Chapter 9

The Behavior of
Solutions
 9.1 Introduction
• Strong interactions exist between atoms,
molecules, or ions in condensed solutions,
and the nature and magnitudes of these
interactions have significant influence on
the thermodynamic behavior of the solution.
9.2 Raoult’s Law and
Henry’s Law
 9.2 Raoult’s Law and Henry’s Law
• Now imagine what happens if the liquid is in a closed container.
Common sense tells you that water in a sealed bottle doesn't seem to
evaporate - or at least, it doesn't disappear over time.
• But there is constant evaporation from the surface. Particles continue to
break away from the surface of the liquid - but this time they are
trapped in the space above the liquid.
• As the gaseous particles bounce around, some of them will hit the
surface of the liquid again, and be trapped there. There will rapidly be
an equilibrium set up in which the number of particles leaving the
surface is exactly balanced by the number rejoining it.
In this equilibrium, there will be a fixed
number of the gaseous particles in the
space above the liquid.
When these particles hit the walls of the
container, they exert a pressure. This
pressure is called the saturated vapour
pressure pAo(also known as saturation
vapour pressure) of the liquid.
 9.2 Raoult’s Law and Henry’s Law
• When dynamic equilibrium is established in which the rate of
evaporation of liquid A equals the rate of condensation of A vapor
• The rate of evaporation, re(A), is determined by the magnitude of the
energy of the bonds between the atoms of A at the surface of the liquid.
• The rate of condensation, rc(A), is proportional to the number of A atoms
in the vapor phase which strike the surface of the liquid in unit time.
• For a given temperature, this is proportional to the pressure of the vapor,
Thus rc(A)=kpAo, and at equilibrium re(A)=kpAo

For liquid B, re(B)=k’pBo

 9.2 Raoult’s Law and Henry’s Law
• Add a small amount of liquid B (solute) to liquid A (solvent) in tank
• If the composition of the surface is the same as the bulk, then the fraction
of surface sites occupied by A atoms is XA.
• The evaporation rate will decrease accordingly along with the vapor
pressure of A above the liquid (decreasing by the factor XA). Condensation
should be the same. The equilibrium vapor pressure of A exerted by the A-
B solution is decreased from pAo to pA where
re(A)XA=kpA ∵ re(A)=kpAo XA kpAo =kpA XA pAo =pA
Assumes: A, B evaporation rates
PA  X A P
0
A are independent of composition
PA  vapor pressure of the solution (A - B) A-B bond strength is the same as
X A  mole fraction of the solvent A-A and B-B or
A-B bond strength is the mean of
PA0  vapor pressure of pure solvent
A-A and B-B
• Similarly, for liquid B containing a small amount of A,
• re(B)XB=k’pB  XB pBo =pB
9.2 Raoult’s Law and Henry’s Law
 • Raoult’s law: 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
saturated vapor
pressure of pure liquid i
at the temperature of
the solution.

PA  partial pressure of A  X A PAo

PB  partial pressure of B  X B PBo
Ptotal  X A PAo  X B PBo

Figure 9.1 The vapor pressures exerted by

the components of a binary Raoultian
solution.
9.2 Raoult’s Law and Henry’s Law
• The vapor pressure of A over a dilute solution of A in B is
proportional to XA.
• If A-B bonds are stronger than A-A and B-B (or the mean A-
A/B-B strength) then every A atom on the surface will be
surrounded by B. On average, A will be more strongly bound
than B and its vapor pressure will be lower than predicted on the
basis of XA. In this case, the intrinsic rate of evaporation of A is
decreased from re(A) to r’e(A)
• r’e(A)XA =kpA ∵ rc(A)=kpAo∴ pA= (r’e(A)/ rc(A)) XApAo = kAXA
• If A-B bonds are weaker than A-A and B-B bonds, then A will
evaporate at a faster rate than it would if it were pure A.

• Henry's law :At a constant temperature, the amount of a given

gas dissolved in a given type and volume of liquid is directly
proportional to the partial pressure of that gas in equilibrium
with that liquid.
Positive deviations indicate repulsive solvent-solute interactions relative to an ideal
solution. (Vapor pressures are higher than expected because it is less favorable for the
molecules to be in the liquid phase).
Negative deviations indicate attractive solvent-solute interactions relative to an ideal
solution. (Vapor pressures are lower than expected because it is more favorable for the
molecules to be in the liquid phase).

