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6DA 5A? @ =M B 6DAH @O = E?I =I M=I E JH @K?A@ >O + =KIEKI = @ A LE EI B H K =JA@ JDA >=IEI B JDA HAJE?= = = OIAI B HALAHIE> A ?O? AI AI J=> EIDA@ >O +=H J .H JDA HALAHIE> A +=H J ?O? A EJ B MI =JDA =JE?= O JD=J JDA HALAHIE> A AN?D= CA B DA=J dQrev >AJMAA IOIJA I = @ IKHH K @E CI @ELE@A@ >O JDA =>I KJA JA FAH=JKHA T EI = J J= @E AHA JE= dS MDAHA S EI JDA FH FAHJO B JDA IJ=JA ?= A@ A JH FO JD=J EI

dS =

dQ T

! &

6DA 5A? @ =M ?= JDAHAB HA >A IJ=JA@ =I JDA J J= A JH FO ?D= CA E = IOIJA HAIK JE C BH = O HA= FH ?AIIAI E JDA IOIJA EI F IEJELA = @ =FFH =?DAI = E EJE C L= KA B AH B H = O FH ?AII JD=J =FFH =?DAI HALAHIE>E EJO 6DA A JH FO B = HALAHIE> A FH ?AII EI AGK= J JDA DA=J =>I H>A@ @KHE C JDA FH ?AII @ELE@A@ >O JDA JA FAH=JKHA =J MDE?D JDA DA=J EI =>I H>A@ AGK=JE ! & 4ALAHIE>E EJO @A JAI = FH ?AII MDE?D EI ?=HHEA@ KJ K @AH A=H AGKE E>HEK ? @EJE I = @ JDAHAB HA A= I JD=J EJ EI ?=HHEA@ KJ IJ A ?EA J O + >E E C JDA .EHIJ =M = @ JDA 5A? @ =M CELAI JDA ANFHAIIE

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dS =
BH

dU + pdV dH = T T

! '

MDE?D ?= >A @A@K?A@ JD=J

( (

1 S )V = U T S p )U = V T

!  !  !   ?O? E? FH ?AIIAI = @ HALAHIE> A

S = S (U, V )
9EJD JDAIA ANFHAIIE I JDA @AHEL=JE BH

DA=J AN?D= CA ? K @ >A =>= @ A@ E AN?D= CA B H JDA IJ=JA BK ?JE I T p V U = @ S B JDA E @ELE@K= IOIJA I 5E E =H O J JDA .EHIJ =M JDA J J= A JH FO B = ?DA E?= IFA?EAI i =J EJI AGKE E>HEK =I IJ=JA JA FAH=JKHA T = @ IJ= @=H@ FHAIIKHA p0 ?= >A ANFHAIIA@

T 0 + Si = Si T0

Cp dT + T

Htrans ) Ttrans

! !

0 MDAHA Si EI JDA J J= A JH FO B JDA IFA?EAI =J EJI AGKE E>HEK IJ=JA = @ =J T0  '& #  = @ IJ= @=H@ FHAIIKHA p0  >=H H  =J  -GK=JE =FF EAI =J 0 = 0 = @ T0 = 0 )J  JDA A JH FO =>I KJA AH JA FAH=JKHAI >O IAJJE C Si

B = ?HOIJ= E A A A A JI = @ ? F K @I EI AH = @ B H = JDAH IFA?EAI =O 0 >A AH JD=J EI Sf = 0 = IJ=JA A J JD=J @A AI JDA 6DEH@ =M B 6DAH @O = E?I )?? H@E C J /E>>I = FD=IA EI K @AHIJ @ J >A = ?DA E?= O = @ FDOIE?= O D CA A KI IK>IJ= ?A EHHAIFA?JELA B JDA = K J = @ ID=FA -LAHO FD=IA D=I = E EJA@ HACE B ANEIJA ?A MEJD HAIFA?J J ? F IEJE JA FAH= JKHA = @ FHAIIKHA 2D=IAI E AGKE E>HEK MEJD A=?D JDAH =HA ?= A@ ? ANEIJE C FD=IAI 5E C A FD=IA IOIJA I =HA D CA A KI FD=IAI MDE A K JE FD=IA IOI JA I =HA DAJAH CA A KI + IA@ D CA A KI H DAJAH CA A KI AGKE E>HEK IOIJA I D=LA =NE K A JH FO JD=J EI = BK ?JE B U = @ V AGK=JE I ! ' J !   6DA /E>>I BHAA A AHCO G B = IFA?EAI EI = BK ?JE B EJI A JD= FO = @ A JH FO = @ EI @A A@ =I

