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Chapter10 Gibbs Free Energy-Composition

Curves and Binary Phase Diagrams


§10-1. Introduction

§10-2. Gibbs Free Energy Curve, ∆ G M (X B )

§10-3. ∆ G M (X B ) of a Regular Solution

§10-4. Criteria For Phase Stability in Regular Solutions

§10-5. Standard States and Two-Phase Equilibrium

§10-6. Binary Phase Diagrams with Liquid and Solid Exhibiting

Regular Solution.

§10-7. Eutectic Phase Diagrams and Monotectic Phase Diagram


§10-1. Introduction
1. At constant T, P

(1) Stable (equilibrium) state ⇔ G = G min

(2) When phases coexist, ( a、ß、?… )


α β γ
G i = G i = G i =… … .

2. Isobaric binary phase diagrams can be determined from ∆ G M (X i ) curves at

different T for each phase.


e.g : Si-Ge isomorphous phase diagram.
T > Tm (Si ) : Liquid
T ≤ Tm (Si ) or liquidus line: solid phase coexists with liquid phase

X si (T ) 、 X λi (T ) can be determined.

§10-2. Gibbs Free Energy Curve, △ G M (X B )


∆G M =RT( X A ln a A + X B ln a B )

∵ ∆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

*When X B = X °B ,tangent intercept at X B =1 is ∆ G B


M

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)∣

∴ γ B (II) > γ idB = 1 > γ B (III)

* X i → 0 , ai → 0 , ∆ G i = RT ln a i → −∞

§10-3. ∆ G M (X B ) of a Regular Solution


∵Regular Solution, S xs = 0

∆G M − ∆G M ,id = G xs = ∆ H M =RT α X A X B = Ω X A X B

* For ∆ H M <0, ∆G M is more negative than ∆G M,id <0

a homogeneous solution is stable for all X B .

* For ∆ H M >0, a>0

∆G M ∆G M ,id ∆H M
- = =a X A X B
RT RT RT

∆G M ,id ∆SM ,id


ideal solution =- = X A ln X A + X B ln X B
RT R
∆G M ,id
Figure 10.2 I: (a=0)
RT
∆G M
When a ↑ ⇒ part of curve is convex upward.
RT

* When all ∆ G M (X B ) curve is 〝convex downward〞.


Figure 10.3 at any specific X °B , ( )
∆ G M X °B =d.

if it is mixed by any other two different compositions


(a + b ) → c
∆ G M (c ) > ∆ G M (d )

i.e. no phase separation.

* When part of ∆ G M (X B ) curve is 〝convex upward〞.

i. m< X B <q

∆ G M is minimized when two solutions(m, q)coexist

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.

a ↑ ⇒ clustering causes phase separation


curve AmqB represents the equilibrium state of the system, curve mnopq has
no physical significance.

§10-4. Criteria For Phase Stability in Regular Solutions


* Given T, a critical α cr occurs ,

α < α cr , hom ogeneous solution is stable.



α > α cr , phase separation occurs .

∂∆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

T > Tcr , α < 2, hom ogeneous solution .


When 
T < Tcr , α > 2, phase separation occurs .

∵ ∆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

T ≤ Tcr ⇒ eventually , at X B = 0.5, ∆G M is positive

∆G M ( X i ) is convex upward.

* Miscibility curve bounding two-phase region in phase diagram is the locus of


common tangent compositions .
Figure 10.5 (a),(b) for Ω =16630J , Tcr =1000K

* a B (X B ) at different T : Figure 10.5 (c)

(1) at T= Tcr , X B = 0.5, inflexion occurs (i).

∂a B ∂ 2 aB
i.e. =0 and =0
∂X B ∂X B
2

(2) T < Tcr , a B (X B ) has a maximum, and minimum point.


∂a B ∂ 2 ∆G M
B
e.g. Figure 10.6 points b, c where =0 and =0
∂X B ∂X B 2

⇒ spinodal compositio ns.


∩ ∂a B
* a B (X B ) curve between bc , ( )<0 ,
∂X B

∂a B
this violates the stability criterion : X B ↑ , ( )↑
∂X B


⇒ curve bc has no physical significance.

⇒ horizontal ad is actual constant activity in the two-phase region.

Points a, d are the common tangent of the ∆G M ( X B ) curve.

§10-5. Standard States and Two-Phase Equilibrium


1. Standard states: pure component in its stable state at specific T, P.
* ∵Standard state changes with T.
∴Choice of standard state is based on convenience.

2. Consider phase diagram in Figure 10.7 and Tm ( A) < T < Tm ( B )

Choose standard states: G οA (λ) = 0, G οA(S) = 0


∴ G οA(S) - G οA (λ) =- ∆G οm (A ) =-( ∆H οm (A ) − T∆Sοm( A) )

∆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 ) 

∴point c, G οA(s ) is more positive, when T ↑ ( T> Tm( A) )

solid A
line cb is Gibbs free energy of unmixed 
 solid B

∆ G=- X A ⋅ ∆Gοm (A)

 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)

* Assume : Ideal solution for solid and liquid solutions.

