Entropy

The second law leads to the definition of a new property called entropy.

The Clausius Inequality

The first law is simply an energy balance. However, the second law leads to an
inequality; an irreversible process is less efficient than a reversible process. Another
important inequality in thermodynamics is the Clausius inequality:
δQ
∲ ≤0
T

That is, the cyclic integral of δQ / T is always less than or equal to zero. This is valid
for all cycles, reversible or irreversible.
For internally reversible cycles, it can be shown that:
δQ
∮ =0
T

Entropy
The Clausius inequality forms the basis for the definition of a new property called
entropy. As can be seen in the equation above, for an internally reversible process
the cyclic integral of δQ / T is zero. A quantity whose cyclic integral is zero depends
on the state only and not the process path, and thus it is a property.
Clausius in 1865 realized that he discovered a new property and he called it entropy:

δQ
∲
T
Entropy per unit mass is designated by s (kJ/kg.K).
The entropy change of a system during a process can be calculated:
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Q (kJ/K)
S  S2 S1  1  T int,rev

To perform this integral, one needs to know the relation between Q and T during the
process.
Note that the cyclic integral of δQ / T will give us the entropy change only if the
integration carried out along an internally reversible path between two states.
For irreversible processes, we may imagine a reversible process between the two
states
(initial and final) and calculate the entropy change (since entropy is a property).

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 The Increase of Entropy Principle
Entropy change of a closed system during an irreversible process is greater that the
integral of δQ / T evaluated for the process. In the limiting case of a reversible
process, they become equal.

dS  QT
The entropy generated during a process is called entropy generation, and is denoted
by
Sgen,
2

S  S2 S1  TQ Sgen

1

Note that the entropy generation Sgen is always a positive quantity or zero (reversible
process). Its value depends on the process, thus it is not a property of a system.
The entropy of an isolated system during a process always increases, or in the limiting
case of a reversible process remains constant (it never decreases). This is known as
the increase of entropy principle.
The entropy change of a system or its surroundings can be negative; but entropy
generation cannot.
 0 irreversible process

Sgen    0 reversible process

 0 impossible process
1‐ A process must proceeds in the direction that complies with the increase of
entropy principle, Sgen > 0. A process that violates this principle is impossible.
2‐ Entropy is a non‐conserved property, and there is no such thing as the
conservation of entropy. Therefore, the entropy of universe is continuously
increasing.
3‐ The performance of engineering systems is degraded by the presence of
irreversibility. The entropy generation is a measure of the magnitudes of the
irreversibilities present during the process.

Entropy Balance
Entropy is a measure of molecular disorder or randomness of a system, and the
second law states that entropy can be created but it cannot be destroyed.
The increase of entropy principle is expressed as
Entropy change = Entropy transfer + Entropy generation

Ssystem Stransfer Sgen

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This is called the entropy balance.
Entropy Change
The entropy balance is easier to apply that energy balance, since unlike energy
(which has many forms such as heat and work) entropy has only one form. The
entropy change for a system during a process is:
Entropy change = Entropy at final state ‐ Entropy at initial state

Ssystem  S final  Sinitial

Therefore, the entropy change of a system is zero if the state of the system does not
change during the process. For example entropy change of steady flow devices such
as nozzles, compressors, turbines, pumps, and heat exchangers is zero during steady
operation.

Mechanisms of Entropy Transfer

Entropy can be transferred to or from a system in two forms: heat transfer and mass
flow. Thus, the entropy transfer for an adiabatic closed system is zero.
Heat Transfer: heat is a form of disorganized energy and some disorganization
(entropy) will flow with heat. Heat rejection is the only way that the entropy of a
fixed mass can be decreased. The ratio of the heat transfer Q/ T (absolute
temperature) at a location is called entropy flow or entropy transfer
Q
Entropy transfer with heat (T  const.) Sheat 
T
Since T (in Kelvin) is always positive, the direction of entropy transfer is the same of
the direction of heat transfer.
When two systems are in contact, the entropy transfer from warmer system is equal
to the entropy transfer to the colder system since the boundary has no thickness and
occupies no volume.
Note that work is entropy‐free, and no entropy is transferred with work.
Mass Flow: mass contains entropy as well as energy, both entropy and energy
contents of a system are proportional to the mass. When a mass in the amount of m
enters or leaves a system, entropy in the amount of ms (s is the specific entropy)
accompanies it.

