THE SECOND LAW OF

THERMODYNAMICS
CHE 433 THERMODYNAMICS
Chapter 6:
2
INTRODUCTION TO THE SECOND
LAW
A cup of hot cofee left in a cooler roo
e!entuall" cool# of$
First law: aount of ener%" lo#t &" the
cofee i# e'ual to the aount %aine( &"
the #urroun(in% air$
A proce## u#t #ati#f" the )#t la* to occur$ Ho*e!er+ #ati#f"in%
the )r#t la* alone (oe# not en#ure that the proce## *ill actuall"
ta,e place$
BUT the hot cofee (oe# not %et hotter
in a cooler roo$
Thi# proce## e!er ta"es pla#e$ Doin%
#o *oul( $t !i$late the %rst law a#
lon% a# the aount of ener%" lo#t &"
the air i# e'ual to the aount %aine( &"
the cofee$
A cup of hot cofee
(oe# not %et hotter
in a cooler roo$
Tran#ferrin% heat to
a *ire *ill not
%enerate electricit"$
Heatin% of a roo &" the pa##a%e of
electric current throu%h a re#i#tor
First law: aount of electric ener%"
#upplie( to the re#i#tance *ire# i#
e'ual to the aount of ener%"
tran#ferre( to the roo a# heat$
BUT tran#ferrin% #oe heat to the
*ire# (oe# not cau#e an e'ui!alent
aount of electric ener%" to &e
%enerate( &" the *ire#$
Thi# proce## &$es $t $##'r+
althou%h (oin% #o *oul( $t
!i$late the %rst law of
thero("naic#$
3
4
-roce##e# occur in a
certain (irection+ an(
not in the re!er#e
(irection$
A proce## u#t #ati#f"
&oth the )r#t an( #econ(
la*# of thero("naic#
to procee($
MA(OR USES OF THE SECOND LAW
.$ The #econ( la* a" &e u#e( to i(entif" the (irection of
proce##e#$
2$ The #econ( la* al#o a##ert# that ener%" ha# quality a# *ell a#
'uantit"$ The )r#t la* i# concerne( *ith the 'uantit" of ener%"
an( the tran#foration# of ener%" fro one for to another *ith
no re%ar( to it# 'ualit"$
3$ The #econ( la* of thero("naic# i# al#o u#e( in (eterinin%
the theoretical limits for the perforance of coonl" u#e(
en%ineerin% #"#te#+ #uch a# heat en%ine# an( refri%erator#+ a#
*ell a# pre(ictin% the degree of completion of cheical
reaction#$
The )r#t la* place# no re#triction on the (irection of a proce##+ &ut
#ati#f"in% the )r#t la* (oe# not en#ure that the proce## can
actuall" occur$ Therefore the #econ( la* of thero("naic# i#
intro(uce( to i(entif" *hether a proce## can ta,e place$
/
THERMAL ENER)Y
RESER*OIRS
0o(ie# *ith relati!el" lar%e
theral ener%" capacit" can
&e o(ele( a# theral ener%"
re#er!oir#$
A re#er!oir
that #upplie#
ener%" in the
for of heat
i# calle( a
s$'r#e+ an(
one that
a&#or&#
ener%" in the
for of heat
i# calle( a
si"$

A h"pothetical &o(" *ith a relati!el" lar%e thermal energy capacity

1a## 2 #peci)c heat3 that can #uppl" or a&#or& )nite aount# of
heat *ithout un(er%oin% an" chan%e in teperature i# calle( a
ther+al eer,- reser!$ir+ or 4u#t a re#er!oir$

