Binary Solutions

Composition as a thermodynamic variable Gibbs free energy of binary solutions Entropy of formation and Gibbs free energy of an ideal solution Chemical potential of an ideal solution Regular solutions: Heat of formation of a solution Activity of a component, Henrys and Raoults laws Real solutions: interstitial solid solutions, ordered phases, intermediate phases, compounds Equilibrium in heterogeneous systems Reading: Chapter 1.3 of Porter and Easterling, Chapters 9.5, 9.6, 9.9, 9.10 of Gaskell

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Solid Solutions (terminology)

Solid solutions are made of a host (the solvent or matrix) which dissolves the minor component (solute). The ability to dissolve is called solubility. Solvent: in an alloy, the element or compound present in greater amount Solute: in an alloy, the element or compound present in lesser amount Solid Solution: 9 homogeneous 9 maintains crystal structure 9 contains randomly dispersed impurities (substitutional or interstitial) Second Phase: as solute atoms are added, new compounds / structures are formed, or solute forms local precipitates Solubility Limit of a component in a phase is the maximum amount of the component that can be dissolved in it (e.g. alcohol has unlimited solubility in water, sugar has a limited solubility, oil is virtually insoluble). The same concepts apply to solid phases: Cu and Ni are mutually soluble in any amount (unlimited solid solubility), while C has a limited solubility in Fe. Whether the addition of impurities results in formation of solid solution or second phase depends the nature of the impurities, their concentration and temperature, pressure
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Composition as a thermodynamic variable

Real materials are almost always mixtures of different elements rather than pure substances: in addition to T and P, composition is also a variable. To understand conditions for equilibrium and phase diagrams (like the one below) we have to understand how the Gibbs free energy of a given phase depends on composition, temperature and pressure. Since many real experiments are performed at fixed pressure of 1 atm, we will focus on G(T, composition).

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Gibbs free energy of a binary solution (I)

Lets consider a binary solution of A and B atoms that have the same crystal structures in their pure states and can be mixed in any proportions - form a solid solution with the same crystal structure (unlimited solid solubility). Example: Cu and Ni. 1 mol of homogeneous solid solution contains XA mol of A and XB mol of B. XA and XB are the mole fractions of A and B in the alloy.

XA + XB = 1

Lets consider two steps of mixing: 1. Bring together XA mol of pure A and XB mol of pure B 2. Mix A and B to make a homogeneous solution After step 1 the free energy of the system is

Gstep1 = XAGA + XBGB

G
Gstep1
GA

X AG A GB
Gibbs free energy per mole before mixing

X BG B

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Gibbs free energy of a binary solution (II)

After step 2 the free energy of the system is

G step2 = G step1 + G mix

Where Gmix is the change of the Gibbs free energy caused by the mixing.

G mix = H mix T Smix

H mix = H step2 H step1 Smix = Sstep2 Sstep1

- heat of mixing of the components (heat of formation of a solution) - difference in entropy between mixed and unmixed states (entropy of formation of a solution)

Lets first consider an ideal solution interactions between atoms A-A, B-B and A-B are identical, and Hmix = 0. The free energy change upon mixing is only due to the change in configurational entropy:

Gid mix = T Smix

Smix = Sstep2 Sstep1

Sstep1 = k Bln1 = 0 - there is only one way the atoms can be

arranged before mixing Therefore Smix = Sstep2
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Entropy of formation of an ideal solution (I)

Statistical definition of entropy:

S = kB ln

Statistical mechanics: if we have Ntot objects and Nspec of them are special or different, the number of ways the objects can be arranged (number of microstates) is Remember for vacancies we had Ntot = N number of lattice sites, Nspec = n number of vacancies.

N tot ! = N spec !(N tot N spec )!

For mixing of NA particles of type A with NB atoms of type B:

( N A + N B )! =
N B! N A !

S mix = k B ln = k B ln

(N A + N B )!
N B! N A !

