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Introduction

Introduction
To
To
The
The
Thermodynamics
Thermodynamics
of Materials
of Materials
Dr.
Dr.
Mingxia
Mingxia
Gao
Gao

Department of Materials Science & Engineering Department of Materials Science & Engineering
Zhejiang University
Zhejiang University
E E- -mail: mail: gaomx@zju.edu.cn gaomx@zju.edu.cn
Tel.: 0571 Tel.: 0571- -87952615 87952615
Address Address 419 419- -2 2
Preface
Preface
Composition Composition
Structure Structure Properties Properties
The central importance is to predominate the relations among them.
Substances Materials Apparatus
Characteristics Properties Functions
Any material is synthesized by mixing substances.
Thermodynamics of materials usually deals with the equilibrium
process, and gives a right answer of what phases (solutions or
chemical compounds) will form in the final state, i.e. the
equilibrium state. It describes the basic principle between the
composition and the structure.
j ji
j j i
M P C = =

(j = , , ); (i= 1, 2, 3)
synthesis
Thermodynamics of materials:
a. It evolves systematically a method of strictly describing the
behavior of matter in a manner which is devoid of temporal
theories. Use simple tool to solve real problem. (simplicity)
b. It is initial conceptual difficult and there are large numbers of
equations. (complicacy)
c. It is a subject between physical principal and practical
application.
T The main contents of this course include five parts: he main contents of this course include five parts:
1.The behavior of solutions 1.The behavior of solutions
( (Raoult Raoult s s law and Henry law and Henry s s law; Thermodynamic Activity; Partial ; Thermodynamic Activity; Partial
Molar Quantities Molar Quantities Relative Partial Molar Quantities Relative Partial Molar Quantities Properties Properties
of Ideal Solution; Gibbs of Ideal Solution; Gibbs- -Duhem DuhemEquation and its application; Equation and its application;
Gibbs Free Energy of Gibbs Free Energy of formation; ; Nonideal Nonideal Solutions; Regular Solutions; Regular
solutions; A Statistical Model of Solutions; solutions; A Statistical Model of Solutions; Subregular Subregular Solutions) Solutions)
2. Gibbs free energy-composition relations and phase
diagrams of binary system
(Gibbs Free Energy and Activity; the Gibbs Free Energy of
Formation of Regular Solutions; Criterion of Phase Stability of
Regular Solutions; Spinodal Separation; Liquid and Solid
Standard States; the Curve of the Molar Gibbs Free Energy of
Formation vs. the Composition; Immiscible Binary System
Phase Diagram; Binary Eutectic Systems ) )
3. Reactions involving gases 3. Reactions involving gases
(Reaction Equilibrium; The Effect of Temperature and Pressure; (Reaction Equilibrium; The Effect of Temperature and Pressure;
Reaction Equilibrium as a Compromise between Enthalpy and Reaction Equilibrium as a Compromise between Enthalpy and
Entropy; The Entropy; The Application in Scientific Research) )
4.Reactions involving pure condensed phases and
gaseous phase
(Reaction Equilibrium in a System Containing Pure Condensed
Phases and a Gas Phase; The Application in Scientific Research)
This course is the prelude of the study and
This course is the prelude of the study and
utilization of the
utilization of the
Thermodynamics of Materials
Thermodynamics of Materials
.
.
The main purpose of the course is to introduce and
demonstrate some basic but important principles and their
applicability, thus to evolve us a capacity of fully utilizing the
standard treatises and to a continuity of the development and the
application of the principles.
5. Reaction equilibrium in systems containing
components in condensed solution
Reaction Equilibrium Criteria; Alternative Standard States;
Application in Scientific Research.
Chapter 1
Chapter 1
The behavior of solutions
The behavior of solutions
The concept of solution in terms of the
thermodynamics of materials :
All kinds of mixtures composed of two or more than two
components that are homogenous in structure and
composition throughout, including gas, liquid and the solid
solution of single phase.
1.1
1.1
Raoult
Raoult

s
s
law and Henry
law and Henry

s law
s law
a quantity of pure species A (or B)
condensed state
evaporate
saturated vapor pressure
evaporation rate
condensation rate
A small quantity of liquid A adds to liquid B .
Condition 1:
The atomic diameters of A and B are comparable and assuming
the surface composition of the liquid to be the same as the bulk
liquid composition, and the A-A, A-B and B-B bond energies in
the solution are identical.
0
( ) ( )
c A A e
r A K p r A = =
Raoults Law:
0
0
A A A
B B B
p p X
p p X
=
=
Raoults law states that the vapor pressure exerted by a
component i in a solution is equal to the product of the mole
fraction of i in the solution and the vapor pressure of pure i at the
same temperature of the solution.
A
p
( ) e A A A A
r X K p =
0
A
P
0
A
p
Whats the vapor pressure
exerted by Aor B?
r
c
=r
e
0
( ) ( )
c A A e
r A K p r A = =
The above discussion is based on that the intrinsic evaporation
rate of A and B, r
e(A)
and r
e(B),
are independent of the
composition of the solution. This requires that the magnitudes
of the A-A, B-B and A-B bond energies (interactions) are
identical, such that the depth of the potential energy well of an
atom at the liquid surface is independent of the types of atoms
which it has as nearest neighbors.
A A- -B B bond energy bond energy is considerably much negative is considerably much negative than than A A- -A A or or
B B- -B B bond energy bond energy, (or to say that the , (or to say that the A A- -B B interaction is stronger), interaction is stronger),
and assuming that the solution of and assuming that the solution of A A in in B B is sufficiently is sufficiently dilute dilute, that , that
every every A A atom at the surface of the liquid is surrounded only by atom at the surface of the liquid is surrounded only by B B
atoms. atoms.
( ) '( )
e e
r A r A
Henrys Law:
'
A A A
p K X =
'
( )
0
( )
e A
A A A
e A
r
p p X
r
=
r
e
(A) > r
e
(A)
negative deviation from
Raoultian behavior
Condition 2:
Condition 2:
( )
'
e A A A A
r X K p =
With the increase of X
A
, the probability that all the A atoms at
the surface of the liquid are surrounded only by B decreases,
and there are also some A-A atom pairs. So, the value of r
e(A)
increases (not a constant). Beyond a critical value of X
A
, r
e(A)
becomes composition- dependent. Then, is no
longer obeyed by A in the solution.
is obeyed only over an initial concentration
range of A in B. The extent is dependent on the temperature of
the solution and on the relative magnitudes of A-A, B-B and A-B
interactions.
'
A A A
p K X =
'
A A A
p K X =
A A- -B B attraction attraction is significantly is significantly weaker than weaker than A A- -A A or or B B- -B B attraction attraction
r
e
(A) < r
e
(A)
positive deviation from Raoultian
behavior .
B
B
B
The components of a solution that Raoults law is obeyed are
said to exhibit Raoultian behavior.
In the composition ranges where Henrys law is obeyed, the
solutions are said to exhibit Henrian behavior.
1.2
1.2
The thermodynamic activity of a component in
The thermodynamic activity of a component in
a solution
a solution
(1) concept (1) concept
Three terms (2) the apparent reason Three terms (2) the apparent reason
(3) application (3) application
For an ideal gas: For an ideal gas:
0
ln G G RT p = +
For every component i of a mixture of gases:
0
ln
i i i
u u RT p = +
For a solution obeys Raoults law:
i i i
X p p =
0
Then:
0 0 *
ln ln ln
i i i i i i
u u RT p RT X u RT X = + + = +
But the practical solution normally deviate from the But the practical solution normally deviate from the Rauot Rauot s s Law , Law ,
thus, thermodynamic activity is introduced instead of the mole thus, thermodynamic activity is introduced instead of the mole
fraction fraction X X
i i : :
i i i
X a =
i i i i i i
X RT u a RT u u ln ln
0 0
+ = + =
With respect to a non-ideal gas :
f RT C G ln + =
For a practical mixture of gases:
i i i
f RT k u ln + =
The thermodynamic activity ( ) of a component in any state
at T is formally defined as the ratio of the fugacity of the
substance in that state to its fugacity in its standard state, i.e.,
for the species or substancei.
i
a
0
i
i
i
f
f
a =
If the vapor above the solution is ideal:
i i
p f =
0
i
i
i
p
p
a =
Activities in Fe-Cr at
1600, Raoultian
behavior
Activity of Ni in Fe-Ni at 1600
over the composition range in
which Henrys law is obeyed by
the solution i :
i i i
a k X =
i i
X a =
1.3 Partial molar quantities
(1)The reason of the appearance of partial molar quantity
In order to measure and express the variations of the
thermodynamic properties of a solution when the concentration
of component i of the solution varies.
(2) The physical signification of partial molar quantity:
Normally, partial molar quantity is defined as the variation of
the thermodynamic property of a large solution produced by the
addition of 1 mole of component i at constant P, T and constant
amounts of all the other components in the system.
At constant T and P, the variation of with the variation of
the solution composition:
To suppose that is an To suppose that is an extensive thermodynamic property extensive thermodynamic property of a of a
solution, a capacity property ( solution, a capacity property (V V, ,H H, ,S S, ,G, G,etc etc.). The value .). The value of of
:
:
Q
Q
' Q
,......) , , , , ( ' '
k j i
n n n P T Q Q =
K +

