Chapter 7 - Entropy and The Second Law (Full)

A final point is that the molecular interpretation of heat
and work elucidates one aspect of the rise of civilization.

Fire preceded the harnessing of fuels to achieve work. The
heat of fire the tumbling of out of energy as the chaotic
motion of atoms is easily contrived for the tumbling is
unconstrained.
Work is energy tamed, and requires greater sophistication
to contrive.
Thus humanity stumbled easily on to fire but needed
millennia to arrive at the sophistication of the steam
engine, the internal combustion engine and the jet engine.
Peter Atkins (The Four Laws)
ENGI 2102 Thermo-Fluid Engineering I
Chapter 7 Entropy and the Second Law of

Thermodynamics
Michele Hastie
Process Engineering and Applied Science
Dalhousie University
Fall 2016
Added Slide 22 showing work done in a cycle on a Pv diagram.

Slide 23: Area inside the Pv diagram should be the work input
to the refrigeration cycle, not the work output.
Outline
7.1 Statements of the Second Law of Thermodynamics
7.1.1 Thermodynamic Spontaneity

7.1.2 Equivalence of the Kelvin and Clausius Statements
7.2 Reversible vs. Irreversible Processes

7.3 Heat Engines
7.4 The Carnot Cycle
7.5 The Thermodynamic Temperature Scale
7.6 Refrigerators and Heat Pumps
7.7 Definition of Entropy
7.7.1 Mathematical Expression of the Second Law of

Thermodynamics
7.7.2 The Molecular Interpretation of Entropy
Outline
7.8 Entropy Changes of Pure Substances
7.8.1 Property Diagrams (T-s and h-s)

7.8.2 The Tds Relations
7.8.3 Entropy Changes of Incompressible Substances
7.8.4 Entropy Changes of Ideal Gases
7.9 Reversible Steady-Flow Work
7.10 Entropy Balances
7.10.1 Entropy Balance for Closed Systems

7.10.2 Entropy Balance for Open Systems
7.11 Second Law Efficiencies
7.11.1 Isentropic Efficiency of Steady-Flow Devices

7.11.2 Second Law Efficiency
7.11.3 Lost Work
Introduction
The first three laws of thermodynamics are summarized

below:
Laws of
Thermodynamics
Concept
Property
Defined
Zeroth Law
Thermal equilibrium
Temperature
First Law
Energy conservation
Energy
Second Law
Direction of processes
Entropy
The first law only states that energy is conserved.

It does not give any information about:
(page 153)
The direction of energy transfer

The quality or usefulness of that energy
The second law answers these questions.
7.1 Statements of the Second Law of Thermodynamics (page 154)
Fig. 7.1: A cup of hot water will spontaneously transfer heat to

the ambient surroundings, but the reverse process will not occur
Fig. 7.2: Dissipation of thermal energy when a ball bounces on a

floor and the reverse (impossible) process
A heat engine is a
system that converts
thermal energy
(transferred as heat)
into mechanical energy
(transferred as
work).
Examples: Otto cycle,
Diesel cycle, Rankine
steam cycle (Chapter 8).
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
W = QH QL
QL
Cold Reservoir
Thermal reservoir:
A system that can absorb or supply large quantities of heat at

constant temperature.
Source or sink.
Fig. 7.3: Sketch of a system that violates the Kelvin form of the Second Law of Thermodynamics
The Second Law can be stated in a variety of different, but

equivalent ways.
Kelvin statement:
It is impossible for any cyclic process to convert the heat absorbed

from a hot source completely into work.
Clausius statement:
It is impossible for a
cyclic process to
transfer the heat
absorbed from a
body at a low
temperature to a
body at a higher
temperature
without producing
any other effects.
Fig. 7.4: Sketch of a system that violates the Clausius

form of the Second Law of Thermodynamics
7.1.1 Thermodynamic Spontaneity

Heat does not naturally (spontaneously) flow from a cold
object/system to a hot object/system.
In thermodynamics, spontaneity refers to the tendency
for a process to occur (no information about time/rate).
Some examples of spontaneous processes:
https://en.wikipedia.org/wiki/Combustion
http://www.theguardian.com/science/2011/apr/28/wellcome-science-writing-prize
https://physics.aps.org/story/v22/st5
http://phys.org/news/2013-03-unusual-recrystallization-behavior-one-dimensional-electron.html
Process A is a
contradiction of
the Kelvin form of
the Second Law.
The work from
Process A is used
to drive Process B.
The net result of this