Using Stirling formula for big numbers: ln N! N ln N N

S mix = k B [ln (N A + N B )!-lnN A !-lnN B !] =

= kB[(NA + NB )ln(NA + NB ) - (NA + NB ) - NAlnNA + NA - NBlnNB + NB ] =

N B NA = k B N A ln N +N + N B ln N +N B B A A
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Entropy of formation of an ideal solution (II)

NA XA = NA + NB NB XB = NA + NB

If the total amount of material is 1 mol, NA + NB = Avogadros number (Na), and NA = XANa, NB = XBNa, NakB = R. Therefore

S mix

N B NA = k B N A ln = N +N + N B ln N +N B B A A

= R [X A lnX A + X B lnX B ]

Gid mix = T Smix = RT[X A lnX A + X B lnX B ]

For the total Gibbs free energy of an ideal solution:

G id = G step2 = G step1 + G id mix

Gstep1 = XAGA + XBGB

G id = X A G A + X BG B + RT[X A lnXA + X BlnXB ]

For a nonideal solution we have to take into account heat of formation Hmix: G mix = H mix T Smix
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Gibbs free energy of an ideal solution

Gid mix = T Smix = RT[X A lnX A + X B lnX B ]

G id = X A G A + X BG B + RT[X A lnXA + X BlnXB ]

0
Gid mix

T1 T2
XB

T2 > T1

0
Gid

1
GB T GB T

GA T GA T

Decrease of GA and GB with T is due to the temperature dependence of the free energy:

id mix

G = S T P

XB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Chemical potential of an ideal solution

Remember definition of the chemical potential of the species i :
G i = n i P ,T ,n j ,...
G dG = SdT + VdP + dn i n i =1 i P ,T , n i ,...
i=k

For a binary solution at constant P and T: dG = A dn A + Bdn B Addition of XA mol of atoms A and XB mol of atoms B (i. e. dnA/dnB = XA/XB) will increase the size of the system by 1 mol without changing composition and, therefore without changing A and B. The Gibbs free energy of an ideal solution will increase in this case by the molar Gibbs free energy G:

G = A X A + BX B [J/mol]
Since XA + XB = 1

G = A + ( B A )X B

G = B A X B

Also, G id = X A G A + X B G B + RT [X A lnX A + X B lnX B ]

Gid

GB

Therefore, for an ideal solution:

GA

RTlnX B

A = G A + RTlnX A B = G B + RTlnX B

B
XB

A and B depend on the composition of the phase.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (I)

For a nonideal solution we have to take into account heat of formation Hmix 0:

G mix = H mix T Smix

H mix > 0 H mix < 0

- mixing is endothermic (heat absorbed) - mixing is exothermic (heat released)

Lets account for the heat of formation Hmix 0 using a simple model called statistical or quasi-chemical model. In this model the heat of mixing is only related to the bond energies between adjacent atoms. The assumption is that the interatomic distances and bond energies are independent of composition.
B B A B A B A A B A B A A A A B

3 types of bonds: A A bond (energy EAA) A B bond (energy EAB) B B bond (energy EBB)

If there are PAA, PBB, PAB bonds of each type, the internal energy of the solution is

E = PAA E AA + PBBE BB + PABE AB

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (II)

Lets calculate the internal energy of the solution:

E = PAA E AA + PBBE BB + PABE AB

If z is the coordination number of an atom in a crystal, then the number of atoms NA and NB are related to the number of bonds as

N A z = 2PAA + PAB

N B z = 2PBB + PAB

PAA

N A z PAB = 2 2

PBB =

N B z PAB 2 2

Using these expressions for PAA and PBB in the expression for energy, we have

N z P N z P E = A AB E AA + B AB E BB + PABE AB = 2 2 2 2 E AA + E BB NAz N Bz = E AA + E BB + PAB E AB 2 2 2

energy of unmixed components Therefore, the energy of mixing (heat of formation Hmix) is

H mix = H step2 H step1 E mix

E AA + E BB = PAB E AB 2

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Heat of formation of a solution (III)

The energy of mixing (heat of formation Hmix) calculated within statistical or quasi-chemical model is

E + E BB H mix = PAB E AB AA 2 E + E BB If E AB = AA the solution is ideal: Hmix = 0 2

E AA + E BB If E AB > 2 E AA + E BB If E AB < 2

Hmix > 0 atoms will tend to be surrounded by atoms of the same type Hmix < 0 atoms will tend to be surrounded by atoms of different type

