HARARE INSTITUTE OF TECHNOLOGY

Chemical & Process Systems Engineering

Chemical Engineering Thermodynamics
ECP 216 Lecture Notes
BY F.M. Saziya

1
 Lecture 7
Entropy
Much as the new property energy arose via consideration of
the first law of thermodynamics, we will find it useful to
introduce
•Entropy: a thermodynamic property which provides a
quantitative measure of the disorder of a given
thermodynamic state, from consideration of the
second law of thermodynamics.
The word itself was coined by Clausius, who based it on the
combination of ǫν- (en-) “to put into,” and τρoπ´η (trop¯e),
“turn” or “conversion.” The Greek here is a modification of
the original Greek of Clausius, who employed `η τρoπ`η.

2
 7.1 Theoretical development
• Let us motivate the property of entropy by considering Fig.
7.1. Here, we perform our analysis on a differential basis.
• We have a thermal reservoir at Tres which delivers a small
amount of heat δQ′ to a reversible cyclic engine, labelled
“1.” This engine delivers a small amount of work δW′ and
rejects a small amount of heat δQ to another reservoir at
variable T, labelled “2.” This reservoir itself delivers a
different small amount of work δW to the surroundings.
• We examine the implications of our temperature definition
and the second law of thermodynamics on this scenario.

3
 7.1 Theoretical development

Fig7.1: Sketch of heat engine configuration to motivate the

development of entropy. 4
• We first apply the Carnot Eq. to the configuration of Fig. 7.1:

• Now, let us take the combined system, enclosed within the

dotted box, to be composed of 1 and 2.
• The first law in differential form for the combined system is

• note that δQ is internal and so does not cross the boundary of

the combined system and is not present in our first law
formulation. Rearrange Eq. (7.3) to get

• Now, use Eq. (7.2) to eliminate δQ′ in Eq. (7.4):

5
• Now, let us let this configuration undergo a thermodynamic
cycle, indicated by the operation applied to Eq. (7.5):

• Because U is a thermodynamic property, its cyclic integral is zero. But Q

and W are not properties, so they have non-zero values when integrated
through a cycle.
• Performing the integration of Eq. (7.6) and realizing that, by definition, T res
is a constant, we get
• 7
• Applying the Kelvin-Planck form of the second law of thermodynamics to
the configuration of Fig. 7.1; thus, we require simply that
• 8
• That is, we cannot convert all the heat to work, but we can convert all the
work to heat, Eq 7.7 thus gives:

6
• And since Tres > 0, we can divide Eq. (7.9) by it without changing the
sense of the inequality to get a mathematical representation of the
second law of thermodynamics:
10
second law of thermodynamics.
Eq. 7.10 is also known as The Clausius inequality
If all processes are reversible, we lose the inequality, and get simply
11
second law of thermodynamics all processes reversible.

7
 entropy production

• The Clausius inequality, Equation 7.10 can be expressed equivalently as:

7,12

• where 𝜎cycle can be viewed as representing the “strength” of the inequality.

The value of 𝜎cycle is positive when internal irreversibilities are present, zero
when no internal irreversibilities are present, and can never be negative.
• In summary, the nature of a cycle executed by a system is indicated by the
value for 𝜎cycle as follows:

• Accordingly, 𝜎cycle is a measure of the effect of the irreversibilities present

within the system executing the cycle.
• 𝜎cycle is the entropy produced (or generated) by internal irreversibilities
during the cycle
8
 Defining Entropy Change
• Consider various combinations forming cyclic processes (Fig 7.2)
• Now, consider two cycles, each passing through points 1 and 2,
albeit via different paths:
• Cycle I: 1 to 2 on Path A followed by 2 to 1 on Path B,
• Cycle II: 1 to 2 on Path A followed by 2 to 1 on Path C.
• Let us restrict our discussion to reversible processes, which are the
best we could hope for in an ideal world. So we demand that Eq.
(7.11) holds.
• Now, from Fig. 7.2, consider starting from 1, proceeding on path A
to 2, and returning to 1 via path B. The cyclic integral
• decomposes to:

7.13

9
Figure 7.2: Sketch of P − V diagram for various combinations of processes
forming cyclic integrals.

10
• Now, perform the same exercise going from 1 to 2 on path A and returning
on path C, yielding

7.14

• Now, subtract Eq. (7.13) from Eq. (7.12) to get

7.15

• Thus
7.16
• We can reverse direction and recover the same result, since

7.17
11
 Definition of Entropy
• Since paths B and C are different and arbitrary, but is the same on either
path, the integral must be path-independent. It therefore defines a
thermodynamic property of the system. We define that property as
entropy, S, an extensive thermodynamic property:

7.18

• Note the units of S must be kJ/K in the SI system. We also can scale by the
constant mass m to get the corresponding intensive variable s = S/m:

7.19

• The units for s are kJ/(kg K); note they are the same as cP , cv, and R. In
differential form,
• we can say
7.20
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 Entropy Change in Internally Reversible Processes
• Consider the entropy change and heat transfer for internally reversible
processes :
• As a closed system undergoes an internally reversible process, its entropy
can increase, decrease, or remain constant. This can be brought out using
Eq. 7.20

• which indicates that when a closed system undergoing an internally

reversible process receives energy by heat transfer, the system
experiences an increase in entropy.
• Conversely, when energy is removed from the system by heat transfer, the
entropy of the system decreases.
• This can be interpreted to mean that an entropy transfer accompanies
heat transfer. The direction of the entropy transfer is the same as that of
the heat transfer.

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• This leads us to
2.21

• Integrating Eq. (7.20), we get

2.22

• Thus, we get
2.23

• This is the heat transfer equivalent to . So we see the heat transfer for a
process from 1 to 2 is given by the area under the curve in the T −s plane;
see Fig. 7.4.
• Note if our process lies on a so-called
• Isentrope: a line on which entropy s is constant
then by Eq. (7.22), q12 = 0; thus, the process is adiabatic.

14
Fig 8.4: Sketch of process in the T − s plane, with the associated heat transfer.
15
 Third law of thermodynamics

• Now, Eq. (7.22) only applies for a reversible process. Combining

these notions, we summarize with the important equivalence:

• For problems in which no chemical reactions are present, we are

interested only in entropy differences.
• For problems with chemical reactions, the absolute values of
entropy will be important. Such values can be obtained by
consideration of the
• Third law of thermodynamics: “every substance has a finite
positive entropy, but at the absolute zero of temperature the
entropy may become zero, and does so become in the case of
perfect crystalline substances,”
• The law, another axiom of thermodynamics, was developed over several
years by Walther Hermann Nernst (1864-1941), German physical chemist.
It will not be considered further here.

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• Because entropy is a thermodynamic property, it can be used
to help determine the state.
• That is we can say any of the following:

• For two-phase mixtures, we have, as expected,

• 5

• We now have a statement of the second law, , valid for reversible or

irreversible heat transfer, and a definition of entropy provided the heat
transfer is reversible.
• The two seem similar. Let us combine them to cast the second law in
terms of entropy.

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 7.2 Second law in terms of entropy
• Consider the cycle in the T − S diagram of Fig. 7.3. We start at 1, and
proceed to 2 along path I, which represents an irreversible process.
• We return from 2 to 1 along path R, which represents a reversible
process. The second law, Eq. (7.10), holds

Fig 7.3: Sketch of cycle in the T − S plane composed of irreversible process I

from 1 to 2, followed by reversible process R from 2 back to 1. 18
 2nd Law in terms of Entropy

• The second law, Eq. (7.10), holds

7.26

7.27

• The equality implies all processes are reversible; the inequality implies
some portion of the process is irreversible.
• Now, for a reversible process we also have

7.28
• Since the process is reversible, we reverse to get

7.29
• Now, apply the second law, Eq. (7.10), to the scenario of Fig. 7.3:

7.30
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 2nd Law I terms of Entropy
• Now, substitute Eq. (7.28) into Eq. (7.29) to eliminate the integral along R to get

7.31

7.32

• More generally, we can write the second law of thermodynamics as

• If 1 → 2 is reversible, the equality holds; if 1 → 2 is irreversible, the inequality

holds. Now, if the system is isolated, there can be no heat transfer interactions and
δQ = 0. So

7.34
• This implies 2 occurs later in time than 1. Thus, for isolated systems, the
entropy increases as time moves forward.

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 Example 7.1

• Two large thermal reservoirs, one at TA and the other at TB,

exchange a finite amount of heat Q with no accompanying work
exchange. The reservoirs are otherwise isolated and thus form their
own universe, when considered as a combined system. Consider the
implications for entropy and the second law.
• The scenario is sketched in Fig. 7.5. Assume for now that positive Q
leaves A and enters B.

Fig 7.5 Sketch of heat transfer from A to B.

