11/9/20

BKF1253 Physical Chemistry

Chapter 3: Second Law of

Thermodynamic

Prof. Madya Dr. Syed Mohd Saufi

Dr SMS

Subtopics
• Introduction to Second Law of Thermodynamic
• Heat Engine
• Entropy
• Entropy Changes
• The Gibbs Energy

1
 11/9/20

Why We Need Second Laws?

https://www.youtube.com/watch?v=WTtxlaeC9PY

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Page 280
280
Dr SMS

3 cen84959_ch06.qxd 4/25/05 3:10 PM Page 280

280 || Thermodynamics
280 Thermodynamics

INTERACTIVE
6–1 ■
■ INTRODUCTION TO THE SECOND
INTERACTIVE
TUTORIAL In
280 | TUTORIAL
Thermodynamics In Chaps.
Chaps. 44 and and 5, 5, wewe applied
applied the the firstfirst law law of of thermodynam
thermodynam
SEE
SEE TUTORIAL
TUTORIAL CH. CH. 6,
6, SEC.
SEC. 11 ONON THETHE DVD.
vation
vation of
of energy principle, to
energy principle, to processes
processes involving involving closed closed a
INTERACTIVE
DVD.
6–1 As
■
As pointed INTRODUCTION
pointed out repeatedlyTO
out repeatedly in THE chapters,
in those
those SECONDenergy
chapters, energyLAWisis aa co c
TUTORIAL and
and no
In Chaps. no process
4 and 5, we is
process is known
known
applied the toto have
first have
law of taken
taken place
place in
thermodynamics, in violation
violation
or the co
SEE TUTORIAL CH. 6, SEC. 1 ON THE DVD. vation of energy principle,
thermodynamics.
thermodynamics. to processes
Therefore,
Therefore, itit isisinvolving
reasonable
reasonable closed toand
to open sys
conclude
conclude thth
As pointed
satisfy out
satisfy therepeatedly
the first
first law law in tothose
to occur.
occur. chapters,
However,
However, energy as isexplained
as a conserved
explained here,
here,prop
and no process is known to have taken place in violation of the first la
law
law alonealone does does not
not ensure
ensure that
that the the process
process will
willthat actually
actually tak
tak
thermodynamics. Therefore, it is reasonable to conclude a process
satisfyIt Ittheis common experience that aa cup
cup of hot coffee
coffee left
Second Law of Thermodynamic
isfirst
common
law to occur. experienceHowever, that as explained ofhere,
hot satisfying left
the
law eventually
eventually
alone does not cools
coolsensure off
offthat(Fig.
(Fig.the6–1).
6–1).
process This
This willprocess
actually satisfies
process satisfies
take place.thethe fifi
It dynamics
is common since
dynamics since
experience the
the amount
that a cupof
amount ofofenergy
energy
hot coffee lost
lostleftbybyin thethe coffe
coffe
a cooler
amount
eventually
amount cools gained
off (Fig.
gained by
by6–1).the
the Thissurrounding
process satisfies
surrounding air.
air. Now the firstlet
Now letlawususof conthe
con
dynamics
process—the
process—the since thehot amount
hot coffee
coffee of getting
energy lost
getting even
even byhotter
the coffee
hotter in aa iscooler
in equal ro
cooler roto

• The second law of thermodynamics states that process HOT

HOT
COFFEE
COFFEE Heat
Heat
amount
heatgained
heat
process—the
place.
place.
transfer
transfer
Yet,
Yet,
hot
by from
doing
doing
the surrounding
from
coffee
so
so
the
getting
would
would
room air.
the room
even
not
not
air. Now
air.
hotter
We
We all
violate
violate
in a
let know
all us consider
know
cooler
the
the first
first
room
that
that this
law
law
as
as
as
the re
this
a
pr
p
resu
long
long
occur in a certain direction, not in any direction. heat transfer from the room air. We all know that this process never
HOT
COFFEE Heat energy
place.energy
Yet, doing lost
lost by bywould
so the
the air airnotis equal
isviolate
equal the to
to the firstamount
the amount
law as long gained
gained as the by
byamouthe
the
energyAs Aslostanother
another
by the air familiar
is equalexample,
familiar example,
to the amount consider
considergainedthe by heating
the heating
the coffee. of
of aa ro ro
• A cup of hot coffee left in a cooler room eventually cools Asof
of electric
electric
ofanother
electric current
current
familiar
current
through
through
example,
through
aa resistor
consider
a resistor
resistor
the heating
(Fig. 6–2).
(Fig.
(Fig.of6–2).
Again,
6–2).
a room Again,
by the the
Again, th
pa
that
that the amount of
of electric energy supplied tothe
to thefirst
the law dic
resistance
off. FIGURE
FIGURE 6–1 6–1
FIGURE 6–1
that the
the amount
the
the amount
amountofof
amount ofelectric
energy
energy
electric
energy
energy
supplied to
transferred
transferred
the amount of energy transferred to the room air as heat. Now let us att
supplied
to the
to theresistance
the room
room air
resistance
airwires
as
as heat.be equ
heat. NN
to
to reverse
reverse this
this process.
process. ItIt will will comecome as as no no surprise
surprise that that trantran
• This process satisfies the first law of thermodynamics A
AA
in
cup
cup ofofhot
cupof
aa cooler
inin
hot
coolerroom.
acooler
coffee
hot coffee
room.
room.
does not
doesnot
coffee does not get
getget
hotter
hotterto reverse
hotter
to
to the the
to wires
this process. It will come as no surprise that transferring some
the wires
wires
does not does
does causenot
notancause
cause an
an equivalent
equivalent amount of amount
equivalent amount
electric energy of
of ele ele
since the amount of energy lost by the coffee is equal to generated
generated
generated
Finally,
Finally,Finally,
in thein
consider
in the
the wires.
wires.
consider
consider
wires.
aa paddle-wheel
a paddle-wheel paddle-wheel
mechanism mechanism
mechanism
that is operated that
that by is
is oper
oper
the f
the amount gained by the surrounding air. Heat
Heat
Heat a mass
aa mass
fluidfluid
mass(Fig. (Fig.
within
fluid
6–3). 6–3).
(Fig.
an insulated
within
within an
The
6–3).paddle
an insulated
The wheel
The
container.
insulated
paddlerotates
paddle wheel
As a result,
container.
container.
wheel as rotates
Asthe
As
the massas
rotates asfalls
potentialthe
aa result,
result,
theand
the
theenergy
mas
mas
poten
poten
s
o

• Let us consider the reverse process—the hot coffee mass decreases, and the internal energy of the fluid increases in accord
I=0
II == 00 mass
mass decreases,
decreases, and and the the internal
internal energy energy of of the
the fluid
fluid increa
increa
with the conservation of energy principle. However, the reverse pro
with
with thethethe conservation
conservation of energy
of heat
energy fromprinciple.
the fluid toHowever,
principle. the paddlethe
However, thw
getting even hotter in a cooler room as a result of heat
raising mass by transferring
FIGURE 6–2 doesraising
raising
not occur the
theinmass nature,by
mass by transferring
although doing soheat
transferring heat
would from
from not thethe
violate fluidthe to
fluid first
to
does not
does not occur
occur in in nature,
nature, although
although doing doing so so would
would not not vi vi
transfer from the room air. This process never takes place. FIGURE
FIGURE 6–2 heat to a wire will not
6–2
Transferring
generate electricity.
Transferring
Transferring heat to
heat to aa wire
wire will
will not
of thermodynamics.
of
It of thermodynamics.
thermodynamics.
is clear from these arguments that processes proceed in a certain d
not tion and not in the reverse direction (Fig. 6–4). The first law place
ItIt isis clear
clear from from these these arguments
arguments that that processes
processes proceed proceed
• It is clear from these arguments that processes proceed in generate electricity.
generate electricity. restriction
tion and
tion on the
and notdirection
not in the
in theofreverse
a process,
reverse but satisfying
direction
direction
ensure that the process can actually occur. This inadequacy of the first la
(Fig.the
(Fig. 6–4).
6–4).first law
Thedoe
The fifi
a certain direction and not in the reverse direction. restriction
restriction
identify
ensure
ensure
whetheron
that
that
on
the
the
the direction
the
a process
direction
process
process
can take of
can
can
of aa process,
place
actually
actually
general principle, the second law of thermodynamics. We show later in
process,
is remedied
occur.
occur.
butbysatisfying
but
This
This
satisfying
introducingthe
inadequacy
inadequacy
thean

• The first law places no restriction on the direction of a identify

identify
chapter
general
that the
general principle,
thermodynamics.
whether
reverse aaprocesses
whether
principle,
This violation
processdiscussed
process
the second
the second
can take
can
is easily law
law
takeabove placeviolate
place is remedied
is
of thermodynamics.
of
detected
remedied
thermodynamics.
the second
with the help of a We
by in
by
We
prop
in
la

process, but satisfying the first law does not ensure that
Heat called entropy, defined in Chap.processes7. A process cannot occur unless it sat
chapter
chapter that
that the reverse
the reverse processes discussed
discussed above
above violate
violate
boththermodynamics.
the first and the second
thermodynamics. Thislaws
This of thermodynamics
violation
violation is easily
is easily detected (Fig. 6–5).
detected with the
with the
the process can actually occur Heat
Heat There are numerous valid statements of the second law of thermody
called entropy,
called
both the
entropy, defined defined in in Chap.
Chap. 7.
ics. Two such statements are presented and discussed later in this chap
first and the second laws
7. AA process
of
process cannot
thermodynamics
cannot occur occu
(Fig
both the first and the second laws of thermodynamics (Fig.
A process will not occur unless it satisfies both the first
relation to some engineering devices that operate on cycles.
• FIGURE 6–3
Transferring heat to a paddle wheel
There
The There
use of the
ics. Two Twoofsuch
aresecond
are
such
numerous
numerous law ofvalid
statements
valid statementsisof
statements
thermodynamics
areThe presented
of the
notthe
andalso
second
second
limited
discussed
law
law
to identi
later
ics.
the direction statements
processes, however. are presented
second law and discussed
asserts that later en
and the second law of thermodynamics. will not cause it to rotate.
FIGURE 6–3
FIGURE 6–3 relationasto
has relation
quality
of energy and
towell
the
some
some engineering
as quantity.
engineering
transformations
The first
of of
devices
devices
energy
law isthat that operate
concerned
operate
from one form is
with onthe
on
to not
cycle
cycle
another
qua
Transferring heat heat toto aa paddle
paddle wheel The
The use
use of
of the
the second
second law
law of
wheel no regard to its quality. Preserving the quality of energy is a major con thermodynamics
thermodynamics is not lim
lim
Transferring
will not
will not cause
cause itit to
to rotate.
rotate. the direction
the direction of of processes,
processes, however. however. The The second second law law also also a
has quality
has quality as as well
well as as quantity.
quantity. The The first first law law is is concerned
concerned
of energy
of energy and and the the transformations
transformations of of energy
energy from from one one for for
no regard
no regard to to itsits quality.
quality. Preserving
Preserving the the quality
quality of of energy
energy ii