5ar%e &o(ie# of *ater #uch a# ocean#+ la,e#+ an( ri!er# a# *ell a#

the ato#pheric air can &e o(ele( accuratel" a# theral ener%"
re#er!oir# &ecau#e of their lar%e theral ener%" #tora%e
capa&ilitie#$
HEAT EN)INES
6
7or, can
al*a"# &e
con!erte(
to heat
(irectl"
an(
copletel"+
&ut the
re!er#e i#
not true$
-art of the heat
recei!e( &" a
heat en%ine i#
con!erte( to
*or,+ *hile the
re#t i# re4ecte( to
a #in,$
The (e!ice# that con!ert heat to
*or,$
.$ The" re#ei!e heat fro a
hi,h.te+perat're s$'r#e
1#olar ener%"+ oil furnace+
nuclear reactor+ etc$3$
2$ The" #$!ert part of thi#
heat t$ w$r" 1u#uall" in the
for of a rotatin% #haft$3
3$ The" re/e#t the reainin%
waste heat t$ a l$w.
te+perat're si" 1the
ato#phere+ ri!er#+ etc$3$
4$ The" operate on a #-#le$
Heat en%ine# an( other c"clic
(e!ice# u#uall" in!ol!e a 8ui(
to an( fro *hich heat i#
tran#ferre( *hile un(er%oin%
a c"cle$ Thi# 8ui( i# calle(
the w$r"i, 0'i&$
The (e!ice# that con!ert heat to
*or,$
.$ The" re#ei!e heat fro a
hi,h.te+perat're s$'r#e
1#olar ener%"+ oil furnace+
nuclear reactor+ etc$3$
2$ The" #$!ert part of thi#
heat t$ w$r" 1u#uall" in the
for of a rotatin% #haft$3
3$ The" re/e#t the reainin%
waste heat t$ a l$w.
te+perat're si" 1the
ato#phere+ ri!er#+ etc$3$
4$ The" operate on a #-#le$
Heat en%ine# an( other c"clic
(e!ice# u#uall" in!ol!e a 8ui(
to an( fro *hich heat i#
tran#ferre( *hile un(er%oin%
a c"cle$ Thi# 8ui( i# calle(
the w$r"i, 0'i&$
9
A stea+ p$wer plat
A portion of the *or,
output of a heat en%ine i#
con#ue( internall" to
aintain continuou#
operation$
:
Ther+al e1#ie#-
Soe heat en%ine# perfor
&etter than other# 1con!ert
ore of the heat the" recei!e
to *or,3$
Scheatic of
a heat
en%ine$
Theral e;cienc" ea#ure
ho* e;cient a heat en%ine
con!ert# the heat that it
recei!e# to *or,$
<
H = a%nitu(e of heat tran#fer
&et*een the c"clic (e!ice an( the hi%h
teperature e(iu at TH
<5 = a%nitu(e of heat tran#fer
&et*een the c"clic (e!ice an( the lo*
teperature e(iu at T5
>
Ca we sa!e Q
$'t2
In a #tea po*er plant+ the con(en#er i# the (e!ice *here
lar%e 'uantitie# of *a#te heat i# re4ecte( to ri!er#+ la,e#+ or
the ato#phere$

Can *e not 4u#t ta,e the con(en#er out of the plant an( #a!e
all that *a#te ener%"?
The an#*er i#+ unfortunatel"+ a )r no for the #iple rea#on
that *ithout a heat re4ection proce## in a con(en#er+ the
c"cle cannot &e coplete($
E!er- heat e,ie +'st waste s$+e eer,-
3- tras4erri, it t$ a l$w.te+perat're
reser!$ir i $r&er t$ #$+plete the #-#le5
e!e '&er i&eali6e& #$&iti$s7
E!er- heat e,ie +'st waste s$+e eer,-
3- tras4erri, it t$ a l$w.te+perat're
reser!$ir i $r&er t$ #$+plete the #-#le5
e!e '&er i&eali6e& #$&iti$s7
E8AM9LE :
A heat en%ine *ith a theral e;cienc" of 4@
percent re4ect# .@@@ ,AB,% of heat$ Ho* uch
heat (oe# it recei!e?
.@
E8AM9LE ;
A #tea po*er plant *ith a po*er output of ./@
M7 con#ue# coal at a rate of 6@ ton#Bh$ If the
heatin% !alue of the coal i# 3@ @@@ ,AB,%+
(eterine the o!erall e;cienc" of thi# plant$
..
.2
The Se#$& Law $4 Ther+$&-a+i#s:
<el!i=9la#" State+et
A heat en%ine that !iolate# the
Cel!inD-lanc, #tateent of the
#econ( la*$
It i# ipo##i&le for an" (e!ice
that operate# on a c"cle to
recei!e heat fro a #in%le
re#er!oir an( pro(uce a net
aount of *or,$
No heat engine can have a
thermal efciency of 100
percent+ or a# for a power plant
to operate, the working fuid
must exchange heat with the
environment as well as the
furnace$
N$ heat e,ie #a
#$!ert all the heat it
re#ei!es t$ 'se4'l w$r"7
N$ heat e,ie #a
#$!ert all the heat it
re#ei!es t$ 'se4'l w$r"7
REFRI)ERATORS AND HEAT
9UM9S
.3

