G M Madhu

Department of Chemical Engineering

R V College of Engineering, Bangalore

Session-15
 Properties of solutions
The relationships for pure component are not
applicable to solutions.
Which needs modification because of the change
in thermodynamic properties of solution. The
pressure temperature and amount of various
constituents determines an extensive state. The
pressure, temperature and composition determine
intensive state of a system.
 Partial Molar properties:
The properties of a solution are not additive
properties, it means volume of solution is not
the sum of pure components volume.

When a substance becomes a part of a solution it

looses its identity but it still contributes to the
property of the solution.
The term partial molar property is used to designate
the component property when it is admixture with one
or more component solution.
A mole of component “i” is a particular solution at specified
temperature and pressure has got a set of properties associated
with it like.
VP , Si etc

These properties are partially responsible for the

properties of solution and it is known as partial
molar property
 It is defined as
 ∂( nM ) 
Mi =   j ≠i
 ∂ni T ,P ,n j

Mi = Partial molar property of component i.

M = Any thermodynamic property of the solution
n = Total number moles in a solution
ni=Number of moles of component i in the
solution
The above expression is applicable only for an extensive property

We can write nM = ∑ ni M i ni
= xi
n
M = ∑ xi M i
xi =Mole fraction of component i in the solution.
Physical Significance of Partial Molar
Properties
To understand the meaning of physical molar
properties consider a open beaker containing huge
volume of water, if one mole of water is added to it, the
volume increase is 18x 10-6 m3 If the same amount of
water is added to pure ethanol the volume increased is
approximately 14 x 10-6 m3 this is the partial molar
volume of H2O in pure ethanol.
• Therefore Partial molar property change with composition. The
intermolecular forces also changes with change in thermodynamic
property.

Vw = Partial molar volume of the water in

ethanol water solution
Vw= Molar volume of pure water at same
temperature and pressure
V =Total volume of solution when water added to
t

ethanol water mixture and allowed for sufficient

time so that the temperature remains constant
∆ V = ∆ n w Vw
t ∆V t
Vw =
∆ nw
Vw = property of solution for all infinitely small
amount of water.

∆V  ∂V 
t t
Vw = lim = 
v → 0 ∆n
w  ∂nw 
Temperature, pressure an number of moles of ethanol
remains constant during addition of water.

nE- no of moles of ethanol

 ∂V t 
Vw =  
 ∂nw  T ,P ,nE
The partial molar volume of component i
 ∂V t 
Vi =  
 ∂ni T ,P ,n j ≠i
Partial molar properties and properties of the solution
Let total property of the solution M = nM
t

n = n1 + n2 + n3 + − − − − − −

1,2,3 represents number of constituents

(
Thermodynamic property is a f T , P , n1 , n2 , n3 − − − − − n j )
For small change in the pressure and temperature and
amount of various constituents can be written as

 ∂M t
  ∂M t
  ∂M t

dM = 
t
 dP +   dT +   dn1
 ∂P T ,n  ∂T  p ,n  ∂n1 T , p ,n2 ,n3 − − −
 ∂M t 
+−−−−  dni + − −
 ∂ni  P ,T ,n j ≠ i
At constant temperature and pressure dP and
dT are equal to zero.
The above equation reduces to
 ∂M 
i =n t
dM = ∑
t
 dni
i =1  ∂ni  P .T ,n
j ≠i

dMt in terms of partial molar property

n
dM = ∑M i dn i
t

i =1
Mi is an extensive property depends on
composition and relative amount of constituents.
All constituent properties at constant temperature
and pressure are added to give the property of
the solution
dM = M 1dn1 + M 2 dn2 + M 3 dn3 + − − − − −
t

( )
dM = M 1 x1 + M 2 x 2 + M 3 x 3 + − − − − − dn
t
 ( )
M = M 1 x1 + M 2 x 2 + M 3 x 3 + − − − − − n
t

= M 1 n1 + M 2 n 2 + M 3 n 3

M = ∑ ni M i
t
• Problem
• A 30% mole by methanol –water solution
is to be prepared. How many m3 of pure
methanol (molar volume =40.7x10-3m3/mol)
and pure water (molar volume =
18.068x10-6m3/mol) are to be mixed to
prepare 2m3 of desired solution. The
partial molar volume of methanol and
water in 30% solution are 38.36x10-6
m3/mol and 17.765x10-6 m3/mol
respectively.
 Methanol =0.3 mole fraction
Water=0.7 mole fraction

Vt=0.3 x38.36x10-6 +0.7x17.765x10-6

=24.025x10-6 m3/mol

For 2 m3 solution
2
= −6
= 83.246 × 10 mol
3

24.025 × 10
 Number of moles of methanol in 2m3solution
•
=83.246x103x0.3= 24.97x103mol
•

Number of moles of water in 2m3solution

=83.246x103x07= 58.272x103mol
Volume of pure methanol to be taken
= 24.97x103 x 40.7x10-3 =1.0717 m3

Volume of pure water to be taken

= 58.272x103 x 18.068x10-6 =1.0529 m3
Estimation of Partial molar
properties for a binary
mixture
Two methods for estimation
Analytical Method and
Graphical Method(Tangent Intercept method)
 Analytical Method
The general relation between partial molar property
and molar property of the solution is given by

 ∂M 
M i = M − ∑ x k   k≠i
 ∂x K T ,P ,nk
For binary mixture i = 1, k = 2
  ∂M 
M 1 = M − x 2  
 ∂x 2  T , P
x 2 + x1 = 1 x 2 = 1 − x1 ∂x 2 = −∂ x1
,,
At constant Temperature and pressure
 dM 
M1 = M + ( 1 − x1 )  --(a)
 d x1 
 d M
M2 = M − x  
1  d x1  ---(b)
Tangent -Intercept method
If the partial molar property (M) is plotted
against the composition we get the curve
as shown in the figure.
 The intercept of the tangent with two axis x1=1 and
x1=0 are I1 and I2.
dM M − I 2
Slope of the tangent =
dx1 x1
dM dM
M − I 2 = x1 I 2 = M − x1
dx1 dx 1

Comparing I2 with equation (b) I2 = M2

 dM I 1 − M
=
dx1 1 − x1
dM
dM I 1 − M = 1 − x1
I 1 = M + 1 − x1 dx1
dx1
Comparing with equation(a) I1 = M 1

The intercept of the tangent gives the partial molar

properties
Limiting cases: For infinite dilution of component
when a tangent is drawn at x1=0, will give the ∞
partial molar property of component 1 at infinite ( M 1 )
dilution
Tangent is drawn at x2=0 or x1=1 will give infinite
∞
dilution the partial molar property of component 2 ( M 2 )
Problem:
Find weather the equation given below is thermodynamically
consistent
G = 100 x1 + 150 x 2 + x1 x 2 ( 10 x1 + x 2 )
∂G
G1 = G + ( 1 − x 1 ) 3 2
∂x 1 G1 = 18 x1 + 35 x1 + 16 x1 + 101
∂G
G2 = G − x1 3 2
∂x 1 G2 = 18 x1 − 8 x1 + 150
 d G1 2
= 54 x1 − 70 x1 + 16
dx1
d G2 2
= 54 x1 − 16 x1
dx1
G D equation
d M1 d M2
x1 + ( 1 − x1 ) =0
dx1 dx1
2 2
x1 ( 54 x1 − 70 x1 + 16 ) + ( 1 − x1 )( 54 x1 − 16 x1 ) = 0
It satisfies the GD equation, the above equation is consistent.