G(T, p) = H T S G EI = JDAH
@O = E? ?D=H=?JAHEIJE? BK ?JE

! " JD=J ?= >A ANFHAIIA@ E JAH I

B EJI @AHEL=JELAI MEJD HAIFA?J J JDA ? HHAIF @E C E @AFA @A J L=HE=> AI .H JDA AGKE E>HEK HAGKEHA A J B =NE K A JH FO B MI JDA E E K /E>>I A AHCO B H ?DA E?= AGKE E>HEK JD=J EI

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G=
.H JDA CA AH= @A EJE

E E K

=J ?

IJ= J T = @ p

! # A ?= ANFHAII JDA

B JDA /E>>I BHAA A AHCO

/E>>I BHAA A AHCO B = ?DA E?= IFA?EAI i =J AGKE E>HEK E JAH I B EJI J J= A JD= FO = @ J J= A JH FO =J T = @ IJ= @=H@ FHAIIKHA p0 JD=J EI
0 0 G0 i = Hi T Si

! $

6DA DA=J ?=F=?EJEAI A JD= FEAI A JH FEAI = @ /E>>I BHAA A AHCEAI B ?DA E ?= IFA?EAI =J JDAEH AGKE E>HEK IJ=JA = @ =J IJ= @=H@ JA FAH=JKHA = @ FHAIIKHA ?= >A B K @ E JDA FK> E? @ =E 7IK= O E ? K@A@ E IK?D J=> AI =HA JDA @E A IE AII 2 = ? I BK ?JE E>HEK ? IJ= J =I

B JD=J =

MI = IE F A ?= ?K =JE

B JDA AGKE

0 Bi = G0 i /RT log 10

! % ! &

log Kr =

0 nr i Bi

MDAHA nr AJHE? A BH=?JE I B JDA HA=?JE ) HA=?JE i =HA JDA IJ E?DE ME FH ?AA@ =J = CELA JA FAH=JKHA MDA log Kr  IE E =H J JDA IEJK=JE JD=J M=JAH > E I MDA JDA JA FAH=JKHA HA=?DAI  + ) KIABK J B H AI JE =JE C ?DA E?= JDAH @O = E? ? @EJE I B IALAH= FH ?AIIAI EI JDA 05+ +DA E?= 4A=?JE

2H @K?JI
! !

= @ -GKE E>HEK I BJM=HA DJJF IAHLE?AI 05+ +DA EIJHO  

I

MMM

KJ JA? ?

+= ?K =JE

6DA @ALA F A J B AM ?

>KIJE

JA?D

CO B H I=LE C A AHCO = @ B H IKF LAHIE >KIJ H

FHAIIE C A LEH A J= E F=?J EI B @A?EIELA E F HJ= ?A IE ?A JDA ? B BKA >=IA@ ?DA E?= A AHCO E J JDAH = A AHCO E JDA JH=@EJE = ?

HAIK JI E E JDA =HCAIJ EHHALAHIE> A II HA =JA@ J JDA IA? @ =M B JDAH @O = E?I E F MAH IJ=JE = @ ? >KIJE A CE A @KA J JDA IAHE KI E >= = ?A >AJMAA JDA A AHCO ALA I B JDA HA=?J= JI = @ B JDA FH @K?JI = @ EE = CHA=J = K J B N Ox B H =JE 0 MALAH CHA=J E L=JE =I =E O ? =IIE A@ E J JDA JDAH = = @ BKA N Ox E BKA ? LAHIE E = ? >KIJ H D=I >AA I?=H?A

