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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
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
G
Gstep1
GA
X AG A GB
Gibbs free energy per mole before mixing
X BG B
XB
- 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:
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 A + N B )! =
N B! N A !
S mix = k B ln = k B ln
(N A + N B )!
N B! N A !
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
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 ]
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
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
Gid
GB
GA
RTlnX B
A = G A + RTlnX A B = G B + RTlnX B
B
XB
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
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
E AA + E BB = PAB E AB 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
<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.
> 0, low T
H mix
G mix
- TSmix
XB
G = A X A + BX B
2
A = G A + (1 X A ) + RTlnX A B = G B + (1 X B ) + RTlnX B
2
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
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
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
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.
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
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.
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.
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+
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
G eq
A
G eq
G
B
Geq
X
compositions
eq B
X0 B
XBeq
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
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 = A X A + BX B
A = G A + RTln a A B = G B + RTln a B