Answe r
mol
kJ
Answe r
mol
(b)
Step 12:
Therefore, at constant pressure we have
Q12 H 12=2.91
kJ
mol
[ (b)]
Also,
U 12 =2.079
[ (a)]
U 12=Q12 +W 12
42
kJ
mol
W 12=U 12Q12
W 12=( 2.0792.91 )
kJ
mol
W 12=0.831
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Step 23:
Since for step 23 process is isothermal ( T = Constant)
Therefore
U 23 = H 23=0
Here
T 2 =T 3P 1=P2
W 23=R T 2 ln
P3
P2
W 23=8.314
J
K1 kJ
10
403.15
ln
molK
1000 J
1
W 23=7.718
kJ
mol
U 23 =Q23 +W 23
0=Q23+W 23
Q23=W 23
Q23=7.718
kJ
mol
Work=W =W 12 +W 23
Q=Q12 +Q23
W = (0.831+7.718 )
Q=( 2.917.718 )
U = U 12 + U 23
H= H 12+ H 23
kJ
mol
kJ
mol
Q=4.808
kJ
mol
U =2.079
H= ( 2.91+ 0 )
kJ
mol
H=2.91

Therefore
U 12= H 12=0
43
kJ
Answer
mol
kJ
Answe r
mol
U =( 2.079+0 )
(c)
Here
W =6.887
kJ
Answe r
mol
kJ
Answe r
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
P2=P3
W 12=R T 1 ln
P2
P1
W 12=8.314
W 12=5.8034
J
K1 kJ
10
303.15
ln
molK
1000 J
1
kJ
mol
U 12=Q12 +W 12
0=Q12+W 12
Q12=W 12
Q12=5.8034
kJ
mol
Step 23:
Q23= H 23=2.91
kJ
[ (b)]
mol
Here
T 2 =T 3
Now
U 23=2.079
kJ
[ (a)]
mol
U 23=Q23 +W 23
W 23= U 23Q23
W 23=( 2.0792.91 )
kJ
mol
W 23=0.831
Work=W =W 12 +W 23
44
W = (5.80340.831 )
kJ
mol
W =4.972
kJ
Answer
mol
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
Q=Q 12 +Q23
Q=(5.8034+2.91 )
U = U 12 + U 23
H= H 12+ H 23
kJ
mol
Q=2.894
11-CH-74
kJ
Answe r
mol
U =( 0+2.079 )
kJ
mol
U =2.079
H= ( 0+2.91 )
kJ
mol
H=2.91
kJ
Answe r
mol
kJ
Answe r
mol
Solution:
5
C P= R
2
3
CV = R
2
Each part consist of two steps, 12 & 23

For the overall processes
U = U 12=U 23=CV T
3
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
U = U 12=U 23=1.247
kJ
(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
H= H 12= H 23=2.079
45
kJ
( b ) Answer
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
(a)
Step 12:
Therefore
W 12=0
Here
T 2 =T 3
U 12 =Q12 +W 12
U 12 =Q12
Q12= U 12=C V T
Q12= U 12=1.247
Also we have
H 12=2.079
kJ
[ ( b)]
mol
Step 23:
Since for step 23 process is isothermal
Therefore
U 23 = H 23=0
Here
T 2 =T 3
P1 P2
=
T1 T 2
46
P
P2= 1T 2
T1
403.15 K
303.15 K
P2=
P2=1.329 b ar
kJ
[ ( a) ]
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
W 23=R T 2 ln
P3
P2
W 23=8.314
J
K1 kJ
10
403.15
ln
molK
1000 J
1.329
W 23=6.764
11-CH-74
kJ
mol
U 23=Q23 +W 23
0=Q23+W 23
Q23=W 23
Q23=6.764
kJ
mol
Work=W =W 12 +W 23
Q=Q 12 +Q23
W = ( 0+6.764 )
Q=( 1.2476.764 )
kJ
mol
kJ
mol
W =6.764
Q=5.516
kJ
Answe r
mol
kJ
Answe r
mol
U = U 12 + U 23
U =( 1.247+0 )
kJ
mol
U =1.247
kJ
Answer
mol
H= H 12+ H 23
H= ( 2.079+ 0 )
kJ
mol
H=2.079
kJ
Answe r
mol
(b)
Step 12:
Q12 H 12=2.079
kJ
mol
[ (b)]
Also,
U 12 =1.247
47
kJ
mol
[ (a)]
August 20,
2013
PROBLEMS
ZAID YAHYA
U 12 =Q12 +W 12
W 12=U 12Q12
11-CH-74
W 12=( 1.2472.079 )
kJ
mol
W 12=0.832
Step 23:
Therefore
U 23 = H 23=0
Here
T 2 =T 3P 1=P2
W 23=R T 2 ln
P3
P2
W 23=8.314
J
K1 kJ
10
403.15
ln
molK
1000 J
1
W 23=7.718
kJ
mol
U 23 =Q23 +W 23
0=Q23+W 23
Q23=W 23
Q23=7.718
kJ
mol
Work=W =W 12 +W 23
Q=Q12 +Q23
(c)
Step 12:
48
W = (0.832+7.718 )
Q=( 2.0797.718 )
kJ
mol
kJ
mol
W =6.886
Q=5.639
kJ
Answer
mol
kJ
Answer
mol
U = U 12 + U 23
U =( 1.247+0 )
kJ
mol
U =1.247
kJ
Answer
mol
H= H 12+ H 23
H= ( 2.079+ 0 )
kJ
mol
H=2.079
kJ
Answe r
mol
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74

