Corrigé TD Cristallo-Chimie
Corrigé TD Cristallo-Chimie
Corrigé TD Cristallo-Chimie
c
c’
b’
c’
α’
y β’ βγ b’
a b ’
a’ a’ γ’
x
r r a 3 2 r r 3⋅ a2 r r a2
a '⋅b ' = ( ) ⋅ cos(a ' , b ' ) = ⋅ cos(a ' , b ' ) = − .
2 4 4
r r 1 r r
cos(a ' , b ' ) = − γ ' = (a ' , b ' ) = 109,47° donc α ' = β ' = γ ' = 109,47° = 109° 28'16' ' .
3
+1 +1 −1
r r r a3 a3 a3
4°) Le volume de la maille primitive est : (a '∧b ' ) ⋅ c ' = ⋅ −1 +1 +1 = ⋅ (2 + 2) =
8 8 2
+1 −1 +1
a3
Le volume de la maille conventionnelle est Vm = a 3 . Le volume de la maille primitive est : Ve = .
2
Nous vérifions bien la relation Ve = Vm = Vm pour un c.c
m 2
1
B) Cubique à faces centrées (F) :
z
c
c’
α’
b’ β’ βγ b’
c’
’
b a’ γ’
a y
a’
x
Fig.2 : Maille élémentaire primitive d’un cfc (F).
1°) Maille multiple : c’est la maille conventionnelle du réseau cubique à faces centrées (F).
r r
a = a ⋅ i
r 1 1
Vecteurs de translation : b = a ⋅ j .
r
Volume : Vm = a 3 Multiplicité : m = 8 ⋅ + 6 ⋅ = 4
r r 8 2
c = a ⋅ k
r r r
Maille primitive : Le rhomboèdre obtenu à l’aide du système (a ' , b ' , c ' ) .
r r r r r r
La maille conventionnelle est construite à l’aide de (a , b , c ) dans le système orthonormé (O, i , j , k ) .
Les vecteurs de translation de la maille élémentaire rhomboédrique sont donc :
r a r r 1 r 1 r
a ' = 2 ⋅ ( i + j ) = 2 ⋅ a + 2 ⋅ b
r
a'
r
a
r r r +1 +1 0
a r r 1 r 1 r 1
b ' = ⋅ ( j + k ) = ⋅ b + ⋅ c b ' = ( Ρ) ⋅ b (P) = ⋅ 0 + 1 + 1
2 2 2 r r 2
r a r r 1 r 1 r
c
' c
+ 1 0 + 1
c ' = 2 ⋅ (k + i ) = 2 ⋅ c + 2 ⋅ a
r r v r r v a a⋅ 2
2°) On a a = b = c = a , ce qui implique a ' = b ' = c ' = ⋅ 1 + 1 + 0 =
2 2
3°) Pour des raisons de symétrie α ' = β ' = γ ' , calculons par exemple γ ' :
r r a2 r r r r a2
a '⋅b ' = ⋅ (i + j ) ⋅ ( j + k ) =
4 4
r r a 2 2 r r 2 ⋅ a2 r r a2
a '⋅b ' = ( ) ⋅ cos(a ' , b ' ) = ⋅ cos(a ' , b ' ) =
2 4 4
r r 1 r r π
Ce qui donne : cos(a ' , b ' ) = ou γ ' = (a ' , b ' ) = = 60° Donc : α ' = β ' = γ ' = 60°
2 3
1 1
4°) La multiplicité d’une maille cfc est m = 8 ⋅ + 6 ⋅ = 4
8 2
+1 +1 0
r r r a3 a3 a3
Le volume de la maille primitive est : (a '∧b ' ) ⋅ c ' = ⋅ 0 +1 +1 = ⋅ (1 + 1) =
8 8 4
+1 0 +1
a3
Le volume de la maille conventionnelle est Vm = a 3 . Le volume de la maille primitive est Ve = .
4
V m Vm
Nous vérifions bien la relation Ve = = avec m = 4 pour un cfc.
