Definition of interface

Liquid-gas and liquid-liquid

interfaces
(surface tension, spreading,
adsorption and orientation at
interfaces)

Definition of interface
How can we define the interface? How we
can detect the surface of a condensed
phase?

Definition of interface
If two homogeneous bulk phases meet there is a
region of finite thickness where the properties
changed. That region is called interface.
At a molecular level the thickness of the
interfacial region is not zero, and it is significant!
The properties of interfacial region can be
important for colloid systems, especially for
dispersions, where the surface to volume ratio is
not negligible.

Fluid interfaces
The attractive
forces acting on
molecules at the
surface
are
anisotropic, the
net
force
is
oriented toward
the liquid phase.
As a consequence, liquids tend to reduce their
surface. Energy is required to increase the
surface to overcome the attraction.

Surface tension
The energy (G) required to increase the surface
(A) isothermally and reversibly by a unit amount is
called surface tension ().

dG

dA n , p ,T

The unit of surface tension is J/m2.

This definition are applied only for pure liquid.
Surface tension value is always positive
because of the attraction.

Surface tension

The surface tension () can also be defined as a

force (F) acting to any imaginary line of unit
length (l), on the liquid surface if the force is
perpendicular to the line.

2l

The unit of surface tension is N/m.

This definition is valid for any liquid.

=F/2l

Factors having influence on

surface tension

1. Chemical nature
liquid

Surface tension (mN/m, 20oC)

Water

72.8

Benzene

28.9

Acetic acid

27.6

Acetone

23.7

Ethanol

22.3

n-hexane

18.4

n-octane

21.8

n-octanol

27.5

Mercury

485

Factors having influence on

surface tension

1. Chemical nature

Interfacial tension: surface tension at the

interface of two liquids. It depends on the
asymmetry of the two phases.
liquid

Interfacial tension against the

water (mN/m, 20oC)

Benzene

35.0

n-hexane

51.1

n-octane

50.8

n-octanol

8.5

mercury

375

It is only an estimation!!

Factors having influence on

surface tension
2. Temperature
The secondary interactions depend on temperature,
at higher temperature the attraction is weaker.
Etvs-law (Hungarian physicist):
2
3
m

V constE (Tc T )
Ramsey and Shields law:
2
3
m

V const E (Tc T 6)
Not valid for associating or dissocating compounds!
: surface tension (N/m), Vm: molar volume (m3/mol), T: temperature (K), Tc:
critical temperature (K), constE: Etvs constant (2.1 x 10 -7 J/(K mol2/3)

Factors having influence on

surface tension
3. Presence of solute

0.09

A, Ions, small polar molecules.

These compounds prefer being
solvated (hydrated), so they tend to
move inside the liquid phase where
they can be solvated from all
direction.
Thus
more
solvent
molecule goes toward the surface,
which increase the surface tension.
Surface inactive (capillary inactive
compounds)

(N/m)

0.08

0.07

0.06
0

2000

4000

6000

c(mol/m3)

Factors having influence on

surface tension
3. Presence of solute
B, Amphiphilic molecules (having polar and non-polar
parts).

These molecules are oriented on the surface (gas-liquid

or liquid-liquid surface. The polar ends are oriented
toward the polar solvent, while the non-polar parts are
pointed toward the gas, or the non-polar liquid phase.
This orientation makes possible the smoothest change
of polarity between the phases (Hardy-Harkins rule).

Factors having influence on

surface tension
3. Presence of solute
B, Amphiphilic molecules (having polar and non-polar
parts).

Factors having influence on

surface tension
3. Presence of solute
(having

The
interaction
between
the
amphiphiles are weaker compare to
the solvent, so the orientation of
these molecules decreases the
surface tension.
Surface active
compounds.

(capillary

0.07
0.06

(N/m)

B, Amphiphilic molecules
polar and non-polar parts).

0.08

active)

0.05
0.04
0.03
0

500

1000

1500

2000

c(mol/m3)

Effect of solute concentration on the

surface excess
The Gibbs-isotherm: Describes the relation
between the solute concentration (c) and the
surface excess() at a given temperature.
: Surface excess (mol/m2)
A: surface of a molecule
occupied: (m2/each)
R: gas constant (8.314 J/Kmol)
T: Temperature (K)
c: concentration (mol/m3)
B: constant

Effect of solute concentration on the

surface excess
The Gibbs-equation: Describes the relation
between the solute concentration (c), the
surface tension and the surface excess() at a
given temperature.

