Thermodynamics

Session 6
Prepared by Vinod Kallur, RVCE, Bangalore.
Guidelines to represent processes on p V diagram:
In the figure above there are two isotherms shown. For these isotherms, .
1 2
T T > There is one
isotherm passing through every point on p V diagram. Higher the temperature higher will
be location of the isotherm. As they go downwards they converge as shown. No two
isotherms will ever intersect.
Similarly every point has an adiabatic curve passing through it. The adiabatic curve follows
the relation const pV =

. Thus every point is an intersection of an isotherm and an adiabatic

curve as shown below. The adiabatic curve is steeper.
p
V
T
1
T
2
p
V
Isotherm
Adiabatic curve
No two adiabatic curves will ever intersect.
The mathematical relation between pressure, volume and temperature applicable all ranges of
values has not been possible. However, there are equations which are valid over certain
ranges.
Conditions for any equation to be equation of state:
1. The equation should reduce to
RT pV =
As p 0.
2. p-V curve should have a point of inflexion for isothermal at critical point C,
0 =
|
.
|

\
|
c
c
C
V
p
and 0
2
2
=
|
|
.
|

\
|
c
c
C
V
p
Van der Waals equation of state:
, ) RT b V
V
a
p =
|
.
|

\
|
+
2
Here a and b are constants that depend upon the gas. If we apply the partial derivative
conditions, we get,
C
C
C
C
p
RT
b
p
T R
a
8
;
64
27
2 2
= =
The Van der Waals equation is cubic in V. Therefore it should have three roots for a given
set of values of pressure and temperature and for a given substance. For any temperature
higher than critical temperature, there is one positive root. For critical temperature and
critical pressure, all the three roots will be equal which gives critical volume. For temperature
and pressure less than critical values, there will be three roots, least one gives the molar
volume of saturated liquid and highest gives that of saturated vapor which are volumes given
by the two ends of horizontal section of the isotherm.
Redlich Kwong Equation:
T b V V
a
b V
RT
p
) ( +

=
Applying the partial derivative condition, we get
C
C
C
C
p
RT
b
p
T R
a
0867 . 0
;
4278 . 0
2 / 5 2
= =
Note that the above equations reduce to the equation , RT pV = as p 0.
Other equations of state are Peng Robinson and Virial equations.
Numerical problem:
Air is compressed from an initial state of 1 bar and 298 K to a final state of 5 bar and 298 K
through two mechanically reversible processes in a closed system. First heating at constant
volume followed by cooling at constant pressure. Calculate W, Q, change in enthalpy and
internal energy. Use
2
5
,
2
7 R
C
R
C
V P
= = .
The path is shown in the figure. 1 - a represents heating at constant volume and a - 2
represents cooling at constant pressure. Note that initial and final states lie on a single
isotherm.
Let us do the calculations for one mol of gas.
For the path 1 a, since volume is constant, work done is zero.
dQ dU =
a
1
2
V
p
Isotherm at 298 K
dT C dU
V
=
}
= A

a
T
T
V a
dT C U
1
1
To use this we need to know temperature at a. Since it is closed system and volume is same
at 1 and a,
1 1
T p T p
a a
=
Since pressure at a is same as that at 2,
K
p
T p
p
T p
T
a
a
1490
1
) 298 ( 5
2
1 1 1 1
= = = =
}
= A

a
T
T
V a
dT C U
1
1
kJ
J
R
dT
R
775 . 24
7 . 24775
) 298 1490 (
2
) 314 . 8 ( 5
) 298 1490 (
2
5
2
5
1490
298
=
=
=
=
=
}
Thus Q
1-a
= U
1-a
= 24.775 kJ.
kJ J dT C H
P a
686 . 34 34686 ) 298 1490 (
2
) 314 . 8 ( 7
1490
298
1
= = = = A
}

You can use the formula

) ( ) (
1 1 1 1 1 1
V p V p U pV U H
a a a a a a
+ A = A + A = A

to calculate change in enthalpy.
For the step a 2,
dW dQ dU =
}
= A

2
2
T
T
V a
a
dT C U
kJ
J
R
dT
R
775 . 24
7 . 24775
) 1490 298 (
2
5
2
5
298
1490
=
=
=
=
}
kJ J dT C H
P a
686 . 34 34686 ) 1490 298 (
2
) 314 . 8 ( 7
298
1490
2
= = = = A
}

pdV dW =
}
=

2
2
a
a
pdV W
Along the path a 2, since pressure is constant and equal to 5 bar,
}
=

2
2
a
a
pdV W
) ( 10 5
2
5
a
V V x =
We should know the volume at a.
From gas law, at the initial condition,
3
5 1
02477 . 0
10 1
) 198 ( 314 . 8
m
x
V = =
Note that we have taken one mol.
1
1 1
2
2 2
T
V p
T
V p
=
The temperatures are equal,
2
1 1
2
p
V p
V =
3
004954 . 0
5
) 02477 . 0 ( 1
m =
=
Similarly,
3
5
1245 . 0
10 1
) 1498 ( 314 . 8
m
x p
RT
V
a
a
a
= = =
kJ J x V V p W
a a
773 . 59 59773 ) 1245 . 0 004954 . 0 ( 10 5 ) (
5
2 2
= = = =

Since the volume is decreasing, work is done on the system.

kJ Q
Q
W Q U
a
a
a a a
548 . 84
) 773 . 59 ( 775 . 24
2
2
2 2 2
=
=
= A

For the entire process,
kJ Q Q Q
a a
773 . 59 ) 548 . 84 ( 775 . 24
2 1 2 1
= + = + =

0 686 . 34 686 . 34
0 775 . 24 775 . 24
2 1 2 1
2 1 2 1
= = A + A = A
= = A + A = A


a a
a a
H H H
U U U
kJ W W W
a a
773 . 59 ) 773 . 59 ( 0
2 1 2 1
= + = + =

Since there are no changes in internal energy and enthalpy, work done on the system is given
out as heat.