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“Phase Equilibria in Materials”

Eun Soo Park

Office: 33-313

Telephone: 880-7221 Email: espark@snu.ac.kr

Office hours: by an appointment

2019 Spring

03.20.2019

1

(2)

2

Contents for previous class

- Chemical potential and Activity

- Gibbs Free Energy in Binary System - Binary System

Ideal solution

Regular solution

mixture/ solution / compound

G

2

= G

1

+ ΔG

mix

J/mol G

1

= X

A

G

A

+ X

B

G

B

J/mol

(∆H

mix

=0) G

mix

RT ( X

A

ln X

A

X

B

ln X

B

)

mix

AB

    

AB

1   

AA BB

H P where ( )

2

) ln

ln

(

A A B B

B A B

B A

A

G X G X X RT X X X X

X

G      

  

  A   A T, P, nB

G' n

• μ

A

= G

A

+ RTlna

A

dnA~ small enough (∵ A depends on the composition of phase)

(3)

3

Solid Solution vs. Intermetallic Compounds

Pt0.5Ru0.5 – Pt structure (fcc) PbPt – NiAS structure

*

Binary System (two components)

 A, B

: Equilibrium depends on not only pressure and temperature but also composition.

- atomic scale mixture/ Random distribution on lattice - fixed A, B positions/ Ordered state

(4)

4

Solid solution:

– Crystalline solid

– Multicomponent yet homogeneous

– Impurities are randomly distributed throughout the lattice

Factors favoring solubility of B in A (Hume-Rothery Rules) – Similar atomic size: ∆r/r ≤ 15%

– Same crystal structure for A and B

– Similar electronegativities: |A B| ≤ 0.6 (preferably ≤ 0.4) – Similar valence

If all four criteria are met: complete solid solution

If any criterion is not met: limited solid solution

Empirical rules for substitutional solid-solution formation were identified from experiment that are not exact, but give an expectation of formation.

Hume-Rothery Rules for Mixing

(5)

Cu-Ag Alloys Cu-Ni Alloys

complete solid solution limited solid solution

: in order to introduce some of the basic concepts of the thermodynamics of alloys

Assumption: a simple physical model for “binary solid solutions”

(6)

6

Chemical potential

 

A A

dG' dn

The increase of the total free energy of the system by the increase of very small quantity of A, dn

A

, will be proportional to μ

A

.

dnA~ small enough

(∵ A depends on the composition of phase)

(T, P, n

B

: constant )

G

= H-TS = E+PV-TS

For A-B binary solution, dG'  

A

dn

A

 

B

dn

B

    

A A

 

B B

dG' SdT VdP dn dn

For variable T and P

1) Ideal solution

1.3 Binary Solutions

A

:

partial molar free energy of A or chemical potential of A

  

  A   A T, P, nB

G' n

  

  B   B T, P, nA

G' n

(7)

B B

B A

A

A

RT X X G RT X X

G ln ) ( ln )

(   

1) Ideal solution 1.3 Binary Solutions

μB

μA XB

Fig. 1.12 The relationship between the free energy curve and

Chemical potentials for an ideal solution. 7

(8)

Contents for today’s class

- Equilibrium in heterogeneous system - Binary Solid Solution

Real solution

Ideal solution and Regular solution

- Ordered phases: SRO & LRO, superlattice, Intermediate phase (intermetallic compound) - Clustering

: Chemical potential

and

Activity

8

(9)

Q1: What is “Regular Solution”?

∆Gmix = ∆Hmix - T∆Smix

1.3 Binary Solutions

9

(10)

Ideal solution : H

mix

= 0

Quasi-chemical model assumes that heat of mixing, H

mix

, is only due to the bond energies between adjacent atoms.

Structure model of a binary solution

Regular Solutions

∆Gmix = ∆Hmix - T∆Smix

1.3 Binary Solutions

Assumption: the volumes of pure A and B are equal and do not change during mixing so that the interatomic distance and bond energies are independent of composition.