∆G M = RT (X A ln X A + X B ln X B ) + X B ∆G οm (B) ......(1)


∴  (Mλ) ο
∆G (S) = RT ( X A ln X A + X B ln X B ) − X A ∆G m (A) ......(2)

* Common tangent positions e, f are the compositions of liquid and solid solutions
in equilibrium.

* When T ↓ , ca ↓ and bd ↑ , positions of common tangent shift to left.

X A( λ) ( T) = ? , X A ( s) ( T) = ?

For equilibrium between solid and liquid


∆G MA( s ) = ∆G A(λ) ......(3)
M


∆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 )

∴ ∆ GAM( λ) =RT ln X A ( λ) … … (5)

∂∆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)

From (3),(5),(6), ∴RT ln X A ( λ) = RT ln X A ( S) - ∆G οm (A )

From (1),(2),(4), RT ln X B( S) = RT ln X B( λ) + ∆G οm( B)

 ∆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) 

∴Given Tm( A) , Tm( A) , ∆H οm (A ) , ∆H οm (B ) and

assuming ideal solution model for both liquid and solid solutions.
The solidus and liquidus lines in isomorphous phase diagram can be calculated.

Example: Ge-Si Figure 10.8

*Positions of points of double tangency are not influenced by choice of standard

states; they are determined only by T, ∆G οm (A ) , ∆G οm( B) .


See. Eq.(1),(2) and Figure 10.9

*Values of activity, ai , will depend on the choice of standard state of i and T.


See. Figure 10.7 (a)(b)(c):

Consider a B : Tm ( A) < T < Tm ( B )

If pure B(s) is chosen as standard state,

i.e. G οB(s ) =0 , G οB(λ) >0

∴ a B ( s ) =1, at X B = 1 . i.e. gn =1

point m is a B( λ ) of pure liquid B


mn
∴ a B( λ ) = <1
qn

G = GBο( s ) + RT ln( a B w.r .t . B( S ) )


∵ B ο
 GB = GB ( λ ) + RT ln( a B w.r .t . B( λ ) )

But G B should be independent of choice of standard state.

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

ai w.r .t. solid i ∆G m (i ) ο   Tm (i) − T 


Similarly, =exp( )=exp ∆H οm (i )  
ai w.r .t . liquid i RT  RTT 
m ( i) 
 

∴In Figure 10.7(c) , aB ( X B )


 line jihg is based on B(s) as s tan dard state

line jklm is based on B( λ) as s tan dard state

∆G οm (B)
these two lines vary in a constant ratio of exp( )
RT

* Similar discussions can be applied to a A , Figure 10.7(d)

* When T ↓ , since T< Tm ( B)

∴ ∆G οm( B) >0 , and ∆G οm( B) ↑

aB ( s )  mn 
, i.e. 
gn 
[ ]↑  ↑ or   ↓
aB ( λ )  mn   gn 

When T ↑ , ∆G οm( B) ↓ ; at T= Tm ( B) , ∆G οm( B) =0 , a B( s ) = a B( λ )


Point g and point m coincide.

§10-6. Binary Phase Diagrams with Liquid and Solid

Exhibiting Regular Solution.


1. Tm ( A) = 800 K , Tm ( B) = 1200K Figure 10.10

 ∆G m ( A) = 8000 − 10T Ω λ = −20 KJ (Re gular )



∆G m ( B) = 12000 − 10T Ω s = 0 ( ideal )

(1) Tm( A) < T = 1000K < Tm ( B)

Standard states : G οB(s ) =0 , G οA (λ) =0

∆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

(2) T= Tm( A) =800K , Figure 10.10(b)

(3) 480K<T=600K< Tm( A) =800K , Figure 10.10(c)

Standard states : G οA(s ) , G οB(s )

∆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

(5) T<480K , ∆G SM < ∆G M


λ

Tm( A) = 800 K ∆G m ( A) = 800 − 10T


2. 
Tm( B) = 1200 K ∆G m ( B) = 12000 − 10T

Ω λ = −20KJ (Re gular )



ΩS = +10KJ (Re gular )
Figure 10.11
ΩS 10000
* For solid solution : Tcr = = = 601 (K)
2R 2 × 8.314

λ , at T=661K , X B = 0.35
But ∆G SM = ∆G M

* When Ω λ ↓ and Ω S ↑

Tcr ↑ and point ( ∆G SM = ∆G M


λ )↓

Eventually, these two points merge, then eutectic system occurs.

Ω = +20KJ (Re gular )


3. Same conditions , but  λ
Ω S = +30KJ (Re gular )
Figure 10.12
* Critical temperatures for solid and liquid solutions.
Ωλ
Tcr( λ) = =1203K
2R
ΩS
Tcr(S) = =1804K > Tcr( λ)
2R

Monotectic : λ2 → λ1 + α /
* are shown.
Eutectic : λ → α + α
/
4. Figure 10.13 Different Ω λ , Ω S

* (a) → (d), Ω λ ↑ ⇒ Teutectic ↑ , (e) liquid is unstable ⇒ monotectic.

§7. Eutectic Phase Diagrams and Monotectic Phase


Diagram

1. Complete solid solubility of components A, B:

(1)Same crystal structure



( 2 )Comparable atomic size

( 3)Similar electroneg ativity
( 4 )Similar valence

if any one condition is not met ⇒ miscibility gap.


