Thermodynamique chimique 67

-
- . QP = ∆H .
0 ∆U = Q + W / 0
1 . QV = ∆U .
H = U + PV
∆H = ∆U + ∆ ( PV ) .
1

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D ?FEG:=35>@HI78JKLJ>NM5JO68:P3QH@KIJJ78>@?R:=<ST>NJ3QUWV*HI78XM5KB=Y[Z(\KI:=M^]P68:P<KIST35V*HI:=<_MQHIKLZ`KLB=a=a=b*cdA
e(EG:=68M5K*HL6 \V*?WK*H@Y78KL<><:=6KLVI9UW:?WYVIKL:EGKI9&68KLST786878KIM^KIfQ<V*HI78KIMQHIA
gih[j=k;hhl m
k;pqrslj=lutvPjw lyx;q[pz{qNzj=l|}t~=~=I€‚ƒtO„!rP…
n o

k;pqrslj=lutvPj=l x;†=lyq‡ˆyxQ‰Cq‡yx;h‰Cl|}t~=~=I€‚ƒtŠ=‹=~P„!rŒ…
no o
„!=x;plyq‡pxQ‰Clyh‰Clj=l x;†=k;‡*zˆyxQ‰Czk;h[j=lpw lyx;q ^”=~•!–O—;v=˜Crsk;p#™š
n o Ž8‘’P“
rsx;ˆyˆylrsk;px;z‡ylm=›œƒt‹=vrsk;p˜
∆
n

!!
ž`Ÿ 8¡8¡8¢ £
¤¥¡8¦C§!¤©¨!§!Ÿ¨ 1bar ; (1bar = 10 Pa = 0,9872 atm = 760 mmHg ) !
5

ª 8«y¬G­8Ÿ§!¦C®©Ÿ ¡8¦C§!¤©¨!§!Ÿ8¨

" # "
T = 25o C = 298 K !
! T ( K ) = t (o C ) + 273,15
$ # % # # % # %
PV = nRT p o = 1bar T!
$ & ' (
) *
p = 1bar .
o

¯±° ­8¦C§!¦=¡8¦C§!¤¨!§!Ÿ¨G¨! Ÿ­ ²­8Ÿ 8¤©³´ ¨µ° ®©¤¥­8¶ ­8«· 8¤©¦=³´¸¢ «·¢ ¹©®© 

+
T!

º&» 8«y¬G¶  8¡¨µ° ­8¦C§!¦C¡¡8¦¼§!¤©¨*§!Ÿ¨!¡¨µ° ­8¶ ­8«· 8¤©¦C¡³´¸¢ «·¢ ¹®© 8¡½ T = 298 K

e`68VISTK*?W<J e`<:=<J<:?WZ`:HIZ

+ & ' # % po = 1 bar

, & ' po = 1 bar
+ " & ' " # po = 1 bar
- # & ' # # % po = 1 bar


  
!#"$&%'()*""*!+,
 Thermodynamique chimique 68

$ # X # Xo
X
!
Xo =¾ ni X io,m
i
o
. X i ,m i.

/ #
Uo = ¾ niU io,m * Ho = ¾ ni H io,m
i i

• 0 X mo X
!
• X o
m 1 T!
-
RT 0 22,4 à 273 K.
# % V = o = 1
o
m
p 24,8 à 298 K.

# 298 K & '

U ≈U o
& H ≈ Ho!

2 ξ #
∆r X
¿ À
∂X
∆ r X = ÃÁ ÄÂ !
∂ξ T ,P

/
# Xo =¾ ni X io,m dX o = ¾ dni X io,m !
i i

$ " Æ
Å Å β j dξ : si (i ) produit.
α i Ri → β j Pj ( dni = Ç È
i j −α i dξ : si (i ) réactif .
Å
- # " ν i Ai = 0 !
i

νi 3 !
Æ
ν i > 0 : pour ( Ai ) produit.
o dni = ν i dξ ; avec ν i : ÇÈ
ν i < 0 : pour ( Ai ) réactif .
É Ê É Ê
Å ∂X o Å
o dX o = ÍË ν i X io,m Î Ì dξ ∆ r X o = ÍË ÎÌ = ν i X io, m !
i ∂ξ T , P i



  
!#"$&%'()*""*!+,
 Thermodynamique chimique 69

É Ê É Ê
∂U o Å ∂H o Å
∆ rU o = ÍË ÎÌ = ν iU io,m * ∆ r H o = ÍË ÎÌ = ν i H io,m !
∂ξ T ,P i ∂ξ T ,P i

4 *
! ! + # ∆r H o !