But for small differences between EAB and (EAA+EBB)/2 (and for high T) we can still consider a random arrangement of atoms in a solution (such solutions are called regular solutions). Then

PAB = zNtotXAXB

and

Hmix = XAXB

where

E AA + E BB = zN tot E AB 2

Hmix

>0

0
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

XB

Regular solutions: Gibbs free energy (I)

Gmix = Hmix T Smix = XAXB + RT(XAlnXA + XBlnXB )

<0
H mix

For < 0, Hmix < 0 exothermic solution mixing is favorable at all T For high || and low T PAB max an ordered alloy could be formed the assumption of random mixing is not valid, solution is not regular, Hmix XAXB

- TSmix
G mix

XB

> 0, high T
H mix

> 0, low T
H mix

G mix

G mix

- TSmix

- TSmix
1

XB

XB

For > 0, Hmix > 0 mixing (formation of A-B pairs is avoided at low T. At high T entropy helps to mix. At low T MSE 3050, Phase Diagrams Kinetics, Leonid clustering may occur and solution is notZhigilei regular.

Regular solutions: Gibbs free energy (II)

Gmix = Hmix T Smix = XAXB + RT(XAlnXA + XBlnXB )

Addition of a small amount of solute always leads to the decrease of Gmix and G. Why?

> 0, low T
H mix

G mix

- TSmix

XB

G = X A G A + X B G B + X A X B + RT[X A lnX A + X B lnX B ]

Or, using definition of chemical potential, where, for regular solution

G = A X A + BX B
2

A = G A + (1 X A ) + RTlnX A B = G B + (1 X B ) + RTlnX B
2

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Regular solutions: Gibbs free energy (III)

G = X A G A + X B G B + X A X B + RT[X A lnX A + X B lnX B ]

G = A X A + BX B

A = G A + (1 X A ) + RTlnX A
2

B = G B + (1 X B ) + RTlnX B
2

Or we can introduce activities aA and aB of components A and B so that expressions for the chemical potentials would have the same form as for ideal solution: A = G A + RTln a A

GB
RTln a B

B = G B + RTln a B

GA

B
XB
1

For ideal solutions aA = XA and aB = XB. For regular solutions aA and aB are related to XA and XB by

aA 2 ( ) 1 X ln = A X RT A aB 2 ( ) 1 X ln = B X RT B
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Activity, Henrys law, Raoults law

1
w

H mix > 0
s l a
la w

aA 2 ( ) 1 X ln = A X RT A aB 2 ( ) 1 X ln = B X RT B

nry

aB

o a R

He

ts l u

H mix < 0

XB

For an ideal solution aA = XA and aB = XB. For a regular solution with Hmix < 0 activity of the components is less than in an ideal solution, for Hmix > 0 higher than in an ideal solution. The ratio aA/XA is called the activity coefficient A of A. For a dilute solution of B in A (XB 0) we have

aB const - Henrys law B = XB

aA A = 1 - Raoults law XA

Activity and chemical potential are measures of the tendency of an atom to leave a solution. If the activity or chemical potential is low, the atoms are reluctant to leave the solution.
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Real solutions
For regular solutions we assumed a random arrangement of atoms in a solution. For many real materials this is not a valid assumption. If < 0 the internal energy is minimized by increasing the number of A-B bonds can lead to ordered solution at low T if > 0 the internal energy is minimized by increasing the number of A-A and B-B bonds can lead to clustering at low T The arrangement of atoms is a result of compromise between the lowest internal energy and highest entropy. Degree of clustering or ordering decreases with increasing T since the entropy contribution (-TS) to Gibbs free energy becomes more important.

random

ordered

clustering

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Real solutions
If atoms A and B have different sizes, the statistical or quasichemical model will underestimate Hmix. The energy of the elastic strain fields due to the mismatch in atomic sizes should be taken into account. If the size difference is large, the contribution of the strain energy term could as important as the chemical (bonding) term.

If the size difference between the atoms is very large, then interstitial solid solutions are energetically favorable.

