University of Salahaddin- Hawler - College of Engineering

Chemical and Petrochemical Department

ENGINEERING
THERMODYNAMICS-I

Ch_4: ENTROPY

By: Hardi A. Siwaily

M.Sc. Mechanical Engineering- Thermal Power. Contact: [email protected]
 Introduction
• In heat engine theory, the term entropy plays a vital role and leads to important results which by other methods
can be obtained much more laboriously.

• It may be noted that all heat is not equally valuable for converting into work. Heat that is supplied to a substance
at high temperature has a greater possibility of conversion into work than heat supplied to a substance at a lower
temperature.

• “Entropy is a function of a quantity of heat which shows the possibility of conversion of that heat into work. The
increase in entropy is small when heat is added at a high temperature and is greater when heat addition is made at
a lower temperature. Thus for maximum entropy, there is minimum availability for conversion into work and for
minimum entropy there is maximum availability for conversion into work.”

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 1
 Entropy: a Property of a System
Refer Fig. 1. Let us consider a system undergoing a reversible process from state 1 to state 2 along path L and then
from state 2 to the original state 1 along path M. Applying the Clausius theorem to this reversible cyclic process, we
have:

Hence when the system passes through the cycle 1-L-2-M-1, we have

……….(1)

Now consider another reversible cycle in which the system changes from
state 1 to state 2 along path L, but returns from state 2 to the original state
Fig. 1. Reversible cyclic process between
1 along a different path N. For this reversible cyclic process, we have two fixed end states.

……….(2)

Subtracting equation (1) from equation (2), we have

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 2
 Entropy: a Property of a System
𝛿𝑄
As no restriction is imposed on paths L and M, except that they must be reversible, the quantity is a function of
𝑇

the initial and final states of the system and is independent of the path of the process. Hence it represents a
property of the system. This property is known as the “entropy”.
Change of Entropy in a Reversible Process
Let
S1 = Entropy at the initial state 1, and
S2 = Entropy at the final state 2.
Then, the change in entropy of a system, as it undergoes a change from state 1 to 2, becomes

……….(3)

Lastly, if the two equilibrium states 1 and 2 are infinitesimal near to each other, the integral sign may be omitted and
S2 – S1 becomes equal to dS. ……….(4)
Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 3
 ENTROPY AND IRREVERSIBILITY
𝛿𝑄
We know that change in entropy in a reversible process is equal to 𝑅 (eqn. 4). Let us now find the change in
𝑇

entropy in an irreversible process.

Consider a closed system undergoing a change from state 1 to state 2 by a reversible
process 1-L-2 and returns from state 2 to the initial state 1 by an irreversible process
2-M-1 as shown in Fig. 2 on the thermodynamic coordinates, pressure and volume.
Since entropy is a thermodynamic property, we can write

……….(5)

Now for a reversible process, from eqn. (4), we have

……….(6)

Substituting the value of (dS )R in eqn. (5), we get

……….(7)

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 4
 ENTROPY AND IRREVERSIBILITY
Again, since in eqn. (5) the processes 1-L-2 and 2-M-1 together form an irreversible cycle, applying Clausius equality
to this expression, we get
……….(8)

Now subtracting eqn. (8) from eqn. (7), we get

which for infinitesimal changes in states can be written as

……….(9)

𝑑𝑄
Eqn. (10) states that the change in entropy in an irreversible process is greater than .
𝑇

Combining eqns. (8) and (9), we can write the equation in the general form as

……….(10)
where equality sign stands for the reversible process and inequality sign stands for the irreversible process.
Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 5
 TEMPERATURE-ENTROPY DIAGRAM

If entropy is plotted-horizontally and absolute temperature vertically the diagram so obtained is called temperature-
entropy (T-s) diagram. Such a diagram is shown in Fig. 3. If working fluid receives a small amount of heat dQ in an
elementary portion ab of an operation AB when temperature is T, and if dQ is represented by the shaded area of
which T is the mean ordinate, the width of the figure must be 𝑑𝑄/𝑇 .

