Vous êtes sur la page 1sur 44

SURFACE TENSION

The surface tension is denoted by the Greek letter


gamma ()
The surface tension is the magnitude F of the force
exerted parallel to the surface of a liquid divided by the
length L of the line over which the force acts:
=F/L

SI Unit of Surface Tension: N/m


Liquid:
relatively high density
fixed volume (posses a mobility at the molecular level
than solid)
Interfaces between 2 phases - homogenous mobility

Liquid surface:
Having an elastic skin

Surface Tensions of Common Liquids


Liquid Surface Tension
(N/m)
Benzene
(20 C) 0.029
Blood
(37 C) 0.058
Glycerin
(20 C) 0.063
Mercury
(20 C) 0.47
Water
(20 C) 0.073
Water
(100 C) 0.059

Attraction forces between molecules at the surface


and at the interior of the liquid

Attracted inwards

Attracted inwards

Move upward
Move upward
surface tension decreases with the increase

of

Reduce the number of molecules at surface

temperature, reaching a value of 0 at the critical temperature.


Pressure normally makes the surface tension of
liquid decrease because increase the pressure increases the
density of vapor.

Interuption?!!!!

Lateral tension

T, [], P?!!!
(STRONGER INTERMOLECULAR
ATTRACTIONS GREATER SURFACE
TENSION
T increase -----increase total entropy
(disorganisation of molecules
arrangement)---reduce free energy
(molecules used the free energy for
interaction)

Shape distortion due to


Gravity, magnetic, electrical or other forces

T increase -----increase total entropy


(disorganisation of molecules arrangement)--reduce free energy (molecules used the free
energy for interaction)

At the same time, the gravitational force is balanced by


the repulsive force of nearby molecules. So the
molecules can stay on the surface.
If we want to move the lower molecules to the surface,
we have to do some work opposing the gravitation from
lower molecules.
Therefore the potential energy of molecules increase.
Obviously, the molecules on the surface layer have
higher potential energy than the molecules in the inner
liquid.
As any system always tends to the smallest potential
energy, the molecules on the surface tend to move into
the liquid. Then the surface area will reduce to
minimum. Contrarily, if we want to increase the surface
area, we have to do work to move molecules to the
surface while the potential energy of the surface also
increases.

Surface tension of solution changes with


variation of solute (a substance is dissolved in
another substance.)
Some solutes can decrease surface tension of
solution and some can increase surface
tension.
The former is called surface-active agent and
the latter is called non-surface-active agent.
(solution = solute + solvent )

Surface Tension, o of a liquid is often defined as the force acting at right angles to any line of unit length on the liquid
surface.
The Short-range intermolecular forces which are responsible for surface/interfacial tension include van derWalls forces
and hydrogen bonds (e.g.in water) and metal bonding (e.g. in mercury).

The surface-active agent is called surfactant or a wetting


agent.
For example, organic acid and soap are active agent of
water;
When the surface-active agent dissolves in solvent, the liquid
in which another substance (solute) is dissolved to form a
solution), the attraction of solvent molecules is greater than
attraction between solvent molecule and solute molecule.
In such a case, solvent molecules in the surface layer tend to
move into the liquid because the greater attractions between
solvent molecules.
The solvent molecules move into the liquid as much as
possible as in this way, the surface energy will be lower and
the system will be more stationary.
In the surface layer, the solute molecules will increases in
order to stabilize the system.

salt and gluside are non-active agent of water.

ADSORPTION AT A WATER SURFACE

Pure water
high surface tension
sum of dispersion force (DF) + hydrogen bonding (HB)
Different substances: different intensities of attractive forces, different molecules volumes and shape
Molecules with high force---pass into the interior.smaller force field---remain at the surface
The different [] of molecules (surface and bulk) in solution is adsorption.
Interface: adsorption is partitioning of chemical species between bulk and interface.
Hence, adsorption is a the amount of molecules (moles or number of molecules, weight and volume)
accumulated per unit area (1m2) .
ST is the minimum amount of work needed to create a new unit area of interface resulting thin film .
Desorption: molecules leaving the interface
Water Surface tension: 72.8 mNm-1.
Water: stronger intermolecular attractive force-fields than other solute.
water moves inwards more rapidly than solute molecules
Organic substances (hydrocarbon) : weak intermolecular forces
When these organic substances are brought into solution : reduces the surface tension of water
ST of water higher than HC, water move inwards more rapid than HC
Leaving surface rich with HC
therefore water field force at surface has been declined.
Due to longer the HC chain the greater tendency for the OH molecules (hydrophilic part) adsorbs
at the air-wate .r surface---lower ST

The surface phenomenon of solution:


Is solution homogeneous?
surface adsorption

A
Solvent

B
Solute

the difference in the intermolecular


interaction

A B A B A B

B A B

The less interaction enriches solute molecules at the surface


(positive adsorption), which also causes decrease in surface
tension.

