CHE433 THERMODYNAMICS

Chapter 7:
ENTROPY

CLAUSIUS INEQUALITY
Q

T 0

The cyclic integral of Q/T is always less than or

equal to zero
Q

T 0(reversible)
Q

T 0 (irreversible)
Q

T 0 (impossible)

The sign of Q is determined with respect to the system

(positive if to the system and negative if from the
system).
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ENTROPY
Q

T int rev

dS

kJ /K

Entropy, S (kJ/K) is an extensive property

of a system and sometimes is referred to
as total entropy. Entropy per unit mass, s
(kJ/kg.K) is an intensive property.
Entropy change of a system during a
process:

T int rev

S S2 S1
1

kJ /K

Entropy change for internally

reversible isothermal heat transfer
process:
Q
S
kJ /K
T0

Entropy is a property, it
has fixed values at fixed
states. Therefore the
entropy change between
two specified states is the
same whether the
process is reversible or3

Entropy:
Quantitative measure of molecular disorder or
randomness. As a system becomes more disordered, the
positions of the molecules becomes less predictable and
the entropy increases.
Is a property of a system. It does not depend on process
path and has values at every state.
Quantify lost of energy quality. The decrease in energy
quality is always accompanied by an increase in entropy.
It can be transferred by heat and mass or generated due
to irreversibility factors:
Frictional forces between moving surfaces
Fast expansion & compression
Heat transfer at finite temperature difference
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THE INCREASE OF
ENTROPY PRINCIPLE
Sisolated 0
The entropy of an isolated system (adiabatic closed system) during a
process always increases, it never decreases. This is known as the
increase of entropy principle.
Proof: From Clausius inequality
or
The second integral is entropy change (S
= S1-S2). Therefore,
Rearrange:

A cycle composed of
a reversible and an
irreversible process.

or in differential
form
For an isolated system (an adiabatic
closed system), the heat transfer is zero,
therefore
S
0
isolated

The entropy change of a closed system:

Q
(reversible)
T
1

Ssys S2 S1

Q
T

Ssys S2 S1

Q
(irreversible)
T
1

Ssys S2 S1

The difference between the entropy change and entropy

1 Q T
transfer
is equal to entropy generation, Sgen.

The entropy generation Sgen is always a positive quantity or zero.

In the absence of any entropy transfer, the entropy change of a
system is equal to the entropy generation.
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Entropy change of isolated system is the sum

of the entropy change of the system and its
surroundings which equal to entropy
generation.
The increase of entropy
principle

A system and its

surroundings form
an isolated system.
The entropy change of a
system can be negative,
but the entropy
generation

Some Remarks about

Entropy
1. Processes can occur in a certain direction only, not in any
direction. A process must proceed in the direction that complies
with the increase of entropy principle, that is, Sgen 0. A process
that violates this principle is impossible.
2. Entropy is a nonconserved property, and there is no such thing
as the conservation of entropy principle. Entropy is conserved
during the idealized reversible processes only and increases
during all actual processes.
3. The performance of engineering systems is degraded by the
presence of irreversibilities, and entropy generation is a
measure of the magnitudes of the irreversibilities during that
process. The greater the extent of irreversibilities, the greater
the entropy generation. It is also used to establish criteria for
the performance of engineering devices.

EXAMPLE 1
A completely reversible air conditioner provides
36000 kJ/h of cooling for a space maintained at
20oC while rejecting heat to the environmental air
at 45oC. Calculate the rate at which the entropies
of the two reservoirs change and verify that this
air conditioner satisfies the increase of entropy
principle.

ENTROPY CHANGE OF PURE

SUBSTANCES
Entropy is a property, and thus
the value of entropy of a system
is fixed once the state of the
system is fixed.

The entropy of a pure

substance is determined
from the tables (like other

Schematic of the T-s diagram for

water.

Entropy change

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EXAMPLE 2
A well insulated rigid tank contains 2 kg of
saturated liquid vapor mixture of water at 100
kPa. Initially, three quarters of the mass is in the
liquid phase. An electric resistance heater placed
in the tank is now turned on and kept on until all
the liquid in the tank vaporized. Determine the
entropy change of the steam during this process.

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EXAMPLE 3
An insulated piston cylinder device contains 5 L
of saturated liquid water at a constant pressure
of 150 kPa. An electric resistance heater inside
the cylinder is now turned on, and 2200 kJ of
energy is transferred to the steam. Determine the
entropy change of the water during this process.

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ISENTROPIC PROCESSES
A process during which the entropy remains constant is called
an isentropic process.
A reversible adiabatic process is necessarily isentropic (s 2 = s1), but an
isentropic process is not necessarily a reversible adiabatic process.