system is that heat
(QL) is transferred
from the cold
reservoir to the hot
reservoir with no
change to the
surroundings.
This is a
contradiction of the
Clausius form of the
Second Law.
Fig. 7.5: Sketch of a system showing that failure of the Kelvin statement implies failure
of the Clausius statement
This system contradicts

the Clausius form of the
Second Law.
If it were possible, it
would be in contradiction
of the Kelvin form of the
Second Law.
Fig. 7.6: Sketch of a system showing that failure of the Clausius statement implies
failure of the Kelvin statement
A reversible process is a process that can be reversed

without causing any net change in the surroundings.
Example: Reversible expansion of a gas.
Pexternal
Pexternal
Pile of
sand
Forward
Process
Pexternal
Reverse
Process
P1
P1
P2
P1
(page 159)
P1 > P > P2
P2
P2
Example: Irreversible expansion of a gas.

Pexternal
Pexternal
Forward
Process
Pexternal
Weight
Reverse
Process
P1
P1
P2
P1
P2
P2
P2
In reality, reversible processes do not occur in nature

because there are always some irreversible losses.
Common causes of irreversibilities in real systems are:
(page 159)
frictional effects
unrestrained expansion
mixing of fluids
electric resistance
chemical reactions
heat transfer across a finite temperature difference
Reversible processes are:
relatively easy to analyze

provide efficiency targets for real processes
http://www.learnthermo.com/T1-tutorial/ch06/lesson-D/pg07.php
7.3 Heat Engines
Thermal reservoir A system that can

absorb or supply large quantities of heat
at constant temperature.
Examples of typical heat sources include:
(page 159)
industrial furnaces (combustion) or the

reactors in nuclear power stations
Examples of typical heat sinks include:
the atmosphere, ocean, lakes and rivers
http://www.industrialboiler.com/boilers/watertube-boilers.aspx
http://www.power-eng.com/articles/print/volume-117/issue-10/features/converting-once-through-cooling-to-closed-loop.html
http://peakoil.com/consumption/watering-down-the-energy-debate
7.3 Heat Engines
A typical heat engine will operate

using a working fluid (often steam)
in a cyclic manner to partially
convert heat into work.
The general operation can be
divided into the following steps:
1.
2.
3.
4.
(page 160)
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
W = QH QL
Heat is absorbed by the working

fluid from a high-temperature source
QL
(furnaces, nuclear reactors, etc.).
Cold Reservoir
Part of the absorbed heat is
converted into work (typically the
First Law Energy Balance:
working fluid is used to drive a
W QH QL
rotating shaft).
The remaining heat is rejected to a
low-temperature sink (atmosphere,
Thermal efficiency:
ocean, lakes, etc.)
net work output W
The cycle is repeated.
heat input
QH
(7.1)
(7.2)
7.3 Heat Engines
Combining these equations:
(page 161)
QH QL
QH
QL
QH
From Kelvins statement, we know that QL 0.

Therefore a thermal efficiency of 100% is impossible.
What is the theoretical upper efficiency level of a heat
engine?
(7.3)

1.
(page 162)
Reversible Isothermal
Expansion at TH (1-2):
The system undergoes

reversible isothermal
expansion while in contact
with the hot reservoir.
The expansion is reversible
because the temperature of
the system never drops more
than an infinitesimal amount
dT below the temperature of
the hot reservoir.
During the process, the system
absorbs heat, QH, from the hot
reservoir.
2. Reversible
Fig. 7.8: P- diagram for the Carnot cycle
Adiabatic Expansion (2-3):
The system now undergoes a reversible adiabatic expansion,

during which the temperature drops from TH to TL.