Heat i# tran#ferre( fro hi%h to lo*

teperature e(iu *ithout an"
(e!ice#$

The tran#fer of heat fro a lo*E

teperature e(iu to a hi%hE
teperature one re'uire# #pecial
(e!ice# calle( re4ri,erat$rs$

Refri%erator#+ li,e heat en%ine#+ are

c"clic (e!ice#$

The *or,in% 8ui( u#e( in the

refri%eration c"cle i# calle( a
re4ri,erat$

The o#t fre'uentl" u#e(

refri%eration c"cle i# the vapor-
compression refrigeration cycle$
0a#ic coponent# of a
refri%eration #"#te an(
t"pical operatin%
con(ition#$
In a hou#ehol( refri%erator+ the freeFer
copartent *here heat i# a&#or&e( &" the
refri%erant #er!e# a# the e!aporator+ an( the
coil# u#uall" &ehin( the refri%erator *here
heat i# (i##ipate( to the ,itchen air #er!e a#
the con(en#er$
In a hou#ehol( refri%erator+ the freeFer
copartent *here heat i# a&#or&e( &" the
refri%erant #er!e# a# the e!aporator+ an( the
coil# u#uall" &ehin( the refri%erator *here
heat i# (i##ipate( to the ,itchen air #er!e a#
the con(en#er$
.4
C$e1#iet $4 9er4$r+a#e
The o&4ecti!e of a refri%erator i#
to reo!e
! fro the coole( #pace$
The efciency of a refri%erator i#
e2pre##e( in ter# of the #$e1#iet $4
per4$r+a#e 1CO-3$
The o&4ecti!e of a refri%erator i# to
reo!e heat 1
!3 fro the refri%erate( #pace$
Can the !alue of CO-
R &e %reater than unit"?
"es# $mount of heat removes from the refrigerated space can %e
greater than the amount of work input#
Can the !alue of CO-
R &e %reater than unit"?
"es# $mount of heat removes from the refrigerated space can %e
greater than the amount of work input#
./
Heat 9'+ps
The o&4ecti!e
of a heat
pup i# to
#uppl" heat
&
into the *arer #pace$
The *or,
#upplie( to a
heat pup i#
u#e( to
e2tract
ener%" fro
the col(
out(oor# an(
carr" it into
the *ar
in(oor#$
for )2e( !alue# of
! an( &
E8AM9LE >
A foo( refri%erator i# to pro!i(e a ./ @@@ ,ABh
coolin% efect *hile re4ectin% 22 @@@ ,ABh of heat$
Calculate the CO- of thi# refri%erator$
.6
E8AM9LE ?
A hou#ehol( refri%erator *ith CO- of .$2 reo!e#
heat fro the refri%erate( #pace at a rate of 6@
,ABin$ Deterine 1a3 the electric po*er
con#ue( &" the refri%erator an( 1&3 the rate of
heat tran#fer to the ,itchen air$
.9
E8AM9LE @
Refri%erantE.34a enter# the con(en#er of a
re#i(ential heat pup at :@@ ,-a an( 3/
oC at a rate of
@$@.: ,%B# an( lea!e# at :@@ ,-a a# a #aturate( li'ui($ If the copre##or con#ue#
.$2 ,7 of po*er+ (eterine 1a3 the CO- of the heat pup an( 1&3 the rate of heat
a&#orption fro the out#i(e air$
.:
.>
The Se#$& Law $4
Ther+$&-a+i#s: Cla'si's
State+et
It i# ipo##i&le to con#truct a (e!ice
that operate# in a c"cle an( pro(uce# no
efect other than the tran#fer of heat
fro a lo*erEteperature &o(" to a
hi%herEteperature &o("$
't states that a refrigerator cannot operate
unless its compressor is driven %y an
external power source, such as an electric
motor#
Thi# *a"+ the net efect on the #urroun(in%#
in!ol!e# the con#uption of #oe ener%"
in the for of *or,+ in a((ition to the
tran#fer of heat fro a col(er &o(" to a
*arer one$
A refri%erator that
!iolate# the Clau#iu#
#tateent of the
#econ( la*$
2@
EA'i!ale#e $4 the Tw$ State+ets
The Cel!inD-lanc, an( the Clau#iu# #tateent# are e'ui!alent in their
con#e'uence#+ an( either #tateent can &e u#e( a# the e2pre##ion of
the #econ( la* of thero("naic#$
An" (e!ice that !iolate# the Cel!inD-lanc, #tateent al#o !iolate# the
Clau#iu# #tateent+ an( !ice !er#a$
-roof that the !iolation of the Cel!inD-lanc,
#tateent lea(# to the !iolation of the Clau#iu#
#tateent$
9ER9ETUAL.MOTION
MACHINES
2.
A perpetualEotion achine that
!iolate# the )r#t la* 1-MM.3$
Thi# #"#te i# #uppl"in% ener%" to the
out#i(e at a rate of <
out G 7net+out *ithout
recei!in% an" ener%"$
A perpetualEotion achine that
!iolate# the #econ( la* of
thero("naic# 1-MM23$
In thi# #"#te+ all the heat
tran#ferre( to the #tea in the &oiler
*ill &e con!erte( to *or,$
9erpet'al.+$ti$ +a#hie: An" (e!ice that !iolate# the )r#t or
the #econ( la*$
A (e!ice that !iolate# the )r#t la* 1&" creating ener%"3 i# calle( a
-MM.$
A (e!ice that !iolate# the #econ( la* i# calle( a -MM2$
RE*ERSIBLE AND
IRRE*ERSIBLE 9ROCESSES
22
Re!ersi3le pr$#ess: $ process that can %e reversed without
leaving any trace on the surroundings# That i#+ &oth the #"#te
an( the #urroun(in%# are returne( to their initial #tate# at the
en( of the re!er#e proce##$
Thi# i# po##i&le onl" if the net heat an( net *or, e2chan%e
&et*een the #"#te an( the #urroun(in%# i# Fero for the
co&ine( 1ori%inal an( re!er#e3 proce##$
Irre!ersi3le pr$#ess: A proce## that i# not re!er#i&le$

