CHAPTER 3.

Solution Thermochemistry
Takahiro Miki
Associate Professor, Tohoku University, Japan

3.4.1. PARTIAL MOLAR QUANTITIES

Extensive thermodynamic properties such as volume, V, internal energy, E,
enthalpy, H, entropy, S, the Helmholtz energy, F, and the Gibbs energy, G, can be
expressed by Equation (3.4.1) by using Y to represent forgoing extensive properties:
Y f T ,p,n1 ,n2 ,. . .,ni , .. .

3:4:1

Here, n1, n2, . . ., ni, . . . denotes the number of moles of component 1, 2, . . ., n, present
in multicomponent solution in the system. If we consider an infinitesimal change in the
value of Y, the following relation can be obtained:






@Y
@Y
@Y
dY
dT
dp
dn1   
3:4:2
@T p,n1 ,n2 ,...
@p T ,n1 ,n2 ,...
@n1 p,T ,n2 ,...
At constant temperature and pressure, Equation (3.4.2) will be Equation (3.4.3).




@Y
@Y
dn1
dn2 
3:4:3
dY
@n1 p,T ,n2 ,...
@n2 p,T ,n1 ,...
Now we will introduce a new quantity, Y i , called the partial molar quantity defined as
Equation (3.4.4):


@Y
Yi
3:4:4
@n1 p,T , nj
Here, j 6 i. From substitution of Equation (3.4.4) into Equation (3.4.3), the following
will be derived:
dY Y 1 dn1 Y 2 dn2 Y 3 dn3  

3:4:5

From integration Equation (3.4.6) can be obtained:

Y Y 1 n1 Y 2 n2  

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3:4:6
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517

Takahiro Miki

518

If the Gibbs energy is used in Equation (3.4.6), then we will have Equation (3.4.7):
X
G i ni
3:4:7
G G 1 n1 G 2 n2  
The quantity G i will be the change in the Gibbs energy when 1 mole of i is added to
infinitely large quantity of solution.
Differentiating Equation (3.4.6) will deduce Equation (3.4.8).
dY n1 dY 1 n2 dY 2   Y 1 dn1 Y 2 dn2  

3:4:8

Subtracting Equation (3.4.5) from Equation (3.4.8) will give Equation (3.4.9):
n1 dY 1 n2 dY 2    0
Division with dn1 gives the following equation:






@Y 1
@Y 2
n2
 0
n1
@n1 p,T ,n2 ,...
@n1 p,T ,n2 ,...

3:4:9

3:4:10

n1
X1
From the relation dn
dX
, etc., and Equation (3.4.10), we will have Equation (3.4.11):
1
1






@Y 1
@Y 2
X2
 0
3:4:11
X1
@X1 p,T ,X2 ,...
@X1 p,T ,X2 ,...

The corresponding equation for the Gibbs energy is as follows:





@G 1
@G 2
X2
 0
X1
@X1 p,T ,X2 ,...
@X1 p,T ,X2 ,...

3:4:12

This equation is generally known as the GibbsDuhem equation. This equation is

useful to derive the unknown activity of one component when the others are known.
Another form of the GibbsDuhem equation can be deduced from Equation (3.4.9)
by substituting the Gibbs energy as Y and dividing both sides by n:
X1 dG 1 X2 dG 2   0

3:4:13

3.4.2. INTEGRAL MOLAR QUANTITIES

For multicomponent solution composed of n1 moles of component 1, n2 moles of
component 2, and so forth, the Gibbs energy
P will be Equation (3.4.7). The total number
of moles present in the solution is n( ni). The integral molar Gibbs energy of the
solution can be defined as follows:
G
GX
ni

3:4:14

Solution Thermochemistry

From

519

!
n1
X
x1 ,
ni

!
n2
X
x2 , etc., Equation (3.4.14) will be as follows:
ni
G x1 G 1 x2 G 2   

3:4:15

where G is the Gibbs energy of 1 mole of a multicomponent solution.

3.4.3. RELATIONSHIP BETWEEN PARTIAL MOLAR QUANTITIES

AND INTEGRAL MOLAR QUANTITIES
Differentiating Equation (3.4.15) will give the following equation:
dG X1 dG1 X2 dG 2    G 1 dX1 GdX2  

3:4:16

Combining Equations (3.4.13) and (3.4.16) gives Equation (3.4.17):

dG G 1 dX1 GdX2  

3:4:17

For a two-component solution Equation (3.4.17) will be Equation (3.4.18).

dG G 1 dX1 GdX2
X
Multiply both sides of Equation (3.4.18) by dX
gives Equation (3.4.19):









@G
@X1
@X2
X1 G 1
X1 G 2
X1
@X2 T ,p
@X2 T ,p
@X2 T ,p

3:4:18

From X1 X2 1, Equation (3.4.19) will be Equation (3.4.20):


@G
X1
X1 G 1 1 G 2
@X2 T ,p

3:4:19

3:4:20

Combining Equation (3.4.20) with G X1 G 1 X2 G 2 will have Equation (3.4.21):


@G
G 2 G X1
3:4:21
@X2 T ,p
Similarly, following can be obtained:


G 1 G X2

@G
@X1


T ,p

3:4:22

For a multicomponent solution, the partial molar energy is given by

Equation (3.4.23):

Takahiro Miki

520


@G
G 1 G 1  X1
@X1 T ,p:X2 ,X3 ,...