Figure 9.2 (a) The vapor pressure of a component of a binary solution

which exhibits positive deviation from Raoultian behavior.(b) The vapor
pressure of a component of a binary solution which exhibits negative
deviation from Raoultian behavior.
9.3 The Thermodynamic activity of
a Component in Solution
9.3 The Thermodynamic activity of a Component in Solution

fi
Activity of i ai  o
fi
f i  the fugacity of the component i in the solution
f i o  the fugacity of pure i
If the vapor in equilibrium with the condensed solution is ideal, then
pi
f i  pi  ai  o
pi
If the component i exhibits Raoult' s law
ai  X i See Fig. 3
The composition range in which Henry's law is obeyed by the solute
ai  ki X i See Fig. 9.4
Figure 9.3 Activities in the binary system iron-chromium at
1600℃ .
Figure 9.4 The Activity of nickel in the system iron-nickel
at 1600℃ .
9.4 The Gibbs-Duhem
Equation
9.4 The Gibbs-Duhem Equation
Q '  Q ' (T , P, ni , n j , nk  )
 Q '   Q '   Q ' 
dQ  
'
 dni    dn j    dnki    
 
 ni T , P ,ni ,n j  n j T , P ,ni ,n j  nk T , P ,ni ,n j
 Q ' 
Q i   
 ni T , P ,ni ,n j
 dQ '  Q i dni  Q j dn j  Q k dnk    
Q '  ni Q i  n j Q j  nk Q k    
dQ '  ni d Q i  n j d Q j  nk d Q k     
Q i dni  Q j dn j  Q k dnk    
 ni d Q i  n j d Q j  nk d Q k      0

 n dQ
i
i i 0

 X dQ
i
i i 0
 9.4 The Gibbs-Duhem Equation
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:

 G / 
dG 
c
/
T ,P     dnk
k 1  nk T , P , n j k
 9.4 The Gibbs-Duhem Equation
Using G K as example:
 G / 
G k   
  n k  T , P ,n j  nk
A differential form of G/ (use definition of G k ):
 G /
  G /
 c
dG/    dT    dP  Gk dnk
 T P,nk  P T ,nk k 1

and at constant T & P:

dG 
c
/
T ,P  Gkdnk
k 1
 9.4 The Gibbs-Duhem Equation

The contributions of the components sum to the

c
whole: 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 1
k dGk  0   n dQ
i
i i 0  X dQ
i
i i 0
For a binary system:
n1
dG 2   d G1
n2
9.5 The Gibbs Free Energy of
Formation of a Solution
9.5 The Gibbs Free Energy of Formation of a Solution
For a binary A-B G '  n A G A  nB G B
solution at fixed G  X AG A  X B GB (9.22)
temperature and
dG  X A d G A  X B d G B  G A dX A  G B dX B
pressure
X Ad G A  X B d G B  0
dG  G A dX A  G B dX B
dG
 G A  GB
dX A
dG
XB  X B G A  X Bd G B (9.26)
dX A
dG
(9.22)  (9.26)  G  X B  GA(X A  X B)
dX A
dG
GA  G  XB
dX A
dG
GB  G  X A
dX B
9.5 The Gibbs Free Energy of Formation of a Solution
The Change in Gibb’s Free Energy Due to the formation of a solution
The pure component i, occurring in a condensed state at the
temperature T, exerts an equilibrium vapor pressure pio, and
when occurring in a condensed solution at the temperature T, it
exerts a lower equilibrium pressure pi. Consider the following
isothermal three-step process:

a. The evaporation of 1 mole of pure condensed i to vapor at

pressure pio. G(a)=0 ∵at equilibrium
b. A decrease in the pressure of 1 mole of vapor i from pio to pi.
pi
G( b )  RT ln 0
pi
c. The condensation of 1 mole of vapor i from the pressure pi to
the condensed solution G(c)=0 ∵at equilibrium
9.5 The Gibbs Free Energy of Formation of a Solution
The Change in Gibb’s Free Energy Due to the formation of a solution

Gi (in solution)  Gi ( pure )  G( a )  G(b )  G( c )  G(b )

pi
 G(b )  RT ln
pi0
 G(b )  Gi (in solution)  Gi ( pure )  RT ln ai
M
G i  G i  Gi0  RT ln ai
9.5 The Gibbs Free Energy of Formation of a Solution
The Change in Gibb’s Free Energy Due to the formation of a solution

If nA moles of A and nB moles of B are mixed to form a solution at

constant temperature and pressure,
the Gibbs free energy before mixing  n AG Ao  nB GBo
the Gibbs free energy after mixing  n A G A  nB G B
The change in the Gibbs free energy caused by the mixing process, G 'M

G 'M  (n A G A  nB G B )  n AG A0  nB GB0 
 n A (G A  G A0 )  nB (G B  GB0 )
M M
G 'M
 n A G  n B G
A B

G 'M  RT (n A ln a A  nB ln aB )
For 1 mole of ideal solution become
M M
G M
 X A G  X B G
A B

G M  RT ( XRT ( X A ln X A  X B ln X B )
9.5 The Gibbs Free Energy of Formation of a Solution
The Methods of Tangential Intercepts