Why are we interested in reversible

processes?

B:C the" are ea#" to anal"Fe an( B;C the"

#er!e a# i(ealiFe( o(el# to *hich actual
proce##e# can &e copare($

En%ineer# are intere#te( in re!er#i&le

proce##e# &ecau#e *or,Epro(ucin% (e!ice
1car en%ine+ #tea tur&ine3 (eli!er the o#t
*or, an( *or,Econ#uin% (e!ice
1copre##or+ pup3 con#ue the lea#t *or,
*hen re!er#i&le proce##e# are u#e( in#tea(
of irre!er#i&le proce##e#$
23
Irre!ersi3ilities

The factor# that cau#e a proce## to &e irre!er#i&le are

calle( irre!ersi3ilities$

The" inclu(e friction+ unre#traine( e2pan#ion+ i2in% of

t*o 8ui(#+ heat tran#fer acro## a )nite teperature
(iference+ electric re#i#tance+ inela#tic (eforation of
#oli(#+ an( cheical reaction#$

The pre#ence of an" of the#e efect# ren(er# a proce##

irre!er#i&le$
Hriction
ren(er# a
proce##
irre!er#i&le
$
Irre!er#i&le
copre##ion
an(
e2pan#ion
proce##e#$
1a3 Heat tran#fer throu%h a
teperature (iference i#
irre!er#i&le+ an( 1%3 the re!er#e
proce## i# ipo##i&le$
24
Iterall- a& EDterall- Re!ersi3le 9r$#esses
A re!er#i&le proce##
in!ol!e# no internal an(
e2ternal irre!er#i&ilitie#$