=
k
n n P T
k
j
n n P T
j
i
n n P T
i
dn
n
Q
dn
n
Q
dn
n
Q
dQ
j i
k i
k j
,... , , ,
,... , , ,
,... , , ,
' ' '
'
' Q
The partial molar quantity of of component i is defined as :
, , , ,...
'
j k
i
i
T P n n
Q
Q
n


is the increase of the value of for
a mixture or solution when 1 mole of i
is added to the solution of large
quantity at constant T and P.
i
Q
' Q
Q
(Intensive property: (Intensive property: T,P T,P) )
(3) Stipulation :
The stipulation is that the quantity is large enough so that the
addition of 1 mole of to the solution should not cause a
measurable change in the composition of the solution.
The partial molar quantity can be defined in another case, that is,
the variation of the propertyof a definite solutioncaused byadding
mole of i, which is taken as . Because of the small
quantity of , the composition of the solution is also considered
to be no change. Thus,
i
dn '
i
dQ
i
dn
'
i
i
i
dQ
Q
dn
=
is also taken as the partial molar quantity of Q
of component i.
(4) (4) The extensive thermodynamic property The extensive thermodynamic property can be can be : :
V V (the molar volume of a solution), (the molar volume of a solution), H H (enthalpy), (enthalpy), S S (entropy), (entropy), G G
(Gibbs free energy) (Gibbs free energy) , etc.
For example, the partial molar enthalpy of component i can be
expressed as:
, ,
j i
i
i
i
T P n n
H
H
n


The partial molar Gibbs free energy of i is equal to its chemical
potential : i
i
G u =
So,
for an ideal solution:
For a practical solution:
i i i
X RT u u ln
0
+ =
0
ln
i
i i
G G RT X = +
i i i
a RT u u ln
0
+ =
0
ln
i
i i
G G RT a = +
There are some intrinsic relations between/among the different
partial molar quantities.
The general thermodynamic relationships between/among the
state properties of a system are applicable to the partial molar
properties of the components of a system. Such as:
i i i
G H TS =
i
i
i
P
G
S
T


i
i
T
G
V
P


( / )
(1/ )
i
i
P
G T
H
T


1.4
1.4
Gibbs
Gibbs
-
-
Duhem
Duhem
equation*
equation*
K +

=
k
n n P T
k
j
n n P T
j
i
n n P T
i
dn
n
Q
dn
n
Q
dn
n
Q
dQ
j i
k i
k j
,... , , ,
,... , , ,
,... , , ,
' ' '
'
,... , , ,
'
k j
n n P T
i
i
n
Q
Q

=
If is the value of per mole of i in the solution, then the
value of for the solution (composed of several moles) itself is :
i
Q
Q
'
i j k i j k
Q n Q n Q n Q = + + +L
'

i j k i j k
i j k i j k
dQ n dQ n dQ n dQ
Q dn Q dn Q dn
= + + +
+ + + +
L
L
d
i
f
f
e
r
e
n
t
i
a
t
i
o
n
'
i j k i j k
dQ Q dn Q dn Q dn = + + +L
Q
Thus,
0 = + + + L
k k j j i i
Q d n Q d n Q d n
or
0 =

i
i i
Q d n
The expressions of Gibbs-
Duhemequation
0 =

i
i i
Q d X
d
i
v
i
d
e
d

b
y

n
For a binary solution:
0 = +
B B A A
Q d X Q d X
Gibbs-Duhemequation describes the relationship among
the values of the thermodynamic properties of the
components and the composition of the solution.
Application:
If only one component (or some components) in a binary (or
multi-component) solution can be experimentally measured, the
corresponding property (properties) of the other (other
components) can be obtained by the Gibbs-Duhemequation.
1.5 Relative partial molar quantity
M
o
i i i
Q Q Q =
0
i
Q the partial molar quantity of pure i the molar
quantity.
Since correlates to the composition of a solution,
thus is also a function of composition.
The difference between and is defined as the
relative partial molar quantity, designated as .
i
Q
M
i
Q
i
Q
0
i
Q
M
i
Q
For example:
M M M
i i i
G H T S =
For a binary solution, the Gibbs-Duhemequation in the form of
can be expressed as :
M
i
Q
0
M M
A B A B
X d Q X d Q + =
For enthalpy H:
0 = +
M
B
B
M
A
A
H d X H d X
All of the thermodynamic relations that are applicable to the
partial molar quantities are also applicable to the relative partial
molar quantities.
1.6. The Gibbs free energy and other extensive
thermodynamic properties of a solution
1.6.1 The molar Gibbs free energy of a solution and the
partial molar Gibbs free energies of the components of
the solution
For a binary solution A-B composed of n
A
moles of A and n
B
moles
of B, at fixed T and P , the value of the Gibbs free energy of the
solution, G, is:
B
B
A
A
G n G n G + = '
For 1 mole of solution, X
A
+X
B
=1:
B
B A A
G X G X G + =
A B A B
A B A B
dG X dG X dG G dX G dX = + + +
D
i
f
f
e
r
e
n
t
i
a
t
i
o
n
=
0
(Gibbs-Duhemequation)
Since X
A
+X
B
=1, dX
A
= - dX
B,
B A
A
G G
dX
dG
=
Then,
B
B
A
B
A
B
G X G X
dX
dG
X =
m
u
l
t
i
p
l
y
i
n
g

b
y

X
B
) (
A B
A
A
B
X X G
dX
dG
X G + = +
=
1
So,
A
B
A
dX
dG
X G G + =
Similarly,
B
A
B
dX
dG
X G G + =
1.6.2 The changes in Gibbs free energy and
other thermodynamic properties due to the
formation of a solution
(1) The difference in molar Gibbs free energy of a component i
between pure i andi in asolution at T:
It can be obtained from three steps:
These expressions relate the dependence on compositionof the
partial molar Gibbs free energies of the components of a binary
solution and the molar Gibbs free energy of the solution.
(a)Evaporation of 1 mole of pure condensed i to vapor i at the
pressure at T. (equilibrium process, )
(b)Decrease in the pressure of 1 mole of vapor i from to at T.
(c) Condensation of 1 mole of vapor i fromthe pressure to the
condensed solution at T. (equilibrium process, )
0
i
p
i
p
) (a
G
) (c
G
0
i
p
i
p
Steps (a) and (c) are processes conducted at equilibrium, thus the
Gibbs free energies changed in the two processes are both zero.
The difference between and is the Gibbs free
energy change which accompanies the solution of 1 mole of i in
the solution.
) ( solution in i
G

