Thermodynamics

Session 10
Efficiency of engines:
The efficiency of reversible Carnot Engine is given by
H
C H
H
C H
T
T T
Q
Q Q

The maximum efficiency of any engine operated between two temperatures is always
given by
H
C H
T
T T

as the efficiency of a reversible engine is maximum.

Efficiency of real engine is always less than that of reversible engine. If the engine is
irreversible then efficiency is calculated from
H
C H
Q
Q Q

and not from temperatures.

For any irreversible engine,
H
C H
H
C H
T
T T
dQ
dQ dQ
<

H
C
H
C
T
T
dQ
dQ
<

H
H
C
C
T
dQ
T
dQ
<

Applying sign convention,

0
T
dQ
T
dQ
H
H
C
C
< +
Thus for irreversible engine,
0
T
dQ
<
l
If the processes are all reversible, then
0
T
dQ

l
In general,
0
T
dQ
s
l
This is called Clausius inequality. The sum of dQ / T terms over a cycle is less than or
equal to zero depending upon whether the cycle is irreversible or reversible.
The changes in entropy are always determined using,
Let A1B Represent irreversible process and A2B represent reversible process between
the same states.
A
B
1
2
p
V
T
dQ
dS
v Re

T
dQ
dS
v Re

To determine entropy change we must have only reversible path. However the entropy
change between the states 1 and 2 is same regardless of the path as it is a state function.
What the above equation says is entropy is not equal to dQ/T along an irreversible path.
To determine entropy change for any irreversible path between two states, replace the
path by a reversible path with the same states, and find the entropy of the reversible path.
Entropy and irreversibility:
Let us look at a cyclic process given below.
Let A1B Represent reversible process and B2A represent irreversible process between
the same states. Therefore A2B is also irreversible. Since A1B is reversible,
l

B 1 A
B 1 A
T
dQ
S
Since cycle as a whole is irreversible and as per Clausius inequality,
A
B
1
2
p
V
l

B 2 A
B A
T
dQ
S
l

B 1 A
T
dQ
0
T
dQ
<
l
0
T
dQ
T
dQ
A 2 B B 1 A
< +
l l
RHS is independent of the path which will be equal to
B 1 A
S .
LHS is dQ / T term and it is along an irreversible path and therefore it does not represent
entropy change.
Mathematical Statement of II law:
For a process involving transfer of heat Q from heat source at T
1
to a heat sink at T
2
,
The process can be made less and less irreversible by lowering the temperature T
1
closer
and closer to T
2
.
As the temperatures become closer and closer, irreversibility decreases and
For any heat transfer there has to be some temperature difference. Therefore T
1
> T
2
and
hence,
This is the mathematical statement of II law of thermodynamics. Thus the entropy of the
universe always increases and the energy is conserved.
0
T
dQ
S
A 2 B
B 1 A
< +
l
0
T
dQ
S
A 2 B
A 2 B
< +
l
A 2 B
A 2 B
S
T
dQ
<
l
2 1
total
T
Q
T
Q
) S ( +

,
_

2 1
2 1
total
T T
T T
Q ) S (
. 0 S
total

. 0 S
total
>
Because of irreversibility, there will be some dissipation and degradation of energy which
will not be available as work. This is called lost work which is given by
total 0 lost
S T W
Where T
0
refers to the temperature of the sink to which heat is rejected.
Determination of entropy changes:
This is the basic equation. The heat transfer term may replaced by any term using first
law or any equation applicable to the process for which entropy change is to be
determined. This is applicable only the process is reversible. For example, for an ideal
gas undergoing isothermal reversible process,
pdV dW dQ
T
pdV
dS
V
RdV
dS
1
2
V
V
ln R S
This is how entropy changes may be determined
T
dQ
dS
R