Therefore
U 12= H 12=0
Here
P2=P3
W 12=R T 1 ln
P2
P1
W 12=8.314
W 12=5.8034
J
K1 kJ
10
303.15
ln
molK
1000 J
1
kJ
mol
U 12=Q12 +W 12
0=Q12+W 12
Q12=W 12
Q12=5.8034
kJ
mol
Step 23:
Q23= H 23=2.079
kJ
[ (b)]
mol
Here
T 2 =T 3
Now
U 23=1.247
U 23=Q23 +W 23
49
kJ
[ (a)]
mol
W 23= U 23Q23
W 23=( 1.2472.079 )
kJ
mol
W 23=0.832
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
Work=W =W 12 +W 23
Q=Q 12 +Q23
W = (5.80340.832 )
Q=(5.8034+2.079 )
kJ
mol
11-CH-74
W =4.9714
kJ
mol
Q=3.724
kJ
Answe r
mol
kJ
Answe r
mol
U = U 12 + U 23
U =( 0+1.247 )
kJ
mol
U =1.247
kJ
Answer
mol
H= H 12+ H 23
H= ( 0+2.079 )
kJ
mol
H=2.079
kJ
Answe r
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 3 =393.15 K
T 1 =( 30+273.15 ) K
P3=12
Q=?
T 1 =303.15 K
W =?
P1=1
U =?
H=?
Solution:
The process consist of two steps, 12 & 23
Step 12:
Therefore
U 12= H 12=0
50
T 3 =120
7
C P= R
2
T 3 =( 120+273.15 ) K
5
CV = R
2
August 20,
2013
PROBLEMS
P2
T2
ZAID YAHYA
P
3
T3
P
P2= 3 T 2
T3
12
303.15 K
393.15 K
P2=
P2=9.25 b ar
W 12=R T 1 ln
P2
P1
W 12=8.314
J
K1 kJ
9.25
303.15 .15
ln
molK
1000 J
1
W 12=5.607
11-CH-74
kJ
mol
U 12=Q12 +W 12
0=Q12+W 12
Q12=W 12
Q12=5.607
kJ
mol
Step 23:
Since for step 23 volume is constant
Therefore
W 23=0
U 23 =Q23 +W 23
U 23=Q23
Q23= U 23=CV T
5
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
H 23= R ( T 2T 1 )
2
51
7
J
kJ
H 23= 8.314
(393.15303.15 ) K1
2
molK
1000 J
H 23=2.619
kJ
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Work=W =W 12 +W 23
Q=Q 12 +Q23
W = (5.607 +0 )
Q=(5.607+1.871 )
kJ
mol
kJ
mol
W =5.607
Q=3.736
kJ
Answe r
mol
kJ
Answe r
mol
U = U 12 + U 23
U =( 0+1.871 )
kJ
mol
U =1.871
kJ
Answe r
mol
H= H 12+ H 23
H= ( 0+2.691 )
kJ
mol
H=2.691
kJ
Answe r
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
52
P2 V =R T
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Put in (1)
W =R ( T 3T 2 )
W =R T
Since
T 3 =T 1
Therefore
W =R ( T 1T 2) (2)
W =R T 1 ln
P
(3)
P1
Compare (2) and (3)
P
R ( T 1T 2 )=R T 1 ln
P1
T 2T 1
P
=ln
T1
P1
P
T 2 T 1=T 1 ln
P1
4 0.5698=P
P
4
( 350800 ) K
=ln
800 K
4
P
e0.5625=
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
provides a valve for the pressure change
from the following data:
t
3
a) V A =256 cm
b)
P/ P1=0.0639
Given Data:
53
in the cylinder. Determine the cylinder volume
VB
August 20,
2013
PROBLEMS
V tB =?
ZAID YAHYA
V tA =256 cm3
11-CH-74
P
=0.0639
P1
Solution:
P
=0.0639
P1
P2 P 1
=0.0639
P1
P2
1=0.0639
P1
P2
=0.0639+1
P1
P2
=0.9361 (1)
P1
Assume that gas is ideal & P2 is the pressure of the tank