M dG M
G A  G  X B
M

dX A
M dG M
G B  G  X A
M

dX B
G M  pq X B  rq
dG M rs

dX A rq
M rs
G A  pq  rq  pq  rs  or  rs  os
rq
 the tangential intercept at X A  1 Figure 9.5 The variation, with
M composition, of the molar Gibbs
G B  the tangential intercept at X B  1 free energy of formation of a
binary solution.
 9.6 The Properties of
Raoultian Ideal Solutions
9.6 The Properties of Raoultian Ideal Solutions
The components of a Raoultian ideal solution
obey the relation
ai  X i
For an ideal binary A - B solution,
G M ,id  RT ( X A ln X A  X B ln X B )
M ,id M ,id
G A  RT ln X A and G B  RT ln X B
For the species i occurring in a solution
G i
( )T ,comp  V i
P
and , for pure i
Gio
( )T ,comp  Vi o
P
 9.6 The Properties of Raoultian Ideal Solutions
The Change in volume accompanying the formation of an ideal solution



  G i  Gi0 

  (V i  Vi 0 )
 P  T ,comp
M
G M
)  V i
i
(
P
M ,id
In an ideal solution, G i  RT ln X i
M ,id
 X i  f ( P )  V i 0
The change in volume due to mixing, V 'M
  
V 'M  n AV A  nB V B  n AVA0  nBVB0  Figure 9.6 The variation,
with composition, of the

 n A V A  VA0  n VB B  VB0  molar volume of a binary
 n A V
M
A  nB V
M
B
Raoultian solution.
M ,id M
 V i  0  V A  0  V 'M ,id  0
V A  VA0 V B  VB0
9.6 The Properties of Raoultian Ideal Solutions
The Heat of Formation of an ideal solution

 G i /T  H i
For a component in a solution     2
 T  P , comp T
 G i0 / T H i0
For the pure component  
T T 2
  G i  G i0 
   
  T 
  
H i  H  i
0
    G iM / T


  
H i
M

 T  T2  T  P , comp T2
 
  P , comp
M , id M , id
for an ideal solution G i  RT ln X i   G i / T  R ln X i

d RlnX i 
M
H i
  ( RlnX i  f ( T ))
dT T2
M , id
H i  H i  H i
0
 0  H i  H i
0

The heat of formation of a solution

H 'M

 nA H A  nB H B  n A H 0
A  nB H 0
B 
 nA H  A  H 0
A  n H
B B  H 0
B 
M M
 nA H A  nB H B
M M
 H A  H B  0 (for ideal solution)   H ' M , id
 0
9.6 The Properties of Raoultian Ideal Solutions
The Entropy of Formation of an Ideal Solution

 G 
   S
 T T ,comp
for the formation of a solution
 G M 
    S M
 T T ,comp
ideal solution
G M ,id  RT  X A ln X A  X B ln X B 
 G M ,id 
S M ,id
  
 T  P ,comp
 -R  X A ln X A  X B ln X B 
independent of Teperature
The entropy of formation of an Ideal binary solution is
independent of temperature.
9.6 The Properties of Raoultian Ideal Solutions
For the mixing of NA particles of A with NB particles of B

SConf
'
 k ln
N A  N B !
N A! N B !
 kln  N A  N B ! ln N A! ln N B !
stirling ' s theorem
m! 2m m m e m
1
ln m! ln2m   m ln m  m
2
For large value of m, ln m! m ln m  m
( N A  N B ) ln( N A  N B )  ( N A  N B )
S '
 k 
   
Conf
 N A ln N A N A N B ln N B N B 
  NA   N B 
 k  N A ln   N B ln 
  N A  NB   N A  N B 
 9.6 The Properties of Raoultian Ideal Solutions
NA nA
  XA
N A  N B n A  nB
NB
 XB
N A  NB
NA
NA  mole of A  n A mole of A
N0
NB
NB  mole of B  n B mole of B
N0
S'Conf   kN 0 (n A ln X A  n B ln X B )
SConf   R X A ln X A  X B ln X B 
M M
S  X A  S  X B  S
M
A B

ideal solution Figure 9.7 The Variation, with

M ,id M ,id composition, of the molar entropy
S A   R ln X A S B   R ln X B of formation of a binary Raoultian
any solution solution.
G M  H M  TSM
for ideal solution H M,id  0  G M,id  TSM,id
 Ideal Solution
No heat of mixing. H k  0 H M
0
No volume change. Vk  0 V M  0
No change in internal energy.
U k  0 U M  0
Entropy increases. c
S k   R ln X k S   R  X k ln X k
M

k 1
Helmholtz free energy decreases. c
Fk  RT ln X k  F M
 RT  X k ln X k
k 1
Gibbs free energy decreases. c
Gk  RT ln X k G  RT  X k ln X k
M

k 1
 Ideal Solution

Smix
Hmix Gmix
0 0
X
T 2
X2
9.7 Nonideal Solutions
 9.7 Nonideal Solutions

• A nonideal solution is one in which the activities of

the components are not equal to their mole fraction.
• Activity coefficient
i=ai/Xi
• i=1 ideal Raoultian behavior
• i>1 positive deviation from Raoultian behavior
• i<1 negative deviation from Raoultian behavior
 9.7 Nonideal Solutions
Activity is the same as mole fraction.
Activity coefficient is one.
1

ak  Xk

 k  1 a2 a1

Slope = 1

0
0 X2 1
 i<1 negative deviation from Raoultian behavior

Henry’s law constant k

(slope) for Ni in Fe = 0.66

Figure 9.8 Activities in the system iron-nickel at 1600℃ .

