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is sa id to b e i n th e r m o dyn am ic e qu il ibr iu m pr o pe r t y h a s a s i n g l e v a l u e a t e a c h s t a t e T h i s im pl ie s
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sy ste m is u n de r go i n g a c h a n g e o f s t a t e F o r e x a m pl e
pr o p e r t i e s : ,

w he n a ga s e n c l o se d in a c y l in de r i s he a te d it
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F i r s t La w of T h e r m o d y n a m ic s 45

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y l0 a h i g ï1 t e m ls r u t u r r m c I. e s w l \ l i B\ l l
y I\ l m \\ l i n !: x T h t
:\ u >n ì t l r u d r: x i r> t l c >l c c t o l :\ >c f r i gc r a to r
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,

spont an1 u ; u n t h: \ n sh : Ml y ht u t \ ' hl m w i w u t t h c l l c a t i n t h e


al W t 1 ' " h ic h i s Ml wl i :\ 1 h H h c hm t p u
M\ c xw n \ m p :I :w w n \ h : w C l M i l t >n t i l l g i n t o [ h c
i yst cm ( Q2 ) A n d
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.

1n k c \\ '

w:; nn iu u nt tl t C X 1c 11 1: l ] W { w k (F i g 4 5 )
H i gh \ c n 1p c m u n : :. i nk
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it m Ic e ts Qt hc m t o t he h igh
,
h : n l l w r : \ t u n : n : M : >v o i 1 ( : ; u 11 . cm l ( l i l l g s ) T h c >e >0 >c ,

BB Be a t p \ 1m p
' Qz
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\> t l 1e r m o d y n a m i c s )

A g a in . E 0 = E w
L \ )w tem p e r a t u r e S \ 1 \ 1FC¢ c ! v le c yc le

T O
l Qz = w
Hc tビ C E 닥n (나 3 ) b じ山 川 11C S

C O P R t i r: - (4 3 a )
A he a t p u m p e x t m c t s Q z am o u nt o f he a t f m m th c lo w

t e m pe r a t u r e ( T : ) s o u r c e an d de l iv e r s Ql mm o u n t o f Qz i s t h c h e a t i n l ì l t > a t i n g i n t o t he c o ld s pa c e o f t he

h e a t 10 t h c h i g h t e m w atu r e (T , ) s in k hy c l t t 1s u n 1 n i g m li i g c n \ t o r

w a m o u n t o f ext er nal w o rk

No w Th e Dr s t l a w o t e f fi c i e n c y o f a he a t pu 1r r p
H igh t c m pc m t t u v s in k
c y c le is u su al ly c al le d t h e c tT r Bi > i ¬ n r of pr r T1n1umce T
,
I t i s thc d e s i r e d e ffe c t u po n thc e x tc m n l w o r k

b u ti n in g t h a t d e s ir e d e frec t Q,
su pp l i e d f o r o

D e s ir e d e f fe c t
CO P . (4 2 )
ï B' Rcei i gemt or
N o w Th e d e s i r e d
. e f f e c t fo r a he a t p u m p i s t o su pply
he a t Q ! to t he ho t bo d y T he r e f o re

Q2
C O PH P = ( t h e fi r s t l a w o t (4 2 n )
w Lo w t e m p e r a t l 1r e s o u r c e

A ga i n , E Q = E w L T .

c y cl e yc le ld s pa c e
h e a t i n l ì l t m t i lr g i n t o t h e
c
co
Q: i s t hc
Q, o > t h c 1s ti i g e t l l t o >
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q ,
m es
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e
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r i a n c 7 sta te m e n t is au to m a t ic a l l
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tio n e r w il l fu n c t io n a s a h e a t pu m p c o o l i n g t he su r pu m p (H P ) o r a re f r · g e r a t o r ( R EF '
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d in g bu t he a t i n g t h e ro o m l i,
ro u n
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hi gh te m pe r a t u r e r e se r v o ir ; ho w e v er It \ \
4 5 STA TEM E N T S O F T H E S E CO ND LA W
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o n fy w ì ze n a n ex ter n a l w o r k (e / ¬ ( Ï/ ic a !
eil e
T he r e ar e t w o c l a s s ic a l s t a te m e n t s o f the se c o n d ]a w ,

p u t in to it
o f the m 10 dyn am ic s:
II T he K e lv in Pl a n c k s t a te m e n t Can he e x rc
p ?
ent a n o th e r w a y a s fo llo w
Cï a u s i u s St a t e m s:

f he a t f r o lo te m pe l a tu bo dy to a N o he a t en g i n e (H E ) o ] a he a t pu m p u r >c r i
T r a n sfe r o m a w re

h i g h t e m pe r a t u r e o n e i s n o t f e a s i b l e s p o n t a n e o u s y
l ,
c an o pe r a te in a c yc le by exc h a n g ; n g he

b u t t h i s i s p o s s ib l e o n l y a t t h e e x p e n s e o f t h e e x t e r n a
l a sin g le te m pe r a tu re r e s e r v o il Ie ;L 11

k in p u t t o the s y s te m HP o r R EF essen t ia l ly r e q t Ti r e s 1\ l 0 í t I l lt r
w o r

r eser v o ir s to e n a b 1e i t to o per a te 111 t l x


i ll
I I is i m po s s i b le t o c o n s t r u c t a d e v i c e t h a t w u s fu s St a t e m t Let i
V ï o fa t f n g C f a en u s L (l Il l
t h 1 t h a n t he tr a n s f e r o f he a t
p r o d u c e n o e f fe c t o e
HP an d o n e HE o pe r a ti n g in a c y c l t h: : t \ \ (
f mm a l o w t e m p e r a t u r e b o d y t o a h i g h t e m p e r a t u r e
ir s T , ( h i g l \ l [ 11
bo d y w h i l e o p e r a t i n g i n a c y c l e Te m p e r a t u r e r e se r v o o n e at

an d the o th e r a t Tz (l o w te m pe r a t u re )
Fo r ex am p le He a t p u m p s a n d r e f r i g e r a t o r s n e e d
l o r k (a v a i l a b l e i n t h e f o r m o f e le c tr ic a l
e x te r n a w

he a t fr o lo te m pe r a tu r e T
ene rgy ) t o tr a n s fe r m a w ,

bo d y t o h i g h t e m p e r a t u r e s u tT o u n din gs

Q, Q,
K e l v i n P l a n c k St a t e m ent

No he a t en gin e ,
w hile o pe r a t in g in c y c l e ,
c an

pr o d u c e n e t w ork w hi le e x c ha n gin g he a t fr o m a

s in g le he a t r e se r v o ir
Q Q:
N o he a t en gin e pe r at in g in c y c le c a n c o n v e r t
o ,

e n t i r e he a t in to w o r k I t i s i m p o s s i b l e t o b u i <d a h e a t

en g in e tha t c a n r e g i s t e r 10 0 % e f f i c i e n c y

T ER ï : ; 111

T he H P abstr a c ts Q2 h e a t f r o m
N o t e : w Hi l e t he K e l v in Pla n c k is f h
p t hL
sta te m e n t o .
m
T ER T1 In o r de ] to pu
p a r t ic u l a r r e le v a n c e to a he a t e n g in e Th e C 1a u s i u s Q, to
'
r ;t t l I r L
.

s t a te m e n t r e l a t e s m o re d ir e c t l y to a r e v er se d he a t lo te m pe r a tu r e to a h igh te N p\
w
en gin e f the e x te l n a l w o l k i mut
am o u n t o

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S e c o n d La w of The r m o dyn a m ic s 87

: e t he H E is
, op e r a t i n g i n a c y c l e by e x c h a n g i n g
he a t w ith a s in gle te m
p e r a t u r e r e s e r v o i r T hi s i s i n
Q, Qw i o1at i on o ï t h e K e l v i n P l a n c k s ta t e m e n t
V r o l a f z1zg K e 1p i t 1 P f a k S l t zl e n z e n t L e t
n c u s cons ide r
w = 0 HP HE th e sam e HE d HPw
w Q, an or k i n g be t w een t w o te m pe r a tu r e
=
Qz
r e se r v o ir s

Q, Q,
T

Q, Q,

Ï: the C la u s i u s s t a te m e n t is t o be v io la te d the n w o r lc
i n pu t W i s d e l ib e r a t e l y c u t o fl j.
e w . 0 w he n t he
HE w =
Q, Q2 w Hp :
.