: Surface excess (mol/m2)

R: gas constant (8.314 J/Kmol)
T: Temperature (K)
c: concentration (mol/m3)
: surface tension (N/m)

Surface tension: the consequences

If the gravitational force is smaller than the

surface tension acts, the object can float on
the surface although the density is higher.

Surface tension: the consequences

Surface tension: the consequences

The Laplace pressure
air

p1

p2

The liquid tends to reduce

the surface, so:
p2>p1
Laplace equation:
2
p
r
Consequence:
The pressure is always
higher at the concave side.

Surface tension: the consequences

The Laplace pressure

p2

4
p1
p
r
Double interface!
The pressure difference can be
extremely high at small radius!
Radius

1mm

0.1mm

1m

10nm

p (kPa)

0.29

2.9

290.4

29040

What happens if we open the tap

between the bubbles?
http://www.youtube.com/watch?
v=kvrsAhuvs3M

Surface tension: the consequences

Meniscus
The shape of the fluid surface in a tube depends
on the adhesion and cohesion. If the adhesion
(liquid-solid attraction) is stronger than the
cohesion (interaction of liquid particles) the
meniscus is concave, otherwise it is convex.
r<0

(the centre is outside)

r=

r>0

(the centre is inside)

Surface tension: the consequences

Kelvin equation
It has already been seen that the pressure over
the curved surface is different compared to the
flat one. Thus the vapor pressure of the liquid also
depends on the shape of the surface.

pr Vm 2
ln

p RT r
pr, p: vapor pressure over the curved and flat surface
(Pa), Vm:molar volume (m3/mol), : surface tension (N/m), R:
gas constant (J/Kmol), r: radius of the capillary(m),
T: temperature (K)

Surface tension: the consequences

Capillary condensation
In case of porous materials (solid phase with
capillaries) the vapor can condense even at higher
temperature if the fluid (condensed liquid) phase
wets the surface. This phenomena can be
explained by the Kelvin equation.
(Wetting means r<0, so the ln(pr/p) is negative,
therefore pr<p and if pr<pout then the vapor
condenses)

Surface tension: the consequences

Capillary action
A, r<0
Concave meniscus

B, r>0
Convex meniscus

The pressure inside the liquid

is smaller compared to the
flat surface.
The fluid phase is pushed into
the capillary to balance the
pressure difference

The pressure inside the liquid

is higher compared to the
flat surface.
The fluid phase is pushed out
from the capillary to balance
the pressure difference.

Surface tension: the consequences

The shape of the meniscus
The shape of the liquid surface depends on the ratio of the
adhesion and cohesion. If the cohesion is stronger than the
adhesion the meniscus is concave (r<0, water, aqueous
solutions, polar solvents), while if the adhesion is stronger
than the cohesion, the meniscus is convex (r>0, mercury)

Measurement of surface tension

The difference in pressure (see
the Kelvin eq.) is in equilibrium
with the fluid pressure. Measuring
the capillary rising or depression
makes possible to calculate of
surface tension

1
hgrcap
2

Wilhelmplate
duNouy ring

Measurement of force needed to

remove a plate or ring from the
liquid

2l

Spreading, wetting, contact angle

Contact angle (measured in the liquid phase)

= 1+ 2
Perfect wetting (spreading): =0o
Partial wetting: 0o < < 90o
Non wetting: 90o < <180o
Perfectly non wetted =180o

Spreading, wetting, contact angle

Wettability depends on adhesion /cohesion.
When the forces of adhesion are greater than the forces
of cohesion, the liquid tends to wet the surface (or spread
on the other liquid), when the forces of adhesion are less by
comparison to those of cohesion, the liquid tends to
"refuse" the surface. In this people speak of wettability
between liquids and solids. For example, water wets clean
glass, but it does not wet wax.

Spreading, wetting, contact angle

Spreading, wetting, contact angle

In equilibrium:

2 1 cos1 12 cos 2

GS LS GL cos

Spreading (or wetting) if < 90o

2 ( 1 12 ) 0

GS ( LS GL ) 0

S lower ( interphase upper ) 0

Adhesion and cohesion

Adhesion:
A+ B-AB
S=adhesion-cohesion=
A+ B-AB-2A=
B-(A+AB)

Cohesion:
2A