Entropy Balance for a Closed System

A closed system includes no mass flow across its boundaries, and the entropy change
is simply the difference between the initial and final entropies of the system.
The entropy change of a closed system is due to the entropy transfer accompanying
heat transfer and the entropy generation within the system boundaries:
Entropy change of the system = Entropy transfer with heat + Entropy generation

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 Qk Sgen
S2 S1 Tk 

Therefore, for an adiabatic closed system, we have:

ΔSadiabatic = Sgen
For an internally reversible adiabatic process ΔS = 0, because Sgen= 0.
The total entropy generated during a process can be determined by applying the
entropy balance to an extended system that includes both the system and its
immediate surroundings where external irreversibility might be occurring.
Example 1: Entropy balance for a closed system
Saturated liquid water at 100 C is contained in a piston ‐cylinder assembly. The water
undergoes a process to the corresponding saturated vapor state, during which the
piston moves freely in the cylinder. There is no heat transfer with the surroundings. If
the change of state is brought about by the action of a paddle wheel, determine the
network per unit mass, in kJ/kg, and the amount of entropy produced per unit mass,
in kJ/kg.K.

Insulated
Water

Paddle wheel

Assumptions:
1‐ The water in the piston‐cylinder assembly is a closed system.
2‐ There is no heat transfer with the surroundings.
3‐ The system is at an equilibrium state initially and finally. ΔPE = ΔKE = 0.

Solution
The network can be calculated by using the law:
ΔU + ΔKE + ΔPE = Q – W
That is simplifies to: ΔU = ‐ W
On a unit mass basis, the energy balance becomes:
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 W / m = ‐ (ug – uf)
From Table A‐4,
W / m = ‐ 2087.6 kJ/kg
The negative sign indicates that the work input by the stirring is greater than the
work done by the water as it expands.
Using an entropy balance, the amount of entropy produced can be found. Since there
is no heat transfer,
2

 
S    TQSgen  Sgen
1
0

On a unit mass basis, this becomes:

Sgen / m = sg ‐ sf
Using Table A‐4
Sgen / m = 6.048 kJ / kg.K

Entropy Balance for a Control Volume

In addition to methods discussed for closed system, the entropy can be exchanged
through mass flows across the boundaries of the control volume.

m°i
Control
si volume

Q°
m°o
T se

The entropy balance in the rate form for a control volume becomes:

dSdtCV QTkk misi mese  Sgen ,CV

For a steady‐state steady‐flow process, it simplifies to:

Sgen ,CV mese misi  QTkk

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 Example 2: Entropy balance for a CV
Steam enters a turbine with a pressure of 3 MPa, a temperature of 400 °C, and a
velocity of 160 m/s. Saturated vapor at 100 °C exits with a velocity of 100 m/s. At
steady‐state, the turbine develops work equal to 540 kJ/kg. Heat transfer between
the turbine and its surroundings occur at an average outer surface temperature of
350 K. Determine the rate at which entropy is produced within the turbine per kg of
steam flowing, in kJ/kg.K. Neglect the change in potential energy between inlet and
exit. Assumptions:
1‐ Steady state operation in CV. ΔPE = 0.
2‐ Turbine outer surface is at a specified average temperature.
P1 = 3 MPa
T1 = 400 °C
W° / m = 540 kJ/kg
V1 = 160 m/s

Turbine

T2 = 100 °C
V2 = 100 m/s
Tb = 350 K
Sat. vapor

From the mass balance, we know that m° = m°1 = m°2

Since the process is steady‐state, one can write:


0 QTkk  m(si  se )  Sgen ,CV

The heat transfer occurs at Tb = 350 K, the first term of the right hand side of the
entropy balance reduces to Q°/ Tb