2
 11/9/20

Second Law of Thermodynamic

• Spontaneous change
– change that has a tendency to occur without work having to be done to bring
it about.
– has a natural tendency to occur.
– has nothing to do with speed
– precipitation reaction that occurs when solutions of sodium chloride and silver
nitrate are mixed is fast
– decomposition of benzene into carbon and hydrogen is spontaneous but very
slow
• Nonspontaneous change
– change that can be brought about only by doing work.
– has no natural tendency to occur.
– i.e.: gas can be compressed into a smaller volume by pushing in a piston, the
temperature of a cool object can be raised by forcing an electric current
through a heater attached to it, and water can be decomposed by the passage
of an electric current.

Dr SMS

Second Law of Thermodynamic

• There are numerous valid statements of the second law of
thermodynamics. Two famous statements are Kelvin-Plank Statement and
Clausius Statement.
• The use of the second law of thermodynamics is not limited to identifying
the direction of processes. The second law also asserts that energy has
quality as well as quantity.
• The second law of thermodynamics is also used in determining the
theoretical limits for the performance of commonly used engineering
systems, such as heat engines and refrigerators, as well as predicting the
degree of completion of chemical reactions.

Dr SMS

3
 INTERACTIVE
6–3 ■
HEAT ENGINES
TUTORIAL As pointed out earlier, work can easily b
SEE TUTORIAL CH. 6, SEC. 3 ON THE DVD. but converting other forms of energy to
cal work done by the shaft shown in Fig

Heat Engine
• Work can be converted to heat directly and
completely, but converting heat to work requires
the use of some special devices. These devices are
called heat engines.
• Heat engines differ considerably from one another,
but all can be characterized by the following:
– They receive heat from a high-temperature source
(solar energy, oil furnace, nuclear reactor, etc.).
– They convert part of this heat to work (usually in the
form of a rotating shaft).
– They reject the remaining waste heat to a low-
temperature sink (the atmosphere, rivers, etc.).
– They operate on a cycle.
• Heat engines and other cyclic devices usually
involve a fluid to and from which heat cen84959_ch06.qxd is
transferred while undergoing a cycle. This fluid is
called the working fluid.
284
7
Work No work
11/9/20
to the internal energy of the water. This
heat. We know from experience that any
fail. That is, transferring heat to the wat
From this and other observations, we co
Heat heat directly and completely, but conver
some special devices. These devices are
Heat engines differ considerably from
Heat
terized by the following (Fig. 6–9):
WATER WATER
1. They receive heat from a high-temp
nace, nuclear reactor, etc.).
FIGURE 6–8
Work can always be converted to heat
2. They convert part of this heat to wo
shaft).
directly and completely, but the 3. They reject the remaining waste h
reverse is not true. atmosphere, rivers, etc.).
4. They operate on a cycle.
Heat engines and other cyclic devices
High-temperature which heat is transferred while undergo
SOURCE working fluid.
The term heat engine is often used i
producing devices that do not operate
Qin that involve internal combustion such as
this category. These devices operate i
thermodynamic cycle since the workin
HEAT not undergo a complete cycle. Instead o
ENGINE
Wnet,out ture, the exhaust gases are purged and re
at the end of the cycle.
The work-producing device that bes
Qout
engine is the steam power plant, whic
That is, combustion takes place outside
released during this process is trans
Low-temperature
SINK
schematic of a basic steam power pla
3/31/05 3:51 PM Pagerather
284 simplified diagram, and the disc
is given in later chapters. The various
FIGURE 6–9
as follows:
Part of the heat received by a heat
engine is converted to work, while the Qin ! amount of heat supplied to ste
rest is rejected to a sink. source (furnace)
Qout ! amount of heat rejected fro
| Thermodynamics temperature sink (the atmosph
Wout ! amount of work delivered by
Wor
in ! amount of work required to co
Notice that the directions of the heat
by the subscripts in and out. Therefore
are always positive.
It can also be expressed as

Heat Engine Thermal Efficiency since Wnet,out ! Qin " Qout.

Cyclic devices of practical in
heat pumps operate between
• Thermal efficiency, 𝜂!" - the fraction of the heat temperature TH and a low-tem
input that is converted to net work output TL. To bring uniformity to the
• The thermal efficiencies of work-producing devices High-temperature reservoir heat pumps, we define these tw
are relatively low. at TH
QH ! magnitude of heat tra
• Ordinary spark-ignition automobile engines have a QH temperature medium a
thermal efficiency of about 25 %. QL ! magnitude of heat tra
• Thermal efficiency of diesel engine is 40% and as temperature medium a
Wnet,out
high as 60 % for large combined gas-steam power HE
Notice that both QL and QH
plants, positive quantities. The direc
inspection. Then the net work
𝑊#$!,&'! = 𝑄( − 𝑄) any heat engine (shown in Fig
QL

𝑊#$!,&'! W
𝜂!" =
𝑄( Low-temperature reservoir and
at TL
𝑄)
𝜂!" = 1 − FIGURE 6–13
𝑄(
Schematic of a heat engine. or

Dr SMS
Furnace

8 QH = 100 MJ The thermal efficiency of a he

QL and QH are defined as posi
Thermal efficiency is a mea
Wnet,out = 55 MJ
the heat that it receives to wo
HE converting heat to work, and e
efficiencies of these devices si
sumption and thus lower 4 fuel b
QL = 45 MJ The thermal efficiencies of
Ordinary spark-ignition autom
about 25 percent. That is, an
The atmosphere of the chemical energy of the
 Chapter 6 | 285
Can We Save Qout?
In a steam power plant, the condenser is the device where large quantities of
waste heat is rejected to rivers, lakes, or the atmosphere. Then one may ask,
can we not just take the condenser out of the plant and save all that waste
energy? The answer to this question is, unfortunately, a firm no for the sim-
ple reason that without a heat rejection process in a condenser, the cycle
cannot be completed. (Cyclic devices such as steam power plants cannot run 11/9/20
continuously unless the cycle is completed.) This is demonstrated next with
the help of a simple heat engine.
Consider the simple heat engine shown in Fig. 6–15 that is used to lift
weights. It consists of a piston–cylinder device with two sets of stops. The
working fluid is the gas contained within the cylinder. Initially, the gas tem-
perature is 30°C. The piston, which is loaded with the weights, is resting on
top of the lower stops. Now 100 kJ of heat is transferred to the gas in the
cylinder from a source at 100°C, causing it to expand and to raise the loaded
piston until the piston reaches the upper stops, as shown in the figure. At this
point, the load is removed, and the gas temperature is observed to be 90°C.
The work done on the load during this expansion process is equal to the

Kelvin-Plank Statement increase in its potential energy, say 15 kJ. Even under ideal conditions
(weightless piston, no friction, no heat losses, and quasi-equilibrium expan-
sion), the amount of heat supplied to the gas is greater than the work done
since part of the heat supplied is used to raise the temperature of the gas.
• A heat-engine cycle cannot be completed without rejecting some heat to a
Now let us try to answer this question: Is it possible to transfer the 85 kJ
of excess heat at 90°C back to the reservoir at 100°C for later use? If it is,
low-temperature sink.
then we will have a heat engine that can have a thermal efficiency of
100 percent under ideal conditions. The answer to this question is again
• Kelvin-Plank Statement:
no, for the very simple reason that heat is always transferred from a high-
temperature medium to a low-temperature one, and never the other way
– It is impossible for any
around. Therefore, device
we cannot coolthat operates
this gas from 90 to on30°Cabycycle to receive
transferring heat from a
heat to a reservoir at 100°C. Instead, we have to bring the system into con-
single reservoir and produce
tact with a low-temperature a netsayamount
reservoir, at 20°C, soofthat
work.
the gas can return
to its initial state by rejecting its 85 kJ of excess energy as heat to this reser-
– Or no heat engine can have a thermal efficiency of 100 percent
voir. This energy cannot be recycled, and it is properly called waste energy.
We conclude from this discussion that every heat engine must waste some
energy by transferring it to a low-temperature reservoir in order to complete
(15 kJ)

LOAD

LOAD

GAS
90°C
GAS GAS
30°C 30°C

FIGURE 6–15
Heat in Heat out
Reservoir at (100 kJ) (85 kJ) A heat-engine cycle cannot be
100°C Reservoir at completed without rejecting some heat
20°C
to a low-temperature sink.