H P pu m p s u p Q, he a t fr o m T ER 72 an d de liv e r s the

sam e to T ER T r Q. Q,

T he w o r k o u tp u t o f the he a t en g in e c an be u se d to
Q, Ql
dr i v e the h e a t p u m p

w = 0 HP HE w Q, Qz

Ql Ql
Q1 + Q2

2 : w Q

Now H P de l i v Q , (T E R T ,) w h i c h +s t h e i n t a k e Q,
the ers

f t he H E So w e c an do aw ay w i th t he T ER T r a n d 上 :
o

H E so th a t t h e he a t r e e c te d
j ; 地
cou ple th e H P w i t h t he ,

h HE
by t h e H P b e c o m e s t h e h e a t i n p u t t o t e

is to be
Now jf the K e l v i n Pl a n c k sta te m e n t

t he h e a t e n gin e s ho u l
d
w =
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t he n
al
by e x c han
f
gi n g he a t r o
m a si n gle the r m
w o rk

0 2
m u st be zero :i o i n c C I 1 LU C
Sin k be in g a bse n t ,
Q2
a n e qu i v a le n t
t h e H E pr o d u c e s
he a t go e s to
Q, t ha t w a st a ge T hi s
f w o r k w T ha t is the r e i s n o ,
am o u n t o
am o u n t
d t o the H P
t o p u m p o u t Q2
t i s f e
w o r k o u tpu E R Tz
a l a r ge he
at e n gin e r e s e r v o ir T
te m pe r a tu r e
T ha t i s i n e ffe c t w e ar e o pe r a t in g f he a tf o m the l o w
r
o m T2
,
o
c t s Q, f r
(t h e H E + HP co m bi n e d ) th a t a b s tr a

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88 En g i n e e r in g The r m o d n a m ic s
y

Q1 ÎQ ,
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..Î\ //b
"

c卺 墓 羹

Q2

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r e su ltin g in l a r g e Ì eat p u m
a
p w hic h c a n o pe r a te
w i ï fzo u t a n y e x t e r n a l w o r k i n
p u t a n d still c a a ble
p
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p u m p n g o u t Q2 a m o u n t o f h e a t f r o m t h
e lo w
te m p e r a t u r e r e se r v o ir a n d de li v e r i
n g it to th
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te m pe r a tu r e r e se r v o ir T ER T T fl is is in v i l
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t he C la u s i u s s t a t e m e n t
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47.
CA RNOT CY C L E

T he C a r n o t c c le is e s s e n t ía .l ·
: a re , er s i b +e °

dy n a m ic c1 c l e .

N o t e : A l l pr oes s es ar e mp . d t jo a p ;:
-
·
_
:

G lo w to a r e v e r s ib le
pr oc s s / possi
to ga in the m a x im u m
p o s s îb ï e e c / e n i H .

a l l p r a c t ic a l r o c e s s e s a r e
p i Tever si b+ a s t : :

c a n n o t a tta in i t s o D i
g n al - o r i nì î ov b -
;
p a t h d u e t tD f r i c t i o n a r d i s s i a t i o n f
p o en erg
:

T h e Car not
ycl e c o m p D s e s f o u r re v er s ib le F -
, J ;

(F ig 4 8)
.

. .
.

N o te : T he C
an o t c c l
l e is a
°

d e v e <o e d b hypot het Bc c i : .


·

y x i c h o <a s S a d i C
.

p
a Fre n c h
an o t ( 196 / 8 :: : -

m i <i t a r v
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e n g in e o
r . t 1s m e a n t f o 3
.
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r a r e v
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1
i
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p s s i b l e d e v 1c
c o n s t Tu
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Se c o n d u * o - m ies 89

( Pn x ess 3 4 Re \ e r s i b Be r v 1t he r m a 1 he a t re ec j Do n
.
He a t 1 Q ! 1% r e e c t e j d b: the w o r k 1n g f l u i d t o t h e
. .

\ in k b4 ) t h a re a t a = o n sta n t te m pe r a t u r e Bu t d i f fe r
o n l b an i n fi n i te s im a l am o u n t
:
A ga in t he pr o c e \ s be i n g i m t- = 0
1l v
r y
: '

BB£
Q. - \\ J 1F in t la w o f t he r m o dyn am ic s )
.