This is called ‘increment of entropy’ and is denoted by dS. The total heat
received by the operation will be given by the area under the curve AB and
(SB – SA) will be corresponding increase of entropy.
From above we conclude that : Entropy change,

Fig. 3. Temperature-entropy diagram.

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 6
 ENTROPY CHANGES FOR A CLOSED SYSTEM
I. General Case for Change of Entropy of a Gas

Let 1 kg of gas at a pressure p1, volume v1, absolute temperature T1 and entropy s1, be heated such that its final
pressure, volume, absolute temperature and entropy are p2, v2, T2 and s2 respectively. Then by law of conservation of
energy,

where, But
dQ = Small change of heat,
and as
du = Small internal energy, and
dW = Small change of work done (pdv). Hence
Now
Integrating both sides, we get

Dividing both sides by T, we get

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 7
 ENTROPY CHANGES FOR A CLOSED SYSTEM
II. Heating a Gas at Constant Volume

Refer Fig. 4. Let 1 kg of gas be heated at constant volume and let the change in entropy and absolute temperature be
from s1 to s2 and T1 to T2 respectively.

Then

Differentiating to find small increment of heat dQ corresponding to small rise in

temperature dT. Integrating both sides, we get

Dividing both sides by T, we get

Fig. 4. T-s diagram : Constant

volume process.

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 8
 ENTROPY CHANGES FOR A CLOSED SYSTEM
III. Heating a Gas at Constant Pressure

Refer Fig. 5. Let 1 kg of gas be heated at constant pressure, so that its absolute temperature changes from T1 to T2 and
entropy s1 to s2.
Then,

Differentiating to find small increase in heat, dQ of this gas when the

temperature rise is dT.

Dividing both sides by T, we get

Integrating both sides, we get

Fig. 5. T-s diagram : Constant pressure process.

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 9
 ENTROPY CHANGES FOR A CLOSED SYSTEM
IV. Isothermal Process

An isothermal expansion 1-2 at constant temperature T is shown in Fig.6.

Entropy changes from s1 to s2 when gas absorbs heat during expansion.
The heat taken by the gas is given by the area under the line 1-2 which
also represents the work done during expansion. In other words, Q = W.

But

and

Fig. 6. T-s diagram : Isothermal process.

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 10
 ENTROPY CHANGES FOR A CLOSED SYSTEM
V. Adiabatic Process (Reversible)
During an adiabatic process as heat is neither supplied nor rejected,

This shows that there is no change in entropy and hence it is known

as isentropic process. Fig. 7 represents an adiabatic process. It is a
vertical line (1-2) and therefore area under this line is nil ; hence heat
supplied or rejected and entropy change is zero.

Fig.7. T-s diagram : Adiabatic process.

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 11
 ENTROPY CHANGES FOR A CLOSED SYSTEM
VI. Polytropic Process

Refer Fig. 8. The expression for ‘entropy change’ in polytropic process (pvn = constant) can be obtained from eqn.
for general case-I, i.e.

……....(i)

Fig. 8. T-s diagram : Polytropic proces

……....(ii)

From (i) and (ii), and same procedures as before, we get:

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 12
 ENTROPY CHANGES FOR A CLOSED SYSTEM
Table 1. Summary of Formulae

Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 13
 ENTROPY CHANGES FOR A CLOSED SYSTEM
VII. Approximation For Heat Absorbed
The curve LM shown in the Fig. 9 is obtained by heating 1 kg of gas from initial state L to final state M.
Let temperature during heating increases from T1 to T2. Then heat absorbed by the gas will be given by the area (shown
shaded) under curve LM.

As the curve on T-s diagram which represents the heating of the gas,
usually has very slight curvature, it can be assumed a straight line for a
small temperature range. Then,

Heat absorbed = Area under the curve LM

Fig. 9
Salahaddin University- Hawler/ College of Engineering. Engineering Thermodynamics By: Hardi A. Siwaily 14
End of lecture