MT-29.03.17 - Solutions and Phase Diagrams

Indian Institute of Technology Roorkee
Spring semester-2017
MTN-102 Metallurgical Thermodynamics

and Kinetics
Course Instructor
S.R. Meka
most of the contents are from book titled 47

Introduction to the Thermodynamics of Materials by David R. Gaskell
THE BEHAVIOR OF SOLUTIONS
RAOULT’S LAW
spontaneous evaporation
evacuated
pure dynamic equilibrium
vessel at T
liquid A rate of evap. = rate of cond.
rate of evap. rate of cond.

bond energy of no. of atoms of vapor strike
surface atoms and T liquid surface per unit time
@ equil.
evacuated
pure
vessel at T
liquid B 48
RAOULT’S LAW B add ΔB to A
evacuated
A-B liquid
vessel at T
fraction of surface sites occupied by A is

- decreases by factor
A-B solution A solution
this will be the

49
RAOULT’S LAW
A-B solution
The vapor pressures exerted by the

components of a binary Raoultian solution
Assumption of Raoult’s Law

the magnitudes of the A–A, B–B, and A–B bond energies
in the solution be identical, i.e., Ideal mixing 50
assumption of Raoult’s Law
the magnitudes of the A–A, B–B, and A–B bond energies
in the solution be identical, i.e., Ideal mixing
Henry’s law
consider
• dilute solution of A in B (every A atom has only B surroundings)
• A–B bond energy is greater than A–A and B–B bond energies
rate of evaporation of A in solution decreases as compared
to that of rate of evaporataion of pure A at same T
A-B solution A solution
51
for for
EAB < EAA and EBB EAB > EAA and EBB
positive deviation negative deviation 52

positive deviation negative deviation
Increasing concentration of A in B
decreases the fraction of A surrounded only by B, i.e. AA pairs occur
Henry’s law is obeyed only over an initial range of
concentration of A in B, the extent of which depends on T
and the relative magnitudes of the A–A, B–B, and A–B bond
energies 53
ACTIVITY OF A COMPONENT IN SOLUTION
ideal real
reference i reference i
for a Raoultian solution
i i
in solution in solution
54
ACTIVITY OF A COMPONENT IN RAOULTIAN SOLUTION
ideal
1600°C
a
real
XCr
activities of Cr and Fe
in liquid Fe-Cr
activity normalizes the - relationship with respect to the

55
ACTIVITY OF A COMPONENT IN HENRIAN SOLUTION
ideal
1600°C
real aNi
XNi
activities of Cr and Fe
in liquid Fe-Ni

56
@ constant T and P
(1)
differentiation
(2)
comparison of (1) and (2) proves that
Gibbs-Duhem equation
57
Partial molar Gibbs free energy of component in A-B solution
binary A-B solution @ constant T and P
(1)
=-
(2)
Inserting from (1) into (2)
composition dependence of the partial molar Gibbs free

energies of the components of a binary solution and the
molar Gibbs free energy of the solution 58
Equilibrium solid-liquid: binary systems
 AL   AS
GS  GL GS  GL
 
L
B
S
B
= solid 2 phases liquid
L
GBS
G A
G
GL GBL
GAS
e.g. solid-liquid system, GS
GAS , GAL
T, p = const.
GBS ,
GBL
A xS xL B
xB
59
ΔG due to the solution formation
Pure A + pure B → A-B solution @ constant T
real case
for Raoultian ideal solution

60
ΔG of solution formation
Tangential intercept of extensive

property at represents the
partial molar property of for the
61
given amount of in solution
Raoultian ideal solution model
Ideal solution model
Assumptions: 1) no change in interaction between particles/atoms upon mixing
2) no change in particle/atom volume upon mixing

(no difference in atom size)
H ideal  0 Enthalpy of mixing

Videal  0 Volume change upon mixing
Gideal  T Sideal
3) only change in entropy: configuration entropy
Sideal  Sconf  0
62
Configuration entropy
Statistical thermodynamics: S  k  ln  (Boltzmann)
N tot !
 E
conf 
N A ! N B !
conf
I
1
I - initial state E - end/final state 63

S  k   ln  E  ln  I 
 k   ln conf
E
 ln conf
I

 k  ln conf
E
Inserting  conf : ln conf  ln N tot ! ln N A ! ln N B !