Dr SMS

cen84959_ch06.qxd 3/31/05 3:51 PM Page 286

cen84959_ch06.qxd 3/31/05 3:51 PM Page 286

286 | Thermodynamics
the cycle, even under idealized conditions. The requirement that a heat
engine exchange heat with at least two reservoirs for continuous operation
forms the basis for the Kelvin–Planck expression of the second law of ther-
Exercise
286 | 1
Thermodynamics modynamics discussed later in this section.

the cycle, even under idealized conditions. The requirement that a heat
• Heat is transferred to heat engine
engine
EXAMPLE from
6–1exchange a furnace with at
heatProduction
Net Power aofrate
at least atwo ofreservoirs
Heat 80 MW.forIfcontinuous
Engine the operation
forms the basis for the Kelvin–Planck expression of the second law of ther-
rate of the waste heat rejection to a tonearby
Heat is transferred
modynamics
a river
a heat engine
discussed
from is 50
a furnaceMW, determine
at a rate of 80 MW. If
the rate of waste heat rejection later in this river
to a nearby section.
is 50 MW, determine the
the net
FURNACE
power output and
net
thermal
power
efficiency
output and the
for
thermal
this engine.
efficiency for this heat engine.

· SolutionEXAMPLE
The rates6–1
of heat
QH = 80 MW Nettransfer
PowertoProduction
and from a heat
of a engine are given.
Heat Engine
The net power output and the thermal efficiency are to be determined.
·
Heat Heat
Assumptions is transferred to a heat
losses through the engine
pipes from a furnace
and other at a rateareof 80 MW. If
components
Wnet,out the rate of waste heat rejection to a nearby river is 50 MW, determine the
negligible.
HEFURNACE Analysis net
A power
schematic of the
output andheat
theengine
thermalis given in Fig.
efficiency for6–16. The furnace
this heat engine.
serves as the high-temperature reservoir for this heat engine and the river as
· the low-temperature reservoir. The given quantities can be expressed as
Solution The rates of heat transfer to and from a heat engine are given.
QH = 80 MW
· The net power # output and the thermal # efficiency are to be determined.
QL = 50 MW QH ! 80 MW and QL ! 50 MW
·
Assumptions Heat losses through the pipes and other components are
Wnet,out The net negligible.
power output of this heat engine is
RIVER HE Analysis# A schematic
# # of the heat engine is given in Fig. 6–16. The furnace
Wnet,out ! QH " QL ! 180 " 50 2 MW ! 30 MW
serves as the high-temperature reservoir for this heat engine and the river as
Then thethe
thermal efficiency is reservoir.
low-temperature easily determined to quantities
The given be can be expressed as
FIGURE 6–16 #
· # #
Schematic for ExampleQ6–1.
L = 50 MW
Wnet,out QH30!MW 80 MW and QL ! 50 MW
hth ! # ! ! 0.375 1or 37.5% 2
QH 80 MW
The net power output of this heat engine is
Discussion Note that the
# heat engine
# converts
# 37.5 percent of the heat it
RIVER
receives to work. Wnet,out ! QH " QL ! 180 " 50 2 MW ! 30 MW
Then the thermal efficiency is easily determined to be
FIGURE 6–16 #
Schematic for Example 6–1. Wnet,out 30 MW
m· fuel hth ! # ! ! 0.375 1or 37.5% 2
EXAMPLE 6–2 Fuel Consumption
QH Rate80ofMWa Car
Combustion chamber
10 ·
A car engine with a Note
Discussion
percent.receives
Determine
power that
output
theofheat
65 hp has aconverts
engine thermal 37.5
efficiency of 24
percent of the heat it
the fuel consumption rate of this car if the fuel has a
to work.
QH
heating value of 19,000 Btu/lbm (that is, 19,000 Btu of energy is released
for each lbm of fuel burned).
·
Wnet,out = 65 hp
CAR Solution The power output and the efficiency of a car engine are given.
m· fuel
ENGINE The rateEXAMPLE
of fuel consumption of Consumption
the car is to be determined.
(idealized)
6–2 Fuel Rate of a Car
Assumptions The power output of the car is constant.
Combustion chamber
·
QL
Analysis A Acarschematic
engine ispercent.
engine with
poweredDetermine
a power
of the
the24
by converting
outputis ofgiven
car engine
fuel
65 hp
consumption
percent
has a6–17.
in Fig. thermal
rate ofenergy
of the chemical
The efficiency
this car
car of 24
if the fuel has a
released
5
·
QH during the combustion
heating process
value of 19,000to work. The amount
Btu/lbm (that is,of19,000
energy input required
Btu of energy is released
to produce a power
for each lbmoutput
of fuelofburned).
65 hp is determined from the definition of
Atmosphere · thermal efficiency to be
Wnet,out = 65 hp
CAR Solution
# WThe
net,out
power
65 hpoutput
2545 and
Btu>hthe efficiency of a car engine are given.
ENGINE TheQrate
H ! of fuel ! a
consumption of the bcar 689,270
! is to be Btu>h
determined.
 11/9/20

Refrigerators
• The transfer of heat from a low-temperature medium to a high-
temperature one requires special devices called refrigerators.
• Refrigerators are cyclic devices. The working fluid used in the refrigeration
cycle is called a refrigerant.
cen84959_ch06.qxd 3/31/05 3:51 PM Page 288

• The most frequently used refrigeration cycle is the vapor-compression

refrigeration cycle, which involves four main components: a compressor, a
288 |
condenser,
Thermodynamics
an expansion valve, and an evaporator
Surrounding medium
such as the kitchen air

QH

CONDENSER
800 kPa 800 kPa
30°C 60°C
Wnet,in
EXPANSION
VALVE COMPRESSOR

120 kPa 120 kPa

–25°C –20°C

EVAPORATOR
FIGURE 6–19
QL
Basic components of a refrigeration
system and typical operating Refrigerated space
conditions.
Dr SMS
The refrigerant enters the compressor as a vapor and is compressed to the
condenser pressure. It leaves the compressor at a relatively high temperature
11 and cools down and condenses as it flows through the coils of the condenser
by rejecting heat to the surrounding medium. It then enters a capillary tube
Warm environment where its pressure and temperature drop drastically due to the throttling effect.
at TH > TL
The low-temperature refrigerant then enters the evaporator, where it evapo-
rates by absorbing heat from the refrigerated space. The cycle is completed as
QH
Required the refrigerant leaves the evaporator and reenters the compressor.
input In a household refrigerator, the freezer compartment where heat is absorbed
Wnet,in by the refrigerant serves as the evaporator, and the coils usually behind the
R
refrigerator where heat is dissipated to the kitchen air serve as the condenser.
A refrigerator is shown schematically in Fig. 6–20. Here QL is the magni-
tude of the heat removed from the refrigerated space at temperature TL, QH
Desired

Refrigerators output
is the magnitude of the heat rejected to the warm environment at tempera-
cen84959_ch06.qxd 3/31/05 3:51QPM Page 288
L ture TH, and Wnet,in is the net work input to the refrigerator. As discussed
before, QL and QH represent magnitudes and thus are positive quantities.
Cold refrigerated
Coefficient of Performance
2 It leaves the compressor at a
space at TL

The efficiency of a refrigerator is expressed in terms of the coefficient of

FIGURE 6–20
performance (COP), denoted by COPR. Therelatively
objective of high temperature
a refrigerator is to and
288 |
3
TheThermodynamics
objective of a refrigerator is to remove heat (QL) from the refrigerated space. To accomplish this objective,
remove QItL from
thentheenters a capillary ittube
cooled space. requires a work input of W
cools down and condenses as it
. Then the COP of a refrigerator can be
net,in
flows through the coils of the
where its pressure expressed
and as Surrounding medium
such as the Desired outputcondenser
kitchen air Q by rejecting heat to
temperature drop drastically due COPR ! !
L
(6–7)
Required inputtheWsurrounding medium.
to the throttling effect
net,in
H Q .
This relation
. can also be expressed in rate form by replacing QL by QL and
Wnet,in by Wnet,in. CONDENSER
The conservation
800 kPa
of energy principle for a cyclic device requires that
800 kPa
30°C

EXPANSION
Wnet,in ! QH " QL 60°C
1kJ2
Wnet,in
1 (6–8)
The refrigerant enters
VALVE COMPRESSOR the compressor as a vapor
4 The low-temperature 120 kPa 120 kPa
and is compressed to the
condenser pressure.
refrigerant then enters the –25°C –20°C

evaporator, where it EVAPORATOR

FIGURE 6–19 evaporates by absorbing
QL
Basic components of a refrigeration
heat from the refrigerated
system and typical operating
space. Refrigerated space
conditions. In a household refrigerator, the
freezer compartment where heat is
5
The refrigerant enters
Thethe compressor
cycle as a vapor
is completed absorbed
and is compressed
as the to the by the refrigerant serves
condenser pressure. It leaves the compressor at a relatively high temperature
as the evaporator, and the coils
refrigerant
and cools down and condensesleaves the through
as it flows evaporator
the coils of the usually
condenser behind the refrigerator
by rejecting heatand reenters
to the the compressor.
surrounding medium. It then enters a capillary tube
Warm environment where
where its pressure and temperature drop drastically due to the throttling effect.heat is dissipated to the
The low-temperature refrigerant then enters the evaporator, wherekitchen air serve as the condenser.
at TH > TL
it evapo-
rates by absorbing heat from the refrigerated
Dr SMS space. The cycle is completed as

QH
Required the refrigerant leaves the evaporator and reenters the compressor.
input In a household refrigerator, the freezer compartment where heat is absorbed
12 Wnet,in by the refrigerant serves as the evaporator, and the coils usually behind the
refrigerator where heat is dissipated to the kitchen air serve as the condenser.
R
A refrigerator is shown schematically in Fig. 6–20. Here QL is the magni-
tude of the heat removed from the refrigerated space at temperature TL, QH
Desired
output
is the magnitude of the heat rejected to the warm environment at tempera-
QL ture TH, and Wnet,in is the net work input to the refrigerator. As discussed
before, QL and QH represent magnitudes and thus are positive quantities.
Cold refrigerated
space at TL
Coefficient of Performance 6
The efficiency of a refrigerator is expressed in terms of the coefficient of
FIGURE 6–20
performance (COP), denoted by COPR. The objective of a refrigerator is to
The objective of a refrigerator is to remove heat (QL) from the refrigerated space. To accomplish this objective,
remove QL from the cooled space. it requires a work input of Wnet,in. Then the COP of a refrigerator can be
expressed as
Desired output QL
 11/9/20