= @ E FHA E E =HO IJ=CAI E =JKHA HA HA?A J O MA ?= @ JD=J JDAHA EI = JA @A ?O J @ALA F = AM ? >KIJE =FFH =?D J A A?JELA O KJE E A JDA BKA A AHCO . H AN= F A IALAH= E LAIJEC=J HI D=LA AN= E A@ IK?D EIIKAI JDA HAJE?= O BH JDA JDAH @O = E?I LEAMF E J $ 1 =@@EJE J JDA IFA?E ? N Ox B H =JE A?D= EI I JDA A AHCO A ?EA ?O K J

B JDA ?A A J

= E C FH ?AII EI = I E F HJ= J =I EJ @AJAH E AI JDA =

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"% ) DECD JDAH =

B DA=J E FKJ AA@A@ J FH @K?A = K EJ GK= JEJO B ?A A J

A ?EA ?O M K @ A=@ J AII ? IK FJE B DA=J = @ BKA = @ ID K @ FH @K?A MAH N Ox A EIIE I FAH J B ? E AH JDA FH @K?J B JDA H J=HO E 5E ?A N Ox B H =JE EI @EHA?J O HA =JA@ J JDA = K J B A AHCO ? IK A@ E ?A A J = E C E FH LE C BKA A ?EA ?O = @ FH @K?JELEJO ME HA@K?A N Ox A EIIE I + JE K KI EJ HE C B NOCA = @ ?=H> NE@A A EIIE I E JDA ?A A J E AND=KIJ C=IAI E @E?=JAI JDA = K J B AN?AII =EH )J = CELA AN?AII =EH ALA N Ox A EIIE I E ?HA=IA =I JDA JA FAH=JKHA B JDA ? >KIJE A E ?HA=IAI ) JOFE?= E ? >KIJE A I E@I JA FAH=JKHA H= CA EI => KJ "! J #" + B H ? F AJE B ? E AHE C HA=?JE I = @ J =E J=E JDA GK= EJO B JDA ?A A J FH @K?A@ 6DA ? HHAIF @E C C=I FD=IA JA FAH=JKHA EI KIK= O CHA=JAH JD= % + =E J=E E C JDA ? >KIJE A JA FAH=JKHA =J JDA E E K A?AII=HO L= KA M K @ E E E A > JD JDA FH ?AII A AHCO HAGKEHA A J = @ JDA N Ox A EIIE I ) C MEJD JDA =FFH FHE=JA JA FAH=JKHA EJ EI = I A?AII=HO J =E J=E = NE@E E C =J IFDAHA E JDA ? E AH >KH E C A J A IKHA JDA GK= EJO B JDA ? E AH FH @K?A@ ) JD KCD = E ? K @ >A FAH=JA@ MEJD =I EJJ A =I  # FAH?A J NOCA E JDA AND=KIJ E FAH=J HI JOFE?= O IJHELA B H = NOCA ALA B  J FAH?A J J CK=H= JAA JDA @AIEHA@ NE@E E C ? @EJE I E JDA ? E AH >KH E C A % 6 AL= K=JA JDA BKA JD=J IJ E FH LAI JDA A ?EA ?O B JDA ? >KIJE