3. Reversible
Isothermal Compression at TL (3-4):
At point 3, the system is placed in contact with the cold

reservoir.
The system then undergoes isothermal compression, which is
reversible since the temperature of the system is never more
than an infinitesimal amount dT greater than the temperature
of the cold reservoir.
4. Reversible Adiabatic
(page 162)
Compression (4-1):
The system undergoes reversible adiabatic compression,

during which the temperature changes from TL to TH.
This returns the system to its original state, thereby completing
the cycle.
(page 162)
Work done by a process:

2
w12 P dv Area under curve on Pv diagram

1
P
1
QH
QH
2
TH
Wnet,out
TH
Wnet,out
4
3
TL
4
QL
Green area:
Work done by gas (Steps 1-3)
TH
Wnet,out
4
QL
QH
QL
TL
TL
v
Purple area:
Work done on gas (Steps 3-1)
Blue area:
Work done by cycle
(page 162)
The Carnot cycle can

also be operated in
reverse
Heat is absorbed from

the cold reservoir and
rejected to the hot
reservoir.
This process is
necessarily associated
with a net work input.
in
Fig. 7.9: P- diagram for the Carnot

refrigeration cycle
This is the Carnot refrigeration cycle.
(page 163)
Carnots Theorem:
No heat engine operating between two heat reservoirs can
have a higher thermal efficiency than that of a Carnot engine.
All real engines:
Operate on irreversible processes.

Have a lower thermal efficiency than a Carnot engine
operating between the same two temperatures.
(page 163)
To prove Carnots theorem,

consider the situation shown
in Fig. 7.10
In contradiction with Carnots
theorem we assume that a
heat engine, E, with a higher
efficiency than a Carnot
engine drives a Carnot
refrigerator, C.
From the definition of thermal
efficiency we can write that:
W
W
QH
QH
Fig. 7.10: A hypothetical heat engine, E,

drives a Carnot refrigerator, C. If the
efficiency of engine E is higher than
that of the Carnot refrigerator, the
Second Law is violated.
QH QH
QL QL
(page 163)
A net quantity of heat is transferred from the cold reservoir to

the hot reservoir.
This is in direct contradiction to Clausiuss statement of the
Second Law. Thus, Carnots theorem is proved.
Using the same logic it can be shown that all Carnot engines
operating between heat reservoirs at the same two
temperatures must operate with the same thermal efficiency.
Thus, a direct result of Carnots theorem is that:
The thermal efficiency of a Carnot engine only depends on the
temperature levels of the hot and cold reservoirs.
The efficiency of a Carnot engine is independent of the

working substance and only depends on the temperature of
the hot and cold reservoirs.
7.5 The Thermodynamic Temperature Scale (page 164)
Consider two Carnot

engines with engine A
operating between TH and
TL and engine B operating
between TL and an even
colder temperature TF.
Together, engines A and B
constitute a third Carnot
engine C operating
between TH and TF.
The thermal efficiency of
engine A depends only on
the temperature levels of
the two reservoirs:
QL
QH
f TL , TH
(7.4)
QH
QL
g TL , TH
1 f TL , TH
Engine B:
QL
QF
g TF , TL
Engine C:
QH
QF
g TF , TH
Dividing:
QH
QL
(7.6c)
Remember from Engine A:

QH
QL
g TF , TH
g TF , TL
1
g TL , TH
1 f TL , TH
TF must cancel on the right side:

QH
TH
QL
TL
(7.5)
(7.7)
Suppose that the

working fluid is an
ideal gas.
For the isothermal
processes, 1-2 and 3-4:
QH
V2
RTH ln
V1
V3
QL RTL ln
V4
(7.8a)
(7.8b)
QH
QL
TH lnV2 V1
TL lnV3 V4
(7.9)
For the adiabatic

processes, 2-3 and 4-1:
TH
TH
TL
TL
c v dT
V3
ln
R T
V2
(7.10a)
c v dT
V4
ln
R T
V1
(7.10b)
The integral on the left

side of these two
equations is the same:
V3
V4
ln ln
V2
V1
V3
V2
ln ln
V4
V1
(7.11)
From (7.9):
QH
QL
TH lnV2 V1
TL lnV3 V4
For any Carnot engine:
QH
QL
TH
TL
(7.12)
The thermal efficiency of any Carnot engine:
rev 1
QL
QH
TL
1
TH
(7.13)
rev 1
QL
QH
TL
1
TH
(7.13)
The thermal efficiency of a Carnot engine:
depends only on the temperatures of the reservoirs between

which it is operating.
defines the maximum efficiency that a real heat engine can
operate between two temperatures.
will only be 100% if the cold reservoir has a temperature of
absolute zero or if the hot reservoir has a temperature of
infinity ().
Consider two Carnot engines:
Engine A
Engine B
High temperature (TH) 400 K = 127C 800 K = 527C
Low temperature (TL)

Thermal efficiency
300 K = 27C
300 K = 27C
25%
62.5%
300 K is the typical temperature of cold sinks on Earth.