m 4
2
Corrigé Exercice 2 :
r 1 r r
a ' = 2 ⋅ ( a − b ) r r r
a = a '+b '
r r
1 r r r r
1°) b ' = ⋅ (a + b ) donc b = − a '+b '
r r2 cr = cr '
c ' = c
1 −1 0 1 1 0
1
(Ρ ) = ⋅ 1 1 0 (Ρ −1 ) = − 1 1 0
R→R ' 2 R '→ R 0 0 1
0 0 2
h' h
2°) D’après le cours : k ' = ( P) ⋅ k
l' l
R' R
h' 1 −1 0 1 2 1
1
k ' = ⋅ 1
2
1
1 0 ⋅ − 1 = ⋅ 0 = 0
2
(111)
R → (101)R '
l' 0 2 1 R
R' 0 2 R' 1 R'
h' 1 −1 0 0 − 1
1 1
k ' = ⋅ 1
2
1 0 ⋅1 = ⋅ 1
2
(012 ) R ( )
→ 114 R'
l' 0 2 2 R
R' 0 4 R'
h' 1 −1 0 1 − 1
1 1
k ' = ⋅ 1 1 0 ⋅ 2 = ⋅ 3 (121)R → (132)R '
l' 2 2
R' 0 0 2 1 R 2 R'
h h'
−1
3°) D’après le cours : k = ( P) ⋅ k '
l l'
R R'
h 1 1 0 1 2
k = −1 1 0 ⋅ 1 = 0 (111)R ' → (201)R
l 0 0 1 1 R ' 1 R
R
h 1 1 0 0 1
k = −1 1 0 ⋅1 = 1 (012)R ' → (112 )R
l 0 0 1 2 R ' 2 R
R
h 1 1 0 2 4
k = −1 1 0 ⋅ 2 = 0 (223)R ' → (403)R
l 0 0 1 3
R R' 3 R
u' u
t −1
4°) D’après le cours : v' = ( P ) ⋅ v
w' w
R' R
u' 1 −1 0 0 − 1
v' = 1 1 0 ⋅ 1 = 1 [010 ]R → [11 0 ]R '
w'
R' 0 0 1 0 R 0 R'
3
u' 1 −1 0 2 1
v' = 1 1 0 ⋅ 1 = 3 [213 ]R → [1 3 3]R '
w'
R' 0 0 1 3 R 3 R'
u' 1 − 1 0 3 2
v' = 1 1 0 ⋅ 1 = 4 [313 ]R → [2 4 3]R '
w'
R ' 0 0 1 3 R 3 R'
u u'
t
5°) D’après le cours : v = ( P) ⋅ v'
w w'
R R'
u 1 1 0 0 2 1
1 1
v = ⋅ −1 1 0 ⋅ 2 = ⋅ 2 = 1 [021]R ' → [111]R
w 2 2
R 0 0 2 1 R '
2 R ' 1 R '
u 1 1 0 1 2 1
1 1
v = ⋅ −1 1 0 ⋅ 1 = ⋅ 0 = 0 [113 ]R ' → [1 0 3]R
w 2 2
R 0 0 2 3 R '
6 R ' 3 R'
u 1 1 0 2 4 2
1 1
v = ⋅ −1 1 0 ⋅ 2 = ⋅ 0 = 0 [223 ]R ' → [2 0 3]R
w 2 2
R 0 0 2 3 R' 6 R ' 3 R'
r 2r 1r 1v
a R = 3 a H + 3 bH + 3 cH
(Ρ)
r r
r aR 2 1 1 a H
1r 1r 1v r 1 r
bR = − a H + bH + cH ou sous forme matricielle : bR = ⋅ − 1 1 1 ⋅ bH
3 3 3 cv 3 − 1 − 2 1 cv
v 1r 2 r 1v R H
cR = − 3 a H − 3 bH + 3 cH
H →R
r
arR = bR = cvR
1°) On doit montrer que :
α R = β R = γ R
r 2r 1r 1v
a R = a H + bH + c H
3 3 3
r 2 r r 2r 1r 1v 2r 1r 1v
a R = a R ⋅ a R = ( a H + bH + cH ) ⋅ ( a H + bH + c H )
3 3 3 3 3 3
4
5 2 2 2 1 2 1 2 1 2 1
= ⋅ a H − ⋅ a H + ⋅ cH = ⋅ a H + ⋅ cH = ⋅ (3 ⋅ a H2 + cH2 )
9 9 9 3 9 9
r 1 r 1 r 1
a R = ⋅ 3 ⋅ a H2 + c H2 de même on a par symétrie : bR = ⋅ 3 ⋅ a H2 + cH2 et cR = ⋅ 3 ⋅ a H2 + cH2
3 3 3
r r r r v r
a ⋅b b ⋅c c ⋅a
On a également cos γ R = r R rR ; cos α R = r R rR et cos β R = v R rR
a R ⋅ bR bR ⋅ c R cR ⋅ a R cR
r r r r r r
