Chapter 8

Multicomponent Homogeneous
Nonreacting Systems: Solutions
Notes on
Thermodynamics in Materials Science
by
Robert T. DeHoff
(McGraw-Hill, 1993).

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-1
 Extensive Quantities of the
/ / / / /
State Functions: F , G , H , S , U , V /

Using G/ as example:
G G ( T , P , n1 , n 2 ... n k ... n c )
A differential form of G/:
G/ G/ c
G/
dG / dT dP dnk
T P , nk
P T , nk k 1 nk T , P ,n j k

and at constant T & P:

c
G/
dG / T ,P dnk
k 1 nk T , P ,n j k

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-2
 Partial Molal Quantities of the
State Functions: Fk ,Gk , Hk , Sk ,Uk ,Vk .
Using G K as example:
G/
Gk
nk T , P ,n j nk

A differential form of G/ (use definition of G k ):

/ / c
G G
dG/ dT dP Gk dnk
T P,nk
P T ,nk k 1

and at constant T & P:

c
dG/ T ,P Gkdnk
k 1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-3
 Gibbs-Duhem Equation
The contributions of the components sum to the
whole: /
c
G Gk nk
k 1
Differentiating the products on the right yields:
c c
dG/ Gkdnk nkdGk
k 1 k 1
Inspection yields the Gibbs-Duhem equation:
c
n k dG k 0
k 1
For a binary system:
n1
dG2 d G1
n2 8-4
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993)
 Reference States:
F/O, G/O, H/O, S/O, U/O, V/O
• T, S, V, P have absolute values.
• F, G, H, U have relative values.
• The difference in values between states is unique.
• To compare values, use the same reference state.
• Superscript O refers to the reference state.
c
Rule of G /O O
Gk nk
mixtures. k 1
• Preferably, for a solution use the pure components in
the same phase as the solution as the reference state.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-5
 Rule of Mixtures
2 For binary
Extensive G /O
G kO n k G 1O n 1 G 2O n 2
/O k 1
G O n1 O n2
G 1 G 2
n1 n2 n1 n2 n1 n2
Molar For binary
GO G1O X 1 G2O X 2
O
XG
2
O
G

G1OX

1 X2 2
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-6
 Mixing Values for Solutions
F/mix, G/mix, H/mix, S/mix, U/mix, V/mix
For solution: Gibbs free energy of mixing.
/
G mix G so/ ln G / O
For component k: Change experienced when 1 mole
of k is transferred from its reference state to the
given solution. G G G
O
k k k
Contributions of the components add to the whole:
c c
/ O
G mix G knk G nk
k
k 1 k 1
and c
/
G mix G knk
k 1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-7
 Mixing Values
/ / /O
G mix G so ln G

G2O 0X X 0
X
Gso ln Gmix

G1OX

1 X2 2 1 X2 2
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-8
 Mixing values for Solutions
F/mix, G/mix, H/mix, S/mix, U/mix, V/mix
Differential form: 0 Gibbs-Duhem 0
c
/ O O
d G mix G k dnk nk d G k G dn k
k nk dG k
k 1
c
/
d G mix G k dn k
k 1
Total derivative: c
/
d G mix G k dn k nk d Gk
k 1
Gibbs-Duhem for mixing:
c
nk d G k 0
k 1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-9
 Graphical Evaluation of
Partial Molal Values
Consider a binary system (alloy):
Gmix G1 X1 G2 X2 d Gmix G1dX1 G2dX2
Note:
X1 X2 1 dX 1 dX 2
Substitute & rearrange: G1
d G mix
G2 G mix 1 X2
dX 2 Gmix G2
d G mix
G1 G mix 1 X1
and dX 1 0 X2 1
d Gmix d Gmix
G2 G1 1 X1 0
dX2 dX1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-10
 Derivation: Graphical Evaluation
of Partial Molal Values
Gmix G1 X 1 G2 X 2 1
d Gmix G1dX 1 G2 dX 2 2
X1 X2 1 3a dX 1 dX 2 3b
d G mix 4
Rearrange (2) G2 G1
dX 2
Gmix X2
Rearrange (1) G1 G2 5
X1 X1
Insert X 1 X 2 G mix d G mix
G2
(5) in (4) X 1 X1 dX 2
d G mix
Yielding G2 G mix 1 X2
09/19/2001
dX 2
Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-11
 Integration of the
Gibbs-Duhem Equation(s)
For a binary system (alloy):
X 1d G1 X 2 d G2 0
X2
and d G1 d G2
X1
Integrating the left side from X2 = 0 to X2:
X2 0
d G1 G1 X 2 G1 X1 1 G1 X 2
X2 0
Now integrate right side:
X 2
X 2 d G2
G1 dX 2
X 2 0
X 1 dX 2
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-12
Molar Values of the State Functions
nk
Xk
Note: c
nk
k 1
Then,
c c
dG G k dX k d Gmix G k dX k
k 1 k 1
c c
G Gk X k G mix Gk X k
k 1 k 1
c c
X k dG k 0 X k d Gk 0
k 1 k 1