3:4:23

3.4.4. RELATIVE PARTIAL MOLAR QUANTITIES AND INTEGRAL

MOLAR QUANTITIES
The partial molar quantities refer to absolute values. However, for enthalpy, internal energy, and Gibbs energy, it is not possible to determine absolute values. Therefore, it
is necessary to select some state as a reference and express the relative partial molar quantity. The most common reference is the pure-substance standard state. The relative partial
molar quantity of component i is defined as follows:


Y i Y i  Yi

3:4:24

Here, Y i is defined by Equation (3.4.4) and Yi is the molar quantity for the component i in the reference state. For Gibbs energy it will be Equation (3.4.25):


G i G i  Gi RT ln ai

3:4:25

Relative integral molar quantities can be expressed as follows. If we consider the

formation of multicomponent solution consisting of n1 moles of component 1, n2 moles
of component 2, and so on, for unmixed components that are in their reference states will
be Equation (3.4.26):


Y n1 Y1 n2 Y2  

3:4:26

If we combine Equations (3.4.9) and (3.4.26) and divide by total number of moles n,
we will have relative integral molar property as Equation (3.4.27):
M

Y M X1 Y 1 X2 Y 2  

3:4:27

For the Gibbs energy Equation (3.4.27) will be Equation (3.4.28):

M

GM X1 G 1 X2 G 2  

3:4:28

From Equation(3.4.25) it can be expressed as follows:

GM RT X1 ln a1 X2 ln a2  

3:4:29

Here, GM is the relative integral molar Gibbs energy of mixing.

The relationship between molar quantities and relative for the Gibbs energy is shown
in Figures 3.4.1 and 3.4.2.

Solution Thermochemistry

521
G
G2o
GM

G1o
G = X1G1+X2G2

G2

G1
0

X2

Figure 3.4.1 The relationship between molar quantities for the Gibbs energy.

GM

0
G M=X1G1M+X2G2M
G 2M

G1 M

X2

Figure 3.4.2 The relationship between relative molar quantities for the Gibbs energy.

3.4.5. RAOULTS LAW AND IDEAL SOLUTIONS

If components in the solution are physically and chemically similar, it is
sometimes possible to describe the behavior of solution by Raoults law as shown in
Equation (3.4.30):
ai Xi

3:4:30

Solutions that confirm to Raoults law at all temperatures and pressures are known as
ideal solutions. Most solutions deviate from ideal solution behavior. In general, deviation
from Raoults law will decrease as the mole fraction of the component approaches unity.
For ideal solution, Equation (3.4.30) will stand for all conditions. Combining with
Equation (3.4.25) will give Equation (3.4.31) as the relative integral molar Gibbs energy
of an ideal solution:
M,id

Gi

RT ln Xi

3:4:31

Takahiro Miki

522

Also, the relative integral molar Gibbs energy or the Gibbs energy of formation of an
ideal solution can be expressed as Equation (3.4.32):
G

M,id

RT X1 ln X1 X2 ln X2  

The relative partial molar entropies can be determined as follows:

!
M,id
@G i
M,id
Si 
R ln Xi
@T

3:4:32

3:4:33

The relative integral molar entropy of an ideal solution can be expressed as

Equation (3.4.34):
S

M,id

RX1 ln X1 X2 ln X2  

3:4:34

The relative partial molar enthalpies can be determined as follows:

M,id

Hi

M,id

Gi

M,id

T Si

RT ln Xi  RT ln Xi 0

3:4:35

The enthalpy or the heat of formation of an ideal solution is obtained as follows:

X
M,id
Xi H i 0
3:4:36
H M,id
i

From Equation (3.4.36) heat of formation of an ideal solution is zero.

