Entropy
First Law of Thermodynamics
The First Law of Thermodynamics states that
energy cannot be created nor destroyed.
Therefore, the total energy of the universe is a
constant.
Energy can, however, be converted from one
form to another or transferred from a system to
the surroundings or vice versa.
Spontaneous Processes
Spontaneous processes
are those that can
proceed without any
outside intervention.
The gas in vessel B will
spontaneously effuse
into vessel A, but once
the gas is in both
vessels, it will not
spontaneously
Spontaneous Processes
Processes that are
spontaneous in one
direction are non
spontaneous in the
reverse direction.
Reversible Processes
In a reversible process
the system changes in
such a way that the
system and
surroundings can be
put back in their
original states by
exactly reversing the
process.
Changes are
infinitesimally small in
a reversible process
Irreversible Processes
Irreversible processes cannot be undone by exactly
reversing the change to the system.
All Spontaneous processes are irreversible.
All Real processes are irreversible.
Entropy
Entropy (S) is a term coined by Rudolph Clausius
in the 19th century.
Clausius was convinced of the significance of the
ratio of heat delivered and the temperature at
which it is delivered,
Entropy can be thought of as a measure of the
randomness of a system.
It is related to the various modes of motion in
molecules.
For a process occurring at constant temperature (an
isothermal process)
Like total energy, E, and enthalpy, H, entropy is a state
function.
Therefore,
AS = S
final
S
initial
q
rev
= the heat that is transferred when the process is
carried out reversibly at a constant temperature.
T = temperature in Kelvin.
Entropy and Nature of Process
The definition requires following specifications :
1. The amount of heat transferred
2. The temperature level at which the transfer
occurs
3. The nature of process whether it is reversible or
irreversible
To comply with these requirements we define entropy
change as :
dS= dQR/T
Where ,
S=Entropy
Q=Heat transferred
T=Absolute Temperature
R=Reversibilty of Process
Entropy and Heat
When a certain form of energy is transferred into
heat, the total energy gets degraded with an
increase in the entropy of the system
E.g.: Consider 1 kg of water at the top of
mountain at a height of 426.8 m. At this position
water has a potential energy of 4.187 kJ
(P.E=m*g*h=1*9.81*426.8=4.187kJ)
When water falls and strikes the river at bottom all
its PE gets converted into thermal energy with a
temperature rise of water by approx 1 K
This results in the degradation of the total energy. If
not then reverse the process and raise the water to its
initial position by cooling it by 1 K
The degradation of energy is measured by the net
increase in entropy
Here increase in entropy was due to the degradation of
the mechanical energy into heat
In short the increase in the entropy is due to the
addition of heat through any form of source or any
mechanism
The increase in entropy is proportional to the heat
exchanged but not equal to it
Therefore it is necessary to consider the temperature of
the system when heat is transferred
Second Law of Thermodynamics
The entropy of the universe increases (real,
spontaneous processes).
But, entropy can decrease for individual systems.
Entropy Changes
Entropy changes for a reaction can be calculated
the same way we used for AH:
S for each component is found in a table.
Note for pure elements:
Practical uses: surroundings
& system
Entropy Changes in Surroundings
Heat that flows into or out of the system also
changes the entropy of the surroundings.
For an isothermal process:
Practical uses: surroundings
& system
At constant pressure, q
sys
is simply AH for
the system.
Practical uses: surroundings &
system
Entropy Change in the Universe
The universe is composed of the system and the
surroundings.
Therefore,
AS
universe
= AS
system
+ AS
surroundings
For spontaneous processes
AS
universe
> 0
Practical uses: surroundings &
system
= Gibbs Free Energy
Entropy2
2 1
1 2
2 2 2
2 1
1 1 1
2 1
2 1
1 2
0
From entropy definition
Q Q
dS= , 0
Therefore,
rev
rev rev rev
rev
rev
Q Q Q
T T T
Q Q
dS
T T T T
Q Q
dS S S S
T T
Q
S S S
T
o o o
o o o o
o o
o
   
= + s
 
\ . \ .
       
= = = +
   
\ . \ . \ . \ .
   
s = = = A
 
\ . \ .
 
A = >

\ .
} } }
} } } }
} } }
2
1
, This is valid for all processes
Q Q
, since = ,
T T
rev irrev
Q
dS dS dS
T
o o o
   
> >
 
\ . \ .
}
1
2
reversible
process
any
process
T
S
Entropy2
The entropy change during an irreversible
process is greater than the integral of oQ/T during
the process. If the process is reversible, then the
entropy change is equal to the integral of oQ/T.
For the same entropy change, the heat transfer
for a reversible process is less than that of an
irreversible. Why?
Entropy Increase Principle
2
2 1 gen
1
2 2
2 1
1 1
, define entropy generation S
where 0. If the system is isolated and "no" heat transfer
The entropy will still increase or stay
system gen
gen
Q
S S S
T
Q Q
S S S S
T T
S
o
o o
 
A = >

\ .
   
A = = + >
 
\ . \ .
>
}
} }
the same but never decrease
0, entropy increase principle
system gen
S S A = >
Entropy Increase Principle
A process can take place only in the direction that
complies with the increase of entropy principle, that is,
S
gen
>0.
Entropy is nonconservative since it is always
increasing. The entropy of the universe is
continuously increasing, in other words, it is more
disorganized and is approaching chaotic.
The entropy generation is due to the existence of
irreversibilities. Therefore, the higher the entropy
generation the higher the irreversibilities and,
accordingly, the lower the efficiency of a device since
a reversible system is the most efficient system.
Mathematical statement of Second
Law
The diagram besides shows a
system undergoing a reversible
(1a2b1)and an
irreversible(1a2c1) cycle
Suppose that the system is taken
from the initial state 1 to final
state 2 along a reversible path a
and then restored to the initial
state through irreversible path b
1
2
b
a
T
S
c
Application of Clausius inequality to the
reversible cycle 1a2b1 is :
suppose given cycle is irreversible. If this is
replaced by a large no. of infinitesimal cycles
some of them are reversible and some are
irreversible.
The Carnot principle states that a reversible heat
engines more efficient than an irreversible engine.
The efficiency of a reversible engine is
Now consider an irreversible engine operating between
the same thermal reservoir.
Let dQ1 = Heat absorbed by the engine.
dQ2 = Heat rejected by the engine.
The efficiency of engine is
Then by Carnot principle,
<
<
<
< 0
Applying sign convention ,
Heat rejected dQ2 is negative.
Above equation becomes
+
+ < 0
An irreversible cyclic operation can be divided into a no of heat
engine cycles involving heat interactions.
For each such cycle it is possible to write equation analogous to
the above equation, so that the net result is
Where ,
T: temperature of thermal reservoir
Combining equation for reversible and irreversible cycle we get
Above equation is known as Clausius inequality.
It states that in a cyclic operation the sum of
terms around a complete
cycle
is less than or equal to zero depending on whether the process
is reversible or irreversible.