A B A B A B

A B A A A A A

The greater interaction lessens the concentration of solute at


the surface (negatvie adsorption), which also causes increase
in surface tension.

interaction

concentration
Surface tension
adsorption

A-B > A-A

A-B< A-A

C < Cb

C > Cb

increase

decrease

negative

positive

The concentration difference between surface and


bulk solution is named as surface adsorption.
The excess surface concentration ():
the concentration difference of solute per unit area
in surface layer and in the bulk solution. (mol m-2)

The Gibbs adsorption isotherm

a
b

interface

ni ni ni ni

Interphase
Interfacial
region

a
b

ni ni ni ni
ni

SURFACE EXCESS

Defined as the moles of solute per cm2 of surface


region in excess of the number of moles that
would be associated with a portion of bulk
solution having the same number of moles of
solute.
Symbol,
+ve surface excess- [] of solute is higher at surface
than bulk. Increase the chemical potential will
decrease the surface tension.
, -ve surface excess- [] of solute in bulk is higher
than surface. Increase the chemical potential will
increase the surface tension. (harder to pull
compound from bulk)

If A is the area of the interface, the area surface


excess concentration, is defined as
= ni /A = (na-ni)/A

Where: na = the amount of the solute at or close


to the surface.
ni= the amount of the solute in the presence of a
physically and chemically inert surface
A = surface area
s

= ni total (ni + ni ) /A

Solute (surfactant) dissolved in solvent


solution OR
Solute dissolved partially 2 layers

By preferential accumulation of solute


(surfactant)molecules at the surface of the
solution formed surface layer decrease
in free energy (decrease of attraction force of
water) +ve adsorption surface conc. of
solution > bulk conc.

How to predict the amount of substance adsorb


on the surface?
2 components system (for an ideal solution)

= -c/RT . d/dc
Where
= surface excess moles of component (moles/cm2)
= surface tension (dynes/cm)
Bulk []
R= 8.314x 107 dynes.cm/mol. R = 8.314 J/mol

You add 0.5mmol of sodium dodecylsulfate to


pure water at 25. This leads to a decrease in
the surface tension from 71.99 mJ m-2 to
69.09 mJ m-2. What is the surface excess of
sodium dodecylsulfate?
Solution Because the concentration is so low
that we take an approximation of
d
0.06909 0.07199

5.80mN 2 mol1
dcB cB
0.0005 0

cB d
0.0005
B

(5.80) 1.17 106 mol m2


RT dcB
8.3145 298.15

For 1:1 ionic surfactant (CTAB: CTA+:Br_)-----2


ions are involved (anions and cations) adsorb
at the surface to maintain the local neutrality.
Therefore Gibbs equation will be modified to:
= -c/2RT d/dc OR
integration with ln
= -1/2RT d/d ln c
= -c/2RT d/dc
(provided surface and bulk system in equilibrium.
C- concentration of solute

=-cRT. D/dc -1/RT . d/d ln c 1/2.303RT . d/dlogc

Determination of d/dc by 2 ways:


1. Graphical
2. Empirical
1) Graphical:
Plot a graph of vs c.
At any given c, the slope of the curve (d/dc)
can be found.
Knowing also R, T and c, can be calculated.

