COLLOID CHEMISTRY

Chapter 2 - Surface phenomena

Dr. Ngo Thanh An

1. Surface tension
 1. Surface tension
Surface tension values
 1. Surface tension

dG   SdT  VdP    i dN i  dA

G

A T , P , N i

• The surface tension is the increase in the Gibbs free energy per
increase in surface area at constant T, P and Ni
1. Surface tension
 2. Surface and interfacial tension
• In the liquid state, the cohesive forces between adjacent molecules
are well developed.
For the molecules in the bulk of a liquid
• They are surrounded in all directions by other molecules for which
they have an equal attraction.
For the molecules at the surface (at the liquid/air interface)
 Only attractive cohesive forces with other liquid molecules which
are situated below and adjacent to them.
 They can develop adhesive forces of attraction with the molecules
of the other phase in the interface
 The net effect is that the molecules at the surface of the liquid
experience an inward force towards the bulk of the liquid and pull
the molecules and contract the surface with a force F.
----------------------------------------------------
Cohesive force is the force existing between like mole­cules.
Adhesive force is the force existing between unlike molecules.
 2. Surface and interfacial tension

• To keep the equilibrium, an equal force must be applied to oppose the

inward tension in the surface.
• Thus SURFACE TENSION [γ] is the force per unit length that must be
applied parallel to the surface so as to counterbalance the net inward
pull and has the units of dyne/cm.
• INTERFACIAL TENSION is the force per unit length existing at the
interface between two immiscible liquid phases and has the units of
dyne/cm.
 3. Surface free energy
• The work W required to create a unit area of surface is known as
SURFACE FREE ENERGY/UNIT AREA (ergs/cm2) (1 erg =
dyne.cm)
W = γ x ∆A

• Its equivalent to the surface tension γ

• Thus the greater the area A of interfacial contact between the
phases, the greater the free energy.

For equilibrium, the surface free

energy of a system must be at a
minimum.
Thus liquid droplets tend to assume a
spherical shape since a sphere has
the smallest surface area per unit
volume.
 4. Work of cohension and adhesion

For a single liquid (cohesion):

A
AV
W AA  2 AV A

For two different liquids (adhesion):

A AV
W AB   AV   BV   AB A

AV
AB B B

(V = vapor)
f  f ( x, y) Review
 f   f 
df     dx     dy
 x  y  y  x
Due to the symmetry of the second derivatives,

  f    f 
    
 x  y   y   x 
 dG   SdT  VdP    i dN i  dA
G

A T , P , N i
  G     G  S  T  S 
      T 
A   T  T  A  A T A T

We have T S = Q > 0, because the area enlargement need Q

0
adsorbing heat. This mean that A

Finally, 
0
T
Contact angles
Contact angles
Wettability

Schematics of different wetting regimes: (a) Young’s model, (b) Wenzel model,
and (c) Cassie model.
Wettability
Wettability
Applications of
superhydrophobic surfaces

 Anti-adhesion and self-cleaning.

- Self cleaning glasses.
- Self cleaning textile.
 Anti-biofouling applications.
 Corrosion inhibition.
 Drag reduction.

 Surface roughness increases hydrophobicity

 Superhydrophobic if contact angle > 150°
 Superhydrophobicity leads to self-cleansing
Wettability
Wettability
 Curved interfaces and capillarity
· Often forces that tend to spread a liquid
(interactions with solids or gas pressure
in a bubble) are balanced by surface
tension that tends to minimize interfacial
area, resulting in a curved liquid-gas
interface. Curved Liquid-Vapor Interfaces
· Particularly in porous media, the liquid-
gas interface shape reflects the “need” to
form a particular contact angle with solids
on the one hand, and a tendency to
minimize interfacial area within a pore.
· A pressure difference forms across the
curved interface, where pressure at the DP = Pliq-Pgas When the interface curves
concave side of an interface is larger by into the gaseous phase (water droplet
an amount determined by interfacial in air)
curvature and surface tension.
· These relationships between interfacial DP = Pgas-Pliq When the interface curves
curvature and pressure difference are into the liquid (air bubble in water,
given by the Young-Laplace equation. water in a small glass tube)
Curved interfaces and capillarity
Curved interfaces and capillarity
Curved interfaces and capillarity
Curved interfaces and capillarity

For pendular rings between spherical particles (sand grains) the pressure
difference is given as:

1 1 
P     
 R1 R2 
Curved interfaces and capillarity
Young Laplace equation
From equation:

4 3
V  r dV   4r 2
3
A  4r 2 dA  8r

dN i  0
 2

P P 
dF  0 r
Thompson Kelvin equation
Thompson Kelvin equation
 Capillary rise model
● When a small cylindrical capillary is dipped in a water reservoir a
meniscus is formed in the capillary reflecting balance between contact
angle and minimum surface energy.
● The smaller the tube the larger the degree of curvature, resulting in larger
pressure differences across the air-water interface.
● The pressure in the water is lower than atmospheric pressure (for wetting
fluids) causing water to rise into the capillary until this upward capillary
force is balanced by the weight of the hanging water column (equilibrium).
 Capillary rise model
• Force balance can describe magnitude
of capillary rise.

W  mg  Vg  g  r 2 h  
W  Fsurface
2r g  r 2 h  2r cos 

Capillary rise:

2 cos 
h
w g r
Capillary Rise – Example 1
Problem Statement:
Calculate the height of capillary rise in a glass capillary tube having a
radius of 35 µm. The surface tension of water is assumed to be 72.7 mN/m.
Solution:
We use the capillary rise equation with  = 0o, g=9.81 m/s2, and w=1000
kg/m3; recall that cos(0)=1:

2 cos  2  0.0727  cos(0)

h h  0.423 [m]
w g r 9.81 1000  3.5  10 5

N
m  kg  m   1   s 2m 
 

2   m   kg   m
 m   kg   s     
 2  3   m
 s m 
The capillary rise eq. can be simplified by combining constants to yield:

14.84
h [m] 
r [ m]
Capillarity (and Adsorption) in
Soils
Adsorption and Capillarity in Soils
The complex geometry of the soil pore space creates numerous
combinations of interfaces, capillaries, wedges, and corners around
which water films are formed resulting in a variety of air water and
solid water contact angles.
Water is held within this complex
geometry due to capillary and
adsorptive surface forces.
Due to practical limitations of present
measurement methods no distinction is
made between adsorptive and capillary
forces. All individual contributions are
lumped into the matric potential.

10 m
Bonus…………..!!!!!!!!!
 Summary
Surface tension

Wettability

meniscus

Capillarity

Pressure deviation
Bonus 1
Bonus 2
Bonus 2
Bonus 3
Bonus 4
Bonus 5
Bonus 5
Bonus 5
Bonus 6
Bonus 6
Bonus 7
Bonus 8
Bonus 8