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

t
B
t
A
P1 V =P2 ( V +V
t
B
P2
Vt
= t B t
P1 V A +V B
Put in (1)
V tB
=0.9361
V tA +V tB
V tB =0.9361 ( V tA +V tB )
V tB ( 10.9361 ) =0.9361V tA
V tB =0.9361V tA +0.9361V tB
0.0639 V tB =256 cm 30.9361
V B=
V tB 0.9361V tB=0.9361V tA
239.6461 3
cm
0.0639
V tB =3750.26 cm 3 Answe r
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
T 1 =300 K
PROBLEMS
P1=1 atm
ZAID YAHYA
11-CH-74
7
C P= R
2
Solution:
According to ideal gas equation,
PV =nRT
Applying ideal gas equation for initial conditions
On section A
P1 V A =n A R T 1
V A=
nART1
P1
On section B
P1 V B=n B RT 1
Since
n A =n B
Therefore,
P1 V B=n A R T 1
V B=
n A RT 1
P1
Total initial volume can be given as
V i=V A + V B
V i=
nA R T1 nA R T1
+
P1
P1
V i=2.
n A RT 1
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
V A=
nART A
P2
On section B
P2 V B=n A R T B
Total Final volume can be given as
55
V B=
n A RT B
P2
August 20,
2013
V f =V A +V B
PROBLEMS
Vf=
ZAID YAHYA
nA R T A nA R T B
+
P2
P2
Vf=
11-CH-74
nA R (T A+ T B)
P2
Since the total volume is constant, therefore
V i=V f
2.
n A R T 1 n A R ( T A +T B ) 2. T 1 ( T A +T B )
=
=
(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
T 1 ( P1 )
=T B ( P2 )
T B=T 1
P2
P1
( )
T B=
T 1 ( P1 )
( P 2)
1
(2)
We know that,
C PC V =R
CV =C P R
7
CV = RR
2
CV =
7 R2 R
2
5
CV = R
2
As
CP
CV
7R2
25R
=1.4
Put in (2)
T B=300 K
1.25
1
( )
1.4 1
1.4
T B=300 K1.0658
T B=319.74 K Answe r
56
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
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 A +T B2T 1 ]
Q=n A CV ( T AT 1 ) +n A C V ( T B T 1 )
Q
=C V [ T A +T B 2 T 1 ] (3)
nA
Q 5
J
K1 kJ
= 8.314
150.02
nA 2
molK
1000 J
Q 5
= R ( 430.26+ 319.742300 ) K
nA 2
Q
kJ
=3.118
Answe r
nA
mol
(b)
T A =425 K
From equation (1)
2. T 1 ( T A +T B )
=
P1
P2
Put in (2)
57
Q=n A CV [ T AT 1 +T BT 1 ]
P2 ( T A +T B )
=
P1
2.T 1
August 20,
2013
PROBLEMS
ZAID YAHYA
T B=T 1
Assume
1.41
1.4
T B=300 K( 1.0634 )
Since
T B=319 K
425+ 319
T B=300 K
2300
T A +T B
2. T 1
11-CH-74
T B=319.02 K
319 319.02 , therefore
T B=319.02 K Answe r
Put in (1)
2300 K ( 425+319.02 ) K
=
1 atm
P2
P2=
744.02
atm
600
P2=1.24 atm Answe r
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
T B=T 1
PROBLEMS
P2
P1
( )
ZAID YAHYA
P2
325 K=300 K
1 atm
( )
P2
325
=
300 1 atm
( )
11-CH-74
325
300
( )
P2
1 atm
325
300
( )
P2=
1.4
1.41
P2=1.323 atm Answe r