On doit montrer que a R ⋅ bR = bR ⋅ c R ⋅ = cR ⋅ a R
r r 2 r 1 r 1v 1 r 1 r 1 v βR αR
a R ⋅ bR = ⋅ a H + ⋅ bH + cH ⋅ − ⋅ a H + ⋅ bH + ⋅ cH RR bR
3 3 3 3 3 3 R
2 2 1 1 1 1 1 1 1 γR
= − ⋅ a H2 − ( ) ⋅ ( ) ⋅ a H2 + ⋅ ( ) ⋅ a H2 + ⋅ a H2 + c H2 = − ⋅ a H2 + ⋅ cH2 ’
9 9 2 9 2 9 9 6 9 aR
r r 1r 1r 1v 1r 2r 1v
bR ⋅ c R = − a H + bH + cH ⋅ − a H − bH + c H
3 3 3 3 3 3
1 1 1 2 1 1 1
= ⋅ a H2 − ⋅ a H2 + ⋅ a H2 − ⋅ a H2 + ⋅ c H2 = − ⋅ a H2 + ⋅ cH2
9 9 18 9 9 6 9
v r 1r 2 r 1 v 2 r 1 r 1v
cR ⋅ a R = − a H − bH + cH ⋅ a H + bH + cH
3 3 3 3 3 3
2 1 4 2 1 1 1
= − ⋅ aH2 + ⋅ aH2 + ⋅ aH2 − ⋅ aH2 + ⋅ cH2 = − ⋅ aH2 + ⋅ cH2
9 18 18 9 9 6 9
r r r r r r
a R ⋅ bR = bR ⋅ c R ⋅ = cR ⋅ a R donc cos α R = cos β R = cos γ R et α R = β R = γ R , le réseau est rhomboédrique.
r (Ρ) r r (Ρ) −1 r
aR 2 1 1 a H aH 1 − 1 0 aR
r 1 r r r
bR = ⋅ − 1 1 1 ⋅ bH bH = 0 1 − 1 ⋅ bR
cv 3 − 1 − 2 1 cv cv 1 1 1 cv
R H H R
H →R R→H
3°) Comparaison de VR et VH :
r r r
VR = (aR ∧ bR ) ⋅ cR
142 r
43
S
5
r r r 2 r 1 r 1 r 1 r 1 r 1 r
S = (aR ∧ bR ) = ( ⋅ aH + ⋅ bH + ⋅ cH ) ∧ (− ⋅ aH + ⋅ bH + ⋅ cH )
3 3 3 3 3 3
2 r r 1 r r 2 r r 1 r r 1 r r 1 r r
= ( a H ∧ b H ) + ⋅ ( a H ∧ b H ) + ( a H ∧ c H ) + (b H ∧ c H ) + ( a H ∧ c H ) − (b H ∧ c H )
9 9 9 9 9 9
1 r
[ r r r
]
= ⋅ ( a H ∧ bH ) + ( a H ∧ c H )
3
1 r
3
[ r r r
] 1 r
3
2 r
3
1 r
VR = ⋅ ( a H ∧ bH ) + ( a H ∧ c H ) ⋅ ( − ⋅ a H − ⋅ bH + ⋅ cH )
3
1 1 r r r 2 r r r 1 1 2 1
= ⋅ ⋅ (aH ∧ bH ) ⋅ cH + ⋅ (cH ∧ aH ) ⋅ bH = ⋅ ⋅ VH + ⋅ VH = ⋅ VH
3 3 3 3 3 3 3
r r r
Remarque : VH = a H ∧ bH ⋅ cH = a 2H ⋅ c H ⋅ ( 3 / 2) .
x' x x x'
t −1 t
4°) D’après le cours : y' = ( P ) ⋅ y et y = ( P) ⋅ y '
z' z z z'
R H H R
x' x 1 0 1 1 / 2 1/ 2
t −1 1 1 1 1
x' = ( P ) ⋅ y = − 1 1 1 ⋅ 1 / 2 = 0 M : , ,0 → M : ,0,−
z' z 2 2 H 2 2 R
R H 0 − 1 1 0 H − 1 / 2 R
x x' 2 − 1 − 1 1/ 3 − 1/ 9
t 1 1 2 1 1 1 4
y = ( P) ⋅ y ' = ⋅ 1 1 − 2 ⋅ 2 / 3 = 1 / 9 N : , , → N : − , ,
z z' 3 3 3 3 R 9 9 9 H
H R 1 1 1 1 / 3 R 4 / 9 H
Question supplémentaire : Déterminer les indices des rangées suivantes dans le réseau R :
[001]H → [u ' v ' w']R et [ ] 111 H → [u ' v ' w ']R
u' u 1 0 1 0 1
t −1
v' = ( P ) ⋅ v = − 1 1 1 ⋅ 0 = 1 [001]H → [111]R
w' w
R H 0 − 1 1 1 H 1 R
r
L’axe cH du système hexagonal coincide avec la diagonale principale du rhomboèdre.
