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CHAPTER
0402351
7 Thermodynamics
Entropy
Entropy
The 2nd law states that process occur in a certain
direction, not in any direction.
It leads to the definition of a new property called
entropy, which is a quantitative measure of disorder
for a system.
Entropy can also be explained as a measure of the
unavailability of heat to perform work in a cycle.
The 2nd law predicts that NOT all heat provided to a
cycle can be transformed into an equal amount of
work, some heat rejection must take place.
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Clausius Inequality
As a consequence of the statements of the second law of thermodynamics,
The following inequality holds true for all possible cycles:
Q
Clausius Inequality: T
0
Clausius Inequality holds true for: Heat Engine or Refrigerator
Clausius Inequality holds true for: Reversible or Irreversible cycle
Recall:
Kelvin–Planck Statement of the 2nd law
It is impossible for any device that operates on a cycle to receive heat from a
single reservoir and produce a net amount of work
Clausius Statement of the 2nd law
It is impossible to construct a device that operates in a cycle and produces no effect
other than the transfer of heat from a lower-temperature body to a higher-
temperature body.
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Clausius Inequality
Proof of Clausius Inequality for Heat Engine
Reversible heat engine cycle for demonstration of the inequality of Clausius.
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Clausius Inequality
Proof of Clausius Inequality for Heat Engine
For a Reversible Heat Engine operating between TH and T L :
Q Q H QL 0 (1)
For a reversible cycle: QH
TH
(2)
Q
L rev TL
Q QH QL
T
TH TL
0 (3)
As TH TL : Q 0 (4)
Q
T
0 (5)
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Clausius Inequality
Proof of Clausius Inequality for Heat Engine
For Irreversible Heat Engine operating between TH and T L:
Wirr Wrev (6)
QH QL W (7)
QH QL , irr QH QL , rev (8)
QL , irr QL , rev (9)
Q Q H QL , irr 0 (10)
Q QH QL , irr
T
TH
TL
0 (11)
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Clausius Inequality
Proof of Clausius Inequality for Heat Engine
As the cycle becomes more and more irreversible
(Keeping QH , TH , TL fixed):
Q 0
Q
T
becomes larger negative value
Q
In the limit when W 0 : Q 0 and T
0 (12)
For all Heat Engines [reversible or Q
irreversible from (5) and (12)]: T
0
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Clausius Inequality
Proof of Clausius Inequality for Refrigerator/Heat Pump
For all Refrigeration/Heat Pump Cycles,
[reversible or irreversible: we can show:
Q
T
0
(See Textbook)
Reversible refrigeration cycle for demonstration of the inequality of Clausius.
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Entropy – A Thermodynamic Property
The second law of thermodynamics leads to a property of a system called
entropy. A system (control mass) undergo two reversible processes:
From state 1 to state 2 along a path A, then from State 2 to State 1 a long path B.
From state 1 to state 2 along a path C, then from State 2 to State 1 a long path B
Two reversible cycles demonstrating that entropy is a property of a substance. 9
Entropy – A Thermodynamic Property
For Cycle 1-2-1 (Paths A then B):
Apply Clausius Inequality:
For Cycle 1-2-1 (Paths C then B):
Apply Clausius Inequality:
From the above 2 eqs.:
Q
The quantity is independent of the path and is a function
T
of the end states only;
It is a property. 10
Entropy – A Thermodynamic Property
This property is called entropy and is designated S.
Entropy may be defined as a property of a substance as:
(J/K) Extensive property
1 Q q
ds (J/kg. K) Intensive property
m T rev T rev
The change in the entropy of a system as it undergoes a change of
state may be found by integrating above Eqn.:
Q
2
S 2 S1 (1)
1
T rev
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Entropy – A Thermodynamic Property
Notes on Eqn. (1):
• To perform the integration in (1): Need the relation between T
and Q.
• Entropy is a property the change in the entropy of a substance
in going from one state to another is the same for all processes,
both reversible and irreversible, between these two states.
• Eqn. (1) enables us to find the change in entropy only along a
reversible path. However, once the change has been evaluated,
this value is the magnitude of the entropy change for all
processes between these two states.
• Eqn. (1) enables us to calculate changes of entropy, but it tells
us nothing about absolute values of entropy. [Need a Reference]
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Entropy – A Thermodynamic Property
Entropy Change in Reversible Processes
Carnot Cycle (4 reversible processes)
Process 1-2: Reversible isothermal heat addition at TH
T = TH = Constant
The area under line 1–2, area 1–2–b–a–1, represents
the heat transferred to the working fluid during the process (+ve).