Put in (1)
2. T 1 ( T A +T B )
=
P1
P2
2300 K T A +325 K
=
1 atm
1.323 atm
T A +325 K =600 K1.323
T A =793.9 K325 K
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 )
=
P1
P2
T A +T B=
2.T 1P2
(b )
P1
From equation (3)
Q
=C V [ T A +T B 2 T 1 ]
nA
Comparing (b) and (c)
59
T A +T B2 T 1 =
Q
n AC V
T A +T B=
Q
+ 2T 1 (c )
n AC V
atm
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
2. T 1P2
Q
=
+2 T 1
P1
n ACV
P 2=
P1
Q
+2 T 1
2.T 1 n AC V
P 2=
1 atm
23 kJ
+2300 K
2300 K 5 Rmol
P 2=
6 kJmolK
1000 J
1 atm 5mol8.314 J
P 2=
+600 K
600 K
1 kJ
1 atm
[ 144.335+ 600 ] K P2=1.2406 atm Answe r
600 K
Put in (2)
T B=T 1
P2
P1
( )
T B=300 K
1.2406
1
1.4 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
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
PROBLEMS
ZAID YAHYA
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 PC V =R
C P CV R
=
C V CV C V
CP
R
1=
CV
CV
Since
CP
CV
Therefore,
1=
R
CV
CV =
R
1
Put in (1)
U=
R
( T T )
1 2 1
U=
For one mole of an ideal gas we have
P1 V 1=R T 1 ( a)
Put (a) & (b) in (2)
U=
1
( P V P1 V 1 )
1 2 2
Problem 3.28:
61
1
( R T 2R T 1 ) ( 2)
1
U=
1
( PV ) Proved
1
P2 V 2 =R T 2 ( b)
11-CH-74
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
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
Z=
PV
RT
Therefore,
PV
'
=1+ B P
RT
V=
RT
( 1+ B' P )
P
V =RT
( P1 + B' )
Differentiate both sides w.r.t to pressure
dV
1
=RT 2 +0
dP
P
dV =
RT
dP
P2
Put in (1)
V2
W = PdV
V1
P2
RT
W = P 2 dP
P
P
1
P2
W =RT
P1
W =RT ln
62
1
dP
P
P2
W =RT |ln P|P
P2
Proved
P1
W =RT ( ln P 2ln P1 )
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
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=
Where
B
CB 2
'
C =
RT
( RT )2
Why dont both equations give exactly the same result?

Given Data:
Temperature=T =100
6
C=25200 cm mol
T =( 100+273.15 ) K
T =373.15 K
P1=1
B '=
P2=55
B
RT
B=242.5 cm3 mol1

'
C=
CB2
( RT )2
Solution:
As
B'=
B
RT
1 m3
100 3 cm3
242.5 cm3molK
J
mol8.314 J373.15 K
101325 N
Nm
'
B=
m21.01325
Now,
63
1
B =7.817103
'
W =?
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
21 m6
1006 cm 6
[ 25200(242.5 )2 ] cm6K 2mol 2 J 2
mol28.3142 J 2373.152 K 2
2 2
101325 N
2
2
N m
C' =
m41.013252
CB
C=
( RT )2
'
2
C' =3.492105
(a)
Z =1+
B C
+
V V2
PV
B C
=1+ + 2
RT
V V
P=
RT
B C
1+ + 2 (1)
V
V V

V2
W = PdV (2)
V1
Put (1) in (2)