3.4.6. EXCESS THERMODYNAMIC QUANTITIES

Behavior of real solution deviates from that of ideal solution. To express the
deviation from the ideal, it is useful to use excess functions:
E

M,id

Gi Gi  Gi

3:4:37

Here, G i is known as the excess partial molar Gibbs energy of component i. Also, the
following relation can be obtained:
E

M,id

Gi Gi  Gi

RT ln ai  RT ln Xi RT ln gi

3:4:38

The excess integral molar Gibbs energy of binary solution will be Equation (3.4.39):
GE GM  GM,id RT X1 ln g1 X2 ln g2

3:4:39

Also, from Equation (3.4.36) the excess integral molar enthalpy will be as follows:
H E H M  H M,id H M

3:4:40

Solution Thermochemistry

523

3.4.7. INTEGRATION OF THE GIBBSDUHEM EQUATION

For a binary solution, if the activity of one component is known over a range of
composition, the activity of the other component can be determined by GibbsDuhem
equation. The form of Equation (3.4.41) can be applied for binary solution from
Equation (3.4.13):
X1 dG 1 X2 dG 2 0

3:4:41

At a given temperature, Equations (3.4.42) and (3.4.43) can be utilized:

M

dG 1 dG 1 RT d ln a1

3:4:42

M
dG 2 dG 2

3:4:43

RT d ln a2

Hence, Equation (3.4.44) can be deduced:

X1 d ln a1 X2 d ln a2 0

3:4:44

For an ideal solution, Equation (3.4.44) will be Equation (3.4.45)

X1 d ln X1 X2 d ln X2 0

3:4:45

Subtraction will give Equation (3.4.46):

X1 d ln g1 X2 d ln g2 0
Rearranging and integration will deduce Equation (3.4.47):
X2 X 0 2

X2
0
ln g 1 
d ln g2
X1
X2 0

3:4:46

3:4:47

When X1 1, then g1 1 can be obtained and g1 g0 1 can be determined at

X1 X 0 1 1  X 0 2 from Equation (3.4.47).

3.4.8. REGULAR SOLUTIONS

Regular solution [1] may be introduced to express some nonideal solutions. This is
defined as the solution that the entropy of mixing is the same as that for ideal solution. For
a regular solution with components 1 and 2, Equations (3.4.48)(3.4.50) will stand:
SM,r SM,id RX1 ln X1 X2 ln X2  
GM,r RT X1 ln a1 X2 ln a2  
H M,r RT X ln g X ln g  
1

3:4:48
3:4:49
3:4:50

Takahiro Miki

524

The relative partial molar enthalpies are given by the following equations:
H 1 M,r RT ln g1
H 2 M,r RT ln g2

3:4:51
3:4:52

From statistical analysis using Margules equation [2], the relative partial molar
enthalpies can be expressed as follows for binary 12 system:
RT ln g1 OX22

3:4:53

RT ln g2 OX12

3:4:54

Here, O is the interaction parameter independent of composition and temperature.

The relative integral molar enthalpy and the excess integral molar Gibbs energy of solution can be determined as follows:
H M,r GE,r X1 OX2 2 X2 OX1 2 OX1 X2

3:4:55

It should be pointed out that regular solution is an approximation. For all solutions,
the system approaches regular behavior at higher temperatures due to no ordering and
segregation and entropy of mixing will be ideal.

3.4.9. DARKENS QUADRATIC FORMALISM

Darken [3] suggested that the activity coefficient of binary system can be expressed
using quadratic formalism at high concentration range of component 1 or 2 as Equations (3.4.56)(3.4.59):
logg1 a12 X22 high concentration range of 1




g
log 2 a12 X12  1 high concentration range of 1
g2
logg2 a21 X12 high concentration range of 2




g
log 1 a21 X22  1 high concentration range of 2
g1

3:4:56
3:4:57
3:4:58
3:4:59

If a12 a21, 12 binary solution will be regular solution. However, in general a12 will
not be equal to a21.
The activity coefficient of X in liquid FeX alloys [3] is shown in Figure 3.4.3. This
figure shows that Equation (3.4.56) is valid for wide composition range.
Darken [3] also introduced the concept of excess stability for analysis of the binary
solutions. The excess stability function, c, is defined as follows:

Solution Thermochemistry

525
NX = l-NFa
1

0.1

0.2

0.3

0.4

0.5 0.6

0.81.0

FeCu
FeMn

log gx

FeNi

-1

FeAl
FeSi

-2

FeCu
FeMn
FeNi
FeAl
FeSi

-3
1.0

0.8

0.6

0.4

0.2

N2Fe

Figure 3.4.3 The activity coefficient of X in liquid FeX alloys [3].

d2 GE d2 GE
dG1E
dG2E

2

2
dX12
dX22
dX22
dX12
d logg1
dlogg2
4:605RT
4:605RT
2
dX2
dX12

3:4:60

For the systems having strong interaction, the excess stability has large values and
exhibits a maximum close to the composition corresponding to intermetallic compound.

REFERENCES
[1] J.H. Hildebrand, J. Am. Chem. Soc. 51 (1929) 66.
[2] M. Margules, Sitzungber. Kaiser. Akadem. Wissenschaft. Wien. Mathmatisch- Naturwiss. Class. 104
(1895) 1243.
[3] L.S. Darken, Trans. Met. Soc. AIME 239 (1967) 80.