) (pure i
G
i
i
i
b pure i solution in i
a RT
p
p
RT G G G ln ln
0
) ( ) ( ) (
=

= =

=
0
) (
ln
i
i
b
p
p
RT G ln
RT
dG Vdp dp RTd P
P
= = =
The overall change in Gibbs free energy for the three-step
process equals that for only (b):
Here, = ;
) ( solution in i
G

i
G
) ( pure i
G
0
i
G
=
i
M
i
i
i
a RT G G G ln
0
= =
This difference was designated as . This quantity is just the
relative partial molar Gibbs free energy of component i. It is also
called as the partial molar Gibbs free energy of mixing (solution)
of i.
M
i
G
If, at constant T and P, n
A
moles of A and n
B
moles of B are
mixed forming a binary solution, then
The Gibbs free energy before mixing=
0 0
B B A A
G n G n +
The Gibbs free energy after mixing =
B
B
A
A
G n G n +
The Gibbs free energy change due to mixing =
M
G'
) ( ) ( ) ( ) ( '
0 0 0 0
B
B
B A
A
A B B A A
B
B
A
A
M
G G n G G n G n G n G n G n G + = + + =
M
B
B
M
A
A
M
G n G n G + = '
or
) ln ln ( '
B B A A
M
a n a n RT G + =
In terms of 1 mole of binary A-B solution,
M
B
B
M
A
A
M
G X G X G + =
) ln ln (
B B A A
M
a X a X RT G + = or
M
G
: the molar Gibbs free energy change due to the
mixing of the components to form a solution.
The above two equations give the molar Gibbs free energy
change due to the mixing of the components forming a solution
with a given composition.
A typical form of the variation of with composition of a
binary solution.
M
G
The change of other molar properties due to the formation of a
solution, such as and , can also be obtained by the
similar method.
M
H
M
S
For any extensive thermodynamic property in a binary solution,
M
B B
M
A A
M
Q X Q X Q + =
M
H
M
S
M
i
i
M
i i
M
B B
M
A A
M
Q X Q X Q X Q X Q

= + + + = L L
:the enthalpy change due to mixing X
A
moles of pure A
and X
B
moles of pure B forming 1 mole of solution,
which is also called as the molar enthalpy (change) of
mixing of the solution.
In an A-B binary solution:
:the entropy change due to mixing X
A
moles of pure A and
X
B
moles of pure B forming 1 mole of solution, which is
also called as the molar entropy (change) of mixing of the
solution.
M
G
: is the criterion to estimate whether the formation of
the solution will spontaneously go alongor not.
M
G
M
G
M
G
<0; the formation goes along
>0; solution cannot be formed
=0; equilibrium
M M M
S T H G =
M
P
M
S
T
G
=


also fits the relations interrelated the extensive
thermodynamic properties, , of the solution, such as:
M
Q
Q
1.6.3 The method of tangential intercepts
A
B
A
dX
dG
X G G + =
B
A
B
dX
dG
X G G + =
The relation among the partial molar Gibbs free energy of a
component, the molar Gibbs free energy of the solution and the
composition is also applicable to the relative partial molar Gibbs
free energy and the molar Gibbs free energy of formation of the
solution. That is:
A
M
B
M
M
A
dX
G d
X G G

+ =
B
M
A
M
M
B
dX
G d
X G G

+ =
the slope of the tangent to the
curve at X
A
=X
A
= rs/rq
os rs pq
rq
rs
rq pq G
M
A
= + = + =
OS =the tangential intercept at X
A
=1
=the tangential intercept at X
B
=1
M
B
G

r
s
q
P
A B
The application of tangential intercepts:
It can be used to obtain the partial molar and relative partial molar
values of an extensive property of the components of a binary
solution from the variation of the integral values of the property
with the composition.
For any extensive thermodynamic properties :
A
M
B
M
M
A
dX
Q d
X Q Q

+ =
, Q can be G, H, S, etc.
To obtain the relative partial molar quantities ( , , )
one can be by the calculation from the above equation, and the
other can be by the graphical tangential intercept method.
M
i
G
M
i H
M
i
S
,
(2) Volume change of the formation of an ideal solution
For a species i occurring in a solution,
and for pure i :
i
i
T
G
V
p


0
0
i
i
T
G
V
p

=


Thus,
( )
0
0
,
i
i
i
i
T comp
G G
V V
p



=


or
,
M
M
i
i
T comp
G
V
p


1.7 The properties of Raoultian ideal solution
(1) Activity
i i
X a =
X
i
is independent of T .
partial derivation / derivative
,
ln
M id
i
i
G RT X =
,
0
M id
i
V =
For an ideal solution,
as X
i
is not a function of pressure, then:
( ) ( ) ( ) ( )
' 0 0 0 0
M M
M
A B A B A B
A B A A B B A A B B A B
V n V n V n V n V n V V n V V n V n V = + + = + = +
Since
Thus ,
,
0
M id
V =
,
'
0
M id
V =
The volume of an ideal solution is equal to the sum of the
volumes of the starting pure components of the solution.
0
A A
V V =
0
B B
V V =
The molar volume of an ideal
solution is a linear function of
the composition.
(3) Enthalpy of formation of an ideal solution
From the Gibbs-Helmholtz equation:
( )
2
,
i
i
p comp
G T
H
T T


=


( )
0
0
2
,
i
i
p comp
G T
H
T T



for component i in solution
for pure component i
subtraction
This equation is applicable in a closed system at the
process of constant P.
The complementarity for the Gibbs-Helmholtz equation:
p
G
G H TS H T
T


= = +


GdT HdT TdG = +
Division of the two sides of the equation by T
2
, gives:
2 2
TdG GdT HdT
T T

=
2
( / ) d G T H
dT T
=
2
( / ) d G T H
dT T

=
( )
2
( / ) ( )/ d x y ydx xdy y =
2
1
( )
dT
d
T T
=
Since , thus
( )
/
(1/ )
G T
H
T

=

0
0
2
,
i i
i i
p comp
G G
T
H H
T T




or
( )
2
,
M
M
i
i
p comp
G T
H
T T




=



M
i H
is the partial molar heat of solution of (the relative partial
molar heat of i ).
i
For an ideal solution,
,
ln
M id
i
i
G RT X =
( )
2
ln
M
i
i
d R X
H
dT T

=
substituting into
Then
As X
i
is not a function of temperature, then:
,
0
0
M id
i i
i
H H H = =
,
0
M id
H =
The heat of formation of a solution is obtained as the difference
between the heats (enthalpies) of the components in the solution
and the heats (enthalpies) of the components before mixing.
( )
( )
( ) ( )
' 0 0 0 0

M
A B A B
A B A A B B A A B B
M M
A B
A B
H n H n H n H n H n H H n H H
n H n H
= + + = +
= +
,
' 0
M id
H =
(4) Entropy of formation of an ideal solution
There are two contributions to the entropy of a solid solution:
the thermal contribution, S
th
, and the configuration contribution,
S
config
.
In statistical thermodynamics, entropy is related to the
randomness by the Boltzmann equation, , where k is
Boltzmanns constant, 1.3810
-23
J /C.
ln S k =
(a) With respect to the thermal entropy, is the total number of
ways in which vibration can be set up in the solution.
(b) In solutions, additional randomness exists due to the
different ways in which the atoms can be arranged. This is the
extra entropy of configuration, S
config
. In such condition, is
the number of distinguishable ways of the arrangement of the
atoms in the solution.
For the mixing of N
A
particles of A with N
B
particles of B forming
a substitutional solution, the change of the entropy of
configuration :
( )
( )!
' ln ln ln
! !
ln ln
A B A B
conf A B
A B A B A B
A A B B
N N N N
S k k N N
N N N N N N
k N X N X


+
= = +

+ +


= +
N
A
=N
0
n
A
; N
B
=N
0
n
B
(N
0
is the Avogadros number)
For an ideal solution, there is no volume change or heat change
during mixing. So, the only contribution to is the change in
the configuration entropy , thus:
So,
( )
0
' ln ln ( ln ln )
config A A B B A A B B
S kN n X n X R n X n X = + = +
( ln ln )
config A A B B
S R X X X X = +
For 1 mole of solution,
, M id
S
,
( ln ln )
M M
M id
A B
A A B B A B
S R X X X X X S X S = + = +
Since X
A
<1, X
B
<1, thus
,
0
M id
S >
From the fundamental equation,
( )
,
,
,
ln ln
M id
M id
A A B B
p comp
G
S R X X X X
T

