CHE154 (B.

Tech Biotech)

CHE154: Physical Chemistry for Honors

B. Sc. Biotech. Chemistry Course, Term: II, Session: February 2009 – May 2009

Dr. Shikha Baskar

Sr. Lecturer
Department of Chemistry
Lovely Professional University, Phagwara, Punjab, India

Solutions

Venue: 5-308, LPU

SS Lecture - 7 1
 DALTON’S LAW

Dalton (1811) discovered that, at low total pressures, a mixture of

gases exerts a pressure equal to the sum of the pressures that
each constituent gas would exert if each alone occupied the same
volume.
Strictly true only for ideal gases, but is approximately true at low total
pressure where real gases approach ideality. For each gas we
have:
P1V = n1RT
P2V = n2RT
etc.
For the gas mixture we have:

PtotalV   ni RT
i

SS Lecture - 7 2
If we divide the expression for each constituent by the
expression for the mixture we obtain:
P1 n1 P2 n2
  X1   X2
P  ni P  ni etc.
i i

or
P1 = X1·Ptotal
P2 = X2·Ptotal
etc.
Ptotal = P1 + P2 + P3 + …
P1, P2, etc. are called the partial pressures.
SS Lecture - 7 3
 RAOULT’S LAW

Raoult (1887) studied vapor-liquid systems in

which two or more liquid components were
mixed in known proportions and the liquid
was equilibrated with its own vapor. The
composition of the vapor was then
determined. The total vapor pressure of the
system was low, so the vapor behaved ideally
and conformed to Dalton’s law. In such
systems, the partial pressures of the gaseous
components were found to be a linear
function of the their mole fraction in the liquid.
SS Lecture - 7 4
Thus, for a binary system A-B, he obtained:
PA = XA·PAº and PB = XB·PBº
where PAº and PBº are the vapor pressures of pure components A
and B, respectively.
o
PA 10

8 Pt
otal

6
P PB
o

0
0.0 0.2 0.4 0.6 0.8 1.0
A XB B

SS Lecture - 7 5
The only way that such a simple relationship as Raoult’s
law can hold is if the intermolecular forces between
A-A, B-B, and A-B are identical. Solutions in which
this is the case are called ideal solutions.
The most general way of expressing Raoult’s Law is:
Pi = Xi·Piº

Very few systems follow Raoult’s Law over the entire

range of composition from Xi = 0 to Xi = 1. However,
Raoult’s Law often applies to the solvent in dilute
solutions, whereas the solute in dilute solutions
follows Henry’s Law.
SS Lecture - 7 6
 Non Ideal- Negative deviation

Partial pressure in the

mixture acetone-
chloroform at 35.2°C.
This mixture exhibits
negative deviations
from Raoult’s Law

SS Lecture - 7 7
 Non Ideal – Positive deviation

Partial pressure in the

mixture carbon
disulfide-acetone at
35.2°C. This mixture
exhibits positive
deviations from Raoult’s
Law

SS Lecture - 7 8
PARTIAL AND APPARENT
MOLAR PROPERTIES

SS Lecture - 7 9
 MOLAR VS. PARTIAL MOLAR QUANTITIES

Molar values of state functions are defined as

follows:
U U /n S  S /n V V /n
etc. These are useful only in the case of single-
component systems and dependent only on
pressure and temperature, not composition.
Partial molar quantities are defined according to:
 U   S   V 
U i    Si    Vi   
 ni T ,P ,n j  ni T ,P ,n j  ni T ,P ,n j

These are dependent on T, P, and composition.

SS Lecture - 7 10
PHYSICAL INTERPRETATION OF PARTIAL MOLAR VOLUMES

The partial molar volume of component i in a system is equal to the

infinitesimal increase or decrease in the volume, divided by the
infinitesimal number of moles of the substance which is added,
while maintaining T, P and quantities of all other components
constant.

Another way to visualize this is to think of the change in volume on

adding a small amount of component i to an infinite total volume of
the system.

Note: partial molar quantities can be positive or negative!