Sgen ,CV  Qk   (s2  s1) m m Tk

We need to calculate the rate of heat transfer. The first law (energy balance) can be
used to find the heat transfer rate. Combining the mass balance and the first law, one
finds:

QmCV WmCV h2 h1 V 22 2V12 

From Table A‐6, h1 = 3230.9 kJ/kg, and From A‐4 h 2 = 2676.1 kJ/kg. After substitution,
and converting the units, one finds:

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 QCV
 22.6 kJ / kg m
From Table A‐4, s2 = 7.3549 kJ/kg.K and from Table A‐6, s1 = 6.9212 kJ/kg.K. Inserting
values into the expression for entropy production:

Sgen ,CV  Qk  (s2 s1)  0.4983 kJ / kg.K m m Tk

Entropy
Entropy can be viewed as a measure of molecular disorder, or molecular
randomness. As a system becomes more disordered, the positions of the molecules
become less predictable and the entropy increases.

Entropy
kJ/(kg.K) Gas

Liquid

Solid

Fig. 1: Entropy of a substance (level of disorder) increases when it melts from solid
phase to liquid. Ssolid < Sliquid< Sgas
Some remarks:
Work is an organized form of energy, free of disorder or randomness, thus free of
entropy. Therefore, there is no entropy associated with energy transfer as work.
The quantity of energy is always preserved during an actual process, based on the
first law, but the quality is bound to decrease (the second law).
Processes can occur only in the direction of increased overall entropy or molecular
disorder. Thus, the entire universe is getting more and more chaotic every day.
At absolute zero (0 K), molecules become completely motionless, this represents a
state of ultimate molecular order (and minimum energy). Therefore, the entropy of a
pure crystalline substance at zero temperature is zero. That is because; there is no
uncertainty about the state of the molecules at that instant. This statement is the
third law of thermodynamics.
Since there is a reference for entropy (absolute zero), entropy is an absolute
property. The entropy measured with respect to absolute zero is called absolute
entropy.
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The two diagrams used most extensively in the second‐law analysis are the T ‐s and h ‐
s diagrams. For an internally reversible process, one can write:

Qint,rev Tds (kJ)

T
Internally
reversible
process

Q = ∫Tds

Fig. 2: On a T‐s diagram, the area under an internally reversible process presents the
heat transfer for the process. For an internally reversible isothermal process, we
have:
Q int,rev = T0 ds
In a T‐s diagram, an isentropic process is represented by a vertical line. An isentropic
process is a process in which entropy remains constant. As a result an isentropic
process involves no heat transfer. Therefore:
Isentropic process (s2 = s1) = Reversible + Adiabatic

Evaluation of Entropy Change

The differential form of the conservation of energy for a closed system (fixed mass)
for an internally reversible process is:
δQint,rev ‐ δWint,rev = dU
where,
δQint,rev= TdS δWint,rev = PdV
Thus,
TdS = dU + PdV
or, per unit mass
Tds = du + Pdv
This is called the first Gibbs equation.
From the definition of enthalpy, h = u + Pv, one can find:
h = u + Pv → dh = du + Pdv + vdP
Eliminating du from the first Gibbs equation, one finds the second Gibbs equation:

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 Tds = dh – vdP
Explicit relations for differential changes in entropy can be obtained from Gibbs
equations:
du Pdv
ds  
T T
dh vdP
ds  
T T
To calculate the entropy change, we must know the relationship between du or dh
and temperature.

Calculation of the Entropy for Saturated Mixture

Use Tables A‐4 and A‐5 to find sf, sg and/or sfg for the following:
s = (1 − x)sf + x sg or s = sf + x sfg

Calculation of the Entropy for Superheated Vapor

Given two properties or the state, such as temperature and pressure, use Table A ‐6.