Iterall- re!ersi3le pr$#ess: If no irre!er#i&ilitie# occur *ithin the

&oun(arie# of the #"#te (urin% the proce##$

EDterall- re!ersi3le: If no irre!er#i&ilitie# occur out#i(e the #"#te

&oun(arie#$

T$tall- re!ersi3le pr$#ess: It in!ol!e# no irre!er#i&ilitie# *ithin the

#"#te or it# #urroun(in%#$

A totall" re!er#i&le proce## in!ol!e# no heat tran#fer throu%h a )nite

teperature (iference+ no non'ua#iEe'uili&riu chan%e#+ an( no
friction or other (i##ipati!e efect#$
Totall" an( internall" re!er#i&le heat
tran#fer proce##e#$
THE CARNOT CYCLE
2/
The &e#t ,no*n re!er#i&le c"cle i# the Carnot c"cle$
Carnot c"cle i# copo#e( of four re!er#i&le proce##e# D t*o i#otheral an( t*o
a(ia&atic an( it can &e e2ecute( either in a clo#e( or a #tea(" 8o* #"#te$
Con#i(er a clo#e( #"#te that con#i#t# of a %a# containe( in an a(ia&atic pi#tonD
c"lin(er (e!ice$
The four re!er#i&le proce##e# that a,e up the Carnot c"cle are a# follo*#I
Re!ersi3le Is$ther+al EDpasi$ 1proce## .E2+
(
& = con#tant3
State .I teperature of the %a# i# T
H an( the c"lin(er
hea( i# in clo#e contact *ith a #ource at TH$

The %a# i# e2pan( #lo*l"+ *or, i# (one on the #urroun(in%#$ Teperature of the %a#
ten(# to (ecrea#e$ 0ut a# #oon a# the teperature (rop# &" an in)nite#ial aount (T+
#oe heat i# tran#ferre( fro the re#er!oir into the %a#+ rai#in% the %a# teperature
to TH$ Thu#+ the %a# teperature i# ,ept con#tant at TH$

Since the teperature (iference &et*een the %a# an( the re#er!oir ne!er e2cee(# a
(iferential aount (T+ thi# i# a re!er#i&le heat tran#fer proce##$ It continue# until the
pi#ton reache# po#ition 2$ The aount of total heat tran#ferre( to the %a# i# <H$
Re!ersi3le A&ia3ati# EDpasi$ 1proce##
2E3+ teperature (rop# fro (
& to (!3
State 2I the re#er!oir that *a# in contact
*ith the c"lin(er hea( i# reo!e( an(
replace( &" in#ulation #o that the #"#te
&ecoe# a(ia&atic$
The %a# continue# to e2pan( #lo*l"+ *or, i#
(one on the #urroun(in%# until it#
teperature (rop# fro T
H to T5 1#tate 33$

The pi#ton i# a##ue( to &e frictionle## an( the proce## to &e 'ua#iE
e'uili&riu+ #o the proce## i# re!er#i&le a# *ell a# a(ia&atic$
26
29
Re!ersi3le Is$ther+al C$+pressi$
1proce## 3E4+ T
5 = con#tant3
State 3I the in#ulation at the c"lin(er hea( i#
reo!e(+ an( the c"lin(er i# &rou%ht into
contact *ith a #in, at teperature T
5$

No* the pi#ton i# pu#he( in*ar( &" an e2ternal force+ *or, i# (one on the %a#$

A# the %a# i# copre##e(+ it# teperature ten(# to ri#e$ 0ut a# #oon a# it ri#e#
&" an in)nite#ial aount (T+ heat i# tran#ferre( fro the %a# to the #in,+
cau#in% the %a# teperature to (rop to T5$ Thu#+ the %a# teperature reain#
con#tant at T5$