E E
with Stirling‘s approximation ln N !  N ln N  N and

NA NA
xA  
N A  N B N tot
Sideal   R  x A ln xA  xB ln xB 
64
Sideal   R  x A ln x A  xB ln xB 
-ln XB
65
Configuration entropy: limits for xi → 0 and xi → 1
7
Sideal Siid
Sideal   R  x A ln x A  xB ln xB  
6
S [J·mol ·K ]
-1
 x A    R ln x A   xB    R ln xB  
4
-1
3
 x A  S  xB  S
id id 1
A B 0
0,0 0,2 0,4 0,6 0,8 1,0
A B
x B
Sideal S i
id Maximum
1
lim xi ln xi  0 lim   ln xi   0 x A  xB 
2
xi 1 xi 1
Sideal
max
 R ln 2
lim xi ln xi  0
xi 0
lim   ln xi    J
xi 0  5.76
mol×K
66
Gibbs Energy
G id  x   T S id
Gibbs energy (change) of mixing
 RT  x A ln xA  xB ln xB 
Giid  x, T   RT ln xi i = A, B partial Gibbs energy of mixing
with G
id
 x, T   G id  x, T   G ref  x, T 
G id  x, T   G ref  x, T   T S id  x   Gibbs energy
 x A GA T   xB GB T   TR  xA ln x A  xB ln xB 
 x A GAid  x, T   xB GBid  x, T 
Giid  x, T   Gi T   RT ln xi partial Gibbs energy

67
Entropy & Gibbs Energy
Sideal   R  x A ln x A  xB ln xB  Gideal  T Sideal
68
Entropy
Gibbs energy,
& Gibbs
limits
Energy
for xi → 0 and xi → 1
G id  x   RT  x A ln xA  xB ln xB 
d G id  x  x d G  x  id
 RT  ln xB  ln x A   RT ln B  
dxB 1  xB dxA
-2
d G id  x  d G id  x 
G (x)
 
id
lim   lim
xB  0 dxB -4 xB 1 dxB
-6
A
0,0 0,2 0,4 0,6 0,8 1,0
B
69
xB 
Non Ideal solutions
ideal solution: non Ideal solutions:
positive deviation negative deviation
Fe-Cu at 1550°C Fe-Ni at 1600°C

70
Non Ideal solutions
activity coefficient,
Fe-Cu at 1550°C Fe-Ni at 1600°C
71
Non Ideal solutions- dependence of γ on T
Gibbs-Helmholtz Equation
with increase in T: non-ideal approaches ideal
- for >1, with ↑ T decreases towards 1,

i.e. positive (endothermic) EAB> EAA and EBB
“clustering” - tendency to phase separation
- for 1, with ↑ T increase towards 1,

i.e. negative (exothermic) EAB < EAA and EBB
72
“ordering” - tendency to compound formation
Gibbs-Helmholtz Equation
@constant P and chemistry
divide by and rearrange
G-H equation; for system at constant composition and P
can be obtained from the knowledge of as a function of T
can be obtained from the knowledge of as a function of T

Determination of activity-Gibbs Duhem equation
Binary A-B solution
If we have measured the
74
Determination of activity: Gibbs-Duhem equation
Graphical integration
as → 0, → 0, and -log →
as → 1, , and →0
0
0
as → 1, , and →0
for A-B solution

Integration,
Henrian law
Relation between Henry‘s and Raoult‘s laws
Henrian’s law for solute B in solvent A
Gibbs-Duhem Equation
integration
implies integration constant is 1
Solute Henry’s law then solvent obeys Raoult’s aw

Relation between Henry‘s and Raoult‘s laws
If solute obeys Henry’s law then solvent obeys Raoult’s aw
for solute B in solvent A for solvent A
4 Ideal solution model
Gibbs Energy
G id  x   T S id
Gibbs energy (change) of mixing
 RT  x A ln xA  xB ln xB 
Giid  x, T   RT ln xi i = A, B partial Gibbs energy of mixing
with G
id
 x, T   G id  x, T   G ref  x, T 
G id  x, T   G ref  x, T   T S id  x   Gibbs energy
 x A GA T   xB GB T   TR  xA ln x A  xB ln xB 
 x A GAid  x, T   xB GBid  x, T 
Giid  x, T   Gi T   RT ln xi partial Gibbs energy