= = +


identical with that from the entropy change in the configuration of
the solution. the increase of the number of spatial configuration)
The entropy increases during the formation of an ideal solution.
The increase in molar value of the entropy change of mixing is
dependent only on the mole fraction of the components of the
solution and is independent of T.
The variation of with composition
in an ideal binary A-B solution
, M id
S
For a solution contains n
A
moles of A and n
B
moles of B, the
entropy change of formation is:
'
S
M M
M
A B
A B
S n S n = +
(5) The Gibbs free energy of formation of an ideal solution
For a binary A-B solution, the change of the extensive properties
when 1 mole of solution is formed can be presented as
M M
M
A B A B
Q X Q X Q = +
To suppose that 1 mole of homogeneous solid solution is formed
by mixing together X
A
moles of A and X
B
moles of B, X
A
+X
B
=1.
before mixing: after mixing:
X
A
X
B
0 0
1 A A B B
G X G X G = +
0
A
G and are the molar Gibbs free energy of pure A and pure
B, respectively.
0
B
G
2 1
M
G G G = +
( )
,
ln ln
M id M M
A B
A A B B A B
G RT X X X X X G X G = + = +
X
A
+X
B
Variation of G
1
(the Gibbs free energy per molar
of A and B before mixing) with composition
,
0
M id
S >
, , , ,
0 0
M id M id M id M id
G H T S T S = = <
Since X
A
<1, X
B
<1, thus
So, the Gibbs free energy change of mixing for an ideal
solution is only due to the change in entropy.
(negative values)
, M id
G
is a function of T and composition.
T increasing
, M id
G
more negative

G
M
,
i
d
The actual Gibbs free energy of the solution, G
2
, is certainly
related to the molar Gibbs free energy of pure A and pure B
( and ).
0
A
G
0
B
G
( )
0 0
2
ln ln
A A B B A A B B
G X G X G RT X X X X = + + +
As T increases, and decrease,
and the Gibbs free energy curves
assume a greater curvature.
The decrease of and is due to
the decrease of the thermal entropy of
the both components.
0
A
G
0
B
G
0
A
G
0
B
G
p
G
S
T


This means that G decreases with
increasing T at a rate of S.
G
G
1(L) G
2(L)
G
2(H)
G
1(H)
G
0
A(L)
G
0
B(L)
G
0
A(H)
G
0
B(H)
M
M
0
ln
A A A
u G RT X = +
0
ln
B B B
u G RT X = +
The chemical potential of A and B for an ideal solution:
,
The relationship between the Gibbs free energy curve
and the chemical potentials for an ideal solution.
In practical, the solutions of Sn-Zn, Fe-Cr and AgCu are closed
to ideal solutions.
1.8 Nonideal solution
i i
X
i
i
i
X
a
=
The activity coefficient of a component i , , in a
solution is defined as the ratio of the activity of the
component to its molar fraction.
i

To know the variation of the values of with T and


composition is centrally important in solution thermodynamics.
i

Since,
to determine the equilibrium state of any chemical reaction
involving the components in the solution
M
i
G
is required
i
a
is required
i

is required
The variation of with X
i
for a component i. Fe-Ni
system at 1600
o
C.
<1, negative deviation
from Raoults law.
i
a
i

The variation of with X


i
for a component i. Fe-Ni
system at 1600
o
C.
i

i
The variation of with X
i
for a component i. Fe-Cu
system at 1550
o
C.
The variation of with X
i
for a component i. Fe-Cu
system at 1550
o
C.
>1, positive deviation
from Raoults law.
i

i
a
i

,
ln ln ln
M non id
i
i i i
G RT a RT RT X

= = +
( )
( )
2
ln
M
M
i
i
i
G T
R
H
T T T




= =

ln
1
M
i
i
R H
T

=



2
1
( )
dT
d
T T
=
,
0
M non id
i
H


When
varies with T, thus:
(Gibbs-Helmholtz equation)
then for a nonideal solution
Since
or
( )
Generally, an increase in the temperature of a nonideal solution
decreases the extent of the deviation of its components from
ideal behavior.
From and decreases with increasing T,
it is obtained that
i

1
i
>
( )
1
i i
T ( )
1
i

AA
BB
E
AB E
E <
(a) When >1, an increase in temperature decreases the value of
toward unity;
,
,
,
ln
1
M
i
i
H R
T

=

0.
M
i
H >
Thus,
0
M
H >
When >1, the molar heat of formation of the solution is a
positive quantity. The solution process is endothermic. is the
quantity of heat absorbed for the solution fromthe thermostating
heat reservoir surrounding the solution when 1 mole of the
solution is formed at T.
i

M
H
i

1
i
< ( )
1
i i
T
( )
1
i

AA
BB
E
AB E
E >
(b) When <1, an increase in temperature increases the value of
toward unity;
,
,
,
ln
1
M
i
i
H R
T

=



From and increases with increasing T, it
is obtained that
i

0,
M
i
H <
Thus,
0
M
H <
When <1, the molar heat of formation of the solution is a
negative quantity. The solution process is exothermic. is the
quantity of heat absorbed by the thermostating heat reservoir
surrounding the solution when 1 mole of the solution is formed
at T.
i

M
H
i

(b) For exothermic mixing, the A-B attraction is stronger than


either the A-A or B-B attractions ( <1, E
AB
<E
AA
,E
BB
). There is
a tendency toward compound formation between the two
components, i.e. toward ordering in the solution . A atoms
attempt to have only B atoms as nearest neighbors, and B
atoms attempt to have only A atoms as nearest neighbors.
(a) For endothermic mixing, the A-A and B-B attractions are
stronger than the A-B attraction ( >1, E
AB
>E
AA
,E
BB
). There is
a tendency toward phase separation or clustering in the
solution. A atoms attempt to have only A atoms as nearest
neighbors, and B atoms attempt to have only B atoms as
nearest neighbors.
i

For an A-Bbinary solution:


(c) In both exothermic mixing and endothermic mixing, the
equilibrium configuration of the solution is reached as a
compromise between the enthalpy factors and the entropy factor.
The enthalpy factors are determined by the relative magnitudes of
the atomic interaction, which attempt to either completely order
or completely unmix the solution.
And the entropy factor attempts to maximize the randomness of
mixing of the atoms in the solution.
(a) ordered (b) clustering (c) random
0
M
H <
0 >
M
H
1.9 The excess function of the extensive
thermodynamic properties
The excess function of an extensive thermodynamic property, ,
denotes the difference between the value of the property (Q ) ,
such as H, S and G, etc., of a real solution and the value that the
solution would have if it was ideal.
E
Q
0 0 , ,
( ) ( )
E real id real ieal M real M id
Q Q Q Q Q Q Q Q Q = = =
For a binary system, A-B, the excess Gibbs free energy,
E
G
( ) ( )
( )
, ,
ln ln ln ln
ln ln
E M real M id
A A B B A A B B
A A B B
G G G
RT X a X a RT X X X X
RT X X
=
= +
= +

again from the concept of the excess molar Gibbs free energy of a solution,
real id E
G G G = +
, subtraction of from both sides gives:
0 0
A A B B
X G X G +
, M M id E
G G G = +
As for any solution, , thus
The excess H and S can be expressed as :
( )
, ,
ln ln
( ) ln ln
A B
E
E
A B
p A A B B A B
p X p X
G
S R X X RT X X
T T T