Heat engines operating with a higher-temperature heat
source can produce more work.
We usually say that thermal energy available at a higher
temperature has a higher quality.

Example 7.1: A power
plant produces 500
MW of electricity.
Steam is generated in
the boiler at 650 K and
discharged to a river at
300 K.
If the thermal
efficiency of the power
plant is 60% of the
maximum theoretical
efficiency, how much
heat is discharged to
the river?
Hot Reservoir
QH
A Cyclic
Process
(Heat Engine)
QL
Cold Reservoir
W = QH QL

Example 7.2: An engine operating
with 80% of the maximum
theoretical efficiency operates
between a hot reservoir at 900 K and
a cold reservoir at 300 K. The engine
is used to drive a Carnot refrigerator.
The Carnot refrigerator is to be used
to freeze 5 kg/h of water at 10C.
If the Carnot refrigerator rejects heat
to a hot reservoir at 300 K, what is
the quantity of heat drawn from the
900 K reservoir by the engine? The
latent heat of fusion of water is
334 kJ/kg.
In Chapter 8, we will look at the typical Vapour Power

cycle used by a steam power plant.
Hot Reservoir (i.e. Heat Source), TH
Hot Reservoir
QH
QH
Boiler, T<TH
A Cyclic
Process
(Heat Engine)
W = QH QL
Wnet ,in
Wnet,out
Pump
Turbine
Condenser, T>TL
QL
3
QL
Cold Reservoir
Cold Reservoir (i.e. Cooling Water or Air), TL
(page 171)
Work is required to transfer heat from a low temperature

reservoir and reject it to one at a higher-temperature.
Two devices are commonly used to accomplish this:
Air conditioners are essentially refrigerators.

Both typically operate using a vapour compression cycle.
Hot Reservoir (i.e. Heat Source), TH

QH
Boiler, T<TH
Wnet ,in
Wnet,out
Pump
Turbine
Condenser, T>TL
3
QL
Cold Reservoir (i.e. Cooling Water or Air), TL
(page 171)
(page 172)
The performance of refrigerators and heat pumps is

typically defined using a coefficient of performance
(COP):
Desired Output
COP
Required Input
Refrigerator
(7.14)
Heat Pump
COPR
QL
Wnet ,in
COPHP
QH
Wnet ,in
COPR
QL
QH QL
COPHP
QH
QH QL
COPR
1
QH / QL 1
COPHP
1
1 QL / QH
(page 172)
The maximum efficiency of refrigerators and/or heat

pumps will be when these are operated using a reversed
Carnot cycle.
Refrigerators and heat pumps operating on such a cycle
are called Carnot refrigerators or Carnot heat pumps.
QH
For Carnot engines:
TH
QL
Refrigerator
1
COPR
QH / QL 1
COPR,rev
TH TL 1
(7.12)
TL
Heat Pump
COPHP
1
1 QL / QH
COPHP,rev
1 TL / TH

Example 7.3: All of the work generated
by a Carnot engine is used to drive a
Carnot refrigerator. The refrigerator
extracts heat from a cold reservoir at 0C
at a rate of
35 kW. The energy source for the Carnot
engine is a hot reservoir at 250C. Both
the engine and the refrigerator reject
heat to the surroundings at 25C.
a) How much heat does the Carnot
engine absorb from the hot
reservoir?
b) If the actual COP of the refrigerator is
50% of the maximum value and the
actual efficiency of heat engine is 60%
of the maximum value, how much
heat is absorbed from the hot
reservoir?
(page 173)
For the Carnot cycle (reversible):

QH
QL
QH
TH
(page 175)
TH
TL
QL
TL
(7.12)
(7.22)
Adopting the sign convention for an engine cycle:
heat in (+)
heat out ()
QH QL
TH
TL
(7.23)
QH QL
0
TH TL
(7.24)
(page 175)
If the isothermal steps in the cycle are infinitesimal, only

differential quantities of heat can be transferred:
dQH dQL
0
TH
TL
(7.25)
Adding up all of the differential quantities of heat

transferred for the entire cycle:
dQrev
T 0
(7.26)
Recall from Chapter 3 and Chapter 5:

State function:
(page 175)
A property of a system that depends only on the current state

of a system
Does not depend on the way in which the system acquired that
state
Another characteristic of a property is that its value returns to

its original position upon completion of the cycle. An example
is internal energy:
dQ dW 0
(5.1)
We have therefore identified a new property referred to as

entropy:
dQrev
dQrev
dS
;
(7.27)
T 0
T
(page 175)
The change in entropy between state 1 and state 2:

2
dS
dQrev
T
dQrev
S
T
1
(7.28)
We can still use this equation to evaluate S for an

irreversible process. We do this by choosing an arbitrary
reversible process that has the same initial and final
conditions.
(page 176)
2
S
1
(7.28)
For the special case of an adiabatic, reversible process:
dQrev
T
dQrev = 0 and S = 0
Such a process is called isentropic (constant entropy)
Although such processes cannot exist in reality, they provide a
convenient basis for efficiency calculations.
Reversible isothermal processes are another special case.

The change in entropy can be calculated from:
2
dQrev
Qrev
1
S
dQrev
T
Tconstant 1
Tconstant
1
Qrev
S
Tconstant
(7.29)
(page 176)

Thermodynamics
Mathematical statement of the Second Law:
The total entropy change associated with any spontaneous
process is positive:
S 0
The total entropy change includes entropy changes of the

system and the surroundings.
(page 177)

Thermodynamics
Consider two heat reservoirs at TH and TL:
Hot reservoir, SH Cold reservoir, SL
Q
S H
TH
Q
S L
TL
Total, Stotal
S total
Q
Q
T TL
Q H
TH T L
T H TL
(page 177)

On the molecular scale, entropy can be regarded as a
measure of disorder
vacuum
This process is:
an adiabatic expansion that accomplishes no work:

irreversible total entropy change is > 0
(page 177)
increasing entropy
http://chemwiki.ucdavis.edu/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3A_Lower's_Chem1/
07%3A_Solids_and_Liquids/7.1%3A_Matter_Under_the_Microscope

7.7.2 The Molecular
Interpretation of Entropy
The entropy of a system can
be calculated from:
S k ln
(7.33)
where
k is the Boltzmann constant

(1.380610-23 J/K)
is the total number of
possible microstates of a
system
http://en.wikipedia.org/wiki/Ludwig_Boltzmann
(page 177)
7.8 Entropy Changes of Pure Substances (page 178)
Entropy is fixed once the state

of the system is fixed.
Review:
The state of a single-phase,
single-species (pure) system
can be fixed by specifying
two (2) intensive variables
Often (but not always) P and T

Can also specify v (or ), , h, or s
Example: To use the superheated steam table, you must know
two (2) property values.

Review:
The state of a two-phase,
single-species (pure) system
can be fixed by specifying
one (1) intensive variable
Often (but not always) P and T

Can also specify v (or ), , h, or s
Example: the saturated steam tables (two-phase region), only one

property must be fixed to find the others
This is enough to fix the state of each phase (liquid and vapour). We still
need a second intensive variable to fix the state of the mixture.

7.8.1 Property Diagrams (T-s and h-s)
P
2
P2
Area w12 P dv
1
qrev Tds
dv
Adiabatic
reversible
(7.35)
(7.36)
v1
v2
(7.27)
P1
dQrev
T
dq
ds rev
T
dS
1
h
h'
Adiabatic
irreversible
2
2'
s
s
Fig. 7.17: Adiabatic expansion in a turbine
Fig. 7.18: Reversible heat transfer

Example 7.4: Sketch a T-s diagram for the Carnot cycle. Identify the quantities of heat
absorbed and rejected and the net work output.
Solution:
Recall that the Carnot cycle is:
1. Reversible isothermal expansion at TH.
2. Isentropic expansion from TH to TL.
3. Reversible isothermal compression at TL.
4. Isentropic compression from TL to TH.
Note that S = 0