 i<1 negative deviation from Raoultian behavior

Ni= 0.66

Figure 9.10 Activities coefficients in the system iron-nickel

at 1600℃ .
 i>1 positive deviation from Raoultian behavior

Henry’s law constant k

(slope) for Cu in Fe = 10.1

Figure 9.9 Activities in the system

iron-copper at 1550℃ .
 i>1 positive deviation from Raoultian behavior

Cu= 10.1

Figure 9.11 Activity coefficients in the system iron-copper at 1550℃ .

 9.7 Nonideal Solutions
If  i varies with temperature, then  H iM has a nonzero value


 G / T
M
H
 2
i  M
i

T T
M
G i  RT ln ai  RT ln  i  RT ln X i
 i 
 G / T  R ln  i 
M


H
 2
M
i

T T T
1 dT
d    2
T  T
 R ln  i  M
 H i
1
 
T 
 9.7 Nonideal Solutions
In general, increasing the temperature of a nonideal solutions
cause a decrease in the extent to which its components deviate
from ideal behavior, i.e.,
If i >1  T↑, i ↓ T↑, i 1
If i < 1  T↑, i ↑  T↑, i 1
If i >1 (positive deviations from ideality)
 T↑, i ↓ R ln  i  ln  2  ln  1  0 M
   H i  0
1 1 / T2  1 / T1 0
 
T 
This indicates that the mixing process is endothermic
If i < 1 (negative deviations from ideality)
 T↑, i ↑  R ln  i   ln  2  ln  1   0   H M  0
i
1 1 / T2  1 / T1 0
 
T 
This indicates that the mixing process is exothermic
 9.7 Nonideal Solutions

Exothermic mixing in an A-B binary system occurs when the A-B

bond energy is more negative than both the A-A and B-B bonds
energies, and this causes a tendency toward “ordering” in the
solution. Exothermic mixing thus indicates a tendency toward the
formation of a compound between the two components.

Endothermic mixing occurs when the A-B bond energy is less

negative than both the A-A and B-B bonds energies, and this
causes a tendency toward phase separation or “clustering” in the
solution.
9.8 Application of the Gibb’s-
Duhem relation to the
Determination of Activity
 9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity
Gibbs  Duhem equation  X dQ
i
i i

M M M
For A  B solution  X A dG A  X B dG B  0 G i  RT ln ai
XB
X A d ln a A  X B d ln a B  0 or d log a A   d log aB
XA
log a B , X A  X A XB
integration from X A  1 to X A  log a A    d log aB
log a B , X A 1 XA
Two points are to be noticed in Fig. 9.12
XB
(1) X B  1 a B  1 log a B  0 
XA
XB
(2) X B  0 aB  0 log aB   0
XA
The curve exihibits a tail to minus infinity as X B  0
The tail to minus infinity can be eliminated by considering Figure 9.12 A schematic
activity coefficients instead of activities in the Gibbs - Duhem equation. representation of the variation
dX A dX B
X A  X B  1  dX A  dX B  0  X A  XB 0 of log aB with XB/XA in a binary
XA XB
X A d log X A  X B d log X B  0
solution, and illustration of the
XB application of the Gibbs-
X A d log  A  X B d log  B  0 or d log  A   d log  B
XA Duhem equation to calculation
If the variation of  B with composition is known, of the activity of component A.
log  B , X A  X A XB
log  A at X A    d log  B
log  B , X A 1 XA
9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity

XB
(1) X Ni  1  Ni  1 log  Ni  0 
XA
XB
(2) X Ni  0  B  0.66 log  B  finite  
× 0
XA

Figure 9.13 A schematic representation of the variation of log γB

with XB/XA in a binary solution, and illustration of the application of
the Gibbs-Duhem equation to calculation of the activity co9efficient of
component A.
9.8 Application of the Gibb’s-Duhem relation to the
The  function
Determination of Activity
The second tail to infinity is eliminated by the introduction of the  - function, which is defined as
ln  i
i 
1  X i 2
 i  1 as X i  1  is finite
ln  A ln  B
A  and  B  or ln  A   A  X B  ln  B   B  X A 
2 2
and
X B 
2 2
X A 
XB
d ln  B  2 B X A dX A  X A2 d B (d ln  A   d ln  B )
XA
XB X
d ln  A   2 B X A dX A  B X A2 d B   X B 2 B dX A  X A X B d B
XA XA
X AX A B ,X A  X A
ln  A    2X B B dX A   X B X A d B
X A 1  B , X A 1

 d ( xy)   ydx   xdy

 X X d   d (X X  )    d ( X X )
B A B B A B B B A

ln  (at X )    2 X  dX   d ( X X  )    d ( X X
A A B B A B A B B B A )