Since the teperature (iference &et*een the %a# an( the #in, ne!er e2cee(#
a (iferential aount (T+ thi# i# a re!er#i&le heat tran#fer proce##$
Re!ersi3le A&ia3ati# C$+pressi$
1proce## 4E.+ teperature ri#e# fro (
! to (&3
State 4I the lo*Eteperature re#er!oir i#
reo!e(+ the in#ulation i# put &ac, on the
c"lin(er hea(
The %a# i# copre##e( in a re!er#i&le
anner an( return# to it# initial #tate 1#tate
.3$ The teperature ri#e# fro T
5 to TH+ *hich
coplete# the c"cle$
2:
2>
)-* (ia%ra of the Carnot c"cle$
)-* (ia%ra of the
re!er#e( Carnot c"cle$
The Re!erse& Car$t C-#le
The Carnot heatEen%ine c"cle i# a totall" re!er#i&le c"cle$
Therefore+ all the proce##e# that copri#e it can &e reversed+ in
*hich ca#e it &ecoe# the Car$t re4ri,erati$ #-#le$
The c"cle reain# e2actl" the #ae+ e2cept the (irection# of an"
heat an( *or, interaction# are re!er#e($
THE CARNOT 9RINCI9LES
3@
.$ The e;cienc" of an irre!er#i&le
heat en%ine i# al*a"# le## than
the e;cienc" of a re!er#i&le
one operatin% &et*een the
#ae t*o re#er!oir#$
2$ The e;ciencie# of all re!er#i&le
heat en%ine# operatin%
&et*een the #ae t*o
re#er!oir# are the #ae$
.$ The e;cienc" of an irre!er#i&le
heat en%ine i# al*a"# le## than
the e;cienc" of a re!er#i&le
one operatin% &et*een the
#ae t*o re#er!oir#$
2$ The e;ciencie# of all re!er#i&le
heat en%ine# operatin%
&et*een the #ae t*o
re#er!oir# are the #ae$
The Carnot principle#$
THE THERMODYNAMIC
TEM9ERATURE SCALE
3.
A teperature #cale that i# in(epen(ent of the propertie# of the
#u&#tance# that are u#e( to ea#ure teperature i# calle( a
ther+$&-a+i# te+perat're s#ale$
Since ener%" re#er!oir# are characteriFe( &"
their teperature#+ the theral e;cienc" of
re!er#i&le heat en%ine# i# a function of the
re#er!oir teperature# onl"$
( ) ( )
+
+ or +
&
th rev & ! & !
!

g ( ( f ( (

= =
Thi# teperature #cale i# calle( the <el!i
s#ale+ an( the teperature# on thi# #cale
are calle( a3s$l'te te+perat'res$
Thero("naic teperature
#caleI
Hor re!er#i&le c"cle#+ the
heat tran#fer ratio
& B!
can &e replace( &" the a&#olute
teperature ratio (& B(!$
THE CARNOT HEAT EN)INE
32
The Carnot
heat
en%ine i#
the o#t
e;cient of
all heat
en%ine#
operatin%
&et*een
the #ae
hi%hE an(
lo*E
teperatu
re
re#er!oir#$
No heat en%ine can ha!e a hi%her
e;cienc" than a re!er#i&le heat
en%ine operatin% &et*een the
#ae hi%hE an( lo*Eteperature
re#er!oir#$
An" heat
en%ine
Carnot
heat
en%ine
E8AM9LE 6
A copletel" re!er#i&le heat en%ine operate#
*ith a #ource at :@@ C an( a #in, at 2:@ C$ At
*hat rate u#t heat &e #upplie( to thi# en%ine+
in ,ABh+ for it to pro(uce 4 ,7 of po*er?
33
34
The E'alit- $4 Eer,-
Theral e;cienc" of a
Carnot heat en%ine
that re4ect# heat to a
#in, at 3@3 C at !ariou#
#ource teperature$
The hi%her the
teperature of the
theral ener%"+ the
hi%her it# 'ualit"$
Theral
e;cienc"
(ecrea#e# a#
the #ource
teperature
i# lo*ere($
THE CARNOT REFRI)ERATOR
AND HEAT 9UM9
3/
No refri%erator can ha!e a hi%her
CO-
than a re!er#i&le refri%erator
operatin%
&et*een the #ae teperature
liit#$
An" refri%erator or heat
pup
Carnot refri%erator or heat
pup
E8AM9LE F
A copletel" re!er#i&le refri%erator i# (ri!en &" a
.@ ,7 copre##or an( operate# *ith theral
ener%" re#er!oir# at 2/@ C an( 3@@ C$ Calculate
the rate of coolin% pro!i(e( &" thi# refri%erator$
36
E8AM9LE G
A heat pup i# u#e( to heat a hou#e an(
aintain it at 24
oC$ On a *inter (a" *hen the out(oor air teperature i#
E/oC+ the hou#e i# e#tiate( to lo#e heat at a rate of :@@@@ ,ABh$ Deterine the
iniu po*er re'uire( to operate thi# heat pup$
39
-RE-ARED 0YI
NORASMAH MOHAMMED MANSHOR
HACJ5TY OH CHEMICA5 ENKINEERINK+ JiTM SHAH A5AM$
@.>236:3@3B@3//436333
nora#ahL#ala$uit$e(u$"
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