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ENTROPY CHANGES IN REVERSIBLE AND

IRREVERSIBLE PROCESSES

ABEER BASHARAT
1725107001
BS- III
SEMESTER V
SESSION: 2017-2021
Maj/Chem-301
PHYSICAL CHEMISTRY
SUBMITTED TO:
DR. FOZIA

DEPARTMENT OF CHEMISTRY
LAHORE COLLEGE FOR WOMEN UNIVERSITY
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Contents
1. Entropy – an extensive property:.........................................................................................................1
2. Entropy changes:...................................................................................................................................1
a. Entropy change in reversible process:.............................................................................................1
i. When reversible process is isothermal:.........................................................................................1
ii. When reversible process is adiabatic:..........................................................................................2
b. Entropy change in an irreversible process:.....................................................................................2
3. Physical significance of entropy:..........................................................................................................3
a. In sense of unavailable energy:.........................................................................................................3
b. Entropy and disorder:.......................................................................................................................4
4. References:.............................................................................................................................................6
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Entropy change in reversible and irreversible

processes

1. Entropy – an extensive property:

Entropy depends upon the mass of system. This kind of property is called extensive property.
The absolute value of entropy cannot be determined. Only change in entropy can be calculated.

When a system undergoes a change, there is a change in entropy of the system as well as in
surrounding. The total change in the entropy of the system and surrounding is called as entropy
change of the process.

2. Entropy changes:
a. Entropy change in reversible process:
A change is said to occur reversibly when it can be carried out in a series of infinitesimal steps,
each one of which can be undone by making a similarly minute change to the conditions that
bring the change about.

For example, the reversible expansion of a gas can be achieved by reducing the external pressure
in a series of infinitesimal steps; reversing any step will restore the system and the surroundings
to their previous state.

This is discussed under two criteria:

i. When reversible process is isothermal:

Consider an isothermal reversible process. In this process system absorbs heat Q from
surroundings at temperature T. An amount of heat dQ flows from surrounding to the system.
Consequently, the entropy of the surrounding will be reduced by
 
                                                                                                                      
−Q
∆ Ssurrounding=
T
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and the entropy of the system will increase by

 
+Q
∆ Ssystem=
                                                                                                                              
T
 
It is clear that the total change in the entropy of the process is given by:
ΔSsystem + ΔSsurrounding = Q −Q
+[ ]
So, T T

ΔS = 0

 Change of entropy in isothermal reversible process is zero.

ii. When reversible process is adiabatic:

 Isolated is the name given to a system with a rigid boundary with ideal heat insulation.
The ideal heat insulation prevents any heat exchange between the system and the
surroundings (dQ = 0). 

Q 0
∆ Ssystem= = = 0
T T
Q 0
∆ Ssurrounding= = = 0
T T
ΔSsurrounding + ΔSsystem = 0

 Change of entropy of an adiabatic process is zero.

b. Entropy change in an irreversible process:

Consider the system and surroundings at different temperatures T1 and T2
respectively with T1 > T2. Heat transfer will take place between the system and
surroundings. If an amount of heat dQ flows from system to the surroundings. Consequently,
the entropy of the system will be reduced.

Decrease in entropy of system= - Q/T1

Increase in entropy of the surroundings= +Q/T2

Net entropy change of process = ΔSsystem + ΔSsurroundings

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ΔSprocess = −Q Q
+ =Q ¿]
T1 T2
Since
 

                                            
 
we have
 
                                 ΔSprocess= positive  

 An irreversible process results in an increase in the entropy of an isolated system.

Conclusions:
1. Natural processes in universe are irreversible (spontaneous). So, the entropy of universe is
increasing.

ΔSuniverse > 0

2. The entropy of reversible processes (non-spontaneous) is constant.

ΔS =0

3. Physical significance of entropy:

a. In sense of unavailable energy:
Consider a system in which heat is supplied for doing work. Only some part of that heat will be
used to do work. That part of energy that is available to do work is called available or workable
energy.

There is some amount of energy that could have been converted into work prior to be irreversibly
lost. That remaining portion of energy is called as unavailable energy.

Explanation:
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In a carnot cycle working between a source and a sink, if heat Q1 is supplied to do work W, some
heat Q2 is rejected at sink. So the work done work be given by heat (Q1 – Q2).Whereas, heat Q2
will be unavailable energy.

Hence, Q1−Q2 T 1−T 2

η= Q1
= T1

Q2 T 2
=
Q1 T 1

Q1
Q2= T 1 × T2

Q1/T1 is increase of entropy during isothermal process at T1.

It describes the entropy change for given source or sink. It generally shows the condition
concerning entropy change, irreversibility and the loss of capability to do work.

The above equation shows that for a given sink temperature the unavailable energy can be
determined by Q1/T1.

 So entropy can be explained as the measure of the unavailable energy of the system
(equivalent to law of increase of entropy for irreversible spontaneous processes). Since
all natural spontaneous processes try to attain equilibrium where entropy is maximum,
we can say that nature is trying to achieve the state of maximum entropy.

b. Entropy and disorder:

Entropy is the measure of randomness and disorder of the system.

Whenever there takes place an irreversible spontaneous process, it always decreases the order
and hence increases the entropy. Increase in the entropy means change from an ordered state
to less ordered state. The change comes to halt when entropy attains the maximum value.

For example, flow of water, expansion of gas, melting of ice, ring of school bell, etc. all
increases randomness.
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With respect to the concept of second law of thermodynamics in terms of entropy:

 The total entropy of a system either increases or remains constant in any process, it
never decreases. Entropy is a form of energy that doesn’t remains conserved but it
increases in all the real processes.

For example: heat cannot flow from a cold body to hot body, because entropy would have
decreased during this. So in real process heat always flow from hot to cold body.
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4. References:
http://opentextbc.ca/physicstextbook2/chapter/entropy-and-the-second-law-of-
thermodynamics-disorder-and-the-unavailability-of-energy//

https://web.mit.edu/16.unified/www/FALL/thermodynamics/notes/node49.html

Bajpai, D. N. (2001). Advanced Physical Chemistry. india: S,Chand & company Ltd.