Refrigerator
cen84959_ch06.qxd 3/31/05 3:51 PM Page 288

288 | Thermodynamics

Surrounding medium
such as the kitchen air
cen84959_ch06.qxd 3/31/05 3:51 PM Page 288
QH

CONDENSER
800 kPa 800 kPa
30°C 60°C
Wnet,in
EXPANSION
VALVE COMPRESSOR

120 kPa 120 kPa

–25°C

EVAPORATOR
–20°C
288 | Thermodynamics
FIGURE 6–19
QL
Basic components of a refrigeration
system and typical operating
Surround
Refrigerated space
conditions. such as th

The refrigerant enters the compressor as a vapor and is compressed to the

condenser pressure. It leaves the compressor at a relatively high temperature
and cools down and condenses as it flows through the coils of the condenser
by rejecting heat to the surrounding medium. It then enters a capillary tube CONDE
Warm environment where its pressure and temperature drop drastically due to the throttling effect.
at TH > TL
The low-temperature refrigerant then enters the evaporator, where it evapo- 800 kPa
rates by absorbing heat from the refrigerated space. The cycle is completed as
Required the refrigerant leaves the evaporator and reenters the compressor.
30°C
QH
input In a household refrigerator, the freezer compartment where heat is absorbed
Wnet,in by the refrigerant serves as the evaporator, and the coils usually behind the Dr SMS EXPANSION
refrigerator where heat is dissipated to the kitchen air serve as the condenser.
R
A refrigerator is shown schematically in Fig. 6–20. Here QL is the magni-
VALVE
tude of the heat removed from the refrigerated space at temperature TL, QH

QL
Desired
output 13
is the magnitude of the heat rejected to the warm environment at tempera-
ture TH, and Wnet,in is the net work input to the refrigerator. As discussed
120 kPa
before, QL and QH represent magnitudes and thus are positive quantities. –25°C
Cold refrigerated
space at TL
Coefficient of Performance EVAPOR
FIGURE 6–20
The efficiency of a refrigerator is expressed in terms of the coefficient of FIGURE 6–19
performance (COP), denoted by COPR. The objective of a refrigerator is to
The objective of a refrigerator is to
remove QL from the cooled space.
remove heat (QL) from the refrigerated space. To accomplish this objective, Basic components of a refrigeration
it requires a work input of Wnet,in. Then the COP of a refrigerator can be
expressed as system and typical operating Refrigerate
Desired output QL conditions.
Refrigerators
COPR ! ! (6–7)
Required input Wnet,in
.
This relation
. can also be expressed in rate form by replacing QL by QL and
Wnet,in by Wnet,in.
The conservation of energy principle for a cyclic device requires that The refrigerant enters the compr
• The efficiency of a refrigerator is
Wnet,in ! QH " QL 1kJ2 (6–8) condenser pressure. It leaves the c
and cools down and condenses as
expressed in terms of the coefficient of
by rejecting heat to the surroundin
performance (COP), denoted by COPR Warm environment where its pressure and temperature
at TH > TL
• Notice that the value of COPR can be The low-temperature refrigerant th
greater than unity. That is, the amount rates by absorbing heat from the re
Required the refrigerant leaves the evaporato
of heat removed from the refrigerated QH
input In a household refrigerator, the fr
space can be greater than the amount by the refrigerant serves as the ev
Wnet,in
of work input. R
refrigerator where heat is dissipate
A refrigerator is shown schemat
tude of the heat removed from the
𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑂𝑢𝑡𝑝𝑢𝑡 𝑄) Desired
is the magnitude of the heat rejec
𝐶𝑂𝑃* = = output
𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝐼𝑛𝑝𝑢𝑡 𝑊#$!,+# QL ture TH, and Wnet,in is the net wo
before, QL and QH represent magn
Cold refrigerated
𝑄) 1
𝐶𝑂𝑃* = =
𝑄( − 𝑄) 𝑄(⁄𝑄) − 1
space at TL
Coefficient of Performan
The efficiency of a refrigerator is
FIGURE 6–20
performance (COP), denoted by C
The objective of a refrigerator is to remove heat (QL) from the refrige
remove QL from the cooled space. it requires a work input of Wnet,in
Dr SMS
expressed as
De
14 COPR !
Req
This relation
. can also be expresse
Wnet,in by Wnet,in.
The conservation of energy prin
7
Wnet,in ! Q
 11/9/20
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Chapter 6 | 291
Exercise 2
EXAMPLE 6–3 Heat Rejection by a Refrigerator Kitchen
The food compartment of a refrigerator is maintained at 4°C by removing heat from it
at a rate
The of 360
food kJ/min. If ofthe
compartment required power
a refrigerator, shown ininput
Fig. to theisrefrigerator
6–24, is 2 kW,
maintained at
4°C by ·
determine (a) removing heat from
the coefficient of itperformance
at a rate of 360 kJ/min.
of the If the required
refrigerator and (b)power
the rate of QH
input totothe
heat rejection therefrigerator
room that ishouses
2 kW,thedetermine (a) the coefficient of perfor-
refrigerator.
mance of the refrigerator and (b) the rate of heat rejection to the room that ·
Wnet,in = 2 kW
Answer:houses
a) 3; b)
the480 kJ/min
refrigerator.
R
Solution The power consumption of a refrigerator is given. The COP and
the rate of heat rejection are to be determined.
Assumptions Steady operating conditions exist. ·
QL = 360 kJ/min
Analysis (a) The coefficient of performance of the refrigerator is
#
QL 360 kJ>min 1 kW
COPR ! # ! a b !3 Food
Wnet,in 2 kW 60 kJ>min compartment
4°C
That is, 3 kJ of heat is removed from the refrigerated space for each kJ of
work supplied.
(b) The rate at which heat is rejected to the room that houses the refrigerator FIGURE 6–24
is determined from the conservation of energy relation for cyclic devices, Schematic for Example 6–3.
# # # 60 kJ>min
QH ! QL " Wnet,in ! 360 kJ>min " 12 kW2 a b ! 480 kJ/min
1 kW
Discussion Notice that both the energy
Dr SMSremoved from the refrigerated space

as heat and the energy supplied to the refrigerator as electrical work eventu-
ally show up in the room air and become part of the internal energy of the
15 air. This demonstrates that energy can change from one form to another, can
move from one place to another, but is never destroyed during a process.

EXAMPLE 6–4 Heating a House by a Heat Pump

HeatA heat
Pumps
cen84959_ch06.qxd 3/31/05 5:53 PM Page 289
pump is used to meet the heating requirements of a house and main-
House 80,000 kJ/h
20°C
tain it at 20°C. On a day when the outdoor air temperature drops to #2°C, Heat loss
• Thetheobjective of a heat
house is estimated pump
to lose heat is
at to maintain
a rate of 80,000 a kJ/h. If the heat
heated spacethese
pump under at conditions
a high has temperature.
a COP of 2.5, This is
determine (a) the power
consumed by the heat pump and (b) the rate at which heat is absorbed from ·
accomplished by absorbing heat from a low- QH
the cold outdoor air.
temperature source, such as well water or cold Chapter 6 | 289
·
Wnet,in = ?
outside
Then the COP relation air in
Solution
becomes winter,
The COP ofand supplying
a heat pump isthis heat
given. Thetopower
the consumption and
Warm heated space
the rate of heat absorption are to be determined. COP = 2.5 HP
high-temperatureQL medium1 such as a house at TH > TL
Assumptions
COP R !
Steady
! operating conditions exist. (6–9)
Analysis Q H(a) Q H>Qconsumed
Q L power
# The L # 1 by this heat pump, shown in Fig. 6–25, Desired
output
Notice that the value of COPR can be greater than of
is determined from the definition the That
unity. coefficient
is, theof performance to beQH Q· L = ?
amount of heat removed from the refrigerated space can be greater than the
# Wnet,in
amount of work input. This is in# contrast Q toH the thermal
80,000 efficiency,
kJ>h which
Wnet,in
can never be greater than 1. In fact, one ! reason for
! expressing the 32,000 kJ/h 1or 8.9 kW2HP
! efficiency Outdoor air at – 2°C
COPHP 2.5
of a refrigerator by another term—the coefficient of performance—is the Required
(b) of
desire to avoid the oddity The houseefficiencies
having is losing heat at athan
greater rateunity.
of 80,000 kJ/h. If the house is to be
FIGURE
input 6–25
maintained at a constant temperature of 20°C, the heat pump must deliver
QL
Schematic for Example 6–4.
Heat Pumps
Another device that transfers heat from a low-temperature medium to a Cold environment
at TL
high-temperature one is the heat pump, shown schematically in Fig. 6–21.
Refrigerators and heat pumps operate on the same cycle but differ in their
FIGURE 6–21
objectives. The objective of a refrigerator is to maintain Drthe
SMS
refrigerated
space at a low temperature by removing heat from it. Discharging this heat The objective of a heat pump is to
to a higher-temperature medium is merely a necessary part of the operation, supply heat QH into the warmer space.
16
not the purpose. The objective of a heat pump, however, is to maintain a
heated space at a high temperature. This is accomplished by absorbing heat
from a low-temperature source, such as well water or cold outside air in
winter, and supplying this heat to the high-temperature medium such as a
house (Fig. 6–22). Warm
An ordinary refrigerator that is placed in the window of a house with its indoors
door open to the cold outside air in winter will function as a heat pump at 20°C
8
since it will try to cool the outside by absorbing heat from it and rejecting
this heat into the house through the coils behind it (Fig. 6–23).
The measure of performance of a heat pump is also expressed in terms of QH = 7 kJ
the coefficient of performance COPHP, defined as
 11/9/20