MDE A =J JDA I= A JE A CK=H= JAAI = IJH C ? JH N Ox A EIIE I MA IJK@ EA@ JDA IJ E?DE AJHE? = @ JDAH @O = E? A A?J JDA @E AHA J = A HA=?JE I ) ?DA E?= HA=?JE EI = FH ?AII MDAHA A H HA A?K AI =HA ? LAHJA@ E J A H HA JDAH A?K AI 6DA JH= IEJE BH A IJ=JA J = JDAH IJ=JA HAIK JI E = ?D= CA E A AHCO B JDA IOIJA G EI JDA ?D= CA E /E>>I BHAA A AHCO E K EJI B  = @ EI JDA AJ AN?D= CA B A AHCO >AJMAA JDA IOIJA = @ EJI A LEH A J = @ ?= >A @AI?HE>A@ >O AGK=JE ! $ - JH FO S  HAFHAIA JI JDA A AHCO IFA J >O JDA IOIJA J HC= E A EJIA B E K EJI B  /A AH= O IFA= E C = IF J= A KI IOIJA B=L HI = HA H= @ IOIJA J = H@AHA@ IOIJA 6DA @AI?HEFJE B G E @E?=JAI JD=J EJ EI JA FAH=JKHA @AFA @A J DA ?A = G L= KA =J # + EI J JDA I= A =I MD=J JDA G L= KA ECDJ >A =J ## + )J = CELA JA FAH=JKHA = F IEJELA G L= KA E @E?=JAI JD=J JDA IOIJA ME C E JDA @EHA?JE B FH @K?E C JDA HA=?J= JI  IF J= A KI ) AC=JELA L= KA E @E?=JAI JD=J JDA IOIJA ME C E JDA @EHA?JE B FH @K?E C JDA FH @K?J IF J= A KI .E = O = G L= KA B AH E @E?=JAI JD=J JDA IOIJA EI E AGKE E>HEK = @ JDA H=JA =J MDE?D JDA FH @K?J EI FH @K?A@ AGK= I JDA H=JA B JDA HA=?J= JI >AE C FH @K?A@ - JH FO B = HA=?JE HABAHI J JDA F IEJE ) =J E C=I FD=IA D=I HA FJE = FH >=>E EJEAI B H A=?D HA=?J= J JD= JDA I= A =J E =

I B H F IEJE

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137-5 .

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"& I JDA

I E@ FD=IA 6DEI EI MDO C=IAI D=LA

HA A JH FO JD= I E@I 1 HA=?JE

F IEJE = FH >=>E EJEAI KIJ >A ? F=HA@ B H = JDA HA=?J= JI J JDA FH @K?JI FH @K?A@ 1B JDA HA=?JE E L LAI O C=IAI JDA A JH FO EI HA =JA@ J JDA J J= K >AH B AI AEJDAH IE@A B JDA HA=?JE ) @A?HA=IA E JDA K >AH B AI AI JDA FH @K?J IE@A JDA FH @K?J IE@A A= I MAH A JH FO ) E ?HA=IA E JDA K >AH B A= I DECDAH A JH FO - JH FO EI E A H= @ AII

JDA HA A?K AI H AI O K D=LA JDA HA ?D= ?AI B H= @ EJ ?= >A 5 MDA O K IJ=HJ MEJD JM AI B HA=?J= JI = @ A @ KF = E C ! =I FH @K?JI O K D=LA KIJ E ?HA=IA@ JDA A JH FO JDAHAB HA E ?HA=IE C H= @ AII ) @ MDA A JH FO E ?HA=IAI JDA ?D= CA E S EI F IEJELA ) @A?HA=IA E A JH FO OEA @I = AC=JELA K >AH 1 JDA K ELAHIA E ?HA=IE C H= @ AII = @ @EI H@AH EI B=L H=> A 9A ME M AN= E A JDA HA =JE IDEF >AJMAA G = @ JDA L=HE=JE JDA K >AH B AI n  .ECKHAI ! & J !  @AFE?J JDA L= KAI B n =I = BK ?JE B Gf /n B H JDA N Ox >KH E C E JDA FHAIA ?A B @E AHA J = AI 6DA DECDAIJ n EI DECD ECDJA@ E > KA = @ JDA MAIJ E HA@ . H A=?D = A JDA IJ E?DE AJHO B JDA IFA?E ? AGK=JE I EI ?D= CA@ = @ JDA HAIFA?JELA L= KAI =HA FHAIA JA@ E J=> AI !  J ! # .H CKHA ! & EJ EI IAA JD=J JDA @E AHA ?A E Gf /n L= KAI B H JDA @E AHA J L=HE=JE JDA IJ E?DE JDA K >AH B AI EJ EI AJHO B JDA AGK=JE K?D J IEC E ?= J 1 B=?J MA ?= J L=HO HA JD= = ?AHJ=E H= CA =I EJ EI IAA J= A KI = @

J=> A !  6DA L= KAI B G =HA AC=JELA MDE?D HA A?JI JDA IF HA A AHCAJE?= O B=L KH=> A I HFJE FH ?AII

6=> A !  8= KAI B Gf /n = @ n B JDA N Ox >KH E C E JDA FHAIA ?A B = H2 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 4A=?JE Gf /n n NO H2 N 2 H2 O !$  N O2 "H2 N2 "H2 O #& # 

NO N O2

#H2 N H3 %H2 N H3

H2 O "H2 O

!! $ # "'

! !