 -  2 X  dX  X X     X dX    X d X
B B A B A B B B A B A B

 -  2 X  dX  X X     X dX    X d X
B B A B A B B B A B A A

 - X X    2 X  X  X  dX
B A B B B A B A

X AX A
 -X X   
B A  dX
B B A
X A 1
 log  Ni , X Fe  X Fe X Ni
log  Fe at X Fe    d log  Ni
log  Ni , X Fe 1 X Fe

In the graphical integration,

the integrated area under the
curve between XNi= XNi and XNi
=0 is positive quantity.

log  Ni , X Fe  X Fe

log  Ni , X Fe 1
 log  Fe at X Fe   
X Ni
d log  Ni  0
X Fe
log  Ni , X Fe  X Fe X Ni
d log  Ni  0
log  Ni , X Fe 1 X Fe
Figure 9.14 Application of the
Gibbs-Duhem equation to
determination of the activity of
iron in the system iron-nickel.
 X AX A
ln  A (at X A )  - X B X A B    Bd X A
X A 1
X Fe  X Fe
ln  Fe (at X Fe )  - X Ni X Fe Ni    Ni d X Fe
X Fe 1

Figure 9.16 The variation of

αNi with composition in the
system iron-nickel.
Figure 9.15 Application of the Gibbs-Duhem equation to
determination of the activity of iron in the system iron-copper.
Figure 9.17 The variation of αCu with composition in the
system iron-copper.
9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity
The relationship between Henry’s and Raoult’s Laws

• For A-B solution Henry ' s law

a B  kB X B
ln a B  ln k B  ln X B
d ln a B  d ln X B
Gibb' s Duhem Equation X A d ln a A  X B d ln a B  0
XB X dX B
d ln a A   d ln X B   B
XA XA XB
dX A
  d ln X A
XA
Intg .
ln a A  ln X A  ln const.
 a A  const.  X A
ai=1 Xi=1 const=1⇒ ai=Xi
 if solute B obey’s Henry’s law, the solvent A will obeys Raoult’s law
9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity
Direct calculation of the Integral Molar Gibb’s Free Energy of Mixing

• From Methods of Tangential Intercepts

M dG M
 G  G  X B
A
M

dX A
 X B2  dX A
M
G A dX A X B dG M  G M dX B  G M 
  d  
X B2 X B2  XB 
M
 G M  G A dX A
d   
 XB  X B2
Intg . X A  X A and X A  0
M
G A
XA

G  X B 
M
2
dX A
0
X B
M
 G A  RT ln a A
XA
ln a A
 G  RT  X B 0 X B2 dX A
M
9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity
Ni-Fe system

X Ni
ln a Ni
G  RT  X Fe 
M
( Ni  Fe ) 2
dX Ni
0
X Fe

Cu-Fe System

X Cu
ln aCu
G  RT  X Fe 
M
( Cu  Fe ) 2
dX Cu
0
X Fe
(a) is (lnaCu)/X2Fe vs. XCu
is (lnXi)/(1-Xi)2 vs. Xi
is (lnaNi)/X2Fe vs. XNi

Figure 9.18 Illustration of

the direct calculation of the
integral molar Gibbs free
energies of mixing in the
systems iron-copper at
1550℃ and iron-nickel at
1600℃ .
9.8 Application of the Gibb’s-Duhem relation to the
Determination of Activity
If the solution obey Raoult’s behavior
XA
lna A
ΔG M  RT  X B 
0
XB2
dX A

Xi
lnX i
ΔG  RT  (1  X i ) 
M
dX i
0
(1  X 2
i )
 X lnX i 
 RT  (1  X i )  i  ln(1  X i )
 1  Xi 
 RTX i lnX i  (1  X i )ln(1  X i )
XA M
ΔG

A
ΔG M  X B dX A
0
X 2B
also applied to other extensive thermody. function
XA M
ΔH A
ΔH M  X B 
0
2
XB
dX A

XA M
ΔSA
ΔSM  X B 
0
XB2
dX A
Figure 9.19 The integral molar Gibbs free energies of
mixing in the systems iron-copper at 1500℃ and iron-nickel
at 1600℃ .
 9.9 Regular solutions
M M M
1. ideal soln. a i  X i ,  H i  0,  V i  0 , and  S i   R ln X i
M
2. nonideal soln. a i  X i and  H i  0
1895 Margulus T  const.
A - B soln.
1 1
ln  A   1 X B   2 X 2
B   3 X B3    
2 3
1 1
ln  B   1 X A   2 X B2   3 X B3    
2 3
 Gibb' s Duhem Eq.
X A d ln  A   X B d ln  B   1   1  0   2   2
1929 Hildebrand A - B solution
RTln  B   ' X 2
A and RTln  A   ' X 2
B   ( 9 . 68 )
Hildebrand assigned the term " Regular Solution" to obeying Eg. (9.68)
 9.9 Regular solutions
X AX A

ln  A   X B X A B  
X A 1
B dX A  If  B  f (component )

ln  A   X B X A B   B  X A  1   X B X A B   B X B   B X B 1  X A 
  B X B2
but ln  A   A X B2
  A  B  
RT ln  B   ' X A2 , RT ln  A   ' X B2
'
 