cen84959_ch06.qxd 3/31/05 5:53 PM Page 289

Heat Pumps: Coefficient of Performance

Chapter 6 | 289
Then the COP relation becomes
Warm heated space
Q L 𝐷𝑒𝑠𝑖𝑟𝑒𝑑 𝑂𝑢𝑡𝑝𝑢𝑡
1 𝑄( at TH > TL
COP𝐶𝑂𝑃
R ! (, = ! = (6–9)
QH # Q 𝑅𝑒𝑞𝑢𝑖𝑟𝑒𝑑
L Q H>Q 𝐼𝑛𝑝𝑢𝑡
L # 1 𝑊#$!,+# Desired
QH output
Notice that the value of COPR can be greater than unity. That is, the
amount of heat removed from the = 𝑄( space can1 be greater than the
refrigerated
𝐶𝑂𝑃(, =
𝑄( − 𝑄
amount of work input. This is in contrast − 𝑄) ⁄efficiency,
to) the 1thermal 𝑄( which Wnet,in

can never be greater than 1. In fact, one reason for expressing the efficiency HP
of a refrigerator by another
𝐶𝑂𝑃term—the
(, = 𝐶𝑂𝑃 coefficient
*+1 of performance—is the Required
desire to avoid the oddity of having efficiencies greater than unity. input
QL
Heat Pumps
Another device that transfers heat from a low-temperature medium to a Cold environment
at TL
high-temperature one is the heat pump, shown schematically in Fig. 6–21.
Refrigerators and heat pumps operate on the same cycle but differ in their
FIGURE 6–21
objectives. The objective of a refrigerator is to maintain the refrigerated
space at a low temperature by removing heat from it. Discharging this heat The objective of a heat pump is to
to a higher-temperature medium is merely a necessary part of the operation, supply heat QH into the warmer space.
not the purpose. The objective of a heat pump, however, is to maintain a
Dr SMS
heated space at a high temperature. This is accomplished by absorbing heat
from a low-temperature source, such as well water or cold outside air in
17
winter, and supplying this heat to the high-temperature medium such as a
house (Fig. 6–22). Warm
An ordinary refrigerator that is placed in the window of a house with its indoors
door open to the cold outside air in winter will function as a heat pump at 20°C
since it will try to cool the outside by absorbing heat from it and rejecting
this heat into the house through the coils behind it (Fig. 6–23).
The measure of performance of a heat pump is also expressed in terms of QH = 7 kJ
the coefficient of performance COPHP, defined as
Exercise
Desired output QH
Wnet,in = 2 kJ
COPHP ! ! (6–10) COP = 3.5 HP
Required input Wnet,in
A heat pump is used to meet the heating requirements of a house and
which can also be expressed as
maintain it at 20°C. On a day when the outdoor air temperature drops to -2°C,
the house is Qestimated
COPHP !
H
!
to
1 lose heat at a rate of 80,000 kJ/h. If the
(6–11)
QL heat
= 5 kJ pump
Q H # Q L 1 # Q L >Q
under these conditions has a COP of 2.5, determine (a) the power consumed
H
Cold outdoors
by 6–7
A comparison of Eqs. theand
heat
6–10 pump and
reveals that(b) the rate at which heat is absorbed from the cold
at 4°C
outdoorCOPair. ! COP " 1 (6–12)
HP R
FIGURE 6–22
Answer: a) 32 000 kJ/h; b) 48 000 kJ/h
for fixed values of QL and QH. This relation implies that the coefficient of The work supplied to a heat pump is
performance of a heat pump is always greater than unity since COPR is a used to extract energy from the cold
positive quantity. That is, a heat pump will function, at worst, as a resistance outdoors and carry it into the warm
heater, supplying as much energy to the house as it consumes. In reality, indoors.
however, part of QH is lost to the outside air through piping and other
devices, and COPHP may drop below unity when the outside air temperature
is too low. When this happens, the system usually switches to a resistance
heating mode. Most heat pumps in operation today have a seasonally aver-
aged COP of 2 to 3.

Dr SMS

18

9
 11/9/20

Clausius Statement
• 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.
• Or: Heat cannot flow spontaneously from a cooler to a hotter object if
nothing else happens.
• Or: It simply states that a refrigerator cannot operate unless its
compressor is driven by an external power source, such as an electric
motor

Dr SMS

19

Carnot Cycle
• A reversible process - a process that can be reversed without leaving any trace
on the surroundings. That is, both the system and the surroundings are
returned to their initial states at the end of the reverse process.
• Reversible processes actually do not occur in nature. They are merely
idealizations of actual processes.
• Processes that are not reversible are called irreversible processes.
• Engineers are interested in reversible processes because work-producing
devices such as car engines and gas or steam turbines deliver the most work,
and work-consuming devices such as compressors, fans, and pumps consume
the least work when reversible processes are used instead of irreversible ones
• Reversible processes can be viewed as theoretical limits for the corresponding
irreversible ones
• The factors that cause a process to be irreversible are called irreversibilities.
They include friction, unrestrained expansion, mixing of two fluids, heat
transfer across a finite temperature difference, electric resistance, inelastic
deformation of solids, and chemical reactions.

Dr SMS

20

10
 11/9/20

Carnot Cycle
https://www.youtube.com/watch?v=WkQQebBH7kQ

Dr SMS

21

Carnot Cycle
cen84959_ch06.qxd 3/31/05 3:51 PM Page 300
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cen84959_ch06.qxd 3/31/05 3:51
3:51 PM
PM Page
Page 300
300

• Carnot cycle is the most efficient cycle that operate on reversible process on each
cycle.
300The| Carnot cycle consists of two isothermal and two adiabatic processes:
Thermodynamics
300 | Thermodynamics that is, by using reversible processes. Therefore, it is no surprise that the
300
300 || Thermodynamics
(1) (2)
Thermodynamics
Energy (1) (2) mostis,
that
that is,
efficient
by using
by usingReversible
using
cycles reversible
reversible isothermal
are reversible processes.
processes.
cycles, expansion:
that is, cycles
Therefore,
Therefore,
it is no
itit is is nono
thatsurprise consist that
surprise
entirely
that
the
the
= const.

(1) (2) that is, by Therefore, surprise

source (1) (2) of reversible
most efficient cycles reversible
processes. are reversible processes. cycles, that is, cycles that consistthat the
entirely
Energy
most efficient -Tprocesses.
H constant
cycles are reversible
reversible cycles, that is, cycles
cycles thatthe consist entirely
=THconst.

at TH
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Energy most efficient
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practice because that consist entirely
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of
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eliminated. because However, Q amount
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at Reversible
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cycles
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with cannot
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be
process achieved
onachieved
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the irreversibili-
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H
from aeach heat source at be abecycles
high temperature , expands
TTHHT

QH ties associated with each process cannot eliminated. However, Hwhich

reversible
QH
Q
(a) Process 1-2 ties
and associated
cycles provide with
refrigerators upper that limits
work process
on
on the cannot
performance
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and
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refrigerators upper
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2-3
two
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be consistsin Fig. of
removed oftoaabring
6–37. gas
gas The contained
contained
the insulation
cylinder in an
in an
of
into adiabatic
adiabatic
the cylin-
contact
(4) (3) piston–cylinder device, as shown in Fig.Fig. 6–37. 6–37. Thethe insulation ofintothecontact
cylin-
Energy piston–cylinder
der
withhead reservoirs suchdevice,
is Reversible tothatprovide itas may shown
heat in
be transfer.
isothermal removed Theto bring The
four
compression: insulation
reversiblecylinder of
processesthe cylin-
that
= const.

(4)
(4) (3)
(3)
sink
Energy der
der
with
make head
head up is is such
reservoirs
the such
Carnot that
tothat provideitit may
cycle may are be
be
heat removed
as removed
transfer.
follows: The to bring
to bring
four the the cylinderprocesses
cylinder
reversible into contact
into contactthat
=TLconst.

up the-the tosurroundings do work to reversible

the gas processes at TL, gasthat is
at TL
sink
Energy with reservoirs provide heatastransfer.
transfer. The four four reversible processes that
Lconst.

Energy with
makereservoirs Carnotto provide
cycle are heat follows: The
TTLL=T=const.

at
sink
sinkT Reversible Isothermal
thecompressed cycleExpansion areand (process 1-2, TH ! constant). Initially
QL
at TTLL
at
make
make
Reversible
up the
up
(state 1), the
Carnot cycle
Carnot
Isothermal
temperature
are
Expansion
as follows:
as
of the gas
causes
follows:
(process
is TH and
a1-2,
loss the
of
THcylinder
heat,
! constant).
Q Initially
head Lis
. in close
QLL
QL (c) Process 3-4 Reversible
Reversible
(state
contact1),with Isothermal
Isothermal
the source Expansion
atemperature Expansion
of the gas
at temperature (process
isTHT.HThe
(process 1-2,
and
1-2, the
gas TTHHis cylinder
! constant).
!allowed
constant). head Initially
is in close
Initially
to expand
QL (c) Process 3-4 (state
contact
(state
slowly, 1),doing
1), the temperature
with
the temperature
awork
source onatthe ofsurroundings.
the gas
temperature
of the gas is isTTTHH. The andthe
and thegas
gas
the cylinder
is allowed
cylinder head
head tothe is in
expand
is in close
close
(c) Process
Process 3-4
3-4 H As expands,
(c) contact
slowly,
temperature
contact with
doingaof
with a work
source
the gas
source onatatthetemperature
tends surroundings.
temperatureto decrease. TTHH.. TheThe
As
Butthe gas
as gas
gas is allowed
soon
is allowed
expands,
as theto to expand
the
temperature
expand
(1) (4) slowly,
temperature
drops by
slowly, doing work
ofworkthe gas
an infinitesimal
doing on the
on the
tends surroundings.
amount to decrease.
surroundings. dT, some As
AsBut the
heat
theasgasgas
soon expands,
as the temperature
is transferred
expands, the
thefrom the
(1) (4) temperature
drops
reservoir
temperature by Reversible
an
into ofthe
of thegas,
infinitesimal
the gas raising
gas adiabatic
tends
tends amounttothe
to dT,compression:
decrease.
gas
decrease. some Butheat
temperature
But as soon
as soon
isto as.the
transferred
Tas the temperature
H Thus,
temperature
from
the gas the
Insulation