Q im p l i e s he a t ha s b e e n re e c j te d by t he sy ste m
3 w im do he
p l ie s w o r k ha s be e n ne o n t s v ste m

V o \u m e \ Pm c e s s 4 J Rm e r s i b 1e a d ia ba r i c c o n +p r e s s i o n

(a ) P V d ia g r a m
T he te m p e r a t u r e o f t he w o rk i n g f l u i d is r a i s e d b a c k
to t he te m pe r a t u r e l e v e l o f the hi gh te m pe r a tu r e

® ,
w so u r c e t hr o u gh ad ia b a t ic c o m pr e s s io n I e Q = 0
0 - AL T
4 I
+ ( w . 1)

6 114 - W+ ( F ir s t la w o f t he r m o dyn am ic s)
1 1
B4: t A s t he tw o is o the r m a l an d ' v o a diab a ti c s c o m p le t e
cL
' " y c le
§ L
四国 c

@ Q. - W
Q. . net
.
ccl e q c le

En tr o py s
o r Q a dd
+ ( Q ej) r

(b ) TS d ia g r a m _ [+ W 1 2 + W 2 3l L VH + Wl ]
Fi g 4 吕 T h e C a m o t c yc le or Qa d d Qr e j W e w -
.

T h e r e f o r e t he ,
e Æ c \e n c y
Pm t ess J 2 Re v e r s ible is o the - 1 he a t a d d i Do n

h i g h t e m pe r a t u r e r e s e r v o i r
fro 11
wo r k o u tpu t

H e a t ( Qa d d ) f l o
-
w s m a
N e t he a t in pu t
( s o u r c e ) t o t h e w o r k i n g fl u i d w h i c h i s a t a c o n s a n
t t

te m pe r a t u r e Bu t o n l y i n fi n i t e s i m a y
l l be l o w th a t o f w
:
.

the so u r c e Q a dd
f the r m dyn ic s ]
Q - AU + w 2 [F i r s t l a w o o am
. Dd ,
Q a dd Qr j
t ir e he a t a bs o r be d
e
A s the p r o ce ss i s i s o t he r m a l the
,
en

ha n ic a l w o r k Q a dd
go e s t o pr o d u c e t h e m ec

Qa d d - + WI 2 Q a dd
Pro c e ss 2 3 Re v b ic
e r s i b 1e a d i a a t
ex pa n s i o n Al i t e r :

d s t hr o u gh tu r bin e or
T he w o r k in g fl u i d e x p a n
a R e f e r t o t h e 7 S d i a g r a m ( F i g 4 Bb )

a d i a ba t i c a ll y pr o
du c in g a n et po s it i v e Net w or k do n e Wn et - ar e a 1 2 3 4
ex pa n de r ,

- s ide 1 4 x s ide 1 2
w o r k o u t pu t (w )
:
he a t
A s the p r o c e s s i s a d ia b a t i c .
T11 e r e i s n e i t h e r a n y . (T , T 2) (

N e t he a t in pu t Qa dd - T,(
a bso r pt io n n o r r e j e c t io n .

I e , Q = 0 T he e f f ic i e n c y
k h a s be e n do ne by the s y ste m
So t h e m ec ha n ic a l w o r
(T , T, )( ) (T T. )
on ly a t the e x pe n se o f i t s i n te r n a l ene r gy
q -
h .
_
,
_ 1

la w f the r m o dyn am ic s] Q a dd T, ( ) T, T,
0 - 6 L' 2 3
+ Wz 3 [F i r s t o

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:z w Æ

- La w o f Th e r m o dyn a m ic s 93

o f th e
yste m s T w o ty pe s o f i tT e v e r s ib i l ity h a v be e n
i d:
e i r r e v e r s ib l e C y c l e
r ec o gn z e

I nt er na] On h y c le h a s be e n &
1 rreversi bi l i ty e su c c e s e n te d i n F 1g 4 1 3 ( b )

2 Ex [e m a l im ev er s ibilh y
T he in te r n a t fr r e v er s i b i l i lu i s t h e o T / Hi a B
u tc o m e o f the
i nt erna] d is s ip a t iv e e f fe c t s lik e fD k H
c tio n tu r bu le n c e
e le c t r ic a l
i
r e s s ta n c e ,
an d m a
,

g n e t ic hy s te r e s is w ith i
n
§
the s y s te m g
T he t e r na l in i b M 1y
b ili ty th a t o c cu rs at
- r s

th e s y s t e m b o u n d
r e fers o the irr e v e s i §
ary, I e it i n v o lv es
ei 1 c

or pr e ss u re diffe r e n c e a c r o s s the bo d ar y
u n
En tr o py s

4 10 C LA U S I U S I N E Q UA L IT Y Fi g 4 13 (b ) A n i r r e v e r s i b l e c y c le
A c yc l ic pr o c ess m a y be r e v e r s i b le o r ir r e v e r s ible
F r o m t he f i gu re ,
AB < CD
Re v e r s i b l e C y c l e
o r <
A r e v e r s ib le y c le is e s se
c n tia lly the C a r n o t T,
c y c le
d e p ic te d in F i g 4 13 ( a )
92
or + < 0

Q-

H w Q, Q2
陀 V

En tr o p y s .