The differential form of the First Law for a closed system
undergoing a reversible process is:
dU dQrev PdV
Using the definition of entropy:

dQrev
dS
T
(7.37)
dQrev TdS
(7.38)
Therefore,
dU TdS PdV
(7.39)

Rearranging,
dU PdV
dS
T
T
or
du Pdv
ds
T
T
(7.40)
Substituting dH = dU + d(PV)
dS
dH PdV VdP PdV
T
T
T
T
dH VdP
dS
T
T
or
dh vdP
ds
T
T
(7.41)

7.8.3 Entropy Changes of Incompressible Substances
Solids and liquids are commonly approximated as
incompressible substances:
dv = 0 and c = cv = cp
We can therefore simplify Eq. 7.40:

0
ds
du Pdv c dT
T
T
T
(7.42)
Integrating and taking an average value for c,

2
c dT
dT
T2
s
cave
cave ln
T
T
T1
1
1
(7.44)

Example 7.5: Liquid water undergoes a process where the
pressure and temperature change from 22 MPa and 25C to
5 MPa and 50C.
a) Determine the change in entropy using the approximation
given by Eq. 7.44 (use an average specific heat of
4.18 kJ/[kg.K]).
b) Estimate the entropy change using the compressed liquid
water table.
c) If water at 20 MPa and 50C undergoes isentropic
expansion to 5 MPa, what is the change in temperature?
Solution:
a) Using Eq. 7.44:
s cave ln
T2
T1

Recall from Chapter 5, for an ideal gas:
RT
P
v
du cv dT
dh c p dT
Substituting into Eq. 7.40b gives:

du Pdv
ds
T
T
cv dT Rdv
ds
T
v
cv dT
Rdv
s
T
v
1
1

T2
v2
s cv , ave ln R ln
T1
v1
(7.47b)
We could also substitute dh and v = RT/P into Equation 7.41:

ds
dh vdP
T
T
ds
c p dT RdP
T
P
T2
P2
s c p , ave ln R ln
T1
P1
(7.49b)

Note that when s = 0, these equations reduce to the
isentropic relations we derived in Chapter 5:
cv , ave T2
v2
ln ln
R
T1
v1
cv , ave
T
v
ln 2 ln 2
c p , ave cv , ave T1
v1
1
T2
v2
ln ln
k 1 T1
v1
T2 v1

T1 v2
k 1
(7.50a)
T2
P2
c p , ave ln R ln
T1
P1
T2
P2
c p , ave ln c p , ave cv , ave ln
T1
P1
T
P
k ln 2 k 1 ln 2
T1
P1
T2 P2

T1 P1
k 1
k
(7.50b)

Example 7.6: A closed system containing 0.15 kg of air is initially
at 100 kPa and 303 K. The system undergoes a process that
results in a pressure of 360 kPa and a temperature of 500 K. The
system is in contact with a thermal reservoir at 500 K, from
which 8 kJ of heat is absorbed. Calculate:
a) The change in entropy of the air.
b) The change in entropy of the reservoir.
c) The entropy change in the universe.
Solution:
a) We have: T1 = 303 K; T2 = 500 K; P1 = 100 kPa; P2 = 360 kPa
For air: R = 0.2870 kJ kg1 K1 and cp,ave = 1.01 kJ kg1 K1
The change in entropy of the air is:
(page 186)
The maximum work output for work producing devices

is generated during reversible processes
The minimum work input for work consuming systems is
required during reversible processes
From Chapter 6:
= + +
Definition of entropy: = and
= + +

= + +
= + +
(page 186)
= + +
Integrating,
When ke and pe are negligible,

2
(7.55)
Not the be confused with the reversible work for a closed

system:
2
(page 186)
For the special case of an incompressible fluid, the work

can be calculated from:
=
For systems where no work is done, this equation reduces

to the Bernoulli equation (incompressible flow with no
work or heat transfer):
22 12
2 1 +
+ 2 1 = 0
2
(page 189)
For a given control volume, the general balance equation is:
Accumulation = Input Output + Generation Consumption

Mass:
Accumulation = Input Output (no generation/consumption)
Energy: Accumulation = Input Output (no generation/consumption)
Entropy: Accumulation = Input Output + Generation (no consumption)
(page 189)
Entropy is a nonconserved property. The entropy of the universe is

continuously increasing.
Accumulation = Input Output + Generation
Between two points in time:
On a continuous basis:
S system Sin Sout S gen
dSsystem
Sin Sout S gen
dt
(7.59)
(7.60)
(page 189)
Entropy Inputs and Outputs:

Entropy may be transferred into or out of a system due to
heat transfer or mass flow.
Entropy entering the system due to heat transfer at a
constant temperature can be calculated from:
Q
S heat
T
(7.61)
It is important to note that no entropy is transferred by

doing work.
First Law: Heat and work are equivalent forms of energy.