TH(1)
(1) (4)
(4) drops
reservoir
temperature
drops by -the
by an
into
an isthe system
infinitesimal
kept
infinitesimalgas, constant is thermally
amount
raising
amount atthe dT,
gas
THdT,. Since some insulated.
temperature
some the heat
heat is to
temperature
is TH. Surroundings
transferred
transferred Thus, from
difference the gas
from the
the
Insulation

TH
reservoir
temperature
between
reservoir continue into
the is
gasthe
kept
into the gas, to gas,
and theraising
constant reservoirattheT gas
. temperature
Since
never the
exceeds temperature
a to T .
differentialThus, differencethe
amount gas
TLTTH raisingdoatthe work to the
gas temperature gas, to which
TH. Thus,causes
H the gas dT, the
Insulation

H
Insulation

TL
H temperature
between the is
this is a reversible
temperature is
gas kept
kept and constant
heat thetransfer
constant reservoir H..never
at TTprocess. Sinceexceeds
Since the
It
the temperature
continues a differential
temperature difference
untildifference amount dT,
the piston
H
TTL(d)
L
Process 4-1
between
this
reaches is a temperature
the
positiongas
reversible and
2. heat
Thethe to
reservoir
transfer
amount rise
between the gas and the reservoir never exceeds a differential amount never
process.
of back
total It
heat to
exceeds
continues T a
transferred
H .differential
until to the
the amount
piston
gas during dT,
dT,
this
reaches
this is
this is aa reversible
processreversible
positionis QDr H
heat
2..heat transfer
Thetransfer
SMS amountprocess. process.
of total heat It continues
It continues
transferred untiltothe
until the piston
thepiston
gas during
(d) Process 4-1
FIGURE 6–37 (d)
(d) Process
Process 4-1
4-1
reaches
this process
reaches
Reversible
position
position is Q2.
Adiabatic
2. The
H. The
amount of
amount
Expansion
of(process
total heat
total heat2-3,
transferred
transferred
temperature
to the
to the
drops
gasfrom
gas during
during TH
FIGURE 6–37 this
this
Reversible process
to Tprocess
). At is Q
is
Adiabatic
state Q2,H..theExpansion
reservoir (process
that was in 2-3,
contact temperaturewith the drops
cylinder from headTH
Execution of the Carnot cycle in a L H
FIGURE
FIGURE 6–37
6–37 Reversible
to Adiabatic
TL). AtAdiabaticstate
and2,replaced Expansion
theExpansion
reservoir (process
that wassoin2-3, 2-3,
contacttemperature with thebecomes drops
cylinder from TTHH
head
22 Execution of the Carnot cycle in a
closed system. is removed
Reversible by insulation (process that the system
temperature drops from
Execution
closed of
system.the Carnot
Execution of the Carnot cycle
cycle in
in aa to
is TL).). At
Tremoved
adiabatic.
to At state
state
Theand2, 2,replaced
gas the
the reservoir
continues
reservoir that
by insulation
tothat
expand wasso
was inthat
contact
slowly,
in contact thedoing withwork
system
with thebecomes
the cylinder
on the head
cylinder head
L
closed system.
closed system. is removedThe
adiabatic.
surroundings
is removed anduntil
and replaced
gas
replaced continues by insulation
its temperature
by insulation
to expand drops soslowly,
so that the
from
that theTdoing system
to Twork
H system
becomes
L (state
becomes on3). theThe
adiabatic.
surroundings
piston is assumed
adiabatic. Theuntil
The gas continues
gas continues
itsbe
to temperature to expand
frictionless
to expand drops slowly,
andslowly, from
the process doing
Tdoing
H to T
towork
be
work
L (state on
quasi-
on the
3).
the The
surroundings
piston
equilibrium,
surroundings is assumed sountil
until theto its
its betemperature
process frictionless
temperature is reversible drops
and the
drops from
as
from TTHHasto
process
well toadiabatic.
TL be
Tto (state quasi- 3). The
L (state 3). The
piston
equilibrium,
piston
Reversible is assumed
is assumed so theto
Isothermal toprocess
beCompression
be frictionless
is reversible
frictionless and
and the
(process process
as well
the process
3-4, to!
as Tadiabatic.
to beconstant).
be quasi- At state
quasi-
L
equilibrium,
equilibrium,
Reversible
3, the insulation so the
so
Isothermal the process
at process
the Compression
cylinderis reversible
is reversible
head (process as well
as
is removed, well 3-4, asand
as Tadiabatic.
adiabatic.
theconstant).
cylinder is At state
L!
Reversible
3, the insulation
brought
Reversible Isothermal
into contact
Isothermal at the Compression
withcylinder
a sinkhead
Compression (process
is removed,
at temperature
(process 3-4,
3-4, TLand .TNow !theconstant).
thecylinderpistonAt isis state
T LL ! constant). At state
3, the insulation
brought
pushed
3, the insulation
into contact
inward by at an
at thewith
the cylinder
external a sink
cylinder head
force,
head is removed,
at temperature
doing
is removed,
workTon and
and
L . Now thegas.
the
the cylinder
the
cylinder piston
As theisisis
gas is
brought
pushed
compressed,
brought into contact
inward
into contact
itsby anwith
temperature with
externalaa sink
sinktends at temperature
force,
at temperature
todoing
rise. But work TTLon
as .. Now
Lsoon Now
theasgas.the
theit risespiston
As
piston the
byisis
gas
an is
pushed
compressed,
infinitesimal
pushed
compressed,
infinitesimal
causing the gas
compressed,
inward
inward its
its
by
amount
by
amount
its
an external
temperature
an
temperature
temperature
external
dT, heattends
dT, heat
force,
force,
tends
toisdrop
tends
doing
todoing
is transferred
to to
rise. But
rise.
transferred
to rise. TL.But
work
from
work
But from
Thus,
asonon
as soon
as
soon
the
soon
the
the
the
thegas
gas
gas
as
gas.
as
gas.
as temperature
As
it rises
to thethe
As
itittorises
rises
the
the sink,
gas
bygas
sink,
by an
by
an is
an
is
11
infinitesimal
causing
remains the
infinitesimal gas
constant amount
amount temperature
at TdT, dT,
L. Since
heattois
heat isdrop
the transferred
to TL. Thus,
temperature
transferred from
from the gas
the
difference
the gas temperature
gas to
between
to the sink,
the sink,the gas
causing
remains
and the the
causing the
sink gas
constant
gasnever temperature
temperature TL. Since
atexceeds atotodifferential
thedrop
drop temperature
to . Thus,
to TTL.amount the
dT,gas
difference thistemperature
between
is a reversible the gas
L Thus, the gas temperature
remains
and the sink
remains constant
constant neverat TTLL.. Since
atexceeds Since the temperature
temperature
a differential
the amount difference
dT, thisbetween
difference between
is a reversible the gas
the gas
and the sink never exceeds a differential
and the sink never exceeds a differential amount dT, this is a reversible amount dT, this is a reversible
 11/9/20

Carnot Cycle

Dr SMS

23

Carnot Cycle
• Carnot cycle is the most efficient cycle that operate on reversible process
on each cycle.
• Reversible cycles cannot be achieved in practice. However, reversible
cycles provide upper limits on the performance of real cycles.
• The heat transfers between a reversible device and the high- and low-
temperature reservoirs in the Carnot cycle can be related with following
equation 𝑄( 𝑇(
=
𝑄) -$. 𝑇)
• The thermal efficiency of a Carnot heat engine is given by
𝑇)
𝜂!",-$. = 1 −
𝑇(
• The COPs of reversible refrigerators and heat pumps are given in a similar
manner as
1 1
𝐶𝑂𝑃*,-$. = 𝐶𝑂𝑃(,,-$. =
⁄
𝑇( 𝑇) − 1 1 − 𝑇) ⁄𝑇(

Dr SMS

24

12
 11/9/20

Entropy
https://www.youtube.com/watch?v=MrwW4w2nAMc

Dr SMS

25

Entropy
• The second law of thermodynamics leads to the definition of a new
property called entropy
• Entropy - a measurement of the disorder for a system (how that energy is
dispersed and stored). Low S means little disorder; high S means great
disorder
• Entropy is defined as
𝑑𝑄
𝑑𝑆(𝑘𝐽⁄𝐾) =
𝑇 -$.

• Entropy is state function – value that depends only on the present state of
the system (independent of the patch to achieve the state)
• Entropy changes of a system during a process can be determined between
initial and the final states as
/ 𝑑𝑄
∆𝑆 = 𝑆/ − 𝑆0 = A
0 𝑇 -$.

Dr SMS

26

13
 11/9/20

Entropy Changes
• The changes of entropy accompanying the following related processes:
1) Change in volume
2) Change in temperature
3) Phase transition
4) Entropy change in the surroundings

Dr SMS

27

Entropy Change Accompanying Change in Volume

• Recall the heat of the perfect gas expands reversibly and isothermally
from a volume Vi to Vf is given as:
𝑉1
𝑞-$. = 𝑛𝑅𝑇 𝐼𝑛
𝑉+
• Therefore the change is entropy is
𝑉1
∆𝑆 = 𝑛𝑅 𝐼𝑛
𝑉+

𝑃+
∆𝑆 = 𝑛𝑅 𝐼𝑛
𝑃1

• Entropy of a sample of gas increase as it expands. The molecules get to

move in a greater volume and so have a greater degree of disorder.

Dr SMS

28

14
 11/9/20

Exercise
One mole of ideal gas at 300K is reversibly and isothermally expand from a
volume of 10 L to a volume 25L. Calculate entropy change.

