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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

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

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


floor and the reverse (impossible) process

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

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.

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

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.

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

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 Statements of the Second Law of Thermodynamics (page 157)

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

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

7.1.2 Equivalence of the Kelvin and Clausius Statements

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

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

7.1.2 Equivalence of the Kelvin and Clausius Statements

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

7.2 Reversible vs. Irreversible Processes

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

7.2 Reversible vs. Irreversible Processes

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)

7.4 The Carnot Cycle


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.

7.4 The Carnot Cycle


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.

7.4 The Carnot 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

7.4 The Carnot 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.

7.4 The Carnot 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.

7.4 The Carnot Cycle

(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

7.4 The Carnot Cycle

(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)

7.5 The Thermodynamic Temperature Scale (page 165)

QH
QL

g TL , TH
1 f TL , TH

Engine B:

QL
QF

g TF , TL

Engine C:

QH
QF

g TF , TH

7.5 The Thermodynamic Temperature Scale (page 165)

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)

7.5 The Thermodynamic Temperature Scale (page 166)

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)

7.5 The Thermodynamic Temperature Scale (page 167)

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)

7.5 The Thermodynamic Temperature Scale (page 167)

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)

7.5 The Thermodynamic Temperature Scale (page 167)

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 ().

7.5 The Thermodynamic Temperature Scale (page 167)

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.

7.5 The Thermodynamic Temperature Scale (page 168)


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

7.5 The Thermodynamic Temperature Scale (page 169)


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

7.6 Refrigerators and Heat Pumps

(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.

7.6 Refrigerators and Heat Pumps

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)

7.6 Refrigerators and Heat Pumps

(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

7.6 Refrigerators and Heat Pumps

(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

7.6 Refrigerators and Heat Pumps


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)

7.7 Definition of Entropy

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)

7.7 Definition of Entropy

(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)

7.7 Definition of Entropy

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

7.7 Definition of Entropy

(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.

7.7 Definition of Entropy

(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)

7.7 Definition of Entropy

(page 176)

7.7.1 Mathematical Expression of the Second Law of


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.

7.7 Definition of Entropy

(page 177)

7.7.1 Mathematical Expression of the Second Law of


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

7.7 Definition of Entropy

(page 177)

7.7.2 The Molecular Interpretation of Entropy


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

7.7 Definition of Entropy

(page 177)

7.7.2 The Molecular Interpretation of Entropy

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 Definition of Entropy


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.

7.8 Entropy Changes of Pure Substances (page 178)


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 Entropy Changes of Pure Substances (page 179)


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

7.8 Entropy Changes of Pure Substances (page 180)


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

7.8 Entropy Changes of Pure Substances (page 181)


7.8.2 The Tds Relations
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)

7.8 Entropy Changes of Pure Substances (page 181)


7.8.2 The Tds Relations
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 Entropy Changes of Pure Substances (page 182)


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)

7.8 Entropy Changes of Pure Substances (page 182)


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

7.8 Entropy Changes of Pure Substances (page 184)


7.8.4 Entropy Changes of Ideal Gases
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

7.8 Entropy Changes of Pure Substances (page 184)


7.8.4 Entropy Changes of Ideal Gases
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)

7.8 Entropy Changes of Pure Substances (page 184)


7.8.4 Entropy Changes of Ideal Gases
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)

7.8 Entropy Changes of Pure Substances (page 185)


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:

7.9 Reversible Steady-Flow Work

(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

= + +

= + +

= + +

7.9 Reversible Steady-Flow Work

(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

7.9 Reversible Steady-Flow Work

(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

7.10 Entropy Balances

(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)

7.10 Entropy Balances

(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)

7.10 Entropy Balances

(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.

7.10 Entropy Balances


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.

7.10 Entropy Balances

(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)

7.10 Entropy Balances

(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

7.10 Entropy Balances

(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)

7.11 Second Law Efficiencies

(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

7.11 Second Law Efficiencies

(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

7.11 Second Law Efficiencies

(page 193)

7.11.2 Second Law Efficiency


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)

7.11 Second Law Efficiencies

(page 193)

7.11.2 Second Law Efficiency


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

7.11 Second Law Efficiencies

(page 193)

7.11.2 Second Law Efficiency


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

7.11 Second Law Efficiencies

(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

7.11 Second Law Efficiencies

(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)