= = + +





2
, ,
ln ln
A B
E E E
A B
A B
p X p X
a a
TS G H RT X X
T T



+ = = +






( )
ln ln
E
A A B B
G RT X X = +
The value of can be used to estimate whether the solution is
positive or negative from an ideal solution.
E
G
If =0, the solution is an ideal solution.
>0, positive deviation from the ideal solution.
<0, negative deviation from the ideal solution.
E
G
E
G
E
G
The concept of excess thermodynamic function is also applicable
to the partial molar quantity and relative partial molar quantity.
where Q can be G, H, S, etc.
( )
, ,
ln ln ln
E
M M real M id
i i i
i i i i
G G G RT X RT X RT = = =
( ) ( ) ( )
, ,
0 0
E
M M real M id real id real id E
i i i i i i i i i i
Q Q Q Q Q Q Q Q Q Q = = = =
In terms of the excess relative partial molar Gibbs free energy:
In addition, in terms of excess partial molar Gibbs free energy,
( ) ( ) ( )
( )
, ,
0 0
ln
E real id real ideal M real M id
i i i i i i i
i i
E
M
i
i
G G G G G G G G G
G RT
= = =
= =
E E
E
A B
A B
G X G X G = +
E E
E
A B
A B
S X S X S = +
E E
E
A B
A B
H X H X H = +
For a binary solution:
It should be noted, that is the criterion of the deviation type
from Raoults law. In the case of only one of the values of
and is known, normally, it cannot estimate the type of
deviation from Raoults behavior that the solution has .
E
i
G
E
i
H
E
i
S
1.10 Regular solution
i
id
i
a X =
,
0
M id
i
H =
,
0
M id
i
V =
,
ln
M id
i
i
S R X =
,
0
M id
H =
,
0
M id
V =
,
ln
M id
i i
S R X X =
i i
a X
,
0
M real
i H
,
0
M real
H
1) Raoultian ideal solution:
,
(Review)
2 ) nonideal solution:
Regular solution is the simplification of some nonideal solutions.
A regular solution is defined as the one which has a nonzero
heat of formation and an ideal entropy of formation.
;
,
ln
M id
i
i
G RT X =
,
ln
M id
i i
G RT X X =
,
ln
M real
i i
G RT X a =
For component i :
,
0
M reg
i
H
, ,
ln
M reg M id
i i
i
S S R X = =
,
ln
M reg
i i
S R X X =

,
0
M reg
H
At any given temperature, it is suggested that the activity
coefficients, r
A
and r
B
of an A-B binary solution can be
represented by power series of the form:
L + + + =
3
3
2
2 1
3
1
2
1
ln
B B B A
X X X
L + + + =
3
3
2
2 1
3
1
2
1
ln
A A A B
X X X
1 2 3 1 2 3
, , ......, , , ...... are constants .
by Gibbs-Duhemequation:
0 ( ln )
M M M
A B i
A B i
X d G X d G G RT a + = =
B B A A
d X d X ln ln =
Thus :
(a)If in the entire composition range, the solution obeys the above equation,
then . 1 1
0 = =
(b) further, if the activity coefficient can be represented by the quadratic terms
only, then .
2 2
=
stipulations :

2
ln ,
A B
X =
2
ln
B A
X =
or
where
A regular solution can also be assigned the one obeys the following Eqs:
2
ln ,
A B
RT X

=
2
ln
A B
X RT

=
where is independent of temperature.
'
is an inverse function of temperature,
RT


=
but independent of the composition of the
solution.
Hence,
2 2
1 2 B
1
RTln RT 'X
2
A B B
X X = + Similar for RTln
B

) ( ) ln ln (
B A B A B B A A
E
X X X X RT X X RT G + = + =
The thermodynamic properties of a regular solution can be best
examined via the concept of excess function.
, , M reg M id
i i
S S =
0 0
( ) ( )
id id E
G G G G G G G = +
Since,
and
, , , ,
, , , ,
(or( ) )
( )
E reg M reg E M reg M id
M reg M reg M id M reg
G G G G
H T S S H
=
= =
2
B
X
2
A
X
, ,
'
E reg M reg
A B A B
G RT X X X X H = = =
Therefore,
M
G
id M
G
,

, E reg
G
is independent of temperature, as
,
,
,
E reg
E reg
P comp
G
S
T


0
,
=
reg E
S
Therefore, for a binary regular solution, at any given composition,
1 2
1 ( ) 2 ( )
ln ln
E
A A T A T
G RT RT = =
2
1
( )
1
( ) 2
ln
ln
A T
A T
T
T

=
This equation is practically used in converting activity data at
one temperature to those at other temperatures.
At given temperature, the plots of
vs. display a linear relationship, the
slop of which is . With the increase of
T, decreases.
Additionally, for a regular solution, can also be obtained from
2
2
' (1 ) ' ( )
' ln
E
E
E
A
B A B A A A
A
B A
dG
G G X X X X d X X
dX
X RT


= + = +
= =
E
i
G
Ti
log
2
Sn
X


Example: the Ti-Sn system
vs.
Ti
log
2
Sn
X
RT


= (
)
But, b b Thus, ,
If is strictly adherence to the model,
it should be independent of T, ,
but from experiment, decreases
slowly with T increasing.
T
'
T
R

=
It should be noted that a parabolic
relationship for or with composition
can not be taken as a demonstration that
the solution is regular.
M
H
E
G
B A
M
X bX H =
B A
E
X X b G

= When or
M E
H G
, ,
( )
E M M id M M M id
G G G H T S S = =
M id M
S S
,
So,
T
Ti-Sn at 414
1. Au( aurum / gold) Cu, non-regular at 1550 K,
For examples:
Au Cu
E
X X G 060 , 24 =
joules, but
M
H is asymmetric. Hence, 0
E
S
2. AuAg, non-regular at 1350 K,
Au Ag
M
X X H 590 , 29 =
joules, but
E
G is asymmetric. Hence, 0
E
S
M id M
S S
,
For a regular solution, as ,
Thus, for a Raoultian solution, as ,

=
A
X
A
B
A
B
E
dX
X
RTX G
0
2
ln
, while )
A
E
B
E
E
A
dX
dG
X G G + =
A
E
A
RT G ln =
(from
1 =
A
0
E
G =

=
2
ln
B
A
X
B A
E
X X RT G =
,
,
, , ,
, , ( )
( ln ln )
' ( ln ln )
M regular E reg M i d
A A B B
M reg M reg id
A B A A B B
G RT X X G G
X X RT X X X X H T S

= + = +
= + + =
'
A B
X X
: the nonideality of the mixture.
If is positive, the heat of mixing is positive, endothermic process, 0
M
H >
0
M
H < If is negative, the heat of mixing is negative, exothermic process.
'
'
Another form for G
E
:
, ,
or(( ) ) 0
E M E M reg M id
S S S S = =
For a regular solution,
, , ,
( ) ( ) ( )
M E M E M E E M reg M id M reg
G H T S H H H H = = = =
id M
B B A A
reg M
S X X X X R S
, ,
) ln ln ( = + =
) ln ln (
, , ,
B B A A
reg M reg M reg M
X X RT S T G H + = =
reg E reg M
i
id M
i
reg M
i
E reg M
i
i
G H H H H
, , , , , ,
) ( = = =
i
reg M
i
RT H ln
,
=
, ,
'
E reg M reg
A B A B
G RT X X X X H = = =
1.11 A statistical model of solutions
In the statistical model, it is assumed that the heat of mixing,
,is only caused by the bond energies between the
adjacent atoms, and
M
H
(1)
0 0
A B
V V =
(2) 0
M
V =
0
i
i
V V =
(The quasi-chemical model)
The statistical model of solutions is a theory about the
relationship between the macroscopical thermodynamic
properties and the microstructure of the solutions with
following features.
Thus, the energy of the solution is the sum of the atom-atom
bond energies.
(3) For the two components, in both their pure state and in
solution, the interatomic forces are only significant over short
distance. Only nearest neighboring interactions need to be
considered, or, interactions only exist between neighboring
atoms.
(4) The factors of the atomic size and the structure of the
electron are ignored.
Consider 1 mole of A-B solution containing N
A
atoms of A and N
B
atoms of B ,
AA
E
This solution contains three types of atomic bonds:
1) A-A bonds, the energy of each bond is
2) B-B bonds, the energy of each bond is
.
BB
E
3) A-B bonds, the energy of each bond is
AB
E
0
A A
A
A B
N N
X
N N N
= =
+
0
B
B
N
X
N
=
AB AB BB BB AA AA
E P E P E P E + + =
AA
P
BB
P
AB
P number of A-A bonds; number of B-B bonds; number of A-B bonds
(the energy of the solution)
2
AB AA
A
P P
N
z z
= +
2 2
A AB
AA
N z P
P =
2
AB BB
B
P P
N
z z
= +
2 2
B AB
BB
N z P
P =
or
or
1 1 1
( )
2 2 2
A AA B BB AB AB AA BB
E zN E zN E P E E E