Answer: 7.62 J/K

Dr SMS

29

Entropy Change Accompanying Change in Temperature

• For constant heat capacity, C (independent of temperature), the change in

entropy when the temperature change from Ti to Tf is:
𝑇1
∆𝑆 = 𝐶 ln
𝑇+
• If the pressure is held constant during the heating, we use the constant-
pressure heat capacity, Cp, and if the volume is held constant, we use the
constant-volume heat capacity, CV.
• Entropy of a sample is increase when the temperature raised from Ti to Tf.
Thermal disorder if the system is greater and the molecules move more
vigorously.
• If heat capacity is not constant and function of temperature, we need to
do integration to determine the entropy change

2"
𝐶 𝑇 𝑑𝑇
∆𝑆 = A
2! 𝑇

Dr SMS

30

15
 11/9/20

Exercise
Calculate the change in molar entropy when hydrogen gas is heated from
20°C to 30°C at constant volume (C v=22.44 J/mol.K)

Answer: 0.75J/mol.K

Dr SMS

31

Entropy Change Accompanying a Phase Transition

• Entropy of a substance increases when it melts and boils. Its molecules

become more disordered as it changes from solid to liquid and from liquid
to vapor.
• Entropy of fusion is the change of entropy per mole of substance at the
melting temperature, Tf
∆𝐻1'6 (𝑇1 )
∆𝑆1'6 =
𝑇1

• Entropy of vaporization is the change of entropy per mole of substance at

the boiling temperature, Tb
∆𝐻.34(𝑇5 )
∆𝑆.34 =
𝑇5

• To calculate the entropy of phase transition at a temperature other than

the transition temperature (any temperature) we need to developed
hypothetical process path as shown in following example.

Dr SMS

32

16
 11/9/20

Exercise
Calculate the entropy of vaporization of water at 25°C. Given:
Cp (H2O, liquid) = 75.29 J/mol.K
Cp (H2O, vapor) = 33.58 J/mol.K
ΔHvap = 4.07x104 J/mol

∆𝑺
Water, l, 25C Water, l, 25C

∆𝑆0 ∆𝑆7

Water, l, 100C Water, v, 100C

∆𝑆/

92 CHAPTER 4: THERMODYNAMICS: THE SECOND LAW

Dr SMS
regardless of how the heat i
Then use eqn 4.7 and data from Table 3.1 to calculate
we can drop the label ‘rev’ f
33 the entropy of transition at 100°C. Next, calculate the
change in entropy for cooling the vapour from 100°C to qsur
25°C (using eqn 4.3 again, but now with data for the ∆Ssur =
T
vapour from Table 2.1). Finally, add the three contribu-
tions together. The steps may be hypothetical. This formula can be used
Solution From eqn 4.3 with data for the liquid from change of the surroundings r
Table 2.1: change in the system is rever
Tf
DS1 = C p,m(H2O, liquid) ln
92 CHAPTER 4: THERMODYNAMICS: THE SECOND LAW Ti

Exercise 92 CHAPTER 4: THERMODYNAMICS: THE SECOND LAW = (75.29 J K −1 mol−1) × ln 373 K

Then use eqn 4.7 and data from Table 3.1 to calculate
regardless of how the heat is transferred. Therefore, 298 K
Example 4.2
Estimating the entropy cha
we can drop the label ‘rev’ from q and write= +16.9regardless surroundings
J K−1 mol−1 of how the heat is transferred. Therefore,
the entropy of transition at 100°C. Next, calculate the
Then use eqn 4.7 and data from Table 3.1 to calculate
change in entropy for cooling the vapour from 100°C to qsur we can
From eqn 4.7 and data drop the label
from Table 3.1: ‘rev’ from q and write A typical resting person heats
the entropy∆S =
ofsurtransition at 100°C. Next, calculate the (4.8) of about 100 W. Estimate the
25°C (using eqn 4.3 again, but now with data for the
change in entropy forTcooling the vapour from 100°C D H(T ) 4.07 ×q104 J mol−1
DSto2 = vap b = the(4.8)
surroundings in the course
vapour from Table 2.1). Finally, add the three contribu- ∆S = sur
25°C (using T 373 K
tions together. The steps may be hypothetical. This eqn 4.3 again,
formula can but now with
be used data for the
to calculate the entropy
b sur
T Strategy We can estimate th
vapour from Table
change∆𝑺 2.1). Finally, add the three contribu-
of the surroundings regardless of whether = +109the −1
J K mol −1
Solution From eqn 4.3 with data for the liquid fromtions together. This formula can be used to calculate the entropy entropy from eqn 4.7 once
Table 2.1: changeThe steps may be hypothetical.
in the systemWater,
is reversible
l, 25C or not.
From eqn 4.3 with data for the vapour from Table 2.1: energy
Water, l, 25C
Solution From eqn 4.3 with data for the liquid from change of the surroundings regardless of whether thetransferred as heat. To
Tsystem 1 W = 1 J s−1 and the fact that
DS1 = C p,m(H2O, liquid) ln
Tf
Table 2.1: change in
DS3 = C p,m(H2O, vapour) ln the f is reversible or not.
T T Convert the temperature to ke
i i
∆𝑆! Tf Solution The heat transferred
373 K DS1 = CExample
p ,m(H2O, liquid)
4.2 ln ∆𝑆# 298 K
= (75.29 J K −1 mol−1) × ln Ti = (33.58 J K −1 mol−1) × ln course of a day is
298 K Estimating the entropy change of the 373 K
surroundings 373 K Example 4.2 qsur = (86 400 s) × (100 J s−1
= +16.9 J K−1 mol−1 = (75 .29 J K −1 mol−1) × ln = −7.54 J K−1 mol−1
Water, l, 100C 298 K v, 100C
Water, Estimating the entropy change of the
From eqn 4.7 and data from Table 3.1: A typical resting person heats the surroundings at a rate
The sum of the three entropy changes is the entropy of The increase in entropy of the
K−1 in surroundings
−1
= +16.9 J∆𝑆
of about "100molW. Estimate the entropy you generate
D vap H(Tb) 4.07 × 104 J mol−1 transition at 25°C: q sur 86 400 × 100
DS 2 = = From eqn the
4.7 surroundings
and data frominTable the course
3.1: of a day at 20°C. A typical resting person heats the surroundings at a DS ratesur = T = 293 K
Tb 373 K DvapS (298 K) = DS1 + DS2 + DS3 = +118 J K−1 mol−1
Strategy We can estimate the
− approximate change in of about 100 W. Estimate the entropy you generate in
= +109 J K−1 mol−1 D vap H(Tb) 4.07 × 10 J mol 4 1
DS2 = entropy =
from eqn 4.7 once we have calculated the the surroundings in the course of a day at 20°C. That is, the entropy production
Tb 373 K stay alive, each person on the
From eqn 4.3 with data for the vapour from Table 2.1: energy transferred as heat. To find this quantity, we use
Self-test 4.1 Strategy We can estimate the approximate change
= +109 −1 −1 30 kJinK−1 each day to the entr
Tf 1 W J= K 1 J smol
−1
and the fact that there are 86 400 s in a day. entropy from eqn 4.7 once we have calculated the
DS3 = C p,m(H2O, vapour) ln Calculate the entropy of vaporization of benzene at The use of transport, machin
Convert the temperature to kelvins.
From eqn 4.3 with data for the vapour from Table 2.1: energy transferred as heat.
Ti 25°C from the following data: Tb = 353.2 K, DTo find
- this quantity, we use
vapH (Tb) generates far more in addition
298 K Solution The heat transferred
Tf to the surroundings in the
= 30.8 kJ 1 ,W
mol−1 Cp,m s−1136.1
= 1(l)J = and the
J Kfact
−1 that
mol−1,there are 86 400 s in a day.
Cp,m(g)
= (33.58 J K −1 mol−1) × ln DS3 = Ccourse(H O, vapour)
p ,m 2 of a day is ln Convert the temperature to kelvins.
373 K T i = 81.6 J K−1 mol −1
.
= −7.54 J K−1 mol−1 qsur = (86 400 s) × (100 −1
298J Ks ) = 86 400 × 100 J Solution The heat 96.4 J K−1
transferred
[Answer: the−1surroundings
tomol ] inSelf-test
the 4.7
= (33.58 J K −1 mol−1) × ln
The sum of the three entropy changes is the entropy of The increase in entropy 373 K surroundings is therefore course of a day is
of the Suppose a small reptile op
qsur = (86 400 s) × (100 J s−1) = 86 400 × 100 J entropy does it generate in t
transition at 25°C: = −7.54 J K−1 qmol −1 86 400 × 100 J
DSsur = sur = = + 2.95 × 104 J K −1 water in the lake that it inha
DvapS (298 K) = DS1 + DS2 + DS3 = +118 J K−1 mol−1 The sum of the threeTentropy changes 293 K
is the entropy of The increase in entropy of the surroundings is therefore ature is 15°C?
That
transition at is, the entropy production is about 30 kJ K−1. Just to
25°C:
Dr SMS 4.6 Entropy changes DSsur = in
q sur the
= surroundings
86 400 × 100 J
= + 2.95 × 104 J K −1
stay alive, each person on the planet −1 contributes
−1 about T 293 K
Self-test 4.1 DvapS (298 K) = −1DS1 + DS2 + DS3 = +118 J K mol
30 kJ K each day to the entropy of their Wesurroundings.
can use the definition of entropy in eqn 4.1 to
Calculate the entropy of vaporization of benzene at The use of transport, machinery, andcalculate communications That is, the entropy production is about 30 kJ K−1. Just to
the entropy change of the surroundings in
34 25°C from the following data: Tb = 353.2 K, DvapH-(Tb) generates far more in addition.
Self-test 4.1 contact with the30
stay alive, each person on the planet contributes about
system at the temperature T:
kJ K−1 each day to the entropy of their surroundings.
= 30.8 kJ mol−1, Cp,m(l) = 136.1 J K−1 mol−1, Cp,m(g)
= 81.6 J K−1 mol−1. Calculate the entropy of vaporization of benzene at qsur,revThe use of transport, machinery, and communications Equation 4.8 is expressed
[Answer: 96.4 J K−1 mol−1] 25°C from Self-test 4.7 data: Tb = 353.2 K, DvapH-∆S
the following (Tb)sur = generates far more in addition. supplied to the surrounding
T
mol−1, Cp,m
= 30.8 kJ Suppose a (l) = 136.1
small JK
reptile
−1
mol−1,atC0.50
operates p,m(g)W. What we have information about
= 81.6 J K−1 mol−1.does it generate in the course
entropy The
of asurroundings
day in the are so extensive that they remain escaping from the system as h
Self-test 4.7
[Answer:
water in the lake that
−1
K at
96.4 Jwhere
it inhabits,
−1
constant
the] temper-pressure regardless of any events taking
mol are related by qsur = −q. For i
ature is 15°C? place in the system,Suppose = ∆Hreptile
a small
so qsur,rev What of 100 J, then qsur = −
operates at 0.50 W.influx
sur. The enthalpy is
4.6 Entropy changes in the surroundings [Answer: +150
a state
−1
JK ]
function, soentropy doesin
a change it generate
its valueinisthe course of a daysurroundings
independ- in the 17
have lost that
ent of the path and water
we inget
thethe
lakesame
that itvalue
inhabits,
of where
∆Hsurthe temper-
stage we can replace qsur in e
We can use the definition of entropy in eqn 4.1 to ature is 15°C?
calculate the entropy change of the surroundings in
4.6 Entropy changes in the surroundings [Answer: +150 J K−1]
contact with the system at the temperature T:
We can useEquation
the definition of entropyininterms
4.8 is expressed eqn 4.1
of theto energy
qsur,rev
∆Ssur = calculatesupplied
the entropy
to thechange of the surroundings
surroundings in
as heat, qsur. Normally,
T
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Entropy Changes in the Surroundings