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 Solution Example 7.1

• Assume for now that positive Q leaves A and enters B. Both A and B are so
massive that the respective loss and gain of thermal energy does not alter
their respective temperatures.
• Consider the entropy changes for each system:

7.35

7.36
• The entropy change for A is negative since Q was negative for A; the
entropy change for B is positive since Q for B was positive.
• Now, our universe is the combination of A and B, so the entropy change of
the universe is found by adding the entropy changes of the components of
the universe:

7.37

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• With the universe entropy SU as SU = SA + SB, we get
7.38

The universe is isolated, so the second law holds that SU2 − SU1 ≥ 0; thus,

7.39

• Now, since Q > 0; therefore, we can divide by Q without

changing the sense of the inequality:

7.40

7.41

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• Since TA > 0 and TB > 0, we can multiply both sides by
TATB without changing the sense of the inequality to get
7.42
7.43

• We have thus confirmed that our mathematical

formulation of the second law in terms of entropy
yields a result consistent with the Clausius
statement of the second law. We must have T A ≥ TB
in order to transfer positive heat Q from A to B.

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 Example 7.2
• Saturated Liquid water at P1 = 100 kPa, x1 = 0 is heated
isobarically until T2 = 200oC.
• Find the heat added and the work done.
• Show heat and work in a T-s and p-v diagram respectively
• Solution:
• The saturated steam tables tell us that at state 1,
• we have T1 = 99.62oC, v1 = 0.001043 m3/kg, h1 = 417.44 kJ/kg,
and s1 = 1.3025 kJ/(kg K).
• We note an intermediate stage i when xg = 1 that Tg = T1 =
99.62oC, hg = 2675.46 kJ/kg, and sg = 7.3593 kJ/(kg K).
• At the final state, the superheat tables give us v2 = 2.17226
m3/kg, h2 = 2875.27 kJ/kg, and s2 = 7.8342 kJ/(kgK).

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• For the isobaric process, we have the heat transfer given by h.
For the part of the process under the dome, we have

• This quantity is known as the latent heat. It represents heat

added without increase in temperature. It is easily calculated
by an independent method. We also have

• Since an isobaric process under the vapour dome is also

isothemic, we can say 1qg = T(sg − s1), so

• The difference in the two predictions can be attributed to rounding error.

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• For the part of the process outside of the dome, we have

• This quantity is known as the sensible heat. It represents heat added with
an increase in temperature. We can sense it.
• The total heat added, work, and total entropy change are

• Note that because there is a change in internal energy for this process.
The process is sketched in Fig. 7.6.

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Figure 7.6: T − s and P − v diagrams for isobaric heating of water problem.

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 7.3 The Gibbs equation
• We are now in a position to obtain one of the most important relations in
thermodynamics, the Gibbs equation, named for the great nineteenth
century American engineer, physicist, chemist, and mathematician,
• The Gibbs equation is a re-capitulation of the first law of thermodynamics.
It is taken in the limit that
• all processes are assumed to be reversible.
• And we shall only consider the Gibbs equation for simple compressible
substances, neglecting changes in kinetic and potential energy, though
other forms are possible.
• We first recall the differential form of the first law, dE = δQ − δW, neglect
changes in KE and PE, so that dE = dU, and then consider this on a per
mass basis, obtaining

• Now, for a simple compressible substance undergoing pressure-volume

work, we have, cast on a per mass basis, δw = pdv.
• For the same substance undergoing simultaneous reversible heat transfer,
we have, δq = Tds. 29
 the Gibbs equation
• So we can recast Eq. (7.44) as the Gibbs equation:
7.45
• Note that the Gibbs equation is generally valid for all
materials. It is valid for ideal gases, non-ideal gases, liquids,
solids, or two-phase mixtures. And though we considered
reversible processes in its derivation, once we have it, we
note that only properties are defined, and so we do not have
to restrict ourselves to reversible processes.
• It is commonly rearranged in a way which allows the entropy
to be determined:
7.46 first Gibbs Equation

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 Gibbs Equation
• The Gibbs equation can also be written in terms of enthalpy.
Recall by definition, h = u+pv,
• . Elementary calculus then tells us:
7.47
7.48
7.49
Substitute Eq. (7.49) into the Gibbs relation Eq. (7.46) to yield

7.50
second Gibbs Equation
So we can say 7.51

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 Example 7.3 use of the T dS equations
• Given the enthalpy change, calculate the entropy change for water going
from saturated liquid to saturated vapour along a T = 100oC isotherm.
• Solution
• Under the vapour dome, an isotherm is an isobar, so dp = 0. So Eq. (7.50)
reduces to
• Since T is constant, the integration is easy,

From saturated Steam Tables, we find at T = 100oC, hfg = 2257.03 kJ/kg. Thus,
we must have

• Note that the entropy of the vapour is greater than that of the liquid, s fg = sg − sf > 0.
We easily envision the vapour as having less structure or less order than the liquid.