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.ECKHA ! & n =I = BK ?JE B Gf /n B H JDA N Ox >KH E C E JDA FHAIA ?A B = H2 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 6DA L= KAI B H JDA C2 H6 = A =HA ID M J=> A ! = @ JDA HAFHAIA JA@ CKHA ! ' 6DA L=HE=JE B n E ?HA=IAI >KJ JDA ? HHAIF @E C L= KAI B MAH JD= B H JDA H2 = A

Gf /n =HA

6=> A ! 8= KAI B Gf /n = @ n B JDA N Ox >KH E C E JDA FHAIA ?A B = C2 H6 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 4A=?JE Gf /n n "N O C2 H6 %N2 $H2 O "CO2 '! %  "N O2 "C2 H6 %N2  H2 O &CO2 "$! # ' N O N O2

C2 H6 #N2 "C2 H6 #N2 C2 H6 N H3

$H2 O "CO  H2 O &CO

"

%!

!    !

N O2

CO2
"CO

&& ' # !%" #

N O C2 H6 N H3 CO N O2 %C2 H6 N H3 $H2 O

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.ECKHA ! ' n =I = BK ?JE B Gf /n B H JDA N Ox >KH E C E JDA FHAIA ?A B = C2 H6 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 6DA H2 JDA ? HHAIF

C2 H6 = A FHAIA JI = ME@A L=HE=JE @E C L= KAI B Gf /n =HA HA =JELA O

K >AH B AI >KJ M IAA CKHA !  1 =

F IEJELA JA MA ?= IAA JD=J JDA FH @K?JI B JDA HA=?JE I E ? K@A M=JAH = @ ?=H> @E NE@A J=> A ! ! ME?D = AI JDA HA=?JE I HA ANJA IA 6=> A ! ! 8= KAI B Gf /n = @ n B JDA N Ox >KH E C E JDA FHAIA ?A B = H2 C2 H6 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 4A=?JE Gf /n n &N O C2 H6 H2 &N H3 H2 O CO2 !$ ! # "N O2 C2 H6 %H2 "N H3 "H2 O CO2 "&# # &N O "N O2 "N O N O2 $N O "N O2

C2 H 6 C2 H6 C2 H 6 C2 H6 C2 H 6 C2 H6

H2 "N2 H2 N2

"H2 O "H2 O

CO2 CO2 CO CO

'$ # "$'  %& ' "% # & " "#" &

#H2 "N H3 H2 N H 3

H2 O H2 O

 

H2 !N2 "H2 O CO !H2 N2 $H2 O CO

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.ECKHA !  n =I = BK ?JE B Gf /n B H JDA N Ox >KH E C E JDA FHAIA ?A B = H2 C2 H6 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE .E = O J=> A ! " = @ JDA HAIFA?JELA CKHA !  ? HHAIF @ J @=J= B H N Ox >KIJE MEJD = O2 C2 H6 = A ) J KCD JDA n L= KAI =HA IEC E ?= J O A B JDA FHALE KI = AI JDA Gf /n L= KAI =HA JDA DECDAIJ B

MAH JD= I JDA =

6=> A ! " 8= KAI B Gf /n = @ n B JDA N Ox >KH E C E JDA FHAIA ?A B = O2 C2 H6 = A ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 4A=?JE Gf /n n NO C2 H6 $O2 N2 $H2 O "CO2 #!  N O2 C2 H6 #O2 N2 $H2 O "CO2 "'! '

N O !C2 H6 &O2 N H3 $H2 O $CO2 N O2 !C2 H6 %O2 N H3 $H2 O $CO2 NO N O2 NO N O2 C2 H6 C2 H6

!C2 H6 !C2 H6 "O2 N2 !O2 N2 $H2 O "CO $H2 O "CO $H2 O $H2 O $CO $CO

' #  &&& % # & '%' # #! " % 

 ! " " "