This type of behavior is exceptional in practice and usually mixing is endothermic or exothermic.

Fig. 1.13 The different types of interatomic bond in a solid solution.

10

(11)

Q2: How can you estimate

“ΔH mix of regular solution”?

Gibbs Free Energy of Regular Solutions

∆H

mix

= ΩX

A

X

B

where Ω = N

a

11

(12)

Bond energy Number of bond A-A 

AA

P

AA

B-B 

BB

P

BB

A-B 

AB

P

AB

AA AA

 

BB BB

 

AB AB

E P P P

mix

AB

    

AB

1   

AA BB

H P where ( )

2

Internal energy of the solution

Regular Solutions

1.3 Binary Solutions

12

(13)

 H

mix

 0

Completely random arrangement

ideal solution

AB

a A B

a

P N zX X bonds per mole N : Avogadro's number

z : number of bonds per atom

∆H

mix

= ΩX

A

X

B

where Ω = N

a

 H

mix

 P

AB

Regular Solutions

 0

 ( )

2 1

BB AA

AB

 

  

 0 P

AB

  0 P

AB

 0

Ω >0

1.3 Binary Solutions

(1) (2)

(3)

Fig. 1.14 The variation of ΔHmixwith composition for a regular solution.

(14)

Q3: How can you estimate

“Molar Free energy for regular solution”?

) ln

ln

(

A A B B

B A B

B A

A

G X G X X RT X X X X

X

G      

G2 = G1 + ΔGmix ∆Hmix -T∆Smix

14

Gibbs Free Energy of Regular Solutions

(15)

Regular Solutions

Reference state

Pure metal

G

A0

G

B0

 0

) ln

ln

(

A A B B

B A B

B A

A

G X G X X RT X X X X

X

G      

G2 = G1 + ΔGmix

∆Gmix

= ∆H

mix - T∆Smix

∆Hmix -T∆Smix

15

(16)

Q4: How can you calculate

“critical temperature, T c ”?

16

Gibbs Free Energy of Regular Solutions

(17)

 > 0, H

mix

> 0 / H

mix

~

+17 kJ/mol

(18)

Regular Solutions

∆Gmix

= ∆H

mix - T∆Smix

∆Hmix -T∆Smix

Reference state

Pure metal

G

A0

G

B0

 0

(a)

(b)

(19)

19

where,

: energy term

Low temp.

High temp.

* Variation of free energy with composition for a homogeneous solution with ΔHmix > 0

→The curves with kT/C < 0.5 show two minima, which approach

each other as the temperature rise.

(20)

20

where,

Taking the curve kT/C = 0.25 as an example, we can substitute C=4kT in upper eq. to obtain

∆Hmix ∆Smix

* Free energy curve exhibit two minima at XA

= 0.02 and X

A

=0.98

.

(21)

where,

Low temp.

High temp.

* The curves with kT/C < 0.5 show two minima, which approach each other as the temperature rise.

(22)

22

where,

: energy term

Low temp.

High temp.

* With kT/C ≥ 0.5 there is a

continuous fall in free energy from XA=0 to XA=0.5 and XA=1.0 to

XA=0.5. The free energy curve thus assumes the characteristic from one associates with the formation of homogeneous solutions.

* The curves with kT/C < 0.5 show two minima, which approach

each other as the temperature rise.

(23)

23

where,

: solubility limit

(24)

Figure. 21. Solubility curve obtained from eqn. (100)

by plotting the concentration A in two-existing phases as a function of kT/C.

The solubility of the components in each other increases with temperature until a temperature is reached where the components are completely miscible (soluble) in each other.

The temperature at which complete miscibility occurs is called the critical temperature, Tc.

(25)

25

(26)

26

 > 0, H

mix

> 0 / H

mix

~

+17 kJ/mol

Incentive Homework1:

please find and summary models for asymmetric miscibility gaps as a ppt file.

Ref. Acta Meter. 1 (1953) 202/ Acta Meter. 8 (1960) 711/ etc.