In systems with strong chemical bonding between the atoms there is a tendency for formation of intermediate phases. The intermediate phases can have a different crystal structure and may be highly ordered.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Substitutional Solid Solutions

Max solute concentration = 50 at% e.g. Cu-Ni (unlimited solid solubility)

Factors for high solubility: Atomic size factor - atoms need to fit solute and solvent atomic radii should be within ~ 15% Crystal structures of solute and solvent should be the same Electronegativities of solute and solvent should be comparable (otherwise new intermediate phases are encouraged) Generally, more solute goes into solution when it has higher valency than solvent

Interstitial Solid Solutions

Normally, max. solute concentration 10% e.g. 0.1 at% of C in -Fe (BCC).

Factors for high solubility: For fcc, bcc, hcp structures the voids (or interstices) between the host atoms are relatively small atomic radius of solute should be significantly less than solvent.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (I)

Systems with two or more phases are heterogeneous systems. If pure components A and B have different equilibrium crystal structures, phase and phase , we have to consider two Gibbs free energy curves, one for each phase:

GA

G B

G A

GB

0
homogeneous phase

XB

1
homogeneous phase

For compositions near cross-over of G and G, the total Gibbs free energy can be minimized by separation into two phases.

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (II)

Lets consider a systems with two phases and , that have compositions XB and XB and Gibbs free energies G and G. If the average composition of the system is XB0, the molar free energy G+ is given by the point on a straight line that connects G and G, and the relative number of moles of phases and can be found by the lever rule:

M = (XB - XB0)/(XB - XB) M = (XB0 - XB)/(XB - XB)

L1 = G
G

L4 = G

G+ G L1

L2 L3
0 X X B B

L4

0 L3 X X B B = = M L1 XB X B

L3 = MG
L2 X0 X B B = = M L4 XB X B

XB

Molar free energy of the phase mixture with molar fractions of phases and , M and M

L2 = MG

L3 + L2 = MG + MG = G+

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (III)

G 0 G
0

G1
1 0 1 X X X B B B

For composition XB0 the lowest Gibbs free energy is G0 for a homogeneous system. The total Gibbs free energy can be additionally decreased by separation into two phases, for 1 1 example with compositions X and . X B B

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Equilibrium in Heterogeneous Systems (IV)

G eq
A

G eq

G
B

Geq

X
compositions

eq B

X0 B

XBeq

The total Gibbs free energy is at minimum if phases and have

eq B

and

XBeq

These are the equilibrium compositions of the phases. In equilibrium tangents to G and G curves are the same (lie on a common line). Therefore, the condition for heterogeneous equilibrium is equity of the chemical potentials and activities of each component in the two phases.
A = A B = B a A = aA a B = aB

B = G B + RTln a B A = G A + RTln a A

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Intermediate phases
The intermediate phases can have a crystal structure that is different from the one of the pure components, and an additional Gibbs free energy curve for the intermediate phase should be considered.

GB GA GA XB
Gmix

GB

XB

If an intermediate phase have a specific composition and small deviations from the ideal composition cause a rapid rise in G, the phase is called compound. Compounds typically have a stoichiometric composition (AnBm where n and m are integers). The structure of intermediate phases is determined by Relative atomic size: RA/RB ~ 1.1-1.6 Laves phases (e.g. MgZn2, MgNi2); RA >> RB interstitial compounds, e.g. Fe3C Valency: stability of phases depends on the # of valence electrons per unit cell Electronegativity: different electronegativity of components leads charge transfer and formation of strong ionic bonding, e.g. Mg2+ + Sn4- = Mg2Sn
MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei

Summary
Make sure you understand language and concepts: Gibbs free energy of binary solutions, entropy and heat of formation terms for ideal solution for regular solutions Real solutions: interstitial solid solutions, ordered phases, intermediate phases, compounds Chemical potential and activity of a component, Henrys and Raoults laws - not tested Equilibrium in heterogeneous systems Make sure you understand all the variables, as well as the approximations, basic ideas, and graphical pictures behind these formulas:

G id = X A G A + X BG B + RT[X A lnXA + X BlnXB ]

G reg = X A G A + X BG B + X A X B + RT[X A lnX A + X BlnX B

E AA + E BB = zN tot E AB 2
A = A B = B a A = aA a B = aB

G = A X A + BX B
A = G A + RTln a A B = G B + RTln a B

MSE 3050, Phase Diagrams and Kinetics, Leonid Zhigilei