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Gibbs Isotherm

This document discusses Gibbs adsorption isotherm, which describes how the amount of surfactant adsorbed at an interface varies with concentration. It defines terms like surface excess and dividing surface. The Gibbs adsorption equation relates surface excess to changes in surface tension and chemical potential. For dilute solutions of a non-dissociating surfactant, surface excess can be determined from the slope of a plot of surface tension versus the log of concentration. An example application calculates surface excess and average area per molecule from surface tension measurements of an aqueous surfactant solution.

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Sabharish Murali
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2K views8 pages

Gibbs Isotherm

This document discusses Gibbs adsorption isotherm, which describes how the amount of surfactant adsorbed at an interface varies with concentration. It defines terms like surface excess and dividing surface. The Gibbs adsorption equation relates surface excess to changes in surface tension and chemical potential. For dilute solutions of a non-dissociating surfactant, surface excess can be determined from the slope of a plot of surface tension versus the log of concentration. An example application calculates surface excess and average area per molecule from surface tension measurements of an aqueous surfactant solution.

Uploaded by

Sabharish Murali
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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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

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