2. A-B system with two terminal solid solutions. ( α, β )
e.g. eutectic phase diagram. Figure 10.14

3. Solid solubility in α, β phases are extremely small.

* When solid solubility ↓ ⇒ ∆G M


α is compressed toward X A = 1

i.e. it coincides with vertical axis.

Complete miscibilit y in liquid state


Figure 10.15 * 
Complete immiscibil ity in solid state
Figure 10.16 Liquidus curves can be calculated assuming that liquid solution
is an ideal solution.

a A w.r.t. A (S) at X A = 1 a A =1

Consider at T< Tm( A) , ( pure A (s ) + liquid ) coexist.

∴ G οA(s ) = G A (λ) = G οA (λ) +RT ln a A w.r.t. A (λ)

∴ G οA( λ) − G οA( s) = ∆G οm (A ) =-RT ln a A

assuming ideal liquid solution a A = X A (λ)

∴ ∆G οm (A ) =-RT ln X A (λ)

∆G οm ( A)
i.e. X A (λ) =exp( − )
RT

If ∆G οm (A ) = f (T) is known ⇒ X A (λ) =g (T) can be obtained.

e.g. Bi-Cd phase diagram Figure 10.17


Tm (Bi) = 544 K
 ο
∆H m ( Bi) = 10900 (J )
(3.1) Bi  −3
C P ,Bi(s ) = 18.8 + 22.6 × 10 T (J / K )
C −3 5 −2
 P ,Bi(λ) = 20 + 6 .15 × 10 T + 21.1 × 10 T ( J / K )

∴ At T= Tm (Bi ) =544K, ∆G οm( Bi) = 0 = ∆H οm (Bi ) - Tm ⋅ ∆Sοm (Bi )

∆H οm ( Bi)
∴ ∆Sοm (Bi ) = =20.0 (J/K)
Tm ( Bi)

∆G οm( Bi) (T) = ? T ≠ Tm (Bi )

∴ ∆C P,Bi = C P ,Bi( λ) - C P ,Bi(s ) =1.2-16.45 × 10 −3 T+21.1 × 10 5 T −2

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

ideal solution : -RT ln X Bi( λ) = ∆G οm( Bi)


− 1992 −4 1.269 × 10 5
ln X Bi( λ) = + 2.861 + 0.144 ln T − 9.892 × 10 T + … … (1)
T T2

∴ X Bi (λ) (T) is line(i) in Fig. 10.17


Tm (d ) = 594 K
 ο
∆ H = 6400 J, ∆Sοm (Cd ) = 10.77 J / K
(3.2) Cd  m (Cd ) −3
C P,Cd (s) = 22.2 + 12.3 × 10 T ( J / K)
C P,Cd (λ) = 29.7 ( J / K )

T ∆C P ,(Cd )
∴ ∆G οm (Cd ) = ∆H οm (Cd ) + ∫ ∆C P,Cd dT -T( ∆Sοm(Cd ) + ∫
T
dT )
594 594 T

∗ assume ideal liquid solution


∆G οm (Cd ) =-RT ln XCd( λ) , 
∗ neglect solid so lub ility

− 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

Actual : Te =419K> (Te = 406K )cal.

∵Caculation is based on “ideal” solution.

 from (1) : ∆G οm( Bi) = 2482J


At T=419K ,  ο
from ( 2) : ∆G m (Cd ) = 1898J

 ∆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

∴ positive deviation from ideality ! ⇒ Te > Te(cal.)

4. When positive deviation from ideal liquid solution increase , G XS > 0 , G XS ↑


⇒ Ω > Ω cr (1) Liquidus curve is not a monotonic. Max. and min. of curve
forms.
(2) Liquid miscibility gap forms.
⇒ as conditions (1),(2) merge, monotectic system appears.
* Assuming liquid solution is regular.

∴- ∆G οm (A ) =RT ln a A =RT ln X A +RT ln γ A

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

e.g. Tm( A) =2000K, ∆H οm (A) =10KJ

∴- ∆G οm (A ) =10000+5T=RT ln X A + Ω (1 − X A ) 2

Liquidus curve X A (λ) for different Ω is shown in Figure 10.18

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)

pure A (S) is standard state. ∴ a A =1 w.r.t. A (S)

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

* When Ω =30KJ , for regular liquid solution


Ω 30000
Tcr = = =1804K Figure 10.19.
2R 8.31× 2
Ex: Cs-Rb phase diagram, Figure 10.20

 Tm (Cs ) = 28.4 ο C  ∆G οm (Cs ) = 2100 − 6.95T ( J)


 ο ,  ο
Tm (Rb ) = 39.5 C ∆G m( Rb ) = 2200 − 7.05T (J )

liquid solution : ideal


Compare with theory assuming: 
solid solution : regular , Ω S = ?
Sol: From phase diagram : liquidus and solidus curves touch each other
 X = 0.47
at  Rb ο
 T = 9 .7 C

 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

c.p. When T=20 ο C =293K

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

Very good fitting!! Figure 10.21

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