RT
Hildebrand defined a regular solution as one in which
M M M ,id
H  0
i S  S
i i   R ln X i
 9.9 Regular solutions
The properties of a G M  G M ,id  G xs
regular solution are G M  H M  TS M
best examined by
means of the concept G M ,id  TS M ,id
of excess function 
 G xs  G M  G M ,id  H M  T S M  S M ,id 
G=Gid + Gxs
regular soln.
G=the molar Gibbs
free energy of the S M  S M ,id  G xs  H M
solution G M  RT ( X A ln a A  X B ln aB )
Gid=the molar
G M ,id  RT ( X A ln X A  X B ln X B )
Gibbs free energy
G xs  RT ( X A ln a A  X B ln aB )
of the ideal
solution  RT ( X A ln X A  X B ln X B )
Gxs=the excess G xs  RT  X A ln  A  X B ln  B 
molar Gibbs free xs
 X AG  X B G
A
XS
B
energy of the
ln  A  X B2 ln  B   X A2
solution
 9.9 Regular solutions
For regular soln.
G xs  RT  X A ln  A  X B ln  B   X A G A  X B G B
xs XS

ln  A  X B2 ln  B   X A2
 
G xs  RT X AX B2  X B X A2  RTX A X B  X A  X B 
'
  G xs   ' X A X B independent of Temp.
RT
 G xs 
    S xs
 T  P ,comp
 regular soln. S xs  0  G xs and H M independent of Temp.
xs
G  RT1 ln  A(T1 )  RT2 ln  A(T2 )   ' X B2
A

regular soln.
ln A(T2 ) T1

ln  A(T1 ) T2
Figure 9.20 Activities in the system thallium-tin.
Figure 9.21 Activities coefficients in the system thallium-tin.
Figure 9.22 Log γT1 vs. X2Sn in the system thallium-tin.
Figure 9.23 The variation of the product αT with T in the
system T1-Sn.
Figure 9.24 The molar enthalpy, entropy, and Gibbs free
energy of mixing of thallium and tin at 414℃ .
 9.9 Regular solutions
A parabolic form for ∆HM, or Gxs should not be taken as being a
demonstration that solution is regular, as it is frequently found that ∆HM
or Gxs can be adequately expressed by means of the relations

H M  bX A X B or G XS  b ' X A X B
b  b'  H M  G XS  G XS  H M  T (S M  S M ,id )  S M  S M ,id
For Au  Cu system
15500 K G XS  24060 X Cu X Au joule, H M  asymmetric, S xs  0
For Au  Ag system
13500 K H M  20590 X Ag X Au joule, G xs  asymmetric, S xs  0
ln  A
XA

G XS  RTX B 
0
XB 2
dX A (Eq. 9.63)

Raoult ' s soln.  A  1  G XS  0

A
regular soln.   G XS  RTX A X B
X B2
9.10 A statistical model of
solutions
 9.10 A statistical model of solutions
If 1 mole of mixed crystal containing NA atom A and NB atom B
NA N NB N
XA   A XB   B
N A  N B N0 N A  N B N0
N0=Avogadro’ Number
The mixed crystal contains three types of atomic bond:
EA-A=A-A bonds energy
EB-B=B-B bonds energy
EA-B=A-B bonds energy
Z=coordination number of atom A in crystal
In soln. there are PA-A A-A bonds PB-B B-B bonds
PA-B A-B bonds