V2
RT
B C
W =
1+ + 2 dV
V
V V
V
1
V2
W =RT 1+
V1
B C 1
+
dV (3)
V V2 V
Again using
V 1=
RT
B C
1+ + 2 ( 4 )
P1
V1 V1
Assume that
3
V 1=30780
cm
(a)
mol
Nm
1.01325 m2
J
1003cm 3
101325 N
RT
cm3
molK1
=31023.6
(b)
P1
mol
1 m3
RT 8.314 J373.15 K
=
P1
64
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Put (a) and (b) in (4)
30780
cm3
cm3
242.5 25200
=31023.6
1
+
mol
mol
30780 307802
cm3
cm3 (
30780
=31023.6
10.007878+ 0.000026598 )
mol
mol
cm3
cm3
30780
=31023.60.99215
mol
mol
cm3
cm3
30780
=30780
mol
mol
Since
L. H . S=R . H . S
Therefore
3
Initial volume=V 1=30780
cm
mol
Again using
V 2=
RT
B C
1+ + 2 (5 )
P2
V2 V2
Assume that
V 2=241.33
cm3
( c)
mol
Nm
1.01325 m2
J
100 3cm3
101325 N
RT
cm 3
molK55
=564.067
(d )
P2
mol
1 m3
RT 8.314 J373.15 K
=
P2
Put (c) and (d) in (4)
65
August 20,
2013
PROBLEMS
ZAID YAHYA
241.33
cm
cm
242.5 25200
=564.067
1
+
mol
mol
241.33 241.332
241.33
cm3
cm3
=564.0670.4278
mol
mol
241.33
11-CH-74
3
cm
cm (
241.33
=564.067
11.0048+ 0.4327 )
mol
mol
cm3
cm3
=241.33
mol
mol
Since
L. H . S=R . H . S
Therefore
Finalvolume=V 2=241.33
cm 3
mol
Now from equation (3)

V2
W =RT
V1
B C 1
1+ + 2
dV
V V V
V2
W =RT |ln V|V B
W =RT ln
V2
||
1
V
W =RT
| |]
1
1
C 2
2
V
V
1
V2
V2
V2
V2
V1 dV + B V12 dV +C V13 dV
V
V
V
V1
V2
1
1
1
1
1
B
V1
V 2 V 1 2 V 22 V 12
W =RT ( ln V 2ln V 1 )B
) (
1
1
1
1
1
C
2
2
V2 V1 2 V2 V1
) (
)]
8.314J373.15 K
1 kJ
molK
241.33
1
1
25200
1
1
W=
ln
+242.5
2
2
1000 J
30780
241.33 30780
2
241.33 30780
W =3.102
)]
)]
kJ
kJ
[ 4.848+0.9960.2163 ] W =12.62
Answer
mol
mol
(b)
Z =1+ B' P+C' P 2
PV
=1+ B' P+C ' P2
RT
V=
Differentiate w.r.t to pressure on both sides