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 USING GRAPHICAL ENTROPY DATA
• The use of property diagrams as an adjunct to problem solving is
emphasized. When applying the second law, it is frequently helpful
to locate states and plot processes on diagrams having entropy as a
coordinate.
• Two commonly used figures having entropy as one of the
coordinates are the temperature–entropy diagram and the
enthalpy– entropy (Mollier) diagram.
• TEMPERATURE–ENTROPY DIAGRAM. The main features of a
temperature–entropy diagram are shown in Fig. 7.7
• Observe that lines of constant enthalpy are shown on these figures.
• Also note that in the superheated vapour region constant specific
volume lines have a steeper slope than constant pressure lines.
• Lines of constant quality are shown in the two-phase liquid–vapour
region.

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Fig 7.7 : TEMPERATURE–ENTROPY DIAGRAM.

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• In the superheated vapour region of the T–s diagram,
constant specific enthalpy lines become nearly
horizontal as pressure is reduced.
• These states are shown as the shaded area on Fig. 7.7
For states in this region of the diagram, the enthalpy is
determined primarily by the temperature: h(T, p) ≈ h(T).
• This is the region of the diagram where the ideal gas
model provides a reasonable approximation.
• For superheated vapour states outside the shaded area,
both temperature and pressure are required to evaluate
enthalpy, and the ideal gas model is not suitable.

35
 Mollier diagram
• ENTHALPY–ENTROPY DIAGRAM. The essential features of an enthalpy–
entropy diagram, commonly known as a Mollier Diagram, are shown in
Fig. 7.8
• Note the location of the critical point and the appearance of lines of
constant temperature and constant pressure.
• Lines of constant quality are shown in the two-phase liquid–vapour
region (some figures give lines of constant percent moisture).
• The figure is intended for evaluating properties at superheated vapour
states and for two-phase liquid–vapor mixtures. Liquid data are seldom
shown.
• In the superheated vapor region, constant-temperature lines become
nearly horizontal as pressure is reduced.
• These states are shown, approximately, as the shaded area on Fig. 7.8.
This area corresponds to the shaded area on the temperature–entropy
diagram of Fig. 7.7, where the ideal gas model provides a reasonable
approximation.
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Figure 7.8 Enthalpy–entropy diagram.

37
 7.3.2 Entropy Change of an Ideal Gas
• In this section the T dS equations are used to evaluate the entropy change
between two states of an ideal gas. It is convenient to begin with Gibbs
Eqs. 7-46 & 7-50
• 7.46
• 7.50
• expressed as
7.52
p 7.53
• For an ideal gas, du =cv(T)dT; dh=cp(T)dT; and pv = RT. With
these relations, Eqs. 7-52 and 7-53 become, respectively

• On integration, Eqs. 7.54 give, respectively

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 7.3.3 Entropy Change of an Incompressible Substance
• The incompressible substance model assumes that the specific
volume (density) is constant and the specific heat depends solely on
temperature, cv = c(T).
• Accordingly, the differential change in specific internal energy is du
= c(T) dT and Eq. 7.52 reduces to

• On integration, the change in specific entropy is

• When the specific heat is assumed constant, this becomes

7.57
Ebook 233

39
 E X A M P L E 7 . 4 Internally Reversible Process of Water

• Water, initially a saturated liquid at 100oC, is

contained in a piston–cylinder assembly. The water
undergoes a process to the corresponding saturated
vapour state, during which the piston moves freely in
the cylinder.
• If the change of state is brought about by heating the
water as it undergoes an internally reversible process
at constant pressure and temperature, determine the
work and heat transfer per unit of mass, each in
kJ/kg.

40
 S O L U T I O N 7.4

• Known: Water contained in a piston–cylinder assembly

undergoes an internally reversible process at 100oC from
saturated liquid to saturated vapour.
• Find: Determine the work and heat transfer per unit mass.
• Schematic and Given Data:

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• Assumptions:
1. The water in the piston–cylinder assembly is a closed system.
2. The process is internally reversible.
3. Temperature and pressure are constant during the process.
4. There is no change in kinetic or potential energy between the
two end states.
Analysis: At constant pressure the work is:

With values from saturated steam tables

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• Since the process is internally reversible and at constant
temperature, Eq. 7.20 gives on integration

With values from saturated Steam Table

The heat transfer can be evaluated alternatively from an energy

balance written on a unit mass basis as

Introducing w= p(vg - vf) and solving

43