Prediction of Surface tension


Empirical equation (estimation equation) for variation of surface tension
with concentration can be obtained.
Example; aqueous solution of aliphatic compounds
o/ = 1- B log (c/a +1)
B is constant (~0.41) for many compounds
A decreases rapidly as a homologous series is ascended. (For A particular
compound a is constant)
Differentiating the above equation will give /dc

Surface Pressure () can be defined as


(The change of interfacial tension caused by addition of a given species to a
base solution. When an area of liquid covered with a spread substance is
separated from a clean area of surface by a mechanical barrier, the force
acting on unit length of the barrier is called the surface pressure, or, and is
equal to where is the surface tension of the clean surface and that of the
covered surface:
= o -
Where- o = surface tension of the solvent

Therefore:

= -c/RT. d/dc = c/RT . d/dc

Determination of surface excess

-Plot a graph surface


tension as a function to
concentration, c.
- surface concentration can
be obtained from the slope
of the graph.
- From the relationship of:
- = -1/2RT d/d ln c
- = -c/2RT d/dc

example
Surface tension of aqueous solution of nonionic surfactant CH3(CH2)9(OCH2CH2)5OH at T =
25oC is given in table. Calculate the surface
excess and area occupied per molecules
C (101molm3)
(103Nm1)

0.1 0.3 1.0 2.0 5.0 8.0 10.0 20.0 30.0


63.9 56.2 47.2 41.6 34.0 30.3 29.8 29.6 29.5

2) Empirical:
Empirical equation for variation of surface
tension with concentration can be obtained.
Example: for aqueous solutions of aliphatic
compounds.
/o = 1-B log (c/A +1)

Differentiating the above equation will give


d/dc.

Surface pressure,
= o -
d = -d
o = surfcae tension of pure liquid
= -c /RT. D/dc = c/RT. d/dc
For dilute solution:

c
= RT OR
= RT
= surface area per mole
= 1/

VARIATION OF SURFACE TENSION WITH CONCENTRATION FOR


VARIOUS TYPES OF COMPOUNDS IN AQUEOUS SOLUTION
Type II:

II

salts, non-volatile acids and bases,


sucrose etc.
Type I:
nonionic solvable organic molecule with
low molecular weight / short chains and
containing polar groups such as hydroxyl,
amine groups, etc.

III

The surface tension of solution decreases by 3.2 times for the


increase of per CH2 group in the chain of fatty acid.

Type III:
As the C increase, the of the
solution decrease sharply.
Ionic / nonionic solvable
organic molecule with high
molecular weight / long chains
and containing polar ionic
groups such as COO-, -SO3- NR4+, etc.
For example, the sodium salts of long-chain fatty acids (n >
8) and sodium dodecyl sulfate.
The substances that can drastically lower the surface
tension of water even at low concentrations are called
surface-active compounds / agent or surfactants.

1. Simple Organic Solutes


Slope: -ve ** = +ve. So, +ve adsorption.
2. Simple Electrolytes (Inorganic) and Highly
Hydrated Organic Compounds
Slope: +ve ** = -ve. So, -ve adsorption.
3. Amphipatic Solutes (especially ionic ones)
Here there is a sudden break in the curve
(Micelle Formation).
Slope: -ve ** = +ve. So, +ve adsorption.

ADHESION

= G

equation 2

LIQUID-LIQUID INTERFACE
WORK OF COHESION, (WAA):
Definition: work required to pull a column of
liquid A apart.
= half the work of cohesion.
= free energy change involved when molecules
from the bulk of a liquid are moved to the
surface.
So, WAA = G = 2 A ----------------------------- 1
[cohesion: no surface 2A (or B) surfaces]

WORK OF ADHESION, (WAB):


Definition: work required to separate two
liquids, A and B.
It measures the attraction between the two
different phases, A and B.
So, WAB = G = final - initial
= A + B - AB ----------------------------- 2
[adhesion: 1 AB surface 1A + 1B surface]

MONOLAYER ADSORPTION
Adsorption in which a first or only layer of
molecules become adsorbed at an interface.
In monolayer adsorption, all of the adsorbed
molecules are in contact with the surface of
the adsorbent.
The adsorbed layer is termed as monolayer or
monomolecular film.

PHYSICAL STATES OF MONOMOLECULAR FILMS:


Monolayers can be roughly classified as:
1. Condensed (solid) Films.
2. Expanded Films.- liquid
3. Gaseous or Vapor Films.

Monolayer adsorption on a homogeneous surface at


equilibrium pressure p/p0 . The heat of adsorption of the
first monolayer is much stronger than the heat of
adsorption of the second (and all following)
layers (typical chemisorption case)

Multilayer adsorption/condensation on a
homogeneous surface at equilibrium pressure p/p0 .
The heat of adsorption of the first (blue) layer is
comparable to the heat of condensation of the
subsequent (red) layers. Often observed during
physisorption.