2 " C graphite + O2 ( gaz ) → CO2 ( gaz ) !

∆ r H = ν (CO2 ) H (CO2 ) − ν (C ) H mo (C ) −ν (O2 ) H mo (O2 ) = −393,5 kJ .mol −1 !
o o
m

∆r H o ∆ rU o

5 H io, m = U io,m + p oVi ,om ( Vi ,om

i !
2 i H io, m ≈ U io,m !
2 i # % H io, m = U io,m + RT !
É Ê
Å Å Å Å
5 . ∆r H = o
νiH o
i ,m = ν iU o
i,m + ν i RT = ∆ rU + ÍË ν i Î Ì RT !
i i i i

ÏGÐÑ
ÒsÓÔ_ÑÕ¼ÖÕ@×yØ©ÙÛÚ ÜÛÝ©ÞÑWßÑÔà áÒsÒ^â*Ùãá;ä

−1
∆ r H (298 K ) =−91,8 kJ .mol
 
→ 2 NH 2 ( g )
o

N 2 ( g ) + 3H 2 ( g ) ← 
Å
/
ν i = 2 − 1 − 3 = −2 ∆ rU o (298 K ) = ∆ r H o (298 K ) + 2 RT (
i

" ∆ rU o (298 K ) = −86,85 kJ .mol −1

ÏGÐÑ
ÒsÓÔ_ÑÕ åÕ

∆ r H (298 K )
 → CO2 ( g ) + H 2O( g )
o

CO2 ( g ) + H 2 ( g ) ← 
Å
/
νi = 2 − 2 = 0 ∆ rU o (298 K ) = ∆ r H o (298 K ) (
i
ÏGÐÑ
ÒsÓÔ_ÑÕ æÕ

∆ r H (298 K )
 → H 2O(l )
o

H 2 ( g ) + 1 O2 ( g ) ← 
2
è
ν i = 0 −1 − 1 2 = − 3 2 ç ∆ rU o (298 K ) = ∆ r H o (298 K ) + 3 RT !
2
i

- #
∆ r H o = ∆ rU o + ( ∆ν g ) RT ( ∆ν g Ÿ 8¶ §!¦C¢ 鐠§!®
»F³´£
¤©¡8¦C¢ ¦C®©§!¤©¦C¡êI§!ë 8®
» !



  
!#"$&%'()*""*!+,
 Thermodynamique chimique 70

∆r H o ∆ rU o ! " T# $ % ""

" 6 ∆r H o
# ∆ rU o
) # T = 298 K !
í T
• " ! δ QV = dU = cV dT ì ∆ rU o (T ) = ∆ rU o (To ) + ∆ r CVo dT !
To
í T
• " δ Q p = dH = c p dT î ! ∆ r H o (T ) = ∆ r H o (To ) + ∆ r C po dT !
To
Å Å
" ! ∆ r cVo = ν i cVo ,i * ∆ r c op = ν i c op ,i !
i i
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ñ >N78<68:OHIVI:=9;<78>@?RZ`KL9;>NS±ð·M5J<78>@?RZ`M^STVI<CUW:?WKLò