Q,
Fi g 4 13 (a ) A r e v e r s ib le c y c le

Fr o m the ge o m e tr y o f th e fi gu re :

AB = CD F i g 4 14 A r e v e r s i bl e he a t e n gi n e

122
':
A lit e r :
T; T2 Fo r a r e v e r s ible he at g i n e (F i g 4 14 )
en ope r a t i n g
j tio n by the
T he n e ga tiv e sign i m pli e s h e a t re ec
be tw e en tw o te m pe r a tu r e l i m i t s T 1 a n
d Tz ( T 1 > Tz ) ,

sy s te m
in g Qr he at f r o m the T ER T , an d r e e c tin
j gQ2
.
Re c e i v
fi c ie n c y p a r a m e te r T1 i s g i v en by
or
+ - 0 to T ER Tz ,
the e f

T: T2 T2
Qr Qz
T he r e f o r e f o ,
r a c o m ple te c yc le _

_ - 0
or
.
1
Q2 T2

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94 En g in e e r i n g Th e r m o d n a m ic s
y

T: T2 Q

: ; .:
o r . 0
T: T2
o r
+ - 0

I e ,
r / 1e cy c l ic in te g r a l o f a N ð Q/ T f e r nis o f a

re ver s i ble c y c le is ze r o
F i g 4 15 A n ir r e v e r s ib le he a t e n gi n e
No w c o n s id e r a n i tT e v e r s i ble h e a t e n g i n e (F i g 4 1 5 )
o p e l: r t i n g be t w ee n the s a m e te m p e r a tu r e lim i ts an d T h i s i s t h e C 1a u s i u i n e q u a l i ty
s w hi c h s t ate
s tht
ta k i n g the s a m e a m o u n t o f he a t fr o m the so u r ce

(h e a t
Si n c e i t i s i rT e v e r s i b l e i t s
to w o r k) w
,

i l l be l e s s t h a n t h a t
c o n v er sio n

o f
e

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2
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3 Pu m p t h e r m o dy n a m i c s )
f PM M I i s a lso n o t tr u e
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Se c o n d L a w of The r m o dyn a m ic s 95

ide a l pr i se s t w di a ba tic s d tw o
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C O Pt r =
m p e d t o t he s in k
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W o rk in pu t . Ca r 11o t p r i n c ip l e s :
H e a t p u m pe d fr o
C O P R EF =
out m t h e So u r c e T he r m al e f Dc i e n c i e s o f a ll r e v e r s ible he a t en gin e s
W o r k in pu t o pe r at in g be t w een the sam e tw o r e s e r v o ir s
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o f r / Be seco n d la \ \ ?: N o
ar e th e s a m e a n d i n d e pe n d e n t o f the ir w or kin g
hea t e n g in e O e r a t in
p g in a c yc le Ca n pr o du c e a su bsta n c e
2 N o he a t en gin e i s m ore e f fi c i e n t t h a n a r e v e r s ible
s in gle he a t rese r o ir I Bo t h t h e
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tr a n s f e r h e a t fr o m a lo w te m pe r a tu r e r e s e r v o ir t o a Q2 i s t h e h e a t r e j e c t e d t o s i n k a t T 2 I
M gh te m r e se r v o ir ith o u t t a k in
· Ca r n o t ì 1e t en
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con d it io ns A n y o the r p r o c e s s i s ir r e v e r s ibl e 11 h - 1


t rev
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ir r e v e r s ible T h e C OP s i bl e
o f a rev er s r e f D ge r a t o r an d a he at
Ex am ple s : pu m p are giv en by
1 Fr ic t io n

(I , / T2 ) 1
3 H e a t tr a n s f e r t h r o u gh a f i n i te te m pe r a t u r e dif f e r e n c e
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C OP H P rev
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