66
RT
( 1+ B' P+ C' P2 )
P
V =RT
( P1 + B +C ' P)
'
August 20,
2013
PROBLEMS
ZAID YAHYA
dV
1
=RT 2 +0+C '
dP
P
11-CH-74
( P1 +C ' ) dP
dV =RT
Put in (2)
P2
1
W = PRT 2 +C ' dP
P
P
P2
P2
1
W =RT dP+C ' PdP
P P
P
'
C
W =RT |lnP|P + |P2|P
W =RT ln
P2
+C' ( P22P12 )
P1
P2
1
P2
1
2
2 ( 55 21 )
55 3.492105 1
ln
1
2
8.314J373.15 K
1 k J
molK
W=
1000 J
W =12.268
W=
3.102 kJ
( 3.9545 )
mol
kJ
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
PROBLEMS
ZAID YAHYA
Temperature=T =25
11-CH-74
T =298.15 K
T =( 25+273.15 ) K
Pressure=P=12
Solution:
(a)
3
B=140 cm mol
C=7200 cm mol
Given equation is
Z =1+
B C
+
V V2
PV
B C
=1+ + 2
RT
V V
V=
RT
B C
1+ + 2 ( 1 )
P
V V
molK12Nm
1.01325 m2
J
1003cm 3
101325 N
1 m3
RT 8.314J298.15 K
=
RT
cm3
=2065.68
V
mol
Put in (1)
3
cm
B C
V =2065.68
1+ + 2
mol
V V
Assume
V =1919
cm3
mol
Therefore
3
1919
Since
68
cm
cm
140 7200
=2065.68
1
+
mol
mol
1919 19192
1919
cm
cm (
=2065.68
0.9290 )
mol
mol
1919
cm
cm
=1919
mol
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
L. H . S=R . H . S
Therefore
V =1919
cm3
Answer
mol
We know that
Z=
PV
RT
12 1919cm3molK
J
8.314J298.15Kmol
101325 N
Nm
1m 3
2
1.01325 m
Z=
1003 cm3
Z =0.929 Answer
(b)
Given equation 3.38 is
Z =1+
BP
( 2)
RT
We know that
Reduced temperature=T r =
T
Tc
Reduced Pressure=Pr =
T =T r T c ( a )
Z =1+
B Pr Pc
R T r Tc
Since
^ B Pc
Reduced second virial coefficient =B=
R Tc
Therefore
Z =1+
Also
69
^B P r
(3)
Tr
P
Pc
P=Pr Pc (b)
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
O
^
B=B
+ B1
Put in (3)
Z =1+ ( B O + B1 )
Pr
( 4)
Tr
For ethylene (From Table B.1 Appendix B)
=0.087 (i)
Critical temperature=T c =282.3 K
Critical pressure=Pc =50.40
Tr=
T 298.15 K
=
=1.056(ii)
T c 282.3 K
50.40 =0.238 (iii)
12
P
Pr = =
Pc
Also we have
B o=0.083
0.422
T r1.6
B o=0.083
0.422
1.6
1.056
B o=0.304 ( iv )
B 1=0.139
0.172
4.2
1.056
B 1=2.183103 ( v)
Put (i), (ii), (iii), (iv) & (v) in (4)
Z =1+ (0.304+0.0872.183103 )
0.238
1.056
Z =0.931 Answer
We know that
Z=
PV
RT
V=
ZRT
P
Nm
1.01325 m2
J
3
3
100 cm
101325 N
molK12
1m3
0.9318.314 J298.15 K
V=
(c)
70
The Redlich/Kwong equation is
V =1923.
cm3
Answer
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
Z =1+ q
11-CH-74
Z
( 5)
( Z + ) ( Z + )
Where
Pr
Tr
From table 3.1
=1, =0.08664, =0,=0.42748, ( T r )=T r
1
2
Now
0.086640.238
1.056
=0.0195 (i ' )
Also
q=
( T r )
T r
0.427481.056 2
q=
0.086641.056
q=4.547 (i i' )
Put (i) and (ii) in (5)
Z =1+ 0.01954.5470.0195
Z
( Z + ) ( Z + )
Assume
Z =0.928
0.928=1.01950.08866
0.9280.0195
0.928 ( 0.928+ 0.0195 )
0.928=1.01950.088661.033
Since
L. H . S=R . H . S
Therefore,
Z =0.928 Answer
71
We know that
0.928=0.928
August 20,
2013
Z=
PROBLEMS
PV
RT
V=
ZAID YAHYA
11-CH-74
Nm
2
1.01325
m
J
1003 cm3
101325 N
molK12
1m3
0.9288.314 J298.15 K
V=
ZRT
P
V =1916.8
cm
Answer
mol
(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
[ {
SRK ( T r ; )= 1+ ( 0.480+1.5740.0870.1760.087 ) 11.056
1
2
1
2
)}]
) }]
SRK ( T r ; )=[ 0.9828 ]
SRK ( T r ; )=0.966 (ii i ' )

Now
q=
( T r )
T r
q=
0.427480.966
0.086641.056
'
q=4.515 (ii i )
Put (i) and (iii) in (5)
Z =1+ 0.01954.5150.0195
Z
( Z + )( Z + )
Assume
Z =0.928
0.928=1.01950.08803
0.9280.0195
0.9 ( 0.9+ 0.0195 )
0.928=1.01950.23831.36
Since
L. H . S=R . H . S
72
0.928=0.928
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Therefore,
Z =0.928 Answer
We know that
Z=
PV
RT
V=
Nm
1.01325
m2
J
1003 cm3
101325 N
molK12
1m3
0.9288.314 J298.15 K
V=
ZRT
P
cm3
V =1917
Answer
mol
(e)
From table 3.1
=1+ 2=2.41, =0.07780, =1 2=0.414, =0.45724, ( T r )= SRK ( T r ; )