= + + +


1
2
AA A
P N z =
For N
A
atoms of pure A:
For N
B
atoms of pure B :
1
2
BB B
P N z =
Thus, the change of the energy during mixing,
M
E
M
E

+ ) (
2
1
BB AA AB AB
E E E P
=(the energy of the solution) (the energy of the unmixed components)
=
(Z: coordination number; FCC: 12; BCC:8) Each atom has z nearest neighbors
AB AB BB BB AA AA
E P E P E P E + + =
BB B AA A
E zN E zN
2
1
2
1
+
M M M
H E p V =

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
AA
E
BB
E
AB
E
M
H
AB
P
For given values of , and ,
depends on
id M
H
,

2
BB AA
id
AB
E E
E
+
=
For an ideal solution, =0, thus,
For ideal mixing, it is necessary that E
AA
=E
BB
=E
AB
, so, a sufficient
condition is that E
AB
should be the average of E
AA
and E
BB
.
( )
AB
E / 2
AA BB
E E > +
If
0, 1
M
i
H < <
( )
AB
E / 2
AA BB
E E < +
0, 1
M
i
H > >
,
( ln ln )
M id
A A B B
S R X X X X = +
For ideal solution, the mixing of N
A
atoms of A with N
B
atoms of
B is random, in this case, the measure of the randomness of
the system, , is given as
M
S
0
M
V =
, exothermic mixing.
, endothermic mixing.
In solutions which do not depart too greatly from ideality, that is,
, it may be assumed that the randomness of the
distribution of the atoms is approximately the same as in an ideal
solution. In such case, considering two neighboring lattice sites,
labeled 1 and 2, in the A-B crystal, 1 2
(a) The probability that site 1 is occupied by an A atom is X
A
:
M
H RT
0
the number of A atoms in the crystal
the number of lattice sites in the crystal
A
A
N
X
n
= =
(c) The probability that the site 1 is occupied by A and site 2 is
simultaneously by B is X
A
X
B
. The site 1 is occupied by B and
site 2 is simultaneously by A is also X
A
X
B
. Thus, the probability
that a neighboring pair of sites contains an A-B pair is 2 X
A
X
B
.
(b) The probability that site 2 is occupied by B atom is X
B
.
(d) The probability that a neighboring pair of sites contains an A-A
pair is X
A
2
, and that contains an B-B pair is X
B
2
.
As per mole of crystal contains pairs of lattice sites.
0
2
1
zn
So,
0 0
1
2
2
id
AB A B A B
P zn X X zn X X = =
2
0
1
2
AA A
P zn X =
2
0
1
2
BB B
P zn X =
0
1
( )
2
M
A B AB AA BB
H zn X X E E E

= +


+ = ) (
2
1
BB AA AB AB
M
E E E P H ( )
0
1
( )
2
AB AA BB
zn E E E

= +


B A
M
X X H =
To take
, then
M
H
is a parabolic function of composition.
As random mixing is assumed, the statistical model corresponds
to the regular solution, i.e.,
, M reg E
A B
H G X X = =
Thus, for a regular solution,
, , ,
( ln ln )
M reg M reg M reg
A B A A B B
G H T S X X RT X X X X = = + +
,
1
0, , ( ( ), 0
2
M reg
AB AA BB AB AA BB
E E E H < < > + <
A-B bond is preferred.
(1) when
0
1
( )
2
AB AA BB
zn E E E

= +


T
M
G
(2) when
,
1
0, , ( ( ), 0
2
M reg
AB AA BB AB AA BB
E E E H > > < + >
A-A, B-B bond is preferred.
Mixing at high T ,
0
M
G <
Mixing at low T , positive
value of appears.
M
G
Since
,
( )
M reg
B A
A
H
X X
X

, M reg
A B
H X X =
, then
,
, ,
M reg
M reg M reg
A B
A
H
H H X
X

= +

The value of relates to both the values of and T , in other


words, relates to the relative values of , , , z and T.
i


AA
E
BB
E
AB
E
Thus
, 2
( )
M reg
A A B B B A B
H X X X X X X = + =
and similarly,
, 2 M reg
B A
H X =
As the mixing is random, then
A
M
A
X R S ln =
B
M
B
X R S ln =
Hence,
A B
M
A
M
A
M
A
X RT X S T H G ln
2
+ = =
Since
ln ln ln
M
A A A A
G RT a RT RT X = = +
So,
2 2
ln B
B A
X X
RT
=

=
2 2
ln A
B A
X X
RT

= =
RT

=
The applicability of the statistical model to actual solutions
decreases as the magnitude of

If <0, then <1; If


>0, then
>1.
According to the Henrys law, when X
B

0
ln ln
A A
RT


=
1,
i
X
Raoults law is approached asymptotically for the
component i.
As 1,

( ) increases. That is :
1
( )
2
AB AA BB
E E E + ff
If or ,
1
( )
2
AB AA BB
E E E + pp
the random mixing of the A and B atoms can not be assumed.
The equilibrium configuration of a solution at constant T and P is
which minimizes the Gibbs free energy G (G=H-TS ).
Minimization of G occurs as a compromise between minimization
of H and maximization of S.
maximization of the number of A-B pairs (complete ordering of
the solution), and maximization of S corresponds to completely
random mixing. So, minimization of G occurs as a compromise
between maximization of P
AB
(the tendency increases with
decreasing , as there is a negative value) and random
mixing (the tendencyincreases with increasing T )

(a) If
( )/ 2
AB AA BB
E E E > +
, minimization of H corresponds to the

If is appreciably negative, and T is not too high, then


P
AB(actual)
> P
AB(random)
. It cannot assume that the mixing is random.

0
M
H <
, , ,
( ln ln )
M reg M reg M reg
A B A A B B
G H T S X X RT X X X X = = + +

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
0
1
( )
2
AB AA BB
zn E E E

= +

-
(b) IF , minimization of H corresponds to
the minimization of the number of A-B pairs (complete clustering
in the solution). The minimization of G occurs as a compromise
between minimization of P
AB
(the tendency increases with
increasing , as here is a positive value) and random
mixing (maximization of S) .
( )/ 2
AB AA BB
E E E < +

Then, if is appreciably positive, and T is not too high, then
P
AB (actual)
< P
AB (random)
. It also cannot assume that the mixing is
random.


0
M
H >
, , ,
( ln ln )
M reg M reg M reg
A B A A B B
G H T S X X RT X X X X = = + +

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
0
1
( )
2
AB AA BB
zn E E E

= +


+
then (1) For any value of , more-nearly random mixing occurs
as the temperature is increased.
(2) For any given T, more-nearly random mixing occurs with
smaller values of .
For the statistical model to be applicable, the configurationof the
equilibrium solution should be not too far from random mixing.

