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Regular Solution.
X si (T ) 、 X λi (T ) can be determined.
∵ ∆G M ,id =RT( X A ln X A + X B ln X B )
∴ ∆G M = ∆G M ,id +RT( X A ln γ A + X B ln γ B )
Figure 10.1 I . ∆ G M ,id <0
II . γ i >1
III. γ i <1
M M
∴∣ Bb = ∆ G B =RT ln a B (II)∣<∣ Ba = ∆ G B = RT ln a B (I)∣
M
<∣ Bc = ∆ G B = RT ln a B (III)∣
* X i → 0 , ai → 0 , ∆ G i = RT ln a i → −∞
∆G M − ∆G M ,id = G xs = ∆ H M =RT α X A X B = Ω X A X B
∆G M ∆G M ,id ∆H M
- = =a X A X B
RT RT RT
i. m< X B <q
e.g. γ → m+q
ii. m, q are the common tangent of ∆ G M curve.
G (solution m ) = G A (solution q)
∴ A
G B (solution m ) = G B (solution q)
∴ subtracting G °A and G °B
a A ( m ) = a A( q )
then
a B ( m ) = a B ( q )
i.e. solutions m, q are in equilibrium, they coexist.
∂∆G M ∂ 2 ∆G M ∂ 3 ∆G M
* When α = α cr , = 0, = 0 , =0
∂X B ∂X B 2 ∂X B 3
Figure 10.4
∴ ∆G M =RT( X A ln X A + X B ln X B )+RT αX A X B
∂∆G M X
∴ = RT [ ln B + α ( X A − X B )]
∂X B XA
∂ 2 ∆G M 1 1
= RT( + − 2α )
∂X B 2
XA XB
∂ 3 ∆G M 1 1
=( − )
∂X B 3
XA 2
X B2
∂ 3 ∆G M
From = 0 , ∴ X A = X B = 0.5
∂X B 3
∂ 2 ∆G M
Then from =0, α = α cr = 2
∂X B 2
∵ Ω =RT α
Ω Ω
∴For a given positive Ω ( Ω > 0 ) , Tcr = =
α cr R 2R
* Given fixed Ω >0
∵ ∆G M = RT ( X A ln X A + X B ln X B ) + RTα X A X B
(1) (2)
RT α = Ω =constant
term ( 2) is indep . of T
term (1) : T ↓⇒ term (1) is less negative
∆G M ( X i ) is convex upward.
∂a B ∂ 2 aB
i.e. =0 and =0
∂X B ∂X B
2
∂a B
this violates the stability criterion : X B ↑ , ( )↑
∂X B
∩
⇒ curve bc has no physical significance.
∆C P
∆ H= ∆ H ο + ∫ ∆C P dT , ∆ S= ∆ Sο + ∫ dT
T
at T = Tm (A) , ∆G οm (A ) = 0 ∴ ∆H οm ( A) = Tm ∆Sοm (A )
ο ο
if C P,A (S ) = C P,A (λ) , ∆H m (A) , ∆Sm ( A) are indep . of T.
Tm ( A ) − T
∴ ∆G οm (A ) = ∆H οm (A )
Tm (A )
solid A
line cb is Gibbs free energy of unmixed
solid B
Tm ( A ) − T
similarly, G οB(λ) - G οB (S) = ∆G οm ( B) = ∆H οm (B ) -T ∆Sοm( B) ≅ ∆H οm (B )
Tm (A )
line ab , ∆G = X B ⋅ ∆G οm ( B)
∩
curve aed is the liguid solution , ∆G M
( λ)
∩
curve cfb is solid solution , ∆G M
( S)
* Common tangent positions e, f are the compositions of liquid and solid solutions
in equilibrium.
X A( λ) ( T) = ? , X A ( s) ( T) = ?
∆G B(s ) = ∆G B(λ) ......(4)
M M
∂∆G M
( λ)
∵ ∆G AM(λ) = ∆G M
A ( λ) + X B( λ)
∂X A ( λ )
∂∆G M
( λ)
From (1) =RT( ln X A ( λ) -ln X B( λ) )- ∆G οm( B)
∂X A ( λ )
∂∆G M
Similarly, ∆G M
A ( S) = ∆G M
( S) + X B( S)
∂X A (S)
ο
From (2) : ∴ ∆ G M
A( S) =RT ln X A ( S) - ∆G m ( A ) … … (6)
∆G οm (A)
X A(λ) = X A (S) ⋅ exp( − )......(7 )
RT
∴
X ∆G οm (B)
B( λ) = X B (S) ⋅ exp( − )
RT
∆G οm (B)
or (1- X A ( λ) )=(1- X A( S) )exp(- )… … (8)
RT
From (7),(8)
∆G οm (B )
1 − exp( − )
X A ( S) = RT
∆G οm (A ) ∆G οm (B)
exp( − ) − exp( − )
RT RT
∆G οm (B ) ∆G οm (A)
[1 − exp( − )] ⋅ exp( − )
RT RT
X A(λ) =
∆G οm (A ) ∆G οm ( B)
exp( − ) − exp( − )
RT RT
If C P ,i ( λ) = C P ,i ( S)
T − T
∆G οm(i ) ≅ ∆H οm (i ) m ( i )
Tm ( i)
assuming ideal solution model for both liquid and solid solutions.
The solidus and liquidus lines in isomorphous phase diagram can be calculated.