Now
0.077800.238
1.056
Pr
Tr
=0.0175 (iv ' )
[ {
SRK ( T r ; )= 1+ ( 0.37464 +1.54226 0.26992 2 ) 1T r
[ {
1
2
)}]
SRK ( T r ; )= 1+ ( 0.37464+ 1.542260.0870.269920.087 ) 11.056
SRK ( T r ; )=[ 0.986 ]
SRK ( T r ; )=0.9722
Now
q=
73
( T r )
T r
q=
0.427480.9722
0.086641.056
q=4.542 (v ' )
1
2
) }]
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Put (iv) and (v) in (5)
Z =1+ 0.01754.5420.0175
Z
( Z + )( Z+ )
Assume
0.92=1.01750.07949
Z =0.92
0.920.0175
( 0.920.4140.0175 ) ( 0.92+ 2.410.0175 )
0.92=1.01750.079491.027
0.92 0.93
Since
L. H . S R . H . S
Therefore,
Z =0.92 Answer
We know that
Z=
PV
RT
V=
ZRT
P
Nm
1.01325 m2
J
1003 cm3
101325 N
molK12
1m3
0.928.314 J298.15 K
V=
V =1900.4
cm
Answer
mol
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
PROBLEMS
ZAID YAHYA
Temperature=T =50
11-CH-74
T =323.15 K
T =( 50+273.15 ) K
Pressure=P=15
Solution:
(a)
3
B=156.7 cm mol
C=9650 cm mol
Given equation is
Z =1+
B C
+
V V2
PV
B C
=1+ + 2
RT
V V
V=
RT
B C
1+ + 2 ( 1 )
P
V V
molK15Nm
1.01325 m2
J
1003cm 3
101325N
1 m3
RT 8.314J323.15 K
=
RT
cm3
=2065.68
V
mol
Put in (1)
V =1791
cm 3
B C
1+ + 2
mol
V V
Assume
cm3
V =1625
mol
Therefore
1625
75
cm3
cm3
156.7 9650
=1791
1
+
mol
mol
1625 16252
1625
cm3
cm3 (
=1791
0.9072 )
mol
mol
1625
cm3
cm3
=1625
mol
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Since
L. H . S=R . H . S
Therefore
3
V =1625
cm
Answer
mol
We know that
Z=
PV
RT
15 1625cm3molK
J
8.314J323.15Kmol
101325 N
Nm
1m3
2
1.01325 m
Z=
1003 cm3
Z =0.907 Answer
(b)
Given equation 3.38 is
Z =1+
BP
( 2)
RT
We know that
Reduced temperature=T r =
T
Tc
T =T r T c ( a )
Reduced Pressure=Pr =
Z =1+
B Pr Pc
R T r Tc
Since
^ B Pc
Reduced second virial coefficient =B=
R Tc
Therefore
76
P
Pc
P=Pr Pc (b)
August 20,
2013
PROBLEMS
ZAID YAHYA
Z =1+
11-CH-74
^B P r
(3)
Tr
Also
O
^
B=B
+ B1
Put in (3)
Z =1+ ( B O + B1 )
Pr
( 4)
Tr
For ethylene (From Table B.1 Appendix B)
=0.1 (i)
Critical temperature=T c =305.3 K
Critical pressure=Pc =48.72
Tr=
T 323.15 K
=
=1.058 (ii)
T c 305.3 K
48.72 =0.308 (iii )
15
P
Pr = =
Pc
Also we have
o
B =0.083
0.422
T r1.6
B o=0.083
0.422
1.6
1.058
B o=0.303 ( iv )
B 1=0.139
0.172
4.2
1.058
B 1=3.266103 (v)
Put (i), (ii), (iii), (iv) & (v) in (4)
Z =1+ (0.303+ 0.13.266103 )
0.308
1.058
Z =0.912 Answer
We know that
Z=
77
PV
RT
V=
ZRT
P
Nm
1.01325 m2
J
3
3
100 cm
101325 N
molK15
1 m3
0.9128.314 J323.15 K
V=
V =1633.36
cm3
Answer
mol
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
(c)
The Redlich/Kwong equation is
Z =1+ q
Z
( 5)
( Z + ) ( Z + )
Where
Pr
Tr
From table 3.1
=1, =0.08664, =0,=0.42748, ( T r )=T r
1
2
Now
0.086640.308
1.058
'
=0.0252 (i )
Also
( T r )
q=
T r
q=
1
2
0.427481.058
0.086641.058
q=4.533 (ii ' )
Put (i) and (ii) in (5)
Z =1+ 0.02524.5330.0252
Z
( Z+ )( Z+ )
Assume
Z =0.906
0.906=1.02520.114
0.9060.0252
0.906 ( 0.906+ 0.0252 )
0.906=1.02520.1141.044
Since
L. H . S=R . H . S
Therefore,
78
0.906=0.906
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Z =0.906 Answer
We know that
Z=
PV
RT
V=
Nm
2
1.01325 m
J
3
3
100 cm
101325 N
molK15
1 m3
0.9068.314 J323.15 K
V=
ZRT
P
V =1622.7
cm
Answer
mol
(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
[ {
SRK ( T r ; )= 1+ 0.480+1.5740.10.1760.1 11.058
1
2
1
2
)}]
) }]
SRK ( T r ; )=[ 1+0.6374 ]
SRK ( T r ; )=2.681 (ii i' )