6
Corrigé Exercice 4 : Transformation CFC↔ Rhomboédrique↔Hexagonal.
CFC
→ R
→ H
(P ) 1
( P2 )
(P )
r r r r r r
Réseau CFC : Caractérisé par les vecteurs de translation cubiques : a c = a ⋅ i ; bc = a ⋅ j ; cc = a ⋅ k
r r v
a c = bc = c c = a . α c = β c = γ c = 90°
( P1 )
Transformation : CFC → R (voir exo. 1 TD2)
Les vecteurs de translation de la maille élémentaire rhomboédrique sont donc :
r a r r 1 r r
a
R 2 = ⋅ ( i + j ) = ⋅ (a c + bc ) r r
r
2 aR ac 1 1 0
a r r 1 r r r r
bR = (Ρ1 ) ⋅ bc 1
bR = ⋅ ( j + k ) = ⋅ (bc + c c ) ( P1 ) = ⋅ 0 1 1
2 2 r r 2
r c
c
1 0 1
r a r 1 r r R c
c
R 2 = ⋅ ( k + i ) = ⋅ ( c c + a c ) C→R
2
r r v a a⋅ 2 r r a2 r r r r a2
a R = bR = c R = ⋅ 1 + 1 + 0 = a R ⋅ bR = ⋅ (i + j ) ⋅ ( j + k ) =
2 2 4 4
r r a 2 2 r r 2 ⋅ a2 r r a2 r r 1
a R ⋅ bR = ( ) ⋅ cos(a R , bR ) = ⋅ cos(a R , bR ) = cos(a R , bR ) =
2 4 4 2
π
Ce qui donne : γ R = = 60° et donc : α R = β R = γ R = 60° .
3
Le réseau est bien rhomboédrique.
Transformation : CFC →
(P )
H
r r a a⋅ 2 v a
a H = bH = ⋅ 1 + 1 + 0 = cH = ⋅ 1+1+1 = a ⋅ 3
2 2 2
r r 1 r r r r a2 r r r r r a2
cos(a H , bH ) = − (a H , bH ) = 120° aH ⋅ cH = ⋅ ( −i + j ) ⋅ ( i + j + k ) = ⋅ (−1 + 1) = 0
2 2 2
r r a 2 r r r r r a2
bH ⋅ c H = ⋅ ( − j + k ) ⋅ (i + j + k ) = ⋅ (−1 + 1) = 0 donc α H = β H = 90° .
2 2
Le réseau est bien hexagonal.
7
1 1 0 − 1 1 0
1 1
Selon le cours : ( P) = ( P2 ) ⊗ ( P1 ) avec ( P1 ) = ⋅ 0 1 1 et ( P) = ⋅ 0 − 1 1
2 2
1 0 1 2 2 2
( P ) ⊗ ( P1 ) −1 = ( P2 ) ⊗ (( P1 ) ⊗ ( P1 ) −1 ) or ( P1 ) ⊗ ( P1 ) −1 = I Donc : ( P2 ) = ( P ) ⊗ ( P1 ) −1
1 1 0
1 3 2
1 1
∆ = ⋅ [1 + 1] = =
−1 1
Calculons ( P1 ) : ( P1 ) = ⋅ 0 1 1
2 2 2 4
1 0 1
2 1 1 − 1 2 1 −1 1 1 −1 0
1 1 −1
Cofact.( P1 ) = ⋅ − 1 1 1 ; Cofact.( P1 ) = ⋅ 1 1 − 1 ; ( P1 ) = 1 1 − 1
t
8
3°) [u v w]c →[u ' v' w']R →[u ' ' v' ' w' ']H
t −1 t −1
( P1 ) ( P2 )
1 − 1 0 − 1 − 2 1 − 4 − 2 1
−1 −1 1 −1
1
( P) = ( P1 ) ⊗ ( P2 ) = ⋅ 1 1 − 1 ⋅ 2 1 1 = ⋅ 2 − 2 1
3 3 2
− 1 1 1 − 1 1 1 4 1
u' ' − 4 2 2 1 0 0
1 1
v' ' = ⋅ − 2 − 2 4 ⋅ 1 = ⋅ 0 = 0
w' ' 3 3
H 1 1 1 1 C
3H 1 H
On retrouve ainsi le même résultat.
Corrigé Exercice 5 :
1°) Plans réticulaires : (100), (110), (111); (011), (321) .
(010)
(100)