Département de Chimie

Une formation d’excellence pour innover

et transmettre

Thermodynamique
Agrégation de chimie, option chimie
MAROC
 𝜕X
∆r X = 𝜕ξ T,P
∆r X ∆r

∆𝐫 𝐆 = ∆𝐫 𝐇 − 𝐓∆𝐫 𝐒
𝐝𝐆 = −𝐓𝛅𝐒𝐢 ≤ 𝟎

𝛅𝐒𝐢
 𝐝𝐆 = −𝐒𝐝𝐓 + 𝐕𝐝𝐏 + ∆𝒓 𝐆 𝐓, 𝐏, 𝝃 𝐝𝛏

𝐝𝐆 = ∆𝐫 𝐆 𝐓, 𝐏, 𝛏 𝐝𝛏 ≤ 𝟎 (𝐓 𝐞𝐭 𝐏 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭𝐞𝐬)

𝐝𝐗 = ∆𝐫 𝐆 𝐓, 𝐏, 𝛏 𝐝𝛏 < 0

dξ 𝐝𝛏 𝐝𝛏
∆r G

∆𝒓 𝐆 𝐝𝛏 
∆𝒓 𝐆 𝐝𝛏 

dξ
∆𝐫 𝐆 𝐓, 𝐏, 𝛏 𝐝𝛏 = 0
∆𝐫 𝐆 𝐓, 𝐏, 𝛏 = 0
 𝓐
𝛛𝐆 𝐓, 𝐏, 𝛏
𝓐 𝐓, 𝐏, 𝛏 = −∆𝐫 𝐆 𝐓, 𝐏, 𝛏 = − = − ෍ νi µi 𝐓, 𝐏, 𝛏
𝛛𝛏 𝐓,𝐏 i
𝓐 ∆r G
σi νi Ai = 0) ξ

𝓐°

𝓐° = −∆𝐫 𝐆° = − ෍ νi µ°i
i
𝓐°
 𝓐 𝐓, 𝐏, 𝛏 𝐝𝛏 > 0

−TδSi = ∆r G T, P, ξ dξ

𝓐 𝐓, 𝐏, 𝛏 𝐝𝛏 = 𝐓𝛅𝐒𝐢

dξ
𝓐 𝐓, 𝐏, 𝛏 𝐝𝛏 = 0
𝓐 𝐓, 𝐏, 𝛏 = 0
 σi νi Ai = 0)
°
∆𝐫 𝐆° 𝐓 = −𝐑𝐓𝐥𝐧𝐊°(𝐓)

𝐊°(𝐓)

−∆r G° T
K° T = exp
RT

Q = ෑ(a𝑗 )νj
𝑗,𝑐𝑑
νj < 0 νj > 0

ς𝑗,𝑝𝑟𝑜𝑑𝑢𝑖𝑡𝑠(a𝑗 ) νj
Q =
ς𝑗,𝑟é𝑎𝑐𝑡𝑖𝑓𝑠(a𝑗 ) νj
 𝐊°(𝑻)
𝓐 𝐓, 𝐏, 𝛏 = 𝐑𝐓𝐥𝐧( ቇ
𝐐(𝐓, 𝐏, 𝝃)

𝒜 T, P, ξ dξ > 0
𝒜 T, P, ξ = 0

° ξ
K°(T)
 ° 𝐐(𝐓, 𝐏, 𝛏) 𝒜 T, P, ξ > 0 dξ
Q(T,P,ξ)

K°(T)
 ° 𝐐(𝐓, 𝐏, 𝛏) 𝒜 T, P, ξ < 0 dξ
Q(T,P,ξ)

K°(T)
 ° 𝐐(𝐓, 𝐏, 𝛏) 𝒜 T, P, ξ = 0
Q(T,P,ξ)

𝓐 𝐓, 𝐏, 𝛏 ∆𝐫 𝐆
°
 À l’équilibre
𝐐 𝐓, 𝐏, 𝛏 = 𝐊° 𝐓

d d

K° T = Q é𝑞 = ෑ 𝑎𝑘,é𝑞 νk
𝑘
𝑎𝑘,é𝑞
𝑝𝑘
 𝑎𝑘,é𝑞 = 𝑝°
°
 𝑎𝑘,é𝑞 = 1
 𝑎𝑘,é𝑞 = 1
𝐶𝑘
 𝑎𝑘,é𝑞 = °
𝐶°
 𝛛𝐆 𝐓, 𝐏, 𝛏
𝓐 𝐓, 𝐏, 𝛏 = −∆𝐫 𝐆 𝐓, 𝐏, 𝛏 = − = − ෍ νi µi 𝐓, 𝐏, 𝛏
𝛛𝛏 𝐓,𝐏 i
𝓐 𝛏 𝛏