During an internally
reversible, adiabatic
(isentropic) process, the

The isentropic process appears as a

vertical line segment on a T-s
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EXAMPLE 4
An insulated piston-cylinder device contains 0.05
m3 of steam at 300 kPa and 150oC. Steam is now
compressed in a reversible manner to a pressure
of 1 MPa. Determine the work done on the steam
during this process.

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EXAMPLE 5
Steam is expanded in an isentropic turbine with a
single inlet and outlet. At the inlet, the steam is
at 2 MPa and 360oC. The steam pressure at the
outlet is 100 kPa. Determine the work produced
by this turbine, in kJ/kg.

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PROPERTY DIAGRAMS
INVOLVING ENTROPY
From definition of entropy
Total heat transfer during internally
reversible process

On a T-S diagram,
the area under the
process curve
represents the
heat transfer for
internally
reversible
In unit mass
basis
processes.

and
For internally reversible isothermal process
or

For adiabatic steady-flow

devices, the vertical
distance h on an h-s
diagram is a measure of
work, and the horizontal
distance
s is a measure
The h-s diagram
is also of
irreversibilities.
called a Mollier diagram.
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EXAMPLE 6
Determine the heat transfer for the reversible
process 1-3 shown in figure below.

(a)

(b)

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EXAMPLE 7
Refrigerant-134a at 240 kPa and 20oC undergoes
an isothermal process in a closed system until its
quality is 20 percent. On per unit mass basis,
determine how much work and heat transfer are
required.

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THE T-ds RELATIONS

Differential form of the conservation

of energy equation for closed system:
Differential form of the conservation of
energy equation for a closed stationary
system

But
Thus
or
the first T ds, or Gibbs equation

The T ds relations are valid

for both reversible and
irreversible processes and
for both closed and open
systems.

the second T ds equation

Differential changes
in entropy in terms
of other properties
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ENTROPY CHANGE OF
LIQUIDS AND SOLIDS
Since
solids

for liquids and

Liquids and solids can be

approximated as
incompressible substances
since their specific
volumes remain nearly
constant during a process.

For isentropic process of an incompressible

substance
The temperature remains constant during an isentropic process.
Therefore, the isentropic process of an incompressible
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EXAMPLE 8
A 50 kg copper block initially at 80oC is dropped
into an insulated tank that contains 120 L of
water at 25oC. Determine the final equilibrium
temperature and the total entropy change for this
process.

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THE ENTROPY CHANGE OF

IDEAL GASES
From the first T ds
relation

From the second T ds

relation

ds

cpdT
T

dP
P

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Constant Specific Heats (Approximate Analysis

Entropy change of an ideal gas on a unit

mole basis

Under the constant-specific-heat

assumption, the specific heat is
assumed to be constant at some
average value.

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Variable Specific Heats (Exact Analysis)

We choose absolute zero as the
reference temperature and define a
function s as
From equation:

On a unitmass
basis

On a unitmole
basis

s2o is the value of so at T2The entropy of an

s1o is the value of so at T1ideal gas depends on
both T and P. The
function so represents
only the temperaturedependent part of
entropy.
The variation of
entropy with pressure
is accounted for by
the last term in the
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equation.

EXAMPLE 9
Air is expanded from 2000 kPa and 500oC to 100
kPa and 50oC. Determine the entropy change of
air by using (a) constant specific heats and (b)
variable specific heats.

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Isentropic Processes of Ideal Gases

Constant Specific Heats (Approximate Analysis)

Setting this eq. equal to zero

(s1 = s2),

The isentropic relations of

ideal gases are valid for
the isentropic processes of
First isentropic relation (1)
ideal gases only.
From equation:

Substitute (2) into (1):

Third isentropic relation (3)

Second isentropic relation (2)

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Isentropic Processes of Ideal Gases

Variable Specific Heats (Exact Analysis)

lative Pressure and Relative Specific Volume

exp(s/R)
is the
relative
pressure
Pr.

T/Pr is the
relative
specific volume

The use of Pr data

for calculating the
final temperature
during an
isentropic
process.

The use of vr data for

calculating the final
temperature during
an isentropic process

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EXAMPLE 10
Air is compressed in a piston cylinder device from
100 kPa and 17oC to 800 kPa in a reversible,
adiabatic process. Determine the final
temperature and the work done during this
process, assuming (a) constant specific heats and
(b) variable specific heats of air.

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EXAMPLE 11
Air enters an adiabatic nozzle at 400 kPa, 227oC
and 60 m/s and exits at 80 kPa. Assuming air to
be an ideal gas with variable specific heats and
disregarding any irreversibilities, determine the
exit velocity of the air.

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PREPARED BY:
NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING, UiTM SHAH ALAM.
0192368303/0355436333
norasmah@salam.uitm.edu.my

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