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-13
 Chemical Potential of (Open)
Multicomponent Systems
U U ( T , P , n 1 , n 2 ... n k ... n c )
c
dU TdS PdV k dnk c 2 terms
k 1
c
U
k W k dn k
nk S ,V ,nj nk k 1

U H F G
k
nk S ,V ,nj
nk S , P,nj
nk T,V ,nj
nk T,P,nj

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-14
 Chemical Potential of (Open)
Multicomponent Systems
G
k Gk
nk T ,P,n j nk

Gk k k
Sk Hk Gk TSk k T
T P,nk
T P,nk
T P,nk

Gk k k
Vk Fk Uk TSk k P
P T,nk
P T,nk
P T,nk

k k
Uk Hk PVk k P T
P T,nk T P,nk
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-15
 Activities and Activity Coefficients
Definition of activity, ak (dimensionless):
O
k k k RTlnak
Definition of activity coefficient, k (dimensionless):
O
ak k Xk k k k RTln k Xk
If
k<1 ak<Xk k is less apparent than its mole fraction.
k=1 ak=Xk k is as apparent as its mole fraction.
k>1 ak>Xk k is more apparent than its mole
fraction.
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-16
 Ideal Solution
No heat of mixing. Hk 0 H mix 0
No volume change. Vk 0 Vmix 0
No change in internal energy.
Uk 0 U mix 0
Entropy increases. c
Sk R ln X k S mix R X k ln X k
k 1
Helmholtz free energy decreases. c
Fk RT ln X k Fmix RT X k ln X k
k 1
Gibbs free energy decreases. c
Gk RT ln X k G mix RT X k ln X k
k 1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-17
 Ideal Solution

Smix
Hmix Gmix
0 0
X
T 2
X2

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-18
 Ideal Solution

• All plots (e.g. Gmix vs. Xk) are symmetrical

with composition.
• Slopes of plots of Smix, Fmix, Gmix are
infinite at Xk =0 & Xk =1.
• Entropy of mixing is independent of
temperature.

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-19
 Ideal Solution
Activity is the same as mole fraction.
Activity coefficient is one.
1

ak Xk

k 1 a2 a1

Slope = 1

0
0 X2 1

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-20
 Dilute Solutions:
Raoult & Henry’s Laws
Raoult’s Law for the solvent in dilute solutions:
lim a1 X 1
X 1 1
Henry’s Law for the solute in dilute solutions:
O
slope 1 lim a 2 X 2
slope 1
X 2 0
O
slope O
O slope 2
1
0 for small X 2
a1 a2

X 2 X 2
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-21
 Real Solutions: Relation of Activity
Coefficient to Free Energy
ak kXk

k Gk RT ln k Xk RT ln k RT ln Xk
XS ID
k Gk G k G k
Ideal partial molal free energy of mixing:
ID
G k RT ln X k
Excess partial molal free energy of mixing:
XS
G k RT ln k

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-22
 Regular Solution
Heat of mixing is a function of composition, only.
H mix H mix X 1 , X 2 ,... X k ,... X c
H mix H mix T , P
Entropy is the same as for ideal solution.c
Sk R ln X k S mix R X k ln X k
k 1
Helmholtz free energy decreases.
c
Fk U k RT ln X k Fmix Umix RT Xk lnXk
k 1
Gibbs free energy decreases.
c
Gk Hk RT ln X k Gmix Hmix RT X k ln X k
k 1

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-23
 Regular Solution
Smix

0 0
X2 Gmix X2
Hmix T

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-24
 Hmix Regular Solution
Smix

0 0
X2 Gmix X2

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-25
 Hmix Regular Solution
Smix

0 0
X2 Gmix X2

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-26
 Hmix Regular Solution
Smix

0 0
X2 Gmix X2

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-27
 Hmix Regular Solution
Smix

0 0
X2 Gmix X2

09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-28
 Problem 8.6 DeHoff
2
Find: Hmix f (X) Given: HPn 12,500X Pn XCn J mole
2
Rewrite in general form: H 2 aX 2 X 1
Differentiate: d H2 aX22dX1 2aX1 X2dX2
d H2
Substitute dX1= dX2: aX 22 2aX 1 X 2
dX 2
d H2
Substitute X1+X2=1: aX2 X2 2X1 aX2 1 3X1
dX2
X2 X2 d H2
Gibbs-Duhem: H1
X2 0 X
dX 2
1 dX 2
X2 X
2
H1 aX2(1 3X1 dX2
X2 0 X
1
09/19/2001 Notes from R.T. DeHoff, Thermodynamics in Materials Science (McGraw-Hill, 1993) 8-29