SS Lecture - 7 11
 SUMMING PARTIAL MOLAR QUANTITIES

The total value for a state function of a system is obtained

by summing the partial molar volumes of its components
according to:
n
U  n1U1  n2U 2  n3U 3  n4U 4    nnU n   niU i
i 1
n n
H   ni H i V   niVi
i 1 i 1
We can manipulate partial molar quantities in a manner
identical to the way we manipulate total quantities.
As with total state functions, we cannot know absolute
values, only differences (except for V and S)!
SS Lecture - 7 12
We can also express the summations in terms of molar state
functions and mole fractions:
n
V   X iVi
n n
U   X iU i H   X i Hi
i 1 i 1 i 1

ni
Xi  n

n
i 1
i

SS Lecture - 7 13
 CHE154: Physical Chemistry for Honors
B. Sc. Biotech. Chemistry Course, Term: II, Session: February 2009 – May 2009

Dr. Shikha Baskar

Lecture 8
Sr. Lecturer
Department of Chemistry
Lovely Professional University, Phagwara, Punjab, India
Solution

Solutions

SS Lecture - 8 14
In the case of the volume of a two-component system, e.g., NaCl-H2O, we
can write:

Schematic plot of the molar volume of aqueous NaCl solutions as a function

of mole fraction of NaCl.

V  X NaClVNaCl  X H2OVH2O

y
V
A
Vsolution
XH O
2
B
x
XNaCl

0.0 0.2 0.4 0.6 0.8 1.0

XNaCl
SS Lecture - 7 15
 HOW TO DETERMINE
PARTIAL MOLAR VOLUME

Refer to the previous diagram. Triangles A and B are

similar, so it is true that:
X NaCl /(Vsolution  x)  X H2O /( y Vsolution )
X NaCl y  X NaClVsolution  X H2OVsolution  X H2O x
X H2O  X NaCl Vsolution  X NaCl y  X H2O x
but X NaCl  X H 2O  1 so Vsolution  X NaCl y  X H2O x
comparison with V  X NaClVNaCl  X H2OVH2O
shows that VNaCl  y VH2O  x
So the partial molar volumes can be determined from the intercepts of a line
tangent to the plot of volume vs. mole fraction.
SS Lecture - 7 16
 THERMODYNAMICS OF IDEAL SOLUTIONS

An ideal solution is one that satisfies the following equation:

i - i° = RT ln Xi
where i is the chemical potential of some component i in a solution
and i° is the chemical potential of that component in the pure
form.
Partial Molar free energy

G   X i i
i
substituting we get

Gideal sol 'n   X i ( io  RT ln X i )

i
SS Lecture - 7 17
 Gideal sol 'n   X i io  RT  X i ln X i
i i
GPure com ponent   X i io
i

Gideal sol 'n  GPure component  RT  X i ln X i

Gideal mix  Gideal sol 'n  GPure com ponent  RT  X i ln X i
i

i
These equations tell us that the free energy of an ideal
solution is the sum of two terms: the free energy of a
pure component, and a free energy of ideal mixing.

SS Lecture - 7 18
 ENTHALPY AND VOLUME
OF AN IDEAL SOLUTION

H ideal sol 'n  H mech mix   X i H   X i H

i
o o
i
If i is a pure
substance.
i i

Videal sol 'n  Vmech mix   X iVi o   X iVi o

i i

There is no volume or enthalpy change upon

ideal mixing. In other words:
Videal mix  H ideal mix  0
However, there is a change in entropy upon
ideal mixing. Because the solution is more
disordered, entropy increases!
SS Lecture - 7 19
 ENTROPY OF MIXING

Gideal mix  RT  X i ln X i
i

but we have Gideal mix = Hideal mix -TSideal mix

and Hideal mix = 0

Gideal mix  TSideal mix  RT  X i ln X i

so

Sideal mix   R  X i ln X i
i

Thus, the only contribution to Gideal mix is an entropy contribution!

SS Lecture - 7 20
 B
o

o
Molar Gibbs Free Energy 
o
+ X B B
= XA A
ix
G mech m
A
o

G ideal sol'n

0.0 0.2 0.4 0.6 0.8 1.0

XB

SS Lecture - 7 21
 o
Molar Volume

VB
o
o
+ X BV B
= X AV A
V sol'n
sol ution
ideal
o
VA

0.0 0.2 0.4 0.6 0.8 1.0

XB

SS Lecture - 7 22
 PARTIAL MOLAR FREE ENERGY -
THE CHEMICAL POTENTIAL

 G 
Gi     i Chemical potential
 ni T ,P ,n j
The previous relationships also apply:
n
G   ni i
n
G   X i i
i 1
i 1

It can also be shown that:

 U   A   H 
i         
 ni  S ,V ,n j  ni T ,V ,n j  ni  S ,P ,n j

SS Lecture - 7 23
 GIBBS-DUHEM EQUATION

For a homogenous phase of two components, A

and B
dG   SdT  VdP   AdnA  B dnB
If we now specify equilibrium at constant T and
P
dG   AdnA   B dnB  0

