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Liquid surface:
Having an elastic skin
Attracted inwards
Attracted inwards
Move upward
Move upward
surface tension decreases with the increase
of
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)
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).
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
A
Solvent
B
Solute
A B A B A B
B A B
A B A B A B
A B A A A A A
interaction
concentration
Surface tension
adsorption
A-B< A-A
C < Cb
C > Cb
increase
decrease
negative
positive
a
b
interface
ni ni ni ni
Interphase
Interfacial
region
a
b
ni ni ni ni
ni
SURFACE EXCESS
= ni total (ni + ni ) /A
= -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
5.80mN 2 mol1
dcB cB
0.0005 0
cB d
0.0005
B
Therefore:
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)
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)
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/
II
III
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.
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]
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.
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
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)
Tightly packed
A/nm2 molecules-1
2. EXPANDED FILMS
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.
A/nm2 molecules-1
1.
2.
3.
4.
GASEOUS FILMS
= o bc (b is constant)
= o -
= bc
d /dc = -b
Substituting Gibbs equation:
= -c/RT. d/dc
= RT ; = 1/
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