CONCEPT

OF
ENTROPY
 Entropy, the measure of a system's thermal energy per unit
temperature that is unavailable for doing useful work. Because
work is obtained from ordered molecular motion, the amount
of entropy is also a measure of the molecular disorder, or
randomness, of a system
 Its introduction by the German physicist Rudolf Clausius in
1850
 The concept of entropy provides deep insight into the direction
of spontaneous change for many everyday phenomena.

 Clausius introduced the concept of entropy as a precise way of

expressing the second law of thermodynamics.
The Clausius form of the second law states that
spontaneous change for an irreversible process in an
isolated system (that is, one that does not
exchange heat or work with its surroundings) always
proceeds in the direction of increasing entropy.

By the Clausius definition, if an amount of

heat Q flows into a large heat reservoir at
temperature T above absolute zero, then the entropy
increase is ΔS = Q/T.
 Entropy is an extensive property

There are two equivalent definitions of entropy: the

thermodynamic definition and the statistical
mechanics definition.

Historically, the classical thermodynamics definition developed

first. In the classical thermodynamics viewpoint, the microscopic
details of a system are not considered. Rather behavior of a
system is described in terms of a set of empirically defined
thermodynamic variables, such as temperature, pressure,
entropy, and heat capacity.
 In statistical mechanics, It quantifies the number Ω of
microscopic configurations (known as microstates) that are
consistent with the macroscopic quantities that characterize
the system (such as its volume, pressure and temperature)

Under the assumption that each microstate is equally

probable, the entropy S is the natural logarithm of the
number of microstates, multiplied by the Boltzmann
constant

S=KB ln
Macroscopic systems typically have a very large number Ω of possible
microscopic configurations. For example, the entropy of an ideal gas is
proportional to the number of gas molecules N. The number of
molecules in 22.4 liters of gas at standard temperature and
pressure is roughly 6.022 × 1023

The second law of thermodynamics states that the

entropy of an isolated system never decreases over
time. Isolated systems spontaneously evolve
towards thermodynamic equilibrium, the state with
maximum entropy.
Non-isolated systems, may lose entropy, provided their
environment's entropy increases by at least that amount so
that the total entropy either increases or remains constant.
Therefore, the entropy in a specific system can decrease as
long as the total entropy of the Universe does not.
Entropy is a function of the state of the system, so the change
in entropy of a system is determined by its initial and final
states.
In the idealization that a process is reversible, the entropy
does not change, while irreversible processes always
increase the total entropy.
Clausius Theorem OR Clausius Inequality
The Clausius theorem (1855) states that a thermodynamic
system (e.g. heat engine or heat pump) exchanging heat
with external reservoirs and undergoing a thermodynamic
cycle follows the equation given below:

Where δQ is the infinitesimal amount of heat absorbed by the system from the heat reservoir and Tsurr
is the temperature of the external reservoir (surrounding). The closed integral is carried along the
thermodynamic process path from the initial/final state to the same initial/final state.
If there are multiple reservoirs with different
temperatures (T1,T2,T3….Tn) then Clausius inequality
reads as:

In the special case of a reversible process,

the equality holds
The reversible case is used to introduce the state
function known as entropy. This is because in a cyclic
process the variation of a state function is zero.

The generalized "inequality of Clausius

for an infinitesimal change in entropy S applies not only to cyclic

processes, but to any process that occurs in a closed system.
 The Clausius theorem is a mathematical
explanation of the second law of thermodynamics.
 The Clausius theorem provides a quantitative
formula for understanding the second law.
 It was developed by Rudolf Clausius who intended
to explain the relationship between the heat flow in
a system and the entropy of the system and its
surroundings.
 In more direct terms, the theorem gives us a way to
determine if a cyclical process is reversible or
irreversible. Clausius was one of the first to work on the idea of
entropy and is even responsible for giving it that name.
 Second Law of thermodynamics in terms of Entropy
 The first law of thermodynamics provides the
definition of the internal energy of
a thermodynamic system, and expresses the law
of conservation of energy.
 The second law is concerned with the direction of
natural processes. (Heat always flows
spontaneously from a hotter to a colder body.)
In a fictive reversible process, an infinitesimal
increment in the entropy (dS) of a system is defined to
result from an infinitesimal transfer of heat (δQ) divided
by the common temperature (T) of the system in
equilibrium and the surroundings which supply the
heat:[

Closed system, Idealized fictive reversible process

For an actually possible infinitesimal process without
exchange of mass with the surroundings, the second
law requires that the increment in system entropy
fulfills the inequality

Closed system, Actually Possible Irreversible process

Various statement of second law (Clausius, Kelvin, Plank)…most prominent was Clausius.
 Entropy : Carnot Cycle

A
Q1
B
P D T1
Q2
C T2
F Q3
E T3

V
For Carnot cycle ABCD, Q1 amount of heat is absorbed at
constant temp T1 and Q2 heat is ejected at cons. temp. T2

Then efficiency of Carnot engine is:

 ……(1)

Similarly consider Carnot cycle DCEF, Q2 amount of heat is

absorbed at constant temp T2 and Q3 heat is ejected at
cons. temp. T3

….(2)
 From equations 1 and 2

In general if Q is the amount of heat absorbed or rejected at

temperature T in going from one adiabatic to other, then
In two adiabatics are very close to each other and

This constant ratio is called change in entropy dS

 Change in entropy in finite reversible process from A to B is
given by

Entropy is a state function: dS is an exact differential

Entropy is extensive property, it depend on mass of substance
SI Units of entropy Joule/K or Kcal/K
There is no change in entropy during an adiabatic process dS=0
For Reversible cyclic process
 Change in Entropy in an adiabatic process

Since
hange in Entropy in an adiabatic process
Also called isoentropics
 Change in Entropy in a reversible carnot cycle
1) Isothermal Expansion AB
Q1 is quantity of heat absorbed at constant temp T1
We know A

C
2) Adiabatic Expansion BC
No exchange of heat

3) Isothermal Compression CD
Q2 heat is rejected to sink

4) Adiabatic Compression DA
No exchange of heat
NET entropy change in entire cycle
 However for reversible carnot cycle

Entropy of the system remains unchanged or constant

Total change in entropy is zero
 Principal of increase in entropy

Let a system change from state 1 to state 2 by a

reversible process A and return to state 1 by another
reversible process B. Then 1A2B1 is a reversible cycle.
Therefore, the Clausius inequality gives:

T =0
 2

A
P B
C

V
If the system is restored to the initial state from 1 to state 2
by an irreversible process C, then 1A2C1 is an irreversible
cycle. Then the Clausius inequality gives:

T <0

On combining two equations we have

Since B is reversible process and S is state function:

Hence S1-S2=
Using above relation in previous equation we have

2C1

>
 Hence for a general case we can write

dS

Equality and greater than sign hold for

Reversible and irreversible process
This is an important result
it tells us the direction in which a process must evolve
Now let us apply the above result to evaluate the entropy
change of the universe when a system interacts with its
surroundings and exchanges heat with the surroundings.
Let Tsyt and Tsurr be the temperature of the System and
surrounding which exchange

(Irreversible Process)
Decrease in entropy of surrounding =
Increase in entropy of the system=
Change in entropy of the universe:

dSuni=dSsyst+dSsurr=Q/Tsys –Q/Tsurr= + quantity (as Tsurr>Tsys)

Hence dSuni>0
Hence we say that entropy increases in all irreversible
process. This is known as principle of increase of entropy.
All Natural processes taking place in the universe are
irreversible. It means entropy of the universe increases
dS (Universe)