Second Law: Heat is the only mechanism for transferring
entropy.

Entropy Generation:
Reversible processes:
Irreversible processes:
Impossible process:
(page 189)
Sgen = 0
Sgen > 0
Sgen < 0
A process will always proceed in the direction such that

Sgen > 0.
(page 190)
7.10.1 Entropy Balance for Closed Systems
S system Sin Sout S gen
(7.59)
no mass crossing the system boundary

entropy can only be transferred by heat
These equations should

not have dots on each
term. Each term has
units of J/K or J/(kgK)
Q k
S system
S gen
Tk
Taking the universe as an adiabatic system and splitting it

into a system and its surroundings,
S gen Ssystem Ssurroundings
(7.66)
(7.67)
If the surroundings are at constant temperature,

Sgen
surroundings
Q
Ssystem
Tsurroundings
(7.68)
(page 190)
Example 7.8: An inventor claims to have created a non-flow device that

uses air as the working fluid. The device produces the following overall
effects:
The air changes states from 250C and 3 bar to 80C and 1 bar.
The system produces 62 kJ/kg of work.
A certain quantity of heat is transferred to a reservoir at 30C.
According to the Second Law of Thermodynamics, is such a process
feasible? Assume that air is an ideal gas with cp = 1.005 kJ kg-1 K-1.
Solution:
We are given:
P1 = 3 bar; P2 = 1 bar; T1 = 250C = 523.15 K; T2 = 80C = 353.15 K
Treating air as an ideal gas, the entropy change of the air is:
sair
T2
P2
cP ln R ln
T1
P1
(page 191)
7.10.2 Entropy Balance for Open Systems

dSsystem
Sin Sout S gen
dt
At steady-state,
0
dS system
dt
dSsystem
Q k
m i si m e se Sgen
dt
Tk
S gen
Q k
m e se m i si
Tk
(7.70)
(page 192)
For cycles, we compare the actual performance to the

Carnot cycle, which has the maximum possible efficiency.
For steady-flow (open systems), there are two

approaches for calculating efficiency related to the
Second Law:
1.
2.
Isentropic efficiency (adiabatic flow processes)

Second law efficiency (general case: adiabatic or nonadiabatic flow processes)
Another performance indicator is:

3.
Lost work
(page 192)
7.11.1 Isentropic Efficiency of Steady-Flow Devices

Many processes are essentially adiabatic.
Maximum work for these processes is the isentropic (adiabatic
reversible) isentropic work.
For a process that requires a work input, the isentropic

efficiency is:
isentropic work intput
isentropic net work input

(7.71a)
actual work input
Compressors and pumps
For a work-producing process, the isentropic efficiency is:

actual work output
isentropic net work output
(7.71b)
isentropic work output
Turbine
(page 193)

For processes that are non-adiabatic, the ideal work must
include S for any heat that is transferred
For a reversible process, Sgen = 0:
0
S gen
Q k
m e se m i si
0
Tk
(7.72)
Most devices operate in a uniform surroundings

temperature (T):
Q
m e se m i si T 0
Q T m e se m i si
(7.74)
(page 193)

Substituting this expression for Q into our energy balance
equation,
ue2
ui2
m e he gze m i hi gzi T m e se m i si Wideal
2
2
Wideal
where Wideal is the shaft work output from a completely

reversible process
Wideal is the minimum work for a work-consuming device or
Wideal is the maximum work for a work-producing device
ue2
ui2
T m e se m i si m e he gze m i hi gzi
2
2
(page 193)