Now
q=
( T r )
T r
q=
0.427482.681
0.086641.058
'
q=12.50 (iii )
Put (i) and (iii) in (5)
Z =1+ 0.025212.500.0252
Z
( Z + ) ( Z + )
Assume
Z =0.907
79
0.907=1.02520.315
0.9070.0252
0.907 ( 0.907+0.0252 )
0.907=1.02520.3151.0429
0.695=0.695
August 20,
2013
PROBLEMS
ZAID YAHYA
11-CH-74
Since
L. H . S=R . H . S
Therefore,
Z =0.695 Answer
We know that
Z=
PV
RT
V=
ZRT
P
Nm
2
1.01325 m
J
1003 cm3
101325 N
molK12
1m3
0.6958.314 J298.15 K
V=
V =1435.6
cm
Answer
mol
(e)
From table 3.1
=1, =0.07780, =0,=0.45724, ( T r )= SRK ( T r ; )

Now
0.077800.238
1.056
Pr
Tr
=0.0175 (iv ' )
[ {
SRK ( T r ; )= 1+ 0.37464 +1.54226 0.26992 2 1T r
1
2
)}]
2
2
SRK ( T r ; )=[ 1+ {0.37464+1.542260.0870.269920.087 ( 11.056 ) } ]
SRK ( T r ; )=[ 1+0.509 ]

Now
80
SRK ( T r ; )=2.277
August 20,
2013
PROBLEMS
ZAID YAHYA
q=
( T r )
T r
q=
0.427482.277
0.086641.056
11-CH-74
q=10.64 ( v ' )
Put (iv) and (v) in (5)
Z =1+ 0.017510.640.0175
Z
( Z + )( Z+ )
Assume
Z =0.793
0.793=1.01750.1862
0.7930.0175
0.793 ( 0.793+0.0175 )
0.793=1.01750.18621.2066
0.793=0.793
Since
L. H . S=R . H . S
Therefore,
Z =0.793 Answer
We know that
Z=
81
PV
RT
V=
ZRT
P
Nm
1.01325
m2
J
1003 cm3
101325 N
molK12
1m3
0.7938.314 J298.15 K
V=
V =1638.1
cm 3
Answer
mol

Chapter 3

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Chapter 3

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August 20,

Density of water =1=1

Put in (1) & (2)

Integrating on both sides

Since is very small

Differentiate w.r.t Pressure

Since, Temperature is constant

Or, From (1)

Comparing (2) & (3)

W =c|P|P bc|ln (P+b)|P

We know that, work done for a reversible process is

W =V 3.910 P dPV 0.110 P dP

Integrating on both sides,

( T 2T 1 )=( lnV 2ln V 1 )

Now, for total volume,

Taking anti log on both sides,

For a mechanically reversible process, we have,

Integrating on both sides,

Since volume changes from V1 to V2 & pressure changes from P1 to P2 ,

According to first law of thermodynamics,

For T2 , We know that for an ideal gas

For a constant temperature process,

We know that at constant temperature, work done is

We know that for an adiabatic process

Now, according to first law of thermodynamics,

For T2 , We know that for an adiabatic process

For a mechanically reversible adiabatic process we have

Initial Temperature=T 1=600 K

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,

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,

Step 34, an Isobaric process,

For an Isobaric process we have

Step 41, an adiabatic process,

According to first law of thermodynamics

V 2 = 1 m3 by the following mechanically reversible processes:

For an isothermal process, we have

Final pressure=P 2=12

According to first law of thermodynamics

Adiabatic compression followed by cooling at constant pressure

For mono atomic gas, we have

Second step, cooling at constant pressure P2

Adiabatic compression followed by cooling at constant volume

For mono atomic gas, we have

Second step, cooling at constant Volume,

Heating at constant volume followed by cooling at constant pressure

According to first law of thermodynamics

Cooling at constant pressure followed by heating at constant volume

The process completes in two steps

Step 1, Heating at constant Volume V2 to pressure P2

According to first law of thermodynamics

The polytropic relation is

Differentiate w.r.t to Temperature on both sides

We know that, for an ideal gas

R=Specific gas constant=R ' /M