83
H ideal  0, Videal  0, Sideal   R  x A ln x A  xB ln xB 
Application: e.g. ideal solid solutions
T
T1
A B
xBl xBs
Gm (T1 , x)
Gml ,B
Gms ,A Gml
Gms Gms ,B
Gml ,A
Gms ,B ( x)  Gml ,B ( x)
Gms ,A ( x)  Gml ,A ( x)
A B
xBl xBs 84
4 Ideal solution model: phase equilibria
Equilibrium liquid solution - solid solution
 AL   AS  BL   BS
GAL  GAS GBL  GBS
GAL  RT ln x AL  GAS  RT ln x AS GBL  RT ln xBL  GBS  RT ln xBS

assumption: assumption:
H m
H Bm m
RT  ln xAL  ln x AS    mA TAm  T  RT  ln x  ln x    m TB  T 
L
B
S
B
TA TB
R x AL 1 1 R 1  x AL 1 1
ln S  m   ln  m 
H A xA TA
m
T H B 1  x A TB
m S
T
At given T, each single equation gives a s-l-concentration ratio,

using both equations, the phase diagram is fully described. 85
Equilibrium liquid solution - solid solution
Phase diagram Ge-Si:
Comparison of calculated (ideal solution model) and experimental
1683
measured
calculated
temperature (K)
solid solution
liquid solution
86
Si
Equilibrium liquid solution - solid solution Gerechnet-calculated
Examples: Co-Ni, Mo-W, Ag-Au, Cu-Ni
87
When to expect ideal behaviour?
i.e.,Complete solubility in solid and liquid state
1. similar chemical properties (e.g. electronegativity)
2. similar atomic radius
3. no difference in crystal structure
property
crystal structure fcc fcc fcc bcc bcc fcc fcc hcp hcp
atom radius, Å
electronegativity
up to about 700K Co has hcp crystal structure 88

When to expect ideal behaviour?
property
structure fcc fcc fcc fcc bcc fcc fcc
atom radius, Å
electronegativity
89
How realistic is the ideal solution model?
Condition H ≈ 0 is not always fulfilled

for eg.,
Equiatomic Cu-Ni in liquid and solid states:
H = 1,70,4 kJmol-1
Equiatomic liquid Ag-Au:

H = -50,5 kJmol-1
90
Regular solution model
Approach
Ideal solid solution:
Hmix = 0,
Vmix = 0, V1=V2=..=Vk
statistical distribution of atoms
Reality:
endothermal effects (tendency for unmixing)
or
exothermal effects (tendency for mixing)
ordering (tendency to compounds formation)
Extension of the ideal solid solution model by Hmix.
91
Assumptions
1. Enthalpic/energetic mixing effect only due to changes in nearest-neighbour
bond energies
2. No changes in interatomic distances upon mixing, i.e.,
A A B A B B A A Bonding energies
A-A A-B
B A A B A B B A A-A: eAA
B-B
B A B B A A A A B-B: eBB
B B B A B A A B A-B: eAB
A B A B B A A A - negative quantities
A A B A B B B A - temperature independent
92
Calculation of internal energy
1 z: coordination number
number of bonds in 1 mol: n  NL  z NL: Avogadro‘s constant
2 (6,022·1023 mol-1)
1
Pure components A and B: U A  ne AA  N L  z  e AA
2
1
U B  ne BB  N L  z  e BB
2
1
only A-B bonds: U AB  ne AB  N L  z  e AB
2
93
A-A, B-B and A-B pairs: U  nAAe AA  nBBe BB  nABe AB
where n  nAA  nBB  nAB
Probability for neighbouring atoms in case of a random distribution
A on a lattice position → xA
→ A on two neighbouring positions → x A  x A  x A2
B on a lattice position → xB
→ B on two neighbouring positions → xB  xB  xB2
94
1 1
Number of pairs: nAA  N L  z  x A2 nBB  N L  z  xB2
2 2
n  nAA  nBB  nAB
z z 2 z 2
nAB  N L   N L  x A  N L  xB
2 2 2