• The entropy change of the surroundings in contact with system at
temperature, T regardless of whether the change in the system is
reversible or not is given as:
𝑞6'- −𝑞
∆𝑆6'- = =
𝑇 𝑇
• Case 1: Perfect gas expands isothermally and reversibly from Vi to Vf:

−𝑞 𝑛𝑅𝑇 ln 𝑉1 ⁄𝑉+ 𝑉1
∆𝑆6'- = =− = −𝑛𝑅 ln = −∆𝑆686!$9
𝑇 𝑇 𝑉+

• Case 2: For chemical reaction of phase transition at constant pressure, so

𝑞 = ∆𝐻
∆𝐻
∆𝑆6'- = −
𝑇

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Exercise
A typical resting person heats the surroundings at a rate of about 100W.
Estimate the entropy you generate in the surroundings in the course of a day
at 200C. (1W=1Js-1)

(Ans: 2.95 X 104 JK-1)

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The Gibbs Energy

https://www.youtube.com/watch?v=8N1BxHgsoOw&t=239s

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37

The Gibbs Energy

• It is essential to consider the entropy of both the system and its
surroundings when deciding whether a process is spontaneous or not.

∆𝑆!&!3: = ∆𝑆686 + ∆𝑆6'-

• At constant P & T:
∆𝐻
∆𝑆!&!3: = ∆𝑆686 −
𝑇
• The advantage: The total entropy of the system and surrounding is express in terms
of properties of the system alone.
• Limitation: Constant temperature and pressure.

• ∆𝑆!&!3: > 0 : Spontaneous change

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19
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The Gibbs Energy

• Gibbs energy, G is defined as 𝐺 = 𝐻 − 𝑇𝑆
• A change in Gibbs energy at constant temperature
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
• A change in Gibbs energy at constant temperature and pressure
∆𝐻
∆𝑆!&!3: = ∆𝑆686 −
𝑇
𝑇∆𝑆!&!3: = 𝑇∆𝑆686 − ∆𝐻
−𝑇∆𝑆!&!3: = −𝑇∆𝑆686 + ∆𝐻
−𝑻∆𝑺𝒕𝒐𝒕𝒂𝒍 = ∆𝑮

• In a spontaneous change: ∆𝑆!&!3: > 0 or ∆𝐺 < 0 (the Gibbs energy

decreases) at constant temperature and pressure.

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The Gibbs Energy

• The criterion of spontaneous change is the increase in total entropy of the
system and its surroundings. Provided the process is taking at constant
pressure and temperature, the criterion of spontaneity can be expressed
as a tendency to move to lower Gibbs energy.
THE GIBBS ENERGY 99

03), who laid the foundations of chemical Total entropy

namics towards the end of the nineteenth
discovered how to combine the two cal-
Equilibrium

into one. The combination of the two

G or S

s in fact turns out to be of much greater

than just saving a little labour, and
ut this text we shall see consequences of the
he developed. Gibbs energy

cusing on the system
entropy change that accompanies a process
∆S + ∆Ssur, where ∆S is the entropy change
stem; for a spontaneous change, ∆Stotal > 0.
40
cess occurs at constant pressure and tem-
we can use eqn 4.10 to express the change
y of the surroundings in terms of the en-
ange of the system, ∆H. When the resulting
n is inserted into this one, we obtain
tant temperature and pressure:
ntropy Entropy
ange of + change of
ystem surroundings
Progress of change
Fig. 4.16 The criterion of spontaneous change is the increase
in total entropy of the system and its surroundings. Provided
Dr SMS
we accept the limitation of working at constant pressure and
temperature, we can focus entirely on properties of the sys-
tem, and express the criterion as a tendency to move to
lower Gibbs energy.
4.13 Properties of the Gibbs energy
20
The difference in sign between ∆G and ∆Stotal implies
that the condition for a process being spontaneous
changes from ∆Stotal > 0 in terms of the total entropy
(which is universally true) to ∆G < 0 in terms of the
 11/9/20

The Gibbs Energy

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The Gibbs Energy

• The value of ΔG for a process gives the maximum non-expansion work that
can be extracted from the process at constant temperature and pressure.
• By nonexpansion work, wʹ, we mean any work other than that arising from
the expansion of the system.
• It may include electrical work, if the process takes place inside an
electrochemical or biological cell, or other kinds of mechanical work, such
as the winding of a spring or the contraction of a muscle.
@
∆𝐺 = 𝑤#&#$?4,93?

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42

21
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Exercise
Suppose a certain small bird has a mass of 30g. What is the minimum mass of
the glucose that it must consume to fly to a branch 10m above the ground?
The change in Gibbs energy that accompanies the oxidation of 1.0 mol
glucose (MW = 180 g/mol) to carbon dioxide and water vapour at 25°C is -
2828kJ
Ans: 0.19mg

43

Exercise
Test 1 14/15-I

A sample of 1 mole Ar is expanded isothermally at 0 °C from 22.4 L to 44.8 L.

Determine ∆S if the process is carried out
a) Reversible (Answer: 5.763 J/K)
b) Against constant external pressure (Answer: 14.40 J/K)

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Exercise
Test 1 14/15-I

In a particular chemical reaction taking place in the reaction flask at 70 ºC,

the change in enthalpy was -125 kJmol-1 and the change in entropy was -126
JK-1mol-1.
a) Calculate the change in Gibbs energy. (Answer: -81.763 kJ/mol)
b) Determine either this reaction spontaneous or not? (-ve sign,
spontaneous)
c) Calculate the total change in entropy of the system and the surroundings.
(238.27 J/mol)

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45

Exercise
Test 1 15/16-II
Adenosine triphosphate (ATP) is often referred to energy currency of the cell. The reaction occurred in reaction 1
transform ATP to adenosine disphosphate (ADP) and inorganic phosphate (Pi). The Gibbs free energy change due to ATP
hydrolysis depends upon the concentrations of the various participants in the reaction. Reaction 1 occurs at 68 °F, the
change in heat (∆H) = 19,070 cal, and the change in entropy (∆S) = 90 cal/K.

ATP + H2O à ADP + Pi (Reaction 1)

In biochemistry, the glutamate-glutamine cycle is a sequence of events to maintain the supply of glutamate to the
central nervous system as shown in reaction 2. Reaction 2 occurs at 68 °F, the change in heat (∆H) = 4103 cal, and the
change in entropy (∆S) = 2.4 cal/K.

Glutamate + NH3 à Glutamine + H2O (Reaction 2)

a) Calculate the Gibbs free energy change (∆ G) for reaction 1 and reaction 2, respectively. (ΔG1 = –7300 cal = –7.3
kcal; ΔG2 = 3399.8 cal = 3.4 kcal)
b) Determine which of the reactions above occur spontaneously. State the reaction and justify your answer. (The
reaction with ATP in reaction 1. The change in Gibbs free energy (∆G) is negative for exothermic reactions and can only be negative for
spontaneous reactions. However, the activation energy required would still cause this reaction to occur slowly.)
c) Compare the Gibbs free energy in each of the two reactions change if the temperature were raised to normal
body temperature (98.6 °F). (ΔG1 = –8830 cal = –8.83 kcal; ΔG2 = 3359 cal = 3.359 kcal)
d) Determine whether an increase in reaction temperature make each of these reactions more or less likely to occur
spontaneously. Explain your answer. (This reaction now becomes more exothermic and is likely to occur faster/more
spontaneously. Although activation energy remains a hurdle, the entropy of the products is dramatically higher, making this reaction
more thermodynamically favorable)

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Exercise
Test 1 18/19-I

Two moles of water at 50°C are placed in a refrigerator which is maintained at

5°C. Taking the heat capacity of water as 75.3 J K-1 mol-1 and independent of
temperature
Determine:

a) the entropy change for the cooling water to 5 °C. (Answer = -22.58 J/K)
b) the entropy change in the refrigerator. (Answer = 24.36 J/K)
c) the net entropy change. (Answer = 1.78 J/K)

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