(27)

27

> 0, H

mix

> 0 / H

mix

~

+5

kJ/mol

(28)

Q5: “Correlation between chemical potential and free energy”?

Gibbs Free Energy of Binary Solutions

28

(29)

1

 

A A

 

B B

G X X Jmol

For 1 mole of the solution (T, P: constant )

G = E+PV-TS G = H-TS

2) regular solution

A B B

A B

A B A B

AX X X X X X X X X

X ( ) 2 2

B B

B B

A A

A A

X RT

X G

X RT

X G

ln )

1 (

ln )

1 (

2 2

) ln

ln

(

A A B B

B A B

B A

A

G X G X X RT X X X X

X

G      

) ln

) 1

( (

) ln

) 1

(

( A A 2 A B B B 2 B

A G X RT X X G X RT X

X       

  

  

A A A

B B B

G RTln X G RTln X

Correlation between chemical potential and free energy

Ideal solution

복잡해졌네 --;;

Regular solution

29

(30)

Q6: What is “activity”?

Gibbs Free Energy of Binary Solutions

30

(31)

Activity, a : effective concentration for mass action

ideal solution

regular solution

μ

A

= G

A

+ RTlna

A

μ

B

= G

B

+ RTlna

B

 

 

A A A

B B B

G RTln X G RTln X

B B

B B

A A

A

AG   (1  X )2RT ln X

G   (1  X )2RT ln X

 

B

a

B

X

)

2

1 ( )

ln(

B

B

B

X

RT X

a  

31

(32)

 1

A A

X

1

a

A A

X a

Degree of non-ideality

32

(33)

Variation of activity with composition (a) a

B

, (b) a

A

a

B

a

A

Line 1 : (a) aB=XB, (b) aA=XA Line 2 : (a) aB<XB, (b) aA<XA Line 3 : (a) aB>XB, (b) aA>XA

ideal solution…Rault’s law ΔHmix<0

ΔHmix>0

B in A

random mixing

A in B

random mixing

33

(34)

Q7: “Chemical equilibrium of multi‐phases”?

Gibbs Phase Rule

Gibbs Free Energy of Binary Solutions

34

(35)

35

(36)

36 2

(37)

37

Degree of freedom

(number of variables that can be varied independently)

The Gibbs Phase Rule

= the number of variables – the number of constraints

(38)

38

The Gibbs Phase Rule

In chemistry, Gibbs' phase rule describes the possible number of degrees of freedom (F) in a closed system at equilibrium, in terms of the number of separate phases (P) and the number of chemical components (C) in the system. It was deduced from thermodynamic principles by Josiah Willard Gibbs in the 1870s.

In general, Gibbs' rule then follows, as:

F = C − P + 2 (from T, P).

From Wikipedia, the free encyclopedia

1.5 Binary phase diagrams

(39)

2

2 3 2 1

1

1

1 single phase F = C - P + 1

= 2 - 1 + 1 can vary T and = 2 composition independently

2 two phase

F = C - P + 1

= 2 - 2 + 1 can vary T or = 1 composition

3 eutectic point F = C - P + 1

= 2 - 3 + 1 can’t vary T or = 0

composition For Constant Pressure,

P + F = C + 1

The Gibbs Phase Rule

(40)

40

The Gibbs Phase Rule

(41)

41

- Chemical potential and Activity

- Gibbs Free Energy in Binary System - Binary System

Ideal solution

Regular solution

mixture/ solution / compound

G

2

= G

1

+ ΔG

mix

J/mol G

1

= X

A

G

A

+ X

B

G

B

J/mol

(∆H

mix

=0) G

mix

RT ( X

A

ln X

A

X

B

ln X

B

)

mix

AB

    

AB

1   

AA BB

H P where ( )

2

) ln

ln

(

A A B B

B A B

B A

A

G X G X X RT X X X X

X

G      

  

  A   A T, P, nB G'

n

• μ

A

= G

A

+ RTlna

A

- Chemical equilibrium → Gibbs phase rule

dnA~ small enough (∵ A depends on the composition of phase)

참조

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