z
nAB  N L   2 x A xB
2
95
Internal energy:
z z z
U  x   N L  e AA  x A  N L  e BB  xB  N L  e AB  2 x A xB 
2 2
2 2 2
 U A  x A2  U B  xB2  2U AB  x A xB
Internal energy of mixing U:
U  x   U A x A2  U B xB2  2U AB x A xB  U A x A  U B xB 
 ... 
  2U AB  U A  U B  x A xB  x A xB
96
Enthalpy of mixing (binary system)
H  U  pV (p = const.)
since V  0 : H  x   U  x 
Enthalpy of
mixing
H  x   x A xB
Interaction
parameter /
  2U AB  U A  U B
regular solution z
parameter  N L  2e AB  e AA  e BB 
2
97
Regular solution parameter
z
  N L  2e AB  e AA  e BB 
2
e AA  e BB
e AB  Tendency for mixing   0  H  0
2
e AA  e BB
e AB  Ideal solution   0  H  0
2
e AA  e BB
e AB  Tendency for unmixing   0  H  0
2
98
H(x)-curve, partial molar enthalpy of mixing
H  x   x A xB
H ( x) H B
H A
1  xB
A B
xB 
99
H(x)-curve, partial molar enthalpy of mixing
H ( x) H B
H  x   x A xB
d H  x 
H B  x   H  x   1  xB 
H A
1  xB
dxB
A xB  B
d H  x 
with   1  2 xB 
dxB
H B  x    1  xB 
2
follows
d H  x  d H  x 
    H A0  H B0
dxA x dxB x 100
A 0 B 0
partial molar enthalpy of mixing
101
Gibbs energy (of mixing)
G  x   x A GA  xB GB   x A xB  RT  x A ln x A  xB ln xB 
G ref  x  H  x  T  S id  x 
and
G  x   x A 1  xA   xB  1  xB   TxA R ln x A  TxB R ln xB
2 2
H A  x  H B  x  S A  x  S B  x 
102
G(x)-curves Mistake in plots!! Plots are for –TΔS not TΔS
Folding
(+) (+)
0 0 (+)
(-) T0 (-) T0 0
(-) T1  T0
A negative H B A positive H B A x1 x2 B
G  0,  T S  0 id
H  0 H  0 H  0
103
5 Regular solution model
G(x)-curves Mistake in plots!! Plots are for –TΔS not TΔS
Effect on T(x)-diagram. Miscibility gap
T
(+)
0
T1 T1
(-)
A x1 x2 B A x1 x2 B
G  0,  T S  0, H  0
id
104
Miscibility gap: binodal
G  x   x AGA  xB GB   x A xB  RT  x A ln x A  xB ln xB 
G GB
symmetric
double tangent criterion
to x = 0.5
GA G A1  GA 2  GB1  GB 2 

GB   GB 
1 2
GA   GA 
1 2
A B
x1 x2
105
Regular solution model Miscibility gap: binodal
(1) and (2) represent phases
1  2
GA  GA
   
2 2
1 1  2
G   1  xA
L
A  RT ln x A  G   1  x A
L
A  RT ln x A2 (1)
GB1  GB 2  xA  xB  1
       
2 2
1 1  2
 RT ln 1  x A  (2)
2
G   xA
L
B  RT ln 1  x A  G   x A L
B
symmetric to x = 0.5: x A2   1  x A1
1  xB
RT ln   1  2 xB  (3)
xB
In this expression From

106
Regular solution model Miscibility gap: critical temperature
-2000
400 K
500 K Maximum T up to which miscibility gap exists
-1000 600 K
G in J·mol-1
700 K
0
800 K
900 K
- 1000
1000 K
- 2000 1100 K
(K)
Phase I + Phase II
107
Regular solution model Miscibility gap: critical temperature
Miscibility gap critical temperatures for several binary systems
solid solution
liquid solution
108
Regular solution model Activity
GA  x, T   H A  T S A   1  x A   RT ln x A
2
Gi  x, T   RT ln  i  x, T   RT ln xi
 x, T 
ex
G i G i
id
 x, T 
 x, T 
id
 S i
  2 
 A  x, T   exp   A 
1  x
 RT 
  2 
a A  x, T   xA  exp  1  xA  
 RT 
109
Activity
  2    2 
a A  x, T   x A  exp  1  xA   ,  A  x, T   exp  1  xA  
 RT   RT 
Raoult‘s law:
da A   2     2 
 exp   A  A
1  x  x  2   A
1  x  exp   A 
1  x
dx A x A 1  RT  RT  RT  xA 1
1
Henry‘s law:
 daB    
 
B    exp  
dx
 B  xB  0  RT 
110
Activity
e AA  e BB   0  aA  xA  0   A  1
e AB  tendency for mixing
2
e AA  e BB   0 a A  x A   A  1
e AB  tendency for unmixing
2
T  const.