<0 0

ξ ξ ξ
ξ ξ ξ ξ ξ ξ

ξ ξ ξ
 τ τ ξ ξ
ξ
τ 𝒜 T, P, ξ
τ ξ ξ 𝒜 T, P, ξ = Cste > 0

ξ ξ ξ ξ ξ
 ° ∆𝐫 𝐆° 𝐓

 °
 °
 ° 𝒜 T, P, ξ = RTlnK°(T) − RTlnQ(T, P, ξ)

 ° 𝒜 T, P, ξ = RTlnK°(T) − RTlnQ(T, P, ξ)


=0

0
0
 ∆𝐫 𝐇
∆𝐫 𝐔

𝐝 𝐥𝐧𝐊° ∆𝐫 𝐇°
=
𝐝𝐓 𝐑𝐓 𝟐

d d
 ∆𝐫 𝐇
∆𝐫 𝐔

𝐝 𝐥𝐧𝐊° ∆𝐫 𝐇°
=
𝐝𝐓 𝐑𝐓 𝟐

dT d lnK° ∆r H°
°

∆r H ≈ ∆r H°
° 𝒜
 d d
νk
𝑝𝑘
K° T = Q é𝑞 = ෑ
𝑝°
𝑘

PN2O4 xN2O4PP° xN2O4 P°

K° = PNO2 2
= xNO2 P 2
= xNO2 2 P

xN2O4P°
Q=
xNO2 2 P′
°
𝐀(𝐚𝐪) = 𝐁(𝐚𝐪) + 𝒏𝒑
 𝐀𝐁(𝐬) = 𝐀+ 𝐚𝐪 + 𝐁 − 𝐚𝐪 °

Ω Ω Ω Ω

  
 σ = xλ°H 3 O + + xλ°A −

σ
x²
KA =
Ca,0 − x

σ
𝑥=
λ°H 3 O + + λ°A −

2
σ
° ቇ
λH 3 O + + λ°A − 𝝈²
𝐊𝐀 = =
σ 𝐂𝐚,𝟎 𝛌°𝐇𝟑 𝐎+ + 𝛌°𝐀− − 𝝈
Ca,0 − ° ቇ
λH 3 O + + λ°A −
𝐂𝐚,𝟎 𝛔
𝛔 𝛌°𝐇 𝐎+ +𝛌°𝐀−
𝟑
𝟏
𝐊𝐀
𝐂𝐚,𝟎 𝟏 𝛔
= +
𝛔 𝛌°𝐇𝟑 𝐎+ + 𝛌°𝐀− 𝐊 𝐀 𝛌°𝐇𝟑 𝐎+ + 𝛌°𝐀−
 0,1
10
C′ = = 0,0 l −
0
pK + pK − pC 1 + , − 1,
pH = = = ,

𝐕 é𝐪

𝐕 é𝐪
𝟐

𝐕 é𝐪

Vb [H3O]  Vb 10pH  Ka(Vb éq  Vb )

λ
 AM = ε lC + εB lCB

CB
pH = pK + l g
C

AM = ε lC + εB l C0 − C = ε − εB lC + εB lC0 = ε − εB lC + AB

AM = ε l C0 − CB + εB lCB = εB − ε lCB + ε lC0 = εB − ε lCB + A

AM − A
pH = pK + l g
AB − AM

M− A
l g = f(pH)
B− M
 K s = Ap+ x B q− y = (xs)x (ys)y
K s = x x yy s x+y

σ = xsλ°A p + + ysλ°B q − = s(xλ°A p + + yλ°B q − )

x+y
x y
σ
Ks = x y ቇ
xλ°A p + + yλ°B q −
2
2 σ
Ks = s = ቇ
λ °Pb 2+ +λ °
S O 4 2−
3
3 σ
K s = 4s = 4 λ °Pb 2+ +2λ °I −
 n x
x = n=
1+n − x
 𝐓𝐟
∆𝐇 = 𝐐𝐏 = Cp 𝐝𝐓 = mcP ΔT
𝐓𝐢
cp

∆r H

ξ
ξ2

∆1→2 H = ∆r H. dξ
ξ1

∆𝐫 𝐇

∆𝐫 𝐇 (𝐓, 𝐏, 𝛏) ≈ ∆𝐫 𝐇°(𝐓)

∆1→2 H = ∆r H°(𝛏𝟐 − 𝛏𝟏 ) = ∆r H°∆𝛏 = 𝐐𝐏

 ∆𝐇 = ෍ 𝐐𝐢
𝐢

∆𝐇 = ෍ 𝐐𝐢 = 𝟎
𝐢