1. CONDENSED FILMS

Here molecules are closely packed.


Strong lateral adhesion between the film molecules.
Cohesion between hydrocarbon chains is strong.
Example: palmitic, stearic and higher straight-chain fatty
acids at r.t.
At high films area: film molecules group together in small
clusters or islands.
They do not separate into individual molecules due to
strong cohesion between hydrocarbon chain.
P increase

Top view
As P is applied to a condensed film, the adsorbed molecules can rearrange to a small extent
by achange in packing structure. Beyond that point added P wil result in film buckling
(bending)

Initial compression very low surface


pressure,
With > in compression very rapid rise in
(steep slope) molecules become tightly
packed together .

Tightly packed

A/nm2 molecules-1

2. EXPANDED FILMS

Monolayer still coherent, rigid, incompressible and densely packed.


Molecular orientation is still perpendicular to the surface, but the tails are less rigidly packed
Cohesion between hydrocarbon chains is less due to the presence of more than one polar group in
the molecule .
Example: double bond.
Here, there is an attraction between the second polar group and the aqueous substrate.
Compression forces the = above the surface + eventually orientates the hydrocarbon chains in a
vertical position.
Process is gradual.

Gradual process

A/nm2 molecules-1

3. GASEOUS FILMS.

Molecules negligible size, molecules are relatively far apart and have significant
surface mobility.
Molecules act essentially independently, molecules orientation is random.
No lateral adhesion between them
Random movement of molecules on the surface obey an ideal two-dimensional
gas equation. (PV= nRT)

A =kT ( = RT)
Example: cetyltrimethyl ammonium bromide molecules in the film ionised to
(C16H33N(CH3)3+. (CTAB)---repel each other in aqueous phase---- is relatively large at
all points
Film P are greater at oil/water interface than air-water interface (oil penetrates
between the HC chain of the film molecules and remove most of the inter-chain
attraction.

= o bc -----linear relationship between c

A/nm2 molecules-1

FACTOR INFLUENCING THE PHYSICAL STATE OF


MONOMOLECULAR FILMS.

1.

2.

3.
4.

Physical state of amonolayer depends on lateral cohesive forces


between the constituent molecules.The factors exhibit the various
monlayer states.
Head groups bulky or not.(prevent efficient packing and hence
maximum cohesion between the HC chains.
Number of polar groups in molecule ex. unsaturated fatty acids
(existence of =). A film P is required to overcome the attraction
between the second polar group and the aqueos substrate before
the molecules can orienttaed vertically.
Molecule having more than one hydrocarbon chain orientated in
different directions from polar part ex. esters, glycerides.
Straight or bent hydrocarbon chain ex. brassidic acid + erucic acid.

Trans CH3(CH2)7CH=CH(CH2)11COOH (straight) gives condensed film


Cis CH3(CH2)7CH=CH(CH2)11COOH (bent) gives a very expanded film

5. Branched hydrocarbon chain.


6. pH of aqueous substrate (if monolayer is
ionisable).
7. Dissolved electrolytes ex. Ca2+.

GASEOUS FILMS

Monolayer of soluble material are normally gaseous.


For dilute surfactant solutions, allow solute-solute interactions at
surface to be neglected, the surface tension will be approximately
linear with [].

= o bc (b is constant)
= o -
= bc
d /dc = -b
Substituting Gibbs equation:
= -c/RT. d/dc
= RT ; = 1/

the 2-dimensional gas law is obeyed.


= RT

= surface area per mole.

is also known as the spreading pressure.

EXAMPLE:
A 2 x 10-4 M aqueous solution of a surface-active is
being studied. With a device known as a
microtome, it is possible to skim off a thin layer
of known area, and by this means, it is
determined that the surface excess of the
surfactant is 3 x 10-10 mole/cm2. Calculate the
surface tension of the solution, making
reasonable assumptions. The temperature is
25OC. (Surface tension is a linear function of
concentration: = o bc)
R = 8.314 x 107 dynes cm/mol.K
0 = 72 dyne/cm at 25OC

d/dc = b
= -c/RT. d/dc = bc/RT
bc= RT
= o - RT