  2
 A  x, T   exp   A 
1  x aA
 RT 
  2
a A  x, T   xA  exp  1  xA  
 RT 
A  xA 111B
Activity
Regular solution model   2
aB  x, T   xB  exp  1  xB  
 RT 
112
Activity
Temperature dependency
With Gi  x   RT ln ai  x, T  and H A 


 G A T 
 1 T 
 H A  ln a A
follows 
R  1 T 
G A  x, T 
With G A  x, T    H A  x, T   T
T
1 dT
d  2
T T  ln a A
follows RT ln a A   RT 2
 T S A
T
and  ln a A T ln a A
 S A   RT  R ln a A  R
T T
113
Activity
Reference states
Gi  x   RT ln ai  x, T 
G
GB
GA
RT ln aB ,ref 
RT ln aA ,ref  mixG
GA
GB
A B
xB
… reference state: pure components in the phase, Raoultian reference state

114
Activity
Reference states
Gi  x   RT ln ai  x, T 
G
GB
GA
mixG GBe
 RT ln aB ,ref e
GA
RT ln aA ,ref l GB
GAl
A B
xB
… reference state: pure components in the lphase and in the ephase

115
Activity
Reference states
T-x-diagram: 2 phases (s) & (l)
G-x-diagram: ideal solution model for

both solid and liquid phase
1
reference state:
pure solid phase
a-x-diagram: straight lines (ideal
behaviour), horizontal
activity of pure lines in 2-phase region
reference state:
component not
pure liquid phase necessarily equal to 1! 116
Activity
Temperature dependency: miscibility gap
System with tendency for unmixing (>0)
117
Activity
Gi  RT ln ai
Tcrit  1000 K
T  800 K
118
Activity
T  Tcrit: activity shows a maximum and a

minimum (point b and c).
a-b: activity of B in phase 1

supersaturated in B
c-d: activity of B in phase 2

supersaturated in A
b-c: negative slope:

 not stable (cf sponodal)
a-d horizontal line of constant activity T  800 K
119
Regular solution model Miscibility gap: spinodal
G GB
G
1st deri.
GA G2
Stability criterion:
G1 points of inversion
2nd deri.
A B
3rd deri.
.
In this composition range any

concentration fluctuation gets stabilized
120
-spinodal decomposition.
Regular solution model Miscibility gap: spinodal
1. derivative:
2. derivative:
RT equation for spinodal composition as a function of T

 xB 1  xB   applicability of this equation requires that
2 third derivative is not zero, i.e., XB ≠ 0.5
3. derivative:
121
Miscibility gap: binodal, spinodal & critical temperature
100 K
200 K
300 K
400 K
G [J/mol]
500 K
600 K
700 K
800 K
T [K]
 = 12 kJ/mol
A xB  B 122
Miscibility gap
CRITICAL
BINODAL SPINODAL
TEMPERATURE
1  xB RT 2
RT ln   1  2 xB  xB 1  xB   Tcrit . 
xB 2 4R
T
1
spinodal
What happens with a
homogeneous phase
whithin region 1, 2, 3?
binodal
c 123
Miscibility gap: decomposition behaviour
T
Case 1: composition within binodal,
outside spinodal
T1
d2G
0
dx 2
G possible tie
GA line of 2-phase
GB
I II III II I Gdecomp
initial
0 mixture
GA
Gdecomp
final
A xBbin x0 xBspin B A xBbin x0 xBspin

xB  124
xB 
T
Case 2: composition within spinodal
T1 d2G
0
dx 2
G Gdecomp
initial
0 possible tie
GA line of 2-phase
GB mixture
I II III II I
GA
Gdecomp
final
A xBspin ,1 x0 xBspin ,2 B A xBspin ,1 x0 xBspin ,2

xB  125
xB  xB 
quenching A  B:
• homogeneous solution becomes metastable
• precipitation by nucleation & growth process
T • initial increase in Gibbs energy, finally decrease
D stable • increase in energy stabilises single phase against
A decomposition in to equilibrium two phase mixture
E
B
quenching A  C or D  E:
C • single phase becomes unstable
instable • immediate amplification of (thermally activated)
concentration fluctuations
c • Gibbs energy decreases continuously,
no nucleation, spinodal decomposition
126
Regular solution model: phase equilibria
Phase equilibria: solid-liquid
equilibrium between solid solution & liquid solution
 AS   AL
G   1  x
S
A
S
A
S 2
 RT ln x  G   1  x
S
A
L
A
L
A 
L 2
 RT ln x AL
(analogous for component B)
H Am  1 1   S L x AS
  m
R  T TA  RT
1  xA  
S 2
RT
1  x A   ln L
L 2
xA
H Bm  1 1   S  L
x S
1  xBS   1  xBL   ln BL
2 2
  m
R  T TB  RT RT xB 127
 variation of S and L
 variation of Tm binary T-x-phase diagrams without
 Hm constant intermetallic phases
 no intermetallic phases allowed
H Am  1 1   S  L
x S
   
