Thermodynamics

Session 9
First deals with law of conservation of energy and defines internal energy.
A stone falls decreasing its potential energy and converting it into kinetic energy. Just
before it strikes the ground, it has maximum kinetic energy. From there why does it not
go up decreasing its kinetic energy and converting it into potential energy?
If we keep two bodies at different temperature in contact, why there is no heat transfer
from a body of low temperature to a body at higher temperature?
When we remove the wall which separates two gases, the two gases mix together without
any external work done on them. Why then the two gases in a mixed state separate
themselves without any external work?
For all the processes mentioned above there is absolutely no violation of I law. In spite of
that, we do not observe these processes. It appears that there is some sense of direction
for spontaneous processes. There is nothing in the first law to indicate any such direction
to any process.
Is there any difference between heat and work though they are both forms of energy? If
they inter-convertible, then any cyclic process should be able to convert all the heat
supplied into work completely as change in internal energy is zero. Does it happen? It has
been found that we cannot have a device whose sole effect is conversion of heat supplied
into work completely. Let us look at why this is so with an example of a process.
In the following figure, there is a heat exchanger where heat is supplied (Q
1
) to the
system which is water in this case and generates steam at high pressure. The steam flows
into a turbine and rotates it producing useful work W
S
. From the turbine, we get steam at
relatively lower pressure than with which it entered. The objective here is to convert heat
Q
1
into work. Since this heat is available, can we send the steam from turbine directly
into the heat exchanger in order to make it work continuously so that we get continuous
supply of work? This is shown by a dotted arrow.
The moment we establish this connection, whole process comes to an abrupt stop! We
have lower pressure steam line going into the heat exchanger in which there is higher
pressure steam. If there is connection like this, why does steam preferentially go into the
turbine line? It will enter into both the lines and stop the turbine. Therefore, in order to
have this going on, we must condense the steam bring about a change in its state so that it
can be fed to the heat exchanger. This state must be same as that of feed water to the heat
exchanger.
Thus there is no way Q
2
= 0. We cannot device any process which converts Q
1
completely into work. The work obtained W
s
is less than Q
1
by an amount equal to Q
2
.
By first law, since for a cycle change in internal energy is zero,
2 1 S
Q Q W =
Practically Q
2
cannot be zero.
If we analyze any cyclic process, there will be several heat and work interactions, such
that net work done is equal to net heat supplied. There will be always one step in which
Q
1
Q
2
W
S
Heat Exchanger
Condenser
Turbine
there is heat removed which brings down the amount of heat that is getting converted into
work.
This fact is the basis of statement of II law of thermodynamics. There are several
statements for the II law which are equivalent. In fact we can deduce one from any other.
All the statements are given below.
Second law of thermodynamics:
1. Heat cannot by itself pass from a cold to a hot body.
2. All spontaneous processes are to some extent irreversible and are
accompanied by degradation of energy.
3. It is impossible to construct a heat engine that operates continuously in a cycle
to produce no effect other than conversion of heat supplied completely into
work. This is called Kelvin Planck statement.
4. It is impossible to construct a heat pump (reverse heat engine) that operates
continuously to produce no effect other than transfer of heat from low
temperature body to a high temperature body.
Carnot cycle and Carnot engine:
The Carnot cycle consists of four steps and all the four steps are reversible. The cycle is
shown in the diagram below.
p
V
A
B
C
D
T
H
T
C
There are two isotherms and two adiabatic processes as shown. The isotherms are at T
H
and T
C
.
AB Reversible isothermal expansion
BC Reversible adiabatic expansion
CD Reversible isothermal compression
DA Reversible adiabatic compression
According to first law, it can be shown that
B
A
H AB AB
p
p
ln RT W Q = =
) T T ( C W
C H V BC
=
D
C
C CD CD
p
p
ln RT W Q = =
) T T ( C W
H C V DA
=
The net work done is given by
DA CD BC AB net
W W W W W + + + =
) T T ( C
p
p
ln RT ) T T ( C
p
p
ln RT
H C V
D
C
C C H V
B
A
H
+ + + =
For adiabatic process BC,
/ ) 1 (
C
B
C
H
p
p
T
T

=
And for the adiabatic process DA,
/ ) 1 (
A
D
H
C
p
p
T
T

=
From these two,
B
A
C
D
p
p
p
p
=
Net work done becomes,
B
A
C H net
p
p
ln ) T T ( R W =
Heat supplied with an objective of converting into work is
B
A
H AB AB
p
p
ln RT W Q = =
The efficiency is defined as
H
C H
B
A
H
B
A
C H
AB
net
T
T T
p
p
ln RT
p
p
ln ) T T ( R
Q
W

= =
It is clear that efficiency of Carnot engine depends upon only the temperatures between
which it is operating and not on the working substance undergoing the cycle. Since
Carnot engine is reversible, it must have maximum efficiency.
From first law,
CD AB net
Q Q W =
H
C
AB
CD
AB
CD AB
AB
net
T
T
1
Q
Q
1
Q
Q Q
Q
W
= =

= =
H
C
AB
CD
T
T
1
Q
Q
1 =
H
C
AB
CD
T
T
Q
Q
=
Let Q
CD
is heat removed, and be equal to Q
C
; and heat added as Q
H
, with sign
convention,
H
C
H
C
T
T
Q
Q
=

which can be simplified to

0
T
Q
T
Q
C
C
H
H
= +
This equation is applicable to the complete cycle and any quantity that adds to zero for
the cycle is a state property. Thus Q/T is a state property called entropy. Thus second law
of thermodynamics brings in the idea of entropy.