(Entropy increases in process 1-2)
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Entropy – A Thermodynamic Property
Entropy Change in Reversible Processes
Carnot Cycle (4 reversible processes)
Process 2-3: Reversible adiabatic expansion from TH to TL
Q
3
S3 S 2 0
2
T rev
Since Q 0 (Adiabatic )
Reversible Adiabatic Process = Isentropic process
(No change in entropy): S 0
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Entropy – A Thermodynamic Property
Entropy Change in Reversible Processes
Carnot Cycle (4 reversible processes)
Process 3-4: Reversible isothermal heat Rejection at TL
T = TL = Constant
The area under line 3–4, area 3–4–a–b–3, represents
the heat removed from the working fluid during the process(-ve).
(Entropy decreases in process 3-4)
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Entropy – A Thermodynamic Property
Entropy Change in Reversible Processes
Carnot Cycle (4 reversible processes)
Process 4-1: Reversible adiabatic compression from TL to TH
Q
1
S1 S 4 0
4
T rev
Since Q 0 (Adiabatic )
Reversible Adiabatic Process = Isentropic process
(No change in entropy): S 0
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Entropy – A Thermodynamic Property
Entropy Change in Reversible Processes
For Carnot Cycle (4 reversible processes)
S cycle 0
The net work of the cycle is equal to the net
heat transfer, Area 1–2–3–4–1 represents the
net work of the cycle.
The efficiency of the cycle may also be
expressed in terms of areas:
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Entropy – A Thermodynamic Property
Notes:
Increasing TH while TL remains constant
increases the efficiency.
Decreasing TL while TH remains constant
increases the efficiency.
The efficiency approaches 100% as TL
approaches 0 K.
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Entropy – A Thermodynamic Property
internally reversible heat-transfer processes
(processes with no irreversibilities)
Processes 1-2:
Phase change from saturated
liquid to saturated vapor at constant
pressure
Temperature–entropy diagram
1 q 2 T ( s g s f ) T s fg 19
Entropy – A Thermodynamic Property
internally reversible heat-transfer processes
(processes with no irreversibilities)
Processes 2-3:
Heat addition to saturated vapor at
constant pressure:
Area 2-3-c-b-2
Temperature–entropy diagram
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Second law in terms of entropy
2nd Law of thermodynamics:
Q
T
0 (1)
(valid for reversible or irreversible cycles)
Entropy definition:
Q
2
S 2 S1 (2)
1
T rev
To re-write 2nd law in terms of entropy:
Combine (1) and (2):
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Second law in terms of entropy
Consider:
A Thermodynamic 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.
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Second law in terms of entropy
For process R: (Reversible)
From (1):
Q
2
S 2 S1
1
T R
Q
1
S1 S 2 (3)
2
T R
From (1):
Q Q
2 1
1 T I 2 T R 0 (4)
Use (3) in (4):
Q
2
1 T I S1 S 2 0 (5)
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Second law in terms of entropy
Q
2
S 2 S1
1
T I
OR:
Q
2
S 2 S1 (6)
1
T
If 1 → 2 is reversible, the equality holds;
If 1 → 2 is irreversible, the inequality holds.
Isolated System:
Q 0 (7)
S 2 S1 0 (Isolated System) (8)
For isolated systems, the entropy increases as time moves forward.
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Second law in terms of entropy
Example (1):
A 10 kg of liquid water at T1 = 0 oC freezes and its final state is solid
water at T2 = 0 oC. The temperature of the surroundings is -10 oC. The
heat of fusion for water is:
h fusion 333 .55 kJ / kg
Assume reversible processes.
(1) Calculate the entropy change of the water.
(2) Calculate the entropy change of the surroundings.
(3) Calculate the entropy change of the universe.
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Second law in terms of entropy
Solution Example 1
Upon freezing: water looses heat to the surroundings
and surroundings gain this heat.
(1) For water:
Q q m q12 10 (333.55)
2 2
S sys m 12.2112 kJ / K
1
T 1
T T (0 273.15)
(1) For the surroundings:
Q mq12 10 333 .55 3335 .5kJ
Q
2
S surr
3335.5
12.6753 kJ / K
1
T (10 273.15)
S universe S sys S surr 12 .2112 12 .6753 0.4641 kJ / K
Entropy of the universe increases
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Second law in terms of entropy
Example (2): (HW)
A 10 kg of solid water at T1 = 0 oC melts and its final state is liquid
water at T2 = 0 oC. The temperature of the surroundings is +10 oC. The
heat of fusion for water is:
h fusion 333 .55 kJ / kg
Assume reversible processes.
(1) Calculate the entropy change of the water.
