Gibbs Adsorption Isotherm

x
0
A
P
Area left of x
0
: represents underestimated value of P
i
Area right of x
0
: represents overestimated value of P
i
SURFACE EXCESS
A Property, P, of system vary across the interface (of thickness S) from that of
phase A and B
If P
i
is the value of the Property P at the ideal border of the interface, then:
A
B
x
0
x
P
A
P
B
B
S

x

A
B
x
0
x
P
P
B
P
A
Interface
P
i
SURFACE EXCESS (Cont.)
X
0
- may be selected such that two shaded areas are equal
-may divide the profiles of other properties differently

Property which is least convenient to handle
mathematically can be eliminated by selecting its surface
excess to be zero.
Note - dividing surface only a Reference Level rather
than a physical boundary.
- Surface excess can be positive or negative.
THE GIBBS ADSORBION EQUATION
Amount of surfactant adsorbed per unit area can be calculated
from surface or interfacial tension measurements


Where, d = change in surface tension
I
i
= surface excess concentration of i
d
i
= change in chemical potential of i


At equilibrium
where a
i
= activity of i in bulk phase
= mole fraction x activity coefficient

i
i
i
d d

I =
i i
a RTd d ln =
THE GIBBS ADSORBION EQUATION
Therefore

For dilute solutions containing one non-dissociating surfactant

Where C = molar concentration of surfactant in bulk


At constant temperature



Surface excess given by slope of plot of versus log C
Knowing I, area per molecule at the interface can be calculated.
i
i
i
a d RT d ln

I =
C d RT d
i
i
ln

I =
T
C d
d
RT
|
.
|

\
|
= I
ln
1
Important in assessing
Degree of packing
Orientation of adsorbed molecules
a = area per molecule (in
2
) at interface, given by



Where N = Avogadro number
I = Surface excess in moles/m
2
AREA PER MOLECULE AT THE INTERFACE
1 x 10
20

N I
a =
APPLICATION OF GIBBS ADSORPTION
Surface tension of aqueous solution of the nonionic surfactant
CH
3
(CH
2
)
9
(OCH
2
CH
2
)
5
OH at 25
0
C is as given:
C (x10
-1
) mol/m
2


0.1

0.3

1.0

2.0

5.0

8.0

10.0

20.0

30.0

(mN/m)

63.
9

56.2

47.2

41.6

34.0

30.3

29.8

29.6

29.5

y = -7.7111 Ln(C) - 24.364
0
15
30
45
60
75
-12 -10 -8 -6
Ln (C)

(
m
N
/
m
)
CMC
2 6
3
/ 10 11 . 3
298 314 . 8
10 711 . 7
m mol

=
=

= I
Surface excess is given by:
Average area occupied by each molecule,
2
o
23 6
20
A 4 . 53
10 023 . 6 10 11 . 3
10 1
=


=

a
T
C d
d
RT
|
.
|

\
|
= I
ln
1
APPLICATION OF GIBBS ADSORPTION