Calculation of the Entropy for Compressed Liquid

In the absence of compressed liquid data for a property s ≈ sf@T

Entropy Change of Solids and Liquids

Solids and liquids can be assumed as incompressible substances since their volumes
remains essentially constant during a process. Thus, the first Gibbs equation
becomes:
du cdT
ds 
T T
2

dT
s2 s1 1 c(T) T

Assuming an averaged value for specific heat, one obtains:

T2
s2  s1  cave ln
T1
Note that the entropy change of an incompressible substance is only a function of
temperature. Therefore, for an isentropic process where s2 = s1, one can find:
T2 = T1
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 Entropy Change of Ideal Gas
The entropy change of an ideal gas can be obtained, by substituting du = cv dT and P =
RT/v into Gibbs equation.
dT dv ds  cv R
T v
2 dT v2
s2  s1 1 cv (T) T  Rln v1

Assuming averaged values for specific heats, one obtains:

T v kJ
s2 s1 cv,ave ln 2 Rln 2
T1 v1 kg.K
T P
s2 s1 cp,ave ln 2 Rln 2 kJ
T1 P1
kg.K
For isentropic processes of ideal gases, the following relationships can be found by
setting ds = 0,
T R v
ln  ln T1 Cv v1
2 2

ln 
T12 lnvv12 k

Cv T12 v12


T  or  isentropic process
Since R = cp – cv, k = cp / cv, and thus R / cv = k – 1.
In a similar manner, one finds:
(k1)/ k

TT2 PP12  isentropic process


 1 
k

 PP2 vv12 isentropic process

1 
These equations can be expressed in the following compact forms:
Tvk ‐1 = constant
TP(1 – k) / k = constant
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 Pvk = constant
The specific ratio k, varies with temperature, and in isentropic relations above an
average k value should be used.
Example 3: Isentropic process of ideal gas
A rigid, well‐insulated tank is filled initially with 5 kg of air at pressure 500 kPa and a
temperature 500 K. A leak develops, and air slowly escapes until the pressure of the
air remaining in the tank is 100 kPa. Using the ideal gas model, determine the
amount of mass remaining in the tank and its temperature.

Mass initially in the Slow leak tank that remains in

the tank (m2)

Insulated tank Mass initially in the

tank that escapes
(m1)

Assumptions:
1‐ As shown in the figure, the closed system is the mass initially in the tank that
remains in the tank.
2‐ There is no significant heat transfer between the system and its surroundings.
3‐ Irreversibilities within the tank can be ignored as the air slowly escapes.
Solutions:
Using the ideal gas equation of state, the mass initially in the tank that remains in the
tank at the end of process is:

P2V 

mm2  RTP 2  mP2 TT12 m1

V  2  1   P1 
1

RT1 
Since the volume of the tank V remains constant during the process. We need to find
the final temperature T2. For the closed system under consideration (m 1), there are
no irreversibilities, and no heat transfer. Accordingly, it is an isentropic process, and
thus the isentropic relationships can be used:

TT2  PP12 k1/ kT2 T1 PP12 k1/ k

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1

With a constant k = 1.4 for air, after substituting values, one finds:
T2 = 315.55 K Finally, inserting values into the
expression for system mass
m2 = (100/500) (500/315.55) (5 kg) = 1.58 kg

Reversible Steady‐Flow Work

The conservation of energy equation for a steady‐flow device undergoing an
internally reversible process can be expressed in differential form as
qrev wrev  dh  dke  dpe
But
qrev  Tds 

qrev  dh vdP Tds  dh vdP
Substituting into the relation above, after canceling dh, it yields,
‐δwrev = vdP + dke + dpe Integrating, we find
2

wrev vdP kepe (kJ / kg)

1

With negligible changes in potential and kinetic energies,

2

wrev vdP (kJ /kg)

1

From the above equation can be seen that, the larger the specific volume the larger
the reversible produced or consumed work by the steady ‐flow device. Thus, every
effort should be made to keep the specific volume of the flow as small as possible
during a compression process to minimize the input work.
When the fluid is incompressible, the specific volume remains constant during the
process, thus the above equation becomes:
δwrev = v(P1 – P2) – Δke – Δpe (kJ/kg)
For a steady‐state flow of a liquid through a device that involves no work interactions
(such as nozzle or a pipe section), the work term is zero,

v P 2  P 1  V 22 V12  gz2  z1  0
2
This is known as Bernoulli equation in fluid mechanics.

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