(2) Calculate the entropy change of the surroundings.
(3) Calculate the entropy change of the universe.
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Some Thermodynamic Property Relations
1st Law:
Q dU W (1)
For a reversible process of a simple compressible substance:
Substitute in (1)
(2)
Also:
(3)
Equations (2) and (3) are called: Gibbs Equations
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Some Thermodynamic Property Relations
Gibbs Equations
Or: per unit mass, Gibbs Equations can be written as:
Notes
1. Gibbs equations are derived for Reversible processes,
hence they can be integrated for any reversible process.
2. Gibbs Equations Deal with Properties!
3. The properties of a substance depend only on the state,
the changes in the properties during a given change of
state are the same for an irreversible process as for a
reversible process.
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ENTROPY CHANGE OF A SOLID OR LIQUID
From Gibbs first Eqn:
For Solid or Liquids:
Tds du CdT
dv 0
dT
ds C
T
2
dT
s 2 s1 C
1
T
In general : C C (T )
T2
For C = constant: s 2 s1 C ln
T1
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ENTROPY CHANGE OF AN IDEAL GAS
From Gibbs first Eqn: From Gibbs second Eqn:
(1) (2)
du C v dT , Pv RT dh C p dT , Pv RT
Substitute in (1): Substitute in (2):
dT dv dT dP
ds C v R ds C p R
T v T P
2 2
dT v2 dT P2
s 2 s1 C v R ln s 2 s1 C p R ln
1
T v1 1
T P1
In general
C v C v (T )
C p C p (T )
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Isentropic Processes of Ideal Gases
Constant Specific Heats (Approximate Analysis)
Setting this eq. equal to zero because s1=s2, we get
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Isentropic Processes of Ideal Gases
Constant Specific Heats (Approximate Analysis)
The isentropic relations of ideal
gases are valid for the isentropic
processes of ideal gases only. 33
REVERSIBLE STEADY-FLOW WORK
dh vdp wrev dh dke dpe
Reversible work
relations for
steady-flow
When kinetic and and closed
potential energies systems.
are negligible
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ISENTROPIC EFFICIENCIES OF
STEADY-FLOW DEVICES
Turbine
A turbine is a rotary engine that extracts
energy from a fluid flow and converts it into
useful work.
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ISENTROPIC EFFICIENCIES OF STEADY-FLOW DEVICES
The isentropic process involves no
irreversibilities and serves as the ideal
process for adiabatic devices.
Isentropic Efficiency of Turbines
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Isentropic Efficiencies of Compressors and Pumps
For a pump
Compressors
are sometimes
intentionally
cooled to The h-s diagram of the actual and
minimize the isentropic processes of an adiabatic
work input. compressor.
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Isentropic Efficiency
of Nozzles
Then,
The h-s diagram
of the actual and
isentropic
processes of an
adiabatic nozzle.
A substance leaves
actual nozzles at a
higher temperature
(thus a lower velocity)
as a result of friction.
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Example
Steam enters an adiabatic turbine at 7 MPa, 6000C, and 80 m/s and leaves at 50 kPa, 1500C,
and 140 m/s. if the power output of the turbine is 6 MW, determine (a) the mass flow rate of the
steam flowing through the turbine and (b) the isentropic efficiency of the turbine.
P1=7MPa
Solution: T1= 6000C
V1= 80 m/s
(a)
P2=50kPa
T2= 1500C,
V2= 140 m/s
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Considering actual turbine h2 = h2a
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Check outlet state of the steam
S f at 50 kPa= 1.0912 kJ/kg.K S2s=S 1= 7.0910 kJ/kg.K
S g at 50 kPa= 7.5931 kJ/kg.K S f S1Sg
h f at 50 kPa= 340.54 kJ/kg.K s f at 50 kPa= 1.0912 kJ/kg.K
h fg at 50 kPa= 2304.7 kJ/kg.K s fg at 50 kPa= 6.5019 kJ/kg.K
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Isentropic Efficiencies of Compressors and Pumps
Compressor
Pump
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Example:
Refrigerent-134a at 240 kPa and 20C 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 are required
Example:
Argon is expanded in an isentropic turbine from
2MPa and 500C to 200 kPa. Determine outlet
temperature and the work produced by this turbine
per unit mass of argon.
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Summary
• Entropy
• The Increase of entropy principle
• Entropy change of pure substances
• Isentropic processes
• Property diagrams involving entropy
• What is entropy?
• The T ds relations
• The entropy change of ideal gases
• Reversible steady-flow work
• Minimizing the compressor work
• Isentropic efficiencies of steady-flow devices
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