#O2 N H3 "O2 N H3

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O2 C2 H6 = A EI JDA >AIJ B H E FH LE C JDA ? >KIJE =>=JA A J = @ JDA LAH= A D= ?E C B JDA FH ?AII

A ?EA ?O JDA N Ox

6=> A ! # 8= KAI B Gf /n = @ n B H JDA N Ox =>>=J A J ?D= CE C JDA IJ E?DE AJHO B JDA AGK=JE 4A=?JE Gf /n n N O !C2 H6 &O2 N H3 $H2 O $CO2 ' #   N O2 !C2 H6 %O2 N H3 $H2 O $CO2 &&& %

NO N O2 NO N O2 NO N O2
"N O2 N O2 N O2

C2 H6 $O2 N2 $H2 O "CO2 C2 H6 #O2 N2 $H2 O "CO2 C2 H6 C2 H6 !C2 H6 !C2 H6

"O2 N2 $H2 O "CO !O2 N2 $H2 O "CO #O2 N H3 $H2 O $CO "O2 N H3 $H2 O $CO

#! "'! ' # & '%' # #! " %  "$! # " $ !%" #

 ! " " " '  !

"C2 H6 %N2  H2 O &CO2 "C2 H6 #N2  H2 O &CO %C2 H6 N H3 $H2 O "CO

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.ECKHA !  n =I = BK ?JE AJHO B JDA AGK=JE

B Gf /n B H JDA N Ox =>>=J A J ?D= CE C JDA IJ E?DE

! !

2D J ?DA

EIJHO
?AH A@ MEJD JDA ?DA E?= A A?JI

2D J ?DA EIJHO EI JDA >H= ?D B ?DA EIJHO ?

B ECDJ B=H 78 J 14 CKHA ! ! 6DAIA A AHCEAI =HA K?D DECDAH JD= JD IA =II ?E=JA@ MEJD JDAH = JE =J = >EA J JA FAH=JKHA = @ =HA ? F=H=> A J JDA A AHCEAI B ?DA E?= > @I 6D=J EI MDO FD J ?DA EIJHO EI BJA HABAHHA@ J =I DECD A AHCO ?DA EIJHO % 9DA = A?K A =>I H>I = FD J B ECDJ EJI A A?JH E? IJHK?JKHA ?D= CAI

= @ EJ HA=?JI @E AHA J O MEJD JDAH A?K AI 6DA A AHCO JD=J EI =>I H>A@ BH ECDJ ?= HAIK J E FD J ?DA E?= ?D= CAI E JDA =>I H>E C A?K A H E = =@ =?A J A?K A A C FD J IA IEJE =JE  6DA A AHCO ?= = I >A CELA =I DA=J H =I HAJKH JDA MAH A AHCO ECDJ E A K HAI?A ?A H FD IFD HAI?A ?A E H@AH J A?K A J EJI CH K @ IJ=JA -=?D JOFA B A?K A D=I = @E AHA J

FHABAHA ?A B H MDE?D B JDAIA @E AHA J A?D= EI I EJ KIAI J CAJ HE@ B =>I H>A@ FD J A AHCO A C I A FHABAH K HAI?A ?A LAH ?DA EIJHO ' 6M BK @= A J= FHE ?EF AI =HA JDA B K @=JE B H K @AHIJ= @E C FD J ?DA E?= JH= IB H =JE I  6DA HIJ =M B FD J ?DA EIJHO JDA /H JJDKII ,H=FAH =M IJ=JAI JD=J ECDJ KIJ >A =>I H>A@ >O = ? F K @ E H@AH B H = FD J ?DA E?= HA=?JE J J= A F =?A   6DA IA? @ =M B FD J ?DA EIJHO JDA 5J=H -E IJAE =M IJ=JAI JD=J B H A=?D FD J B ECDJ =>I H>A@ >O = ?DA E?= IOIJA O A A?K A EI =?JEL=JA@ B H IK>IAGKA J HA=?JE 6DEI FD J A GKEL= A ?A =M M=I @AHELA@ >O ) >AHJ -E IJAE @KHE C DEI @ALA F A J B JDA GK= JK FD J  JDA HO B ECDJ

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=C AJE? IFA?JHK

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