The energy of the solution, E, is

E  PA A E A A  PB  B EB  B  PA B E A B
And the problem of calculating E becomes one of calculating the
values of PAA, PBB, and PAB.
 9.10 A statistical model of solutions
The number of A atoms x the number of bonds per atom = the
number of A-B bonds + 2 x the number of A-A bonds.
N A z PA B
N A z  PA B  2 PA A or PA A  
2 2
N z P
N B z  PA B  2 PB  B or PB  B  B  A B
2 2
N z P  N z P 
E   A  A B  E A A   B  A B  E B  B  PA B E A B
 2 2   2 2 
1 1  1 
 zN A E A A  zN B EB  B  PA B  E A B  E A A  E B  B 
2 2  2 
Energy of the components before mixing
1 1
Eunmix  PA A E A A  PB  B EB  B  zN A E A A  zN B EB  B
2 2
1 1
PA A  zN A PB  B  zN B
2 2
1 1
E M  zN A E A A  zN B EB  B 
2 2
1 1  1 
{ zN A E A A  zN B EB  B  PA B  E A B  E A A  EB  B }
2 2  2 
 9.10 A statistical model of solutions
1 1  1  1 1
 E M  zN A E A A  zN B E B  B  PA B  E A B  E A A  E B  B   zN A E A A  zN B EB  B
2 2  2  2 2
 1 
 PA B  E A B  E A A  E B  B 
 2 
 H  E  PV
H M  E M  PV M
V M  0
 1 
H M  E M  PA B  E A B  E A A  E B  B 
 2 
1
ideal soln. H M  0  E A B  E A A  E B  B 
2
1
E A B  E A A  E B  B  H M  0
2
negative deviation from Raoult' s solution
1
E A B  E A A  EB  B  H M  0
2
positive deviation from Raoult' s solution
 9.10 A statistical model of solutions
If H M  0 and A and B is random mixing
SM  SM,id   R X A ln X A  X B ln X B 
In solutions which exhibit relatively small deviations from ideal behavior, H M  RT ,
it can be assumed that the mixing of the atoms is also approximately random, in which case
PAB can be calculated as follows.
Consider site 1 and 2 in crystal
The probability that site 1 is occupied by an A atom is
the number of A atoms in the crystal N
 A  XA
the number of lattice site in the crystal N o
The probability that site 1 is occupied by an A atom and
site 2 is simultaneously occupied by a B atom is thus
P(1(A),2(B))  X A X B , P(2(A),1(B))  X A X B , P( A  A)  X A2 , P ( B  B )  X B2
The probability that the neighboring sites contain an A - B pair or an A - A pair or a B - B pair is
P (( A  B), ( A  A), ( B  B))  X A2  2X A X B  X B2  X A  X B   1
2

1 mole crystal contain 1/2zN 0 pair lattice sites,  the number of A - B pairs
 the number of pairs of sites x the probability of an A - B pair
1 1 1
PAB  zN 0 2X A X B  zN 0 X A X B , PAA  zN 0 X A2 , PBB  zN 0 X B2
2 2 2
 1   1 
H M  E M  PAB  E AB  E AA  E BB   zN 0 X A X B  E AB  E AA  EBB 
 2   2 
 9.10 A statistical model of solutions
 1 
H M  zN 0 X A X B  E AB  E AA  E BB 
 2 
 1 
  zN 0  E AB  E AA  E BB 
 2 
H M  X A X B
H M  G xs  X A X B  RTX A X B


RT
M H M
H A  H M
 XB
X A
H M  (X A X B ) X B
  X B  X A  X B  X A   X B  X A 
X A X A X A
 X A X B  X B  X B  X A   X B2
M
H A
M
H B  X A2
 9.10 A statistical model of solutions
As the mixing is random, then
M M
S A   R ln X A S B   R ln X B
M M M
G A  H A  T S A

RTlna A  X B2  RT ln X A
RTln A  RT ln X A  X B2  RT ln X A
 RTln A  X B2
 2
ln A  X B  X B2
RT
The value of  thus depends on the value of , which is determined by
the value of the bond energies EAA, EBB, and EAB. If  is negative, then
A < 1, and if  is positive, then A >1. XB1⇒ln A ln Ao=/RT
 9.10 A statistical model of solutions
The applicability of the statistical model to real solutions decreases as the
magnitude of  increases, i.e., if the magnitude of EAB is significantly
greater or less than the average of EAA and EBB then random mixing of A
and B atoms cannot be assumed.
 1   1 
HM  PAB EAB  EAA  EBB   zNo XA XB EAB  EAA  EBB   XA XB
 2   2 
1 1
EAB  EAA  EBB  H  0; EAB  EAA  EBB  HM  0
M

2 2
G  H TS G  0, H  andS  random mixing ↑ as T↑
1
For EAB  EAA  EBB  HM  0 and 0 H PAB  (Complete ordering of the solution)
2
The tendency toward which increases with increasingly negative values of 
1
For EAB  EAA  EBB  HM  0 and 0 H PAB  (Complete clustering of the solution)
2
The tendency toward which increases with increasingly positive values of 
 9.10 A statistical model of solutions

In order for the statistical model to be applicable, the

equilibrium solution configuration be not to distant from
random mixing. As the entropy contribution to the Gibbs
free energy is dependent on temperature, then
1. For any value of , more nearly random mixing occurs as
the temperature is increased.
2. For any given temperature, more nearly random mixing
occurs with smaller values of .
Figure 9.25 Illustration of the origins of deviation from
regular solution behavior.
Clustered Clustered Clustered
Random Random (A and B Random
(A and B (A and B
immiscible) Mixing Ordered immiscible) Mixing Ordered immiscible) Mixing Ordered

SM SM SM

HM HM
HM
GM GM GM

0 0.5 1 0 0.5 1 0 0.5 1

Probability of an A-B pair Probability of an A-B pair Probability of an A-B pair

T= constant, HM=XAXB⇒ ￜￜ ↑, ￜHMￜ ↑

 Clustered
(A and B Random
immiscible) Mixing Ordered

SM
T3 > T2 > T1

GM (T1)
GM (T2) HM

GM (T3)
GM

0 0.5 1
Probability of an A-B pair

 = Constant, T↑, ￜTSMￜ ↑

 9.11 Subregular solutions
regular soln.   const. if more general
  a  bX B  cX B2  dX B3    
subregular soln.
G xs  a  bX B X A X B