, , ,
( ln ln )
M reg M reg M reg
A B A A B B
G H T S X X RT X X X X = = + +

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
0
1
( )
2
AB AA BB
zn E E E

= +


A-50at%B solution
The extreme configurations are complete ordering and complete clustering.
Random configuration occurs between the extremes when the probability of
an A-B pair is 0.5. In both extreme configurations (ordering or clustering),
=0.
M
S
0
M
H < 0
M
H >


1
2
3
4
0
M
H < 0
M
H >
1
2
3
4
*
*
*
1
3
2
4
Variations of the , and with the range of
spatial configuration available to a A-50 at%B solution.
M
S
M
H
M
G
Curve 1 : the relationship between the entropy of mixing ( )
and the solution configuration. The maximum value is ,
occurring in the random configuration.
M
S
id M
S
,

Curve 2 :
M
T S
Line 3: the variation of with configuration, linear to P
AB
.
M
H
curve 4: The sum of curve 2 and line 3, ,
the minimum in this curve occurs at the equilibrium
configuration.
M M M
S T H G =
(*/asterisk : the minimum of the curve).
M
G

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
0
M
H < 0
M
H >


1
2
3
4
0
M
H < 0
M
H >
1
2
3
4
*
*
*
1
3
2
4
The equilibrium configuration of exothermic solution lies
between the ordered and random configuration; The equilibrium
configuration of endothermic solution lies between the clustered
and random configuration.
(1) That the random configuration to be the equilibrium
configuration only occurs in the case that =0 in all the
composition range.
M
H
0
M
H < 0
M
H >


1
2
3
4
0
M
H < 0
M
H >
1
2
3
4
*
*
(3) For any given system (of fixed ), as T and hence
increases, the position of the minimum on the curve
moves toward to the random configuration.
(4) Both extreme configurations are physically unrealizable.
(2) As for the A-B system increases, at a constant T, the
position of the minimum on the curve moves further away
from the random configuration. ( )

M
G
B A
M
X X H =

M
S T
M
G
M
H
varies with

0
M
H < 0
M
H >


1
2
3
4
0
M
H < 0
M
H >


1
2
3
4
T
T

+ = = ) (
2
1
BB AA AB AB
M M
E E E P E H
0
1
( )
2
AB AA BB
zn E E E

= +


In order to have the minimum on the curve coincide with
either extreme, at definite T, infinite values of would be
required (negative for complete ordering and positive for
complete clustering) .
In addition, with a nonzero , only at infinite T, the random
configuration could become the equilibrium configuration.
M
G
M
H
M
H
0
M
H < 0
M
H >


1
2
3
4
0
M
H < 0
M
H >


1
2
3
4
T
T
*
*
The above two are
all unrealizable.

M
H
In the regular solution model:
is a constant;
shows a parabolic variation with composition;
E
G
M
G
and are symmetrical about the composition X
A
=0.5.
0 0
B A
V V
But if :
The lattice parameters of the crystal will vary
with the composition;
The interatomic distance varies with composition;
The bond energies will be composition-dependent.
M E
A B
H X X G = =
, M M id
S S =
The regular solution model can be made more flexible by The regular solution model can be made more flexible by
arbitrarily arbitrarily allowing allowing to vary with composition, such as to vary with composition, such as
L L + + + + =
3 2
B B B
dX cX bX a
The so called subregular solution model is that
B
bX a + =
E
( )
B A B
G a bX X X = +
E
2 2
( )
A
B B B A
G aX bX X X = +
E
2 2
2
B
A A B
G aX bX X = +
A
B
A
dX
dG
X G G + = ( )
1.12
1.12
Subregular
Subregular
solutions
solutions
Empirical equation
a and b have no physical significance.
and a, b, c, d are constants.
Excess molar Gibbs free
energy curves generated by
the subregular solution
model for several
combinations of a and b.
The maximum and minimum
in the curves occur at
E
G
E
0
B
dG
dX
=
a
a ab b a b
X
B
6
2 ) ( 2
2 2
+ +
=
E
( )
B A B
G a bX X X = +
, E
( ln ln )
( )
M M id
A A B B
B A B
G G G
RT X X X X
a bX X X
= +
= +
+ +
Fit the data of a and b to the
subregular solution model.
The variation of The variation of with with
composition in the system of Ag composition in the system of Ag- -
Au, obtained from the Au, obtained from the
experimental measurements experimental measurements
1350K
a=13456 J
b=5412.8 J
The influence of temperature on the behavior of subregular solution can be
accommodated by introducing a third constant, ,
E
0 0
( ) (1 )
B A B
T
G a b X X X

= +
E
E
0 0
( )
A B
a b X X G
S
T
+
= =

E E
0 0
( ) (2 )
M
B A B
T
H G TS a b X X X

= + = +
( ) ( ) ( )
( )
, ,
0 0
ln
E real id real ideal M real M id
i i i i i i i
i i
E
M
i
i
G G G G G G G G G
G RT
= = =
= =
A
E
B
E
E
i
dX
dG
X G G + =
About the example in the text book:
Au-Cu solid solution, between 410~889
o
C, if
Au Cu
28,280
E
G X X =
Calculate the activity coefficient of Au and Cu.
2
2
Cu Au
28,280 0.4
ln 0.624
8.3144 873
X
RT


= = =

(at least not strict)


1.13 Application of the Gibbs-Duhem relation to
the determination of activity
1.13.1 Graphical integration
To obtain
i
a
one experimental method: electromotive force
0
ln
i
M
i
i i
G n F u RT a = = =
F is Faradays constant, 23,060 calories/voltmole.
Normally for low temperature
At high temperature,
(1)
0
i
i
i
p
p
a =
(2) In some binary solutions that the variation with composition
of the activity of only one component can be experimentally
determined, and the activity of the other component can be
determined by means of the Gibbs-Duhemequation.
i
i
i
a
X
=
0 =
i i
Q d X
i
M
i
a RT G ln = 0 ln ln = +
B B A A
a d X a d X
B
A
B
A
a d
X
X
a d log log =
log
log 1
log ( ) log
B A A
A A
B A
a atX X
B
A X X B
a atX
A
X
a d a
X
=
=
=
=

integration
Schematic representation of the
variation of with X
B
/X
A
in
a binary solution
The shaded area under the curve
is the value of at X
A
=X
A
.
log
A
a
B
loga -
Two points should to be noticed:
1) As X
B
1,
B
a
1,
B
a log
0,
and X
B
/ X
A
. Then the curve
exhibits a tail to infinity as X
B
1.
2) As X
B
0,
B
a
0,
B
a log
-,
and- . Then the curve
exhibits another tail to infinity
as X
B
0.
log
B
a
X=
X
A
=X
A2
0

The second point introduces an uncertainty into the calculation at any


composition. However, if to use activity coefficients instead of
activities in the Gibbs-Duhemequation:
In a binary solution,
0 log log = +
B B A A
d X d X
Then
B
A
B
A
d
X
X
d log log =
1
A B
X X + = 0 = +
B A
dX dX
0
A B
A B
A B
dX dX
X X
X X
+ =
ln ln 0
A A B B
X d X X d X + =
0 ln ln = +
B B A A
a d X a d X
subtraction from
(denominator, numerator)
log
log 1
log ( ) log
B A A
A A
B A
atX X
B
A X X B
atX
A
X
d
X


=
=
=
=

As X
A
1 (X
B
0), the solution
is taken as dilute solution:
0
0
,
log log
B B
B B


=
=
The shaded area is
log
A

at X
A
= X
A
The tail to minus infinity ( ) as X
B
0 can be
avoided.
log
B
a
Thus if the variation of ( , ) with composition is known,
the value of at the composition of X
A
can be obtained by
integration of the above equation.
B

B
log
A
log
log
log 1
log ( ) log
B A A
A A
B A
atX X
B
A X X B
atX
A
X
d
X


=
=
=
=

1.13.2 Examples
Ni
a
was experimentally measured.
Fe
a
was obtained from Gibbs-
Duhem equation (by means
of graphical integration)
Ni

Ni
X
Extrapolating
to
the value (0.66) is the Henrys
law constant for Ni in Fe.
= 0 at 0.66,
0.66
Ni
k =
Activities of Ni and Fe in the
system Fe-Ni at 1600
o
C
Ni Ni Ni
a k X =
In the composition range in which
Henrys law is obeyed,
(a) The Ni-Fe system at 1600
o
C
a
0
0.66
Ni Ni
k = =

(1) In the case of is known


To get in the Fe-Ni binary system in the case that the
variation of with composition is known:
Ni