Now, we have shown above that

G   An A   B n B

Differentiating this we obtain

dG   AdnA   B dnB  n Ad A  nB dB
SS Lecture - 7 24
 GIBBS-DUHEM EQUATION –
CONTINUED

At equilibrium
dG   AdnA  B dnB  n Ad A  nB dB  0
Substituting the previous expression
dG   AdnA   B dnB  0
we obtain
n Ad A  nB d B  0

In the general case we get the Gibbs-Duhem

equation n

 n d
i 1
i i 0

SS Lecture - 7 25
 GIBBS-DUHEM EQUATION
- CONTINUED

Starting with the expression:

n Ad A  nB d B  0
If we divide through both sides by dXA we get
  A    B 
n A    nB   0
 X A T ,P ,nB  X A T ,P ,nB
And now dividing by nA + nB we get:
  A    B 
X A    1  X A   0
 X A T ,P ,nB  X A T ,P ,nB

SS Lecture - 7 26 26
 THE GIBBS-DUHEM EQUATION
REVISITED

We derived the Gibbs-Duhem equation for a

binary solution:
  A    B 
1  X B    X B   0
 X B T ,P ,n A  X B T ,P ,n A
This can be rearranged to give:
  A 
 
 X B T ,P ,n A XB

  B  1  X B 
 
 X B T ,P ,n
A

SS Lecture - 7 27 27
This equation shows that the slopes of tangents to curves of
chemical potential vs. mole fraction for binary solutions are not
independent of one another.
For example, if XB = 0, and   A  has a finite value,
 
 X B T ,P ,n A
then .
  B 
  
 X B T ,P ,n A
If XA = 0.5, then etc.

  A    B 
    
 X B T ,P ,n A  X B T ,P ,n A

SS Lecture - 7 28 28
 Chemical potentials in
solutions of carbon disulfide
and acetone.

Gibbs-Duhem Equation

  A 
 
 X B T ,P ,n A XB

  B  1  X B 
 
 X B T ,P ,n
A

SS Lecture - 7 29 29
 THE DUHEM-MARGULES
EQUATION

Starting with the Gibbs-Duhem equation:

  A    B 
1  X B    X B   0
 X B T ,P ,n A  X B T ,P ,n A
Also , di = RT dln i we can make the
substitution and obtain:
  ln f A    ln f B 
1  X B     X B  
 X B T ,P ,n A  X B T ,P ,n A
  ln f A 
 
 X B T ,P ,n A XB

  ln f B  1  X B 
 
 X B T ,P ,n A SS Lecture - 7 30
When the vapors are nearly perfect gases, we may substitute partial pressures
for fugacities to obtain the approximate relation:
  ln PA 
 
 X B T ,P ,n A XB

  ln PB  1  X B 
 
 X B T ,P ,n
A

Realizing that dXB = -dXA, and that d ln P = d P/P we can rewrite this as:

 PA 
  PA

 A T , P ,n B
X XA

 PB  PB
  XB

 B T , P ,n
X
A

SS Lecture - 7 31
 APPLICATION OF THE
GIBBS-DUHEM EQUATION

Task: Prove that, if the solute in a binary solution

obeys Henry’s Law, then the solvent obeys
Raoult’s Law.
Starting with the Gibbs-Duhem equation for a
binary system
n Ad A  nB d B  0

and dividing through both sides by nA + nB we get

X Ad A  X B d B  0
X Ad A   X B d B
At low pressures we have di = RT dln Pi
SS Lecture - 7 32
So we can now write: X Ad ln PA   X B d ln PB

Now if component A is the solute and obeys Henry’s Law

we have: PA = Kh,A·XA
Taking the natural logarithm of both sides we have:
ln PA = ln Kh,A + ln XA
Now differentiating we get:
d ln PA = d ln XA
so now X Ad ln X A   X B d ln PB
dX A
XA   X B d ln PB
XA
dX A   X B d ln PB
SS Lecture - 7 33
Now -dXB = dXA so  dX B   X B d ln PB

dX B
 d ln PB d ln X B  d ln PB
XB
Now we integrate from XB = 1 to XB = XB
XB P
ln  ln Bo
1 PB
where PB° is the partial pressure of B when XB = 1, i.e.,
the partial pressure of pure B.
P PB
ln X B  ln Bo XB  o
PB PB
PB  X B  PBo Raoult’s Law!
SS Lecture - 7 34
SS Lecture - 7 35
SS Lecture - 7 36