∆ r H (298 K ) =−839,5 kJ .mol −1 A

CH 4 ( g ) + 2O2 ( g )  → CO2 ( g ) + H 2O (l )
o

∆ H o (1298 K ) r
óx;„!=x;h‰={ql ò

\K*?W<CUW:=683578KLJ<:?WZ`:HIZ4Z`KGEG:=35>@HI78J:=<78>@?RZ`KL6 \K@:=M^ò A
ô ∆ vap H o (298 K ) = 43,9 kJ .mol −1
KIJÛEG:=68KIMQHIJOST>@õK*??WKIJOZ`KIJO9;:=35:9;78<VIJO<CUWK*HIST78XM5KIJOST>N68:=7 HIKIJOK*?W<CHIKLò K*?
ô 298 K & 1298 K
J>@?W<ò
( J .mol −1.K −1 ) ö
A
c op (CH 4( g ) ) = 55, 2 ; c op (O2( g ) ) = 31,8 ; c op (CO2( g ) ) = 46,8 ; c op ( H 2O( g ) ) = 38,5

" 7
!
3 ! - Qr & # '!
+ QrV = ξ ∆ rU o = ∆U o !
+ Qrp = ξ ∆ r H o = ∆H o !

& ' (
8
" # # !
" T Tf $
* pf $ !
÷ k;pq‰Czk;h[zˆyk;„!=k;‡yl m
o
í T
∆ rU o (To ) + cVfo dT = 0 !
f

To

cVfo
!
÷ k;pq‰Czk;h[zˆyk;øx;‡yl m
o
í T
∆ r H o (To ) + c opf dT = 0 !
f

To

c opf
!


  
!#"$&%'()*""*!+,
 Thermodynamique chimique 71

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cd:=689;M568K*HL68:P<KIST35V*HI:=<_MQHIKLZ`KGú!68:=STSTKL>@ð·<K*?WM`KL35:HL68:P9;>NS±ð·M5J<78>@?RZ`KLZ`KIM5f}ST>N68KIJOZ`K
Z`7 UõZ(HI>NYû*?WKLZ`:?WJO6 \:=7 Hu7 ?W78<78:=68KISTK*?W<] t~=~=I€ A

ü k;hhýylyˆ
2 H2(g) + O2(g) → 2 H2O(g) ∆rHo(373K) = - 498 kJ.mol-1

Cop(H2O(g)) = (30,01 +10,71.10-3T)J.mol-1.K-1 Cop(N2 (g)) = (27,88 +4,27.10-3T)J.mol-1.K-1


 


 
 
 
" ) þ;ÿ

  *
- " ∆f Ho
∆r H o $ "
! Å Å
o 2 " ν i Ai = 0 ( ∆r H o = ν i ∆ f H io !
i i

∆f Ho !

∆ f H o (O2 ( g )) = 0.

∆ r H (298 K )
 → C2 H 2OH (l ) !
o

! 2Cgraphite + 3H 2 ( g ) + 1 O2 ( g ) ← 
2
% 298 K ( ∆ f H o (C2 H 5OH (l )) = −277, 6 kJ .mol −1.
2 ∆ r H (298 K ) = ∆ f H (C2 H 5OH (l )) !
24353568789;:=<78>@? 
A Fò D f;õZ`:µ<78>@?RZ(\ D 
J R:=68Z`A


gih[„!k;hˆyzj y‡yl·px&‡yýyx;„µ‰Czk;h[lyh[†==x;ˆylv=x ;lyqˆylm 
’
"!  $# → % g "& ’ #;g
…
 g
|
& ~=~' )(+*
l@‰=ˆyk;qˆqhl†=‡ylyˆyˆzk;h[„!k;hˆ@‰Cx;h‰Clj=lut~ `x

n
€Ûx;p„!qply‡pw lh‰C=x;p†=zlˆ@‰Cx;hj=x;‡yjPj=lpx&‡yýyx;„µ‰Czk;h[|
& ~=~,Û
' •ˆyx;„!=x;h‰={qlplyˆlyh‰C=x;p†=zlyˆj=l)-;k;‡yrsxQ‰Czk;h[| & ~=~'
l@‰=ˆyk;qˆut~)(+` * x&ˆyk;h‰=m
 g2W 1   ‹–•P 3 —4 ˜Crsk;p#™š˜
∆.8’Œ“0/
 1  n ”=Š• ! —4 ˜Crsk;p#™š˜
W
∆8. ’Œ“0/ ’ …
# g65798:W
© 1  n  ” & —4 ˜Crsk;p#™š˜
∆8. ’Œ“0C/ ’
$ + #
-