∴ a B ( s ) =1, at X B = 1 . i.e. gn =1
aB w.r .t . B( s )
∴ G οB(λ) - G οB(s ) = ∆G οm( B) =RT ln [ ]
aB w.r .t . B( λ )
aB w.r .t . B( s )
Since T< Tm ( B) , ∴ ∆G οm( B) >0 , ∴ [ ] >1
aB w.r .t . B( λ )
aB w.r .t . B( s )
∴ >1
aB w.r .t . B( λ )
i.e. a B( s ) > a B( λ )
aB w.r .t . B( s ) ∆G οm (B)
=exp( )
aB w.r .t . B( λ ) RT
∆G οm (B)
these two lines vary in a constant ratio of exp( )
RT
aB ( s ) mn
, i.e.
gn
[ ]↑ ↑ or ↓
aB ( λ ) mn gn
∆G M = X B ⋅ ∆G οm (B) + RT (X A ln X A + X B ln X B ) + Ω λX A X B
∴ λM ο
∆G S = −X A ⋅ ∆G m (A ) + RT ( X A ln X A + X B ln X B ) + Ω S X A X B
∆G M = X B ∆G οm (B ) + X A ∆G οm ( A) + RT ( X A ln X A + X B ln X B ) + Ω λX A X B
∴ λM
∆G S = RT (X A ln X A + X B ln X B )
(4) T=480K , ∆G SM = ∆G M
λ at X B =0.41
λ , at T=661K , X B = 0.35
But ∆G SM = ∆G M
* When Ω λ ↓ and Ω S ↑
Monotectic : λ2 → λ1 + α /
* are shown.
Eutectic : λ → α + α
/
4. Figure 10.13 Different Ω λ , Ω S
a A w.r.t. A (S) at X A = 1 a A =1
∴ ∆G οm (A ) =-RT ln X A (λ)
∆G οm ( A)
i.e. X A (λ) =exp( − )
RT
∆H οm ( Bi)
∴ ∆Sοm (Bi ) = =20.0 (J/K)
Tm ( Bi)
T ∆C P,Bi
∆G οm( Bi) = ∆H οm (Bi ),544 + ∫ ∆C P,Bi dT -T( ∆Sοm( Bi),544 + ∫
T
dT )
544 T 544
−3 2 5 −1
=16560-23.79T-1.2T lnT+8.225 × 10 T -10.55× 10 T
∴
− 1992 −4 1.269 × 10 5
ln X Bi( λ) = + 2.861 + 0.144 ln T − 9.892 × 10 T + … … (1)
T T2
− 495
∴ ln X Cd (λ) = -4.489+0.90 lnT- 7.397 × 10 −4 T … … (2)
T
∗ (1) X Bi ( λ) = f (T )
(3.3) ∴Eutectic temperature:
∗ ( 2) 1 − X Bi ( λ) = g( T)
∴ 1-f (T)=g (T) ⇒ T= Te =406 K
∆G οm (Bi ) = RT ln aBi
∵
∆G m (Cd ) = RT ln a Cd
aBi = 0 .49
∴ , Actual eutectic composition is X Cd = 0.55, X Bi = 0.45
Cd
a = 0 .58
a Bi
γ Bi = X = 1.09
∴ Bi >1.0
aCd
γ Cd = = 1.05
X Cd
ln γ A Ω
∵regular solution : α = =
(1 − X A ) 2
RT
∴ ∆G οm (A ) =RT ln X A +RT α (1 − X A ) 2
∆G οm (A ) =RT ln X A + Ω (1 − X A ) 2
∴- ∆G οm (A ) =10000+5T=RT ln X A + Ω (1 − X A ) 2
Ω > Ω cr =25.3KJ
max. and min. appears ⇒ part of curve has no physical meaning.
Tcr = 1413K
At Ω = Ω cr
X A = 0 .5
dT d2 T
( )=0, =0
dX A dX 2A
Proof :
a A w.r .t . A ( S) ∆G οm( A) ∆H οm (A ) Tm ( A ) − T
∵ = exp[ ] = exp[ ( )]
a A w.r. t. A (λ) RT RT Tm ( A)
1 ∆H οm (A ) ∆H οm ( A )
∴ =exp[ − ]
a A( l ) RT RT m ( A)
∆H οm (A ) ∆H οm ( A )
∴ln a A =- +
RT RT m ( A)
ο ο
d ln a A ∆H m (A ) da A ∆H m(A )
= 2
, ∴d ln a A = = dT
dT RT aA RT 2
2
dT RT da A
= ⋅
dX A ∆H ο ⋅ aA dX A
m( A )
d 2T 2RT daA dT RT 2 da 1 da
=( ο
⋅ ) -( ο
⋅ A ). 2 .( A )
dX A ∆H m( A ) ⋅ a A dX A dX A
2
∆H m( A ) dX A aA dX A
RT 2 d 2 aA
+ .
∆H mο ( A ) ⋅ a A dX 2A
daA d 2 aA
∵ Ω = Ω cr , T= Tcr , =0 and =0
dX A dX 2A
dT d2 T
∴ =0 and =0
dX A dX 2A
T < Tm(Cs)
when
T < Tm(Rb)
Standard states : G οCs (s) =0 , G οRb (s) =0
ο ο
∆G M( λ) = RT( X Rb ln X Rb + X Cs ln X Cs ) + X Rb ⋅ ∆G m( Rb ) + X Cs ⋅ ∆G m ( Cs )
∴ M
∆G (s ) = RT ( X Rb ln X Rb + X Cs ln X Cs ) + Ω S X Rb X Cs
T = 9.7 οC = 282.7K
at ∆G M
( λ) = ∆G ( s ) , ∴ Ω s =668(J)
M
X Rb = 0.47, X Cs = 0.53
common tangents to ∆G M
( λ) and ∆G ( s )
M
X Rb ( s ) = 0.10 X Rb ( λ) = 0.75
X Rb ( λ) = 0.13 X Rb ( s ) = 0.81