2 2
    1  x S
A  1  x L
A  ln A
R  T TAm  RT RT x AL
H Bm  1 1   S  L
x S
   
2 2
    1  x S
B  1  x L
B  ln B
R  T TBm  RT RT xBL
128
miscibility gap in s & l : varying TB
T
TA
TB TA TA
E
M
E TB
TB
E
A xB→ B A xB→ B A xB→ B
 S  0,  L  0; const.
TA  const. 129
130
131
132
133
J)
-20 -10 0 +10 +20 +30
+30
+15
(KJ)
Ω
0
Effect of changing values of Ω and
Ω on phase diagrams. i.e., melting
temperatures of pure A and B have been
kept constant in calculation
-15
134
Influence of Tm while keeping diff/sum and Hm constant
 S  1,5
 L  1,5
 diff   S   L
S  3
 sum   S   L L  1
S  6
L  2
135
T m 
 S  1.5 L  0  S  const.  L  const.
 diff   S   L
 diff
 sum   S   L
136
 sum
Binary isomorphous system showing miscibility gap in solid state
Figures source: book titled Fundamentals of Materials Science written by Prof.Mittemeijer

Binary system showing miscibility gap in liquid state

Evolution of binary eutectic phase diagram

Melting point depression- congruent melting of alloy

Negligible solubilities in solid state:

Cooling curves

MT-29.03.17 - Solutions and Phase Diagrams

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Indian Institute of Technology Roorkee

MTN-102 Metallurgical Thermodynamics

most of the contents are from book titled 47

rate of evap. rate of cond.

fraction of surface sites occupied by A is

A-B solution A solution

this will be the

The vapor pressures exerted by the

Assumption of Raoult’s Law

A-B solution A solution

positive deviation negative deviation 52

positive deviation negative deviation

for a Raoultian solution

activity normalizes the - relationship with respect to the

activity normalizes the - relationship with respect to the

comparison of (1) and (2) proves that

Inserting from (1) into (2)

composition dependence of the partial molar Gibbs free

= solid 2 phases liquid

for Raoultian ideal solution

Tangential intercept of extensive

2) no change in particle/atom volume upon mixing

H ideal  0 Enthalpy of mixing

3) only change in entropy: configuration entropy

I - initial state E - end/final state 63

Inserting  conf : ln conf  ln N tot ! ln N A ! ln N B !

with Stirling‘s approximation ln N !  N ln N  N and

Giid  x, T   RT ln xi i = A, B partial Gibbs energy of mixing

Giid  x, T   Gi T   RT ln xi partial Gibbs energy

Sideal   R  x A ln x A  xB ln xB  Gideal  T Sideal

positive deviation negative deviation

Fe-Cu at 1550°C Fe-Ni at 1600°C

Fe-Cu at 1550°C Fe-Ni at 1600°C

with increase in T: non-ideal approaches ideal

- for >1, with ↑ T decreases towards 1,

- for 1, with ↑ T increase towards 1,

@constant P and chemistry

divide by and rearrange

G-H equation; for system at constant composition and P

can be obtained from the knowledge of as a function of T

can be obtained from the knowledge of as a function of T

Binary A-B solution

If we have measured the

for A-B solution

implies integration constant is 1

Solute Henry’s law then solvent obeys Raoult’s aw

Giid  x, T   RT ln xi i = A, B partial Gibbs energy of mixing

Giid  x, T   Gi T   RT ln xi partial Gibbs energy

GAL  RT ln x AL  GAS  RT ln x AS GBL  RT ln xBL  GBS  RT ln xBS

At given T, each single equation gives a s-l-concentration ratio,

1. similar chemical properties (e.g. electronegativity)

2. similar atomic radius

3. no difference in crystal structure

up to about 700K Co has hcp crystal structure 88

structure fcc fcc fcc fcc bcc fcc fcc

Condition H ≈ 0 is not always fulfilled

Equiatomic liquid Ag-Au:

ordering (tendency to compounds formation)

Extension of the ideal solid solution model by Hmix.

2. No changes in interatomic distances upon mixing, i.e.,

A-A, B-B and A-B pairs: U  nAAe AA  nBBe BB  nABe AB

where n  nAA  nBB  nAB