∆r H
Réactif  → Produit
o

< <
ν i ∆ f H o ( Réactifs ) ν 'j ∆ f H o ( Produitss )
i j

Corps simples
(dans leurs états st; ndards de références )



  
!#"$&%'()*""*!+,
 Thermodynamique chimique 72

Å Å
∆r H o = ν 'j ∆ f H o ( Produits ) − ν i ∆ f H o ( Réactifs ) ,
j i

-
+ T = 298 K
∆ r H1 (298 K )
 → CO( g ) ;
o

C graphite + 1 O2 ( g ) ← 
2
=
> ∆ H (298 K ) =−282,6 kJ .mol
 → CO2 ( g )
o −1

? CO( g ) + 1 2 O2 ( g ) ← 
r 2

: >@ ∆ H (298 K ) =−392,9 kJ .mol −1

,
 → CO2 ( g )
o

C graphite + O2 ( g ) ← 
r 3

: ∆ r H1
o
(298 K ) .

& ! ∆ r H1o (298 K ) = −∆ r H 2o (298 K ) + ∆ r H 3o (298 K ) = −110, 3 kJ .mol −1 .

.
- # ( DAB ) A− B
AB # % !
∆ diss H
AB( g ) → ACB DEDGFH B IKJ BCFLNMOFPQFR STJ B UVTW
o
A( g ) + B( g ) !
A&B # # %
• •
' A * B !

o DAB = ∆ diss H o !
o + # 6 !
o # #
!

‰Ck;rszˆyxQ‰Czk;h[j=lpw x;„!ý@‰Ck;hl

X
∆ r H (298 K )
CH 3COCH 3 ( g )  → 3C ( g ) + 6 H ( g ) + O ( g ) !
o

∆ r H o = ∆ atm H o = 6 DC − H + 2 DC −C + DC =O = 3923 kJ .mol −1 !

−1365 kJ .mol −1 ( ( )
€Ûk;rsøqˆ@‰Cz´k;h[j=lpw ý@‰C=x;hk;p
!
∆com H (298 K )
C2 H 5OH ( g ) + 3O2 ( g ) 
o
→ 2CO2 ( g ) + 3H 2O (l ) !
%
C −C C−H C =O O=O O−H C −O
/ # DC −C DC − H DC =O DO =O DO − H DC −O

∆ r H o = ∆ com H o = ∆ vap H o + 5 DC − H + DC −C + DC −O + 3 DO =O − 4 DC =O − 5 DO − H = −1218 kJ .mol −1 !



  
!#"$&%'()*""*!+,
 Thermodynamique chimique 73

/ .
# #
# % ! 8
# # % ! -
ER * ∆ RU o
# !

$ # " !
€Û=pk;‡yq‡ylj=l·ˆyk;j=zqr

# #
NaCl ( s ) 
ER
→ Na + ( g ) + Cl − ( g ) !
%
Ei ( Na ) AE (Cl ) DCl −Cl ∆ subU o ( Na ) ∆ f U o ( NaCl ( s ))

+ , - . - / 0, . 1 0+ 2 / 03 4 + .
( kJ .mol ) −1
#
/

5 4 6

2 ∆ rU ( NaCl ( s ))
+   →
o
2 Na ( s ) Cl2 ( g ) 2 NaCl ( s )

2∆ subU o ( Na )
DCl −Cl −2 ER

2 Na ( g ) 
2 Ei ( Na )
→ 2 Na + ( g )
(+) (+)
−2 A. E ( Cl ) −
Cl ( g ) → 2Cl ( g )

- 2∆ rU o ( NaCl ( s )) = 2∆ subU o ( Na ) + DCl −Cl − 2 AE (Cl ) + 2 Ei ( Na ) − 2 ER

" ER = 768 kJ .mol −1 !



  
!#"$&%'()*""*!+,