 G A  aX B2  bX B2  X B  X A 
dG xs
GA  G  X B
dX B
xs
G  aX A2  2bX A2 X B
B

dG xs
The Max. and Min. in the curves occur at 0
dX B
G xs  aX B  2b  a X B2  bX B3
dG xs
 a  2b  a X B  3bX B2  0
dX B
2b  a   2 b 2  ab  a 2
XB 
6b
In Fig. 9.26b
a =4000 J, b=-10000 J
Max. at XB = 0.17,
Min. XB = 0.76

Figure 9.26 Excess molar

Gibbs free energy curves
generated by the subregular
solution model.
 a=-13465, b=5412.8

Figure 9.27 The Variation, with composition, of Ω,

calculated from experimental measurements of Δ GM in the
system Ag-Au at 1350 K.
Figure 9.28 The subregular solution model fitted to
experimental measurements of ΔGM in the system Ag-Au at
1350 K as Δ GM = RT (XAg In XAg + XAu In XAu ) + 5,412.8
XAu – 13,465) XAuXAg.
 9.11 Subregular solutions
The influence of temperature on the behavior of subregular
solutions is accommodated by introducing a third constant .

G  a  b X B X A X B 1  
xs  T
 
 G xs
( a  b) X A X B
S 
xs

T 
H xs  G xs  TS xs

 a  b X B X A X B  2  
 T
 
9.13 Numerical Examples
Example 1

Copper and gold form complete ranges of solid solution at temperatures

between 410 ℃ and 889 ℃, and , at 600 ℃, the excess molar Gibbs
free energy of formation of the solid solution is given by
Gxs = -28280XAuXCu J
Calculate the partial pressures of Au and Cu exerted by the solid
solution of XCu = 0.6 at 600 ℃.
The saturated vapor pressure of solid copper is given by
40920
ln pCu
o
(atm)    0.86 ln T  21.67
T
The saturated vapor pressure of solid gold is given by
45650
ln p Au
o
(atm)    0.306 ln T  10.81
T

T = 600 ℃, Gxs = -28280XAuXCu J, XCu = 0.6

PAu =?, PCu = ?
Solution: Example 1
For the regular solution Gxs = XAuXCu, we know Gxs = -28280XAuXCu J
⇒  = -28280 J  2  2  28280
ln A  X B  X B  ln Cu 
2
X Au 
2
0.4  0.624
RT RT 8.3144x873
  Cu  0.536 and aCu   Cu X Cu  0.536 x0.6  0.322
Similarly
 2  28280
ln Au  X Cu  0.6 2  1.403
RT 8.3144x873
  Au  0.246 and aAu   Au X Au  0.246 x0.4  0.098
The saturated vapor pressure of solid copper is given by
40920
ln pCu
o
(atm)    0.86 ln T  21.67
T
The saturated vapor pressure of solid gold is given by
45650
ln p Au
o
(atm)    0.306 ln T  10.81
T
at T  873K
40920
ln pCu
o
(atm)    0.86 ln 873  21.67  pCu o
 3.35 x10 14 atm
873
45650
ln p Au
o
(atm)    0.306 ln 873  10.81  p oAu  1.52 x10 16 atm
873
pi  ai pio  pCu  0.322 x3.35 x10 14  1.08 x10 14 atm
p Au  0.098 x1.52 x10 16  1.50 x10 16 atm
Example 2
At 700 K, the activity of Ga in a liquid Ga-Cd solution of
composition XGa = 0.5 has value 0.79. On the assumption that
liquid solutions of Ga and Cd exhibit regular solution behavior,
estimate the energy of the Ga-Cd bond in the solution. The molar
enthalpies of evaporation of liquid Ga and liquid Cd at their
melting temperatures are, respectively, 270,000 and 100,000 J.
The coordination numbers of liquid Cd and liquid Ga are,
respectively, 8 and 11.
Solution: Example 2
T=700 K, XGa = 0.5, aGa= 0.79. HGa= 270,000, HCd= 100,000 J.
aGa   Ga X Ga  0.79   Ga x0.5   Ga  1.59

ln1.59  0.52    10,795 J
8.3144x700
2 evap ,Ga Ga
 evap ,Ga Ga   zN o EGa Ga / 2  EGa Ga  
zN o
2 x 270,000  20
EGa Ga   23
 8 . 15 x10 J
11x6.023 x10
2 x100,000  20
ECd Cd   23
 4 . 15 x 10 J
8 x6.023 x10
The bond energy, E Cd -Ga , is obtained from
1
  zN o [ ECd Ga  ( EGa Ga  ECd Cd )]
2
8  11 1
 10795  ( ) x6.023 x10 23 [ ECd Ga  (8.15 x10  20  4.15 x10  20 )]
2 2
 ECd Ga  5.96 x10  20 J