CH24 (SOLUTIONS I: LIQUID-LIQUID)

I. Partial Molar Quantities of Multi-Component Systems

Gibbs Energy of a Solution of n1 and n2 # of moles:

dG=

( TG )

dT +

P , n1 ,n2

( G
P)

( nG )

d P+

T , n1 , n2

d n1+

1 P ,T ,n2

( Gn )

d n2

2 P ,T ,n1

If composition is constant with dn1 = dn2 = 0:

( G
T )
( G
P)

P , n1 ,n2

T , n1 , n 2

=S ( P ,T , n1 , n2 )
=V ( P ,T , n1 , n2 )

Chemical potential (partial molar Gibbs Energy) is equal to the partial derivative of
G with respect to mole #:

( Gn )

j = j ( T , P , n1 ,n 2) =

d G=SdT +VdP+ 1 d n1 + 2 d n2

=G j

j P ,T ,ni j

At constant T & P:

d G=1 d n 1+ 2 d n2

Other EXTENSIVE Thermodynamic Variables (S, V, Y) have associated partial molar

values:

partial molar Entropy

Sj

partial molar Volume

Vj

partial molar quantity/generic

Yj

Partial molar quantities are INTENSIVE Thermodynamic Quantities

Binary Solution = 2 components
Can increase the size of a system with a Scaling Factor () such that:

d n1=n1 d

as 0 to 1, n1 0 to n1

CH24 (SOLUTIONS I: LIQUID-LIQUID)

d n2=n 2 d

dG=Gd

as 0 to 1, n2 0 to n2
1

n1 1 d+ n2 2 d
0

G d=
0

G(T , P , n1 , n 2)=1 n1 + 2 n2

V (T , P , n1 ,n 2)=V 1 n1 +V 2 n2

II. Gibbs-Dunhem Equation Relates Change in Chemical Potential of

One Component of a Solution to the Change in Chemical Potential
of the Other Component

G=H TS

j =G j=H jT S j

d j=S j dT +V j dP

d G=1 d n 1+ 2 d n2 +n1 d 1 +n 2 d 2

Gibbs-Dunhem Equations (Two Versions) Can also be in terms of V or S instead of

n1 d 1 +n 2 d 2=0

(Constant T & P)

x 1 d 1+ x2 d 2=0

(Constant T & P)

For Example, we know:

state)

(* = property of PURE substance,

= standard

2=2 + RTln x 2 0 x2 1
o

Gives:

d 2
RT
=RT dln x 2=
d x2
d x2
x2

CH24 (SOLUTIONS I: LIQUID-LIQUID)

x 1 d 1+ x2 d 2=0
o

Plug

x 2

Gives: d 1= x d 2
1

d 2 into

d 1=

x 2
d 2
x1

x 2
x2
x2 d x2
d

=
RTdln
x
=RT
dln
x
=RT
(
)
1
2
2
o Gives:
x1
x1
x1 x2

( )

d 1=RT
o

dx 2
x1
d x 1=d x 2

Since

d 1=RT

(Because x1 + x2 = 1)

dx1
0 x1 1
x1

x1

x1

d 1= RT

( )

dx 1
x1

1=1 + RTln x1 0 x 1 1

III.At Equilibrium,

j = j

At Equilibrium G = 0
Spontaneous dG < 0

If pressure of the Vapor Phase is low enough, can be considered Ideal

Lj =Vj =j ( T )+ RT ln P j

CH24 (SOLUTIONS I: LIQUID-LIQUID)

IV. Components of an Ideal Solution Obey Raoults Law for ALL

Concentrations

Raoults Law

P j =x j P vap
j

Ideal Solution

Obeys Raouls Law at all compositions

Expected for similar components
Toluene & Benzene

Chemical potential of Ideal Solution

4

CH24 (SOLUTIONS I: LIQUID-LIQUID)

j = j ( l ) + RT ln x j

Total Vapor Pressure over an Ideal Solution

Ptotal=x 1 P1 + x 2 P2

y 1=

P
x P
y 2= 2 = 2 2
Ptotal Ptotal

P1
x P
= 1 1
P total Ptotal

Pvap vs x Graph will be a straight line for each component when Ideal

Lever Rule

L
y x
n
= 2 a
V
x ax 2
n

Gibbs Energy of Mixing

mix G=G solution ( T , P , n1 , n2 ) G 1 ( T , P , n1 ) G2 ( T , P , n2 )

mix Gideal =n 1 1solution+ n2 2solutionn1 1n 2 2

mix G

Ideal

I.

V.

ideal

=RT ( n 1 ln x 1+ n2 ln x2 ) =RT ( x1 ln x 1+ x 2 ln x 2)

mix S ideal=R ( n1 ln x 1+ n2 ln x 2 )=R ( x 1 ln x 1 + x 2 ln x 2 )

ideal

II.

mix V

III.

mix H ideal =mix Gideal +T mix Sideal =0

=0

Most Solutions are NOT Ideal

CH24 (SOLUTIONS I: LIQUID-LIQUID)

Positive deviations from Raoults Law:

occur because partial vapor pressures of

components are greater than the prediction from
Raoults Law
physically the mixture interactions are more
repulsive than either components interaction
with itself
This deviation increases with increasing size of
the hydrocarbon part of the alcohol
Also often increases as Temperature is reduced

Negative deviations from Raoults Law :

occur because partial vapor pressures of

components are less than the prediction from
Raoults Law
physically the mixture interactions are more
attractive
than
either
components
interaction with itself

Henrys Law & constant of Component

k H ,1=P1

Ideal solution Case

Ordinarily

As x1 0, the component-1 molecules are completely surrounded by

component-2 molecules
Value of kH,1 reflects the intermolecular interactions between the two
components
As x1 1, the component-2 molecules are completely surrounded by
component-1 molecules
Value of kH,1 reflects the intermolecular interactions between the two
components
As x j 1 P j x j P j ( Approaches Raoul s Law)

k H ,1 P1

As x j 0 P j x j k H , j (Approaches Henry ' s Law)

CH24 (SOLUTIONS I: LIQUID-LIQUID)

VI.

Gibbs-Dunhem Equations Relates the Vapor Pressures of the Two

Components of a Volatile Binary Solution

Vapor Pressure of component 1 in a Non-Ideal Binary Solution

2

x2 +x 2

x1 +x 1

P1=x 1 P1 e

P2=x 2 P2 e

0 x1 1
0 x 2 1

are parameters used to fit the data

They reflect the extent of the non-ideality of the solution

When

= +

==0 P1P2 reduce theideal solution expressions

3
2