If kinetic and potential energy contributions are negligible we
obtain:
e se m
i si m
e he m
i hi
Wideal T m
(7.77)
And, if there is a single stream flowing through the control

volume we can write:
Wideal m T s h
(7.78)
For a process that requires a work input, the thermodynamic

efficiency is:
ideal work input
thermodynamic net work input
(7.79a)
actual work input
For a work-producing process, the thermodynamic efficiency

is:
actual work output
net
work
output
(7.79b)
thermodynamic
g
ideal work output
(page 194)
7.11.3 Lost Work

The amount of work that is lost due to irreversibilities is
often called lost work.
Wlost Wideal Wact
From the actual energy balance:

Q W act m e he
W act
(7.80)
m h
Q m h m h
e e
i i
i i
From the ideal energy balance:

Wideal T
m s m s m h m h
e e
i i
e e
i i
(page 194)
7.11.3 Lost Work
Wlost T m e se m i si Q
Recall that:
S gen
Q k
m e se m i si
Tk
For a single surroundings temperature (T):
T S gen T m e se m i si Q
Therefore:
Example 7.9
Wlost T S gen
(7.83)
The more the universe approaches this limiting condition in

which the entropy is maximum, the more do the occasions
of further change diminish; and supposing this condition to
be at last completely attained, no further change could
evermore take place, and the universe would be in a state of
unchanging death.
Rudolf Clausius (1868)
as quoted by Jed Z. Buchwald, Robert Fox, The Oxford
Handbook of the History of Physics (2013)

Chapter 7 - Entropy and The Second Law (Full)

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A final point is that the molecular interpretation of heat

and work elucidates one aspect of the rise of civilization.

ENGI 2102 Thermo-Fluid Engineering I

Chapter 7 Entropy and the Second Law of

Added Slide 22 showing work done in a cycle on a Pv diagram.

7.1 Statements of the Second Law of Thermodynamics

7.1.1 Thermodynamic Spontaneity

7.2 Reversible vs. Irreversible Processes

7.7 Definition of Entropy

7.7.1 Mathematical Expression of the Second Law of

7.8 Entropy Changes of Pure Substances

7.8.1 Property Diagrams (T-s and h-s)

7.9 Reversible Steady-Flow Work

7.10 Entropy Balances

7.10.1 Entropy Balance for Closed Systems

7.11 Second Law Efficiencies

7.11.1 Isentropic Efficiency of Steady-Flow Devices

The first three laws of thermodynamics are summarized

The first law only states that energy is conserved.

The direction of energy transfer

The second law answers these questions.

7.1 Statements of the Second Law of Thermodynamics (page 154)

Fig. 7.1: A cup of hot water will spontaneously transfer heat to

7.1 Statements of the Second Law of Thermodynamics (page 155)

Fig. 7.2: Dissipation of thermal energy when a ball bounces on a

7.1 Statements of the Second Law of Thermodynamics (page 155)

A system that can absorb or supply large quantities of heat at

7.1 Statements of the Second Law of Thermodynamics (page 156)

The Second Law can be stated in a variety of different, but

It is impossible for any cyclic process to convert the heat absorbed

7.1 Statements of the Second Law of Thermodynamics (page 156)

Fig. 7.4: Sketch of a system that violates the Clausius

7.1 Statements of the Second Law of Thermodynamics (page 157)

7.1.1 Thermodynamic Spontaneity

7.1 Statements of the Second Law of Thermodynamics (page 162)

7.1.2 Equivalence of the Kelvin and Clausius Statements

The net result of this

7.1 Statements of the Second Law of Thermodynamics (page 162)

7.1.2 Equivalence of the Kelvin and Clausius Statements

This system contradicts

7.2 Reversible vs. Irreversible Processes

A reversible process is a process that can be reversed

Example: Irreversible expansion of a gas.

7.2 Reversible vs. Irreversible Processes

In reality, reversible processes do not occur in nature

Reversible processes are:

relatively easy to analyze

7.3 Heat Engines

Thermal reservoir A system that can

industrial furnaces (combustion) or the

Examples of typical heat sinks include:

the atmosphere, ocean, lakes and rivers

7.3 Heat Engines

A typical heat engine will operate

Heat is absorbed by the working

The cycle is repeated.

7.3 Heat Engines

Combining these equations:

From Kelvins statement, we know that QL 0.

7.4 The Carnot Cycle

The system undergoes

Fig. 7.8: P- diagram for the Carnot cycle

Adiabatic Expansion (2-3):