Fe

can be obtained by means of


graphical integration,

log
log 1
log log
Ni Fe Fe
Fe Fe
Ni Fe
at X X
Ni
Fe X X Ni
at X
Fe
X
d
X


=
=
=
=

Ni
log
As
increases with increasing
X
Ni
/X
Fe,
The integrated area under the
curve between X
Ni
=X
Ni
and X
Ni
=0 is a
positive quantity. Thus, is
everywhere a negative quantity.
log
Fe

Fe

Ni

positive
log
Ni
at X
Fe
=1
log
Ni

at X
Fe
=X
Fe
Variation of
Ni
log
with X
Ni
/X
Fe
at X
Fe
=1
log
Ni

log0.66 0.18 = =
negative
positive
(b) Fe-Cu system at 1550
o
C
Cu

Cu
X
0
10.1
Cu Cu
k = =
Extrapolating
to
= 0 at 10.1
the value (10.1) is the Henrys
law constant for Cu in Fe.
10.1
Cu
K =
Cu Cu Cu
a k X =
10.1
In the composition range in
which Henrys law is obeyed,
a

decreases with increasing X
Cu
/X
Fe
, the integrated area
in is a negative quantity. is positive, .
Cu
log
log
Fe
1
Fe
>
log
log 1
log log
Cu Fe Fe
Fe Fe
Cu Fe
at X X
Cu
Fe X X Cu
at X
Fe
X
d
X


=
=
=
=

negative
negative
positive
X
Fe
=X
Fe
X
Fe
=1
1.13.3 The - Function
-function is a further aid to the integration of the Gibbs-
Duhemequation.

2
ln
(1 )
i
i
i
X

i
X
i

-function is always finite due to the fact that


1,
1.

as
For a binary A-B solution,
2
ln
B
A
A
X

=
2
ln
A
B
B
X

=
2
ln
A A B
X =
or
2
ln
B B A
X =
Differentiation
B A A A B B
d X dX X d
2
2 ln + =
ln ln
B
A B
A
X
d d
X
=
Substitute into
B A B A B B B A
A
B
A A B
A
B
A
d X X dX X d X
X
X
dX X
X
X
d = = 2 2 ln
2
( )
ln 2
A B B A B A B
d X dX X X d =
Integration



1 1
ln 2
A A B A A
A B A
X X a at X X
A B B A B A B
X a at X
X dX X X d
= =
= =
=

( ) ( )
B A B A B B B B A
X X d d X X d X X =

( ) d xy ydx xdy = +

1
ln 2
2
A A
A
A B B A B A B B B A B A B
B B A B A B B B A B A A
X X
B A B B A
X
X dX X X X dX X dX
X dX X X X dX X dX
X X dX



=
=
= + +
= +
=

1
A B
X X + =
0 = +
B A
dX dX
( , )
As is everywhere finite, thus the integration does not involve
a tail to infinity.
B B A
X X
B

at X
A
=X
A
is the value of minus the area
versus X
A
from X
A
=X
A
to X
A
=1.
ln
A

under the plot of


B

1
ln
A A
A
X X
A B A B B A
X
X X dX
=
=
=

(2) Combing-function,

=
=
=
Fe Fe
Fe
X X
X
Fe Ni Ni Ni Fe Fe
dX X X
1
ln
the variation of
Ni

with composition
As is everywhere negative, the
integrated area from X
Fe
=X
Fe
to
X
Fe
=1 is a positive quantity. But the
result of the above two terms cause
a negative value of , so .
Negative deviation from Raoults law.
Ni

ln
Fe
1
Fe
<
2 2
Fe
ln ln
(1 )
Ni Ni
Ni
Ni
X X

= =

+
+
As
positive
X
Fe
=X
Fe
X
Fe
=1
2
ln
Cu
Cu
Fe
X

=
=
=
Fe Fe
Fe
X X
X
Fe Cu Cu Cu Fe Fe
dX X X
1
ln
As is everywhere positive, the integrated area from
X
Fe
=X
Fe
to X
Fe
=1 is negative. But the sum of which is ,
is positive. Positive deviation from Raoults law.
Cu

ln
Fe

X
Fe
=X
Fe
X
Fe
=1
-
-
1.13.4 Direct calculation of the integral Gibbs free
energy of mixing
A
M
B
M
M
A
dX
G d
X G G

+ =
rearranging and dividing by
2
B
X
The integral Gibbs free energy of mixing , , can be obtained
directly from the variation of with composition.
M
G
A
a
2 2
0 0
ln A A
M
X X
M
A A
B A B A
B B
G a
G X dX RTX dX
X X

= =

2 2
M M M M
A A B B
B B B
G dX X d G G dX G
d
X X X


= =


A A
X X =
0
A
X =
integration
A
B
M
A
B
M
dX
X
G
X
G

2
Example:
Ni and Cu in Fe, respectively
( )
2
0
ln Ni
X
M
Ni
Ni Fe Fe Ni
Fe
a
G RTX dX
X

=

( )
2
0
ln Cu
X
M
Cu
Cu Fe Fe Cu
Fe
a
G RTX dX
X

=

) vs.
2
log /
Cu Fe
a X
Cu
X
curve (a) : (
) versus
2
log /
Ni Fe
a X
Ni
X
curve (c) : ( ) vs.
2
log /(1 )
i i
X X
i
X
curve (b): (
2
ln /(1 )
i i
a X
The uncertainty is:
0
i
X
as
The shaded area ( the value of the integral of
between and )
multiplied by the factor 2.3038.314418230.5
is the in the system at .
0.5
Cu
X = 0
Cu
X =
M
G
0.5
Fe
X =
2
log /
Cu Fe
a X
0 1.0
X
Ni
/ X
Cu
With respect to the Raoultian solution (line b):
[ ]
2
0
ln ln
(1 ) (1 ) ln(1 )
(1 ) 1
ln (1 )ln(1 )
i
X
M
i i i
i i i i
i i
i i i i
X X X
G RT X dX RT X X
X X
RT X X X X

= = +



= +

The uncertainty due to the infinite tail as


0 can be eliminated if the
equation is used to calculate the integral
excess Gibbs free energy.
i
X
, , E M reg M id
G G G =
2
0
ln
Cu
X
E
Cu
Cu Fe Fe Cu
Fe
G RTX dX
X

=

0
( 0 log log )
Cu Cu Cu
X = =
The integral molar Gibbs free energies of mixing in the
systems Fe-Cu at 1550 C and Fe-Ni at 1600 C
2
0
A
M
X
M
A
B A
B
Q
Q X dX
X

=

A general equation which relates
the integral and partial molar
values of any extensive
thermodynamic function.


=
A
X
A
B
M
A
B
M
dX
X
H
X H
0
2


=
A
X
A
B
M
A
B
M
dX
X
S
X S
0
2
2 2
0 0
ln A A
M
X X
M
A A
B A B A
B B
G a
G X dX RTX dX
X X

= =

1.13.5 The relationship between Henrys law and
Raoults law
For the solute B in a binary A-B solution, if B obeys Henrys law,
then
B B B
X k a = ln ln ln
B B B
a k X = +
ln ln
B B
d a d X =
Differentiation
ln ln
B
A B
A
X
d a d a
X
=
Inserting into Gibbs-
Duhemequation
A
A
A
A
B
B
B
A
B
B
A
B
A
X d
X
dX
X
dX
X
dX
X
X
X d
X
X
a d ln ln ln = = = = =
when ,
Over the composition range of an A-B binary solution in which
the solute B obeys Henrys law, the solvent A obeys Raoults law.
ln ln ln( )
A A
a X C = +
0 A A
a C X =
1 =
i
a
1 =
i
X
, hence, the integration constant ,C
0
=1.
A A
a X =
ln ln
A A
d a d X =

1.
http://www.hbcpnetbase.com/ CRC Handbook of Chemistry
and Physics ( CRC Handbook)
2. J ANAF Thermodynamic Tables (3rd edn). American
Chemical Society and American Institute of Physics for the
National Bureau of Standards, New York, 1985.
3. MSI EUREKA (
4. SGTEScientific Group Thermodate Europe
Materials Science International, MSI CEO
Gunter Effenberg APDIC

450004000.