Colloid and Interfacial Engineering Slides Part 02

Electrical Double Layer
1000 e 2 N A
=
r 0k B T
1
2
+
+
+
-
Diffuse layer
+
+
+
-
+
-
+
+
-
Distance from the charged surface, x
1/
z i2C i
i
Stern plane
+
+
+
+
+
+
+
+
+
+
+
+
+
Potential
Electrical double layer:

If there is a hydrophilic solid surface dipped in an aqueous
solution it will formed electrical double layer.
Length of Double layer:
The length of the stagnant layer
is called Debye length and presented as 1/.
Charged Surface
Fixed charge: The surface charges are

referred to as fixed charges. Originate
from dissociation or ion adsorption
Diffuse layer
Distance from the charged surface, x
Interfacial Science and Engineering
Distance
Distance
d
Charge reversal due to adsorption of
Surfactant counter-ion
Charge reversal due to adsorption of

Surfactant co-ion
Work of Adhesion and Cohesion

Consider a cylindrical column composed of two types of material, A and B. If we pull this
column apart and separate it into column A and column B, then the change in free energy
can be expressed as
A + B AB = WAB
A, B = Surface free energy per unit area for material A and B, respectively.
AB = Interfacial free energy per unit area between material A and B.
WAB = Work of adhesion (per unit area), which is the work required to separate
the two blocks of material.
A + B is the total surface free energy in the
final state (state 2), and AB accounts for the
interfacial energy between the two materials in
the initial state (state 1).
If materials A and B are the same, then AA =
BB = 0, and W AA = 2 A and W BB = 2 B
WAA (or WBB) is the work of cohesion. The
work of cohesion is simply the work required
to create two surfaces of the same material.
1
2
AB = (WAA + WAB ) W AB
State 1
State 2
AB = Interfacial tension or Interfacial free energy
Surface Wetting vs. Adhesive and

Cohesive Forces
Adhesive forces > cohesive forces: At the liquid-solid surface interface, if the
molecules of the liquid have a stronger attraction to the molecules of the solid
surface than to each other wetting of the surface occurs.
Cohesive forces > adhesive forces: If the liquid molecules are more strongly
attracted to each other than the molecules of the solid surface the liquid beads-up
and does not wet the surface.
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Surface tension and Contact angle

Definition: Surface or interfacial tension can be defined as the force needed to
oppose the natural pull of the molecules in the surface or interface to minimize
the size of that surface or interface.
Contact angle: The angle of contact
between the solid and liquid surface is
called contact angle
Net force is not zero
Net force is zero
Surface tension: Property of the interface between two phases

Contact angle: The edge of the two-phase boundary where it ends at a third
phase
Surface tension
Force per unit length is ,
l
The work done in extending the movable member
a distance dx is
Work = l dx = dA; l dx = dA
Unit: CGS ergs/cm2 ( energy/ area) or dyn/cm (force/length); SI: J/m2 or N/m
Soap bubble:
is in terms of energy per unit area. In the absence of gravitational or other forces, a soap bubble is
spherical, as this is the shape of minimum surface area for an enclosed volume. A soap bubble of
radius r has a total surface free energy 4
r2.
If the radius were to decrease by dr the change in surface free energy would be 4
r2 - 4
(r-dr)2 =
8
rdr.
Shrinking decreases the surface energy, that must be balanced by a pressure difference across the
film P. The work against this pressure difference is equal to decrease in surface free energy
P 4
r2dr = rdr or P = 2 /r
Smaller the bubble grater the pressure of the air inside.
Thermodynamics of surfaces: Surface tension as

surface free energy
The energy spent to increase the area: dA = l dx
Work done on the system is Work = Fdx = l dx = dA
: work required to increase the area of a surface.
(1)
Work is a path dependent process in thermodynamics, how much work

depend on how it is done.
The quantity of work w is define as the work done by the system for that
area change: w= - dA
(2)
Decrease in area (-dA): work done by the system; Increase in area (+dA): work
to be done on the system (- w), i. e. energy is stored in the system.
According to the first law of thermodynamics, the change in energy of a
system:
dE = q - w
(3)
Where w: work done by the
system;
q: heat
absorbed by the system
Interfacial
Scienceand
Engineering
Thermodynamics of surfaces: Surface

tension as surface free energy
w: p-v work and non p-v work
w = wpv + wnon-pv = pdV + wnon-pv
Chemical work is define as non-pv work, define by equation (2)
The second law of thermodynamics
reversible process
qrev = TdS
Substitution of (4) and (5) in equation (3)
dErev = TdS pdV - wnon-pv
Using the definition of Gibbs free energy G:
G = H TS = E + pV TS
Which may be differentiated to give
dG = dE + pdV + vdp TdS SdT
Substituting equation (6) to (8) gives
dGrev = TdS pdV - wnon-pv + pdV + Vdp TdS SdT
For a constant temperature pressure and reversible process
dG = - wnon-pv
(4)
(5)
(6)
(7)
(8)
(9)
(10)
8
Thermodynamics of surfaces: Surface

tension as surface free energy
dG the maximum non-PV work
From equation (2) we can write
dG = dA
Or
G
P, T
A
(11)
(12)
* Surface tension is the increment of Gibbs free energy per unit

increment in area
Surface tension for Curved interfaces:

Young-Laplace equation
Lets consider a small, curved interface
characterized by two principal radii of curvature, R1
and R2 as shown
We now increase the area of the curved surface by
expanding it through a vertical distance dz. The
change in surface area can be expressed as
dA = (x + dx)(y + dy) xy
(1)
= xdy + ydx + (dxdy) = xdy + ydx
The work done for forming this additional surface is
Work = (xdy + ydx) = dA
(2)
10

This increase in free energy is equal to the work done by the pressure difference
to expand the surface, i.e.
dG = dA = (Pc Pv)dV
(3)
where Pc and Pv are the pressures on the concave and convex side, respectively,
and dV xydz is the volume change.
1 dy 1 dx
+
PC Pv =
(xdy+ ydx) = (PC Pv)(xydz) or
(4)
y
dx
x dz
From the geometry of a triangle
Similarly
x + dx R1 + dz dx 1
=
=
x
R1
xdz R1
(5)
dy 1
=
ydz R2
Finally,
1 1
P = PC Pv = +
R1 R2
Which is Young-Laplace equation

11

Young-Laplace equation is applicable locally, i.e. in a macroscopic curved
surface, the principal radii of curvature may vary throughout the entire
surface, which means that the local pressure difference can also be different.
Applying the Young-Laplace equation to a few special interfaces, we see that
Planar:
Cylindrical:
Spherical:
R1, R2 Pc = Pv
R1 Pc Pv = /R
R1 = R2 = R Pc Pv = 2 /R
12
Examples with liquid films

(a)
(b)
Example: (a) A soap film is formed at the ends of two straws, in this case, there
is no pressure difference across the interface. There fore, 1/R1 + 1/R2 = 0 or R1
= - R2. This example also illustrates the fact that curvature can be positive or
negative.
(b) A water film is trapped between two glass slides (b), the air/water interface
can be approximated as a locally cylindrical interface, which means that Patm
Pw = /R, where Pw is the pressure in the water film. Since there is an excess
pressure pressing the two slides together, it is difficult to pull the slides apart.
13
Effect on vapor-liquid equilibria: Kelvin

equation
1.
For liquid
p0 +p
G =
VLdp = VLp =
p0
2VL
Rs
(1)
VL molar volume of the liquid

2. For vapor, since V = RT/p (for ideal gas)
p + p
p
= RT ln
G = RT ln 0
p0
p0
(2)
When liquid and vapor are at equilibrium, these two values of G are
equal
p 2V
2M
RT ln = L =
Rs
p0 Rs
(3)
14
Measurement of surface tension

1. Capillary-rise method
2. Drop-weight method
3. DuNouy-ring method
4. Wilhelmy-plate method
5. Spinning-drop method
15
Capillary-rise method
Consider a semi-submersed capillary tube as
shown in Figure. Using the Young-Laplace
equation, we can write
(1)
1
1
Pg ( h ) Pl ( h ) =
+
R1 R 2
where Pg(h) is the gas pressure at point A, Pl(h) is

the liquid pressure at point A, is the surface
tension, and R1 and R2 are the two principal radii
of curvature of the interface at
point A.
Due to cylindrical symmetry,

R1 = R2 = b at point A, therefore
P g ( h ) Pl ( h ) =
2
b
(2)
16
Now, we also know that, at z = 0,
Pg(0) = Pl(0)
(3)
[Pg(h) Pg(0)] [Pl(h) Pl(0)] = 2/b
(4)
ggh + lgh = 2 /b = gh(g + l)
(5)
where g and l are the gas and liquid densities, respectively.
If the contact angle, , equals to 0, then b = r, the radius of the
capillary tube.
1
= ( l g )ghr
2
(6)
If 0, then, for a narrow tube, we can treat the meniscus as part
of a sphere. The contact angle can then be expressed as
cos = r/b or b = r/cos
(7)
17
Substituting b in equation (5) we get
2 cos
= ( l g )gh
r
( l g )ghr
=
2 cos
or
) ga
(8)
(9)
where a2 = hr/ cos is called the capillary constant.
18
Drop-weight method
Consider the situation where a liquid drop is hanging at the end of a
tube. Assuming that at the point of detachment, the shape of the
drop is as shown in Figure (a), and the surface-tension force is
acting upward.
The force pulling upward is given by
F = 2r
where is the surface tension.
By force balance, F is equal to the
weight of the drop, i.e.
2r = drop weight
If the liquid does not wet the

tube, i.e. > 90, then r = rin, the inside radius of the tube.
If the liquid wets the tube, i.e. < 90, then r = rout (Figure(b)) 19
Drop-weight method
In practice, however, we need a correction factor, f, to account for
the real weight of the drop, i.e.
2rf = Vg
where is the liquid density and V is the drop volume, determined
by V = m/, where m is the measured mass of the drop. Thus, the
surface tension can be obtained as = Vg
2rf
1
2
1V
2V
1
2
20
DuNouy-ring method
For a ring total force
F = Wring + 2(2
r)
Ideal surface tension can be determined as
=
F W ring
4 r
In practice, however, a correction factor is

needed to obtain the true surface tension,
= fideal
The correction factor, f, depends on two
dimensionless parameters: R3/V and R/r, where
V is the volume of liquid pulled up.
21
DuNouy-ring method
As the film is stretched a maximum force is

experienced; this is recorded in the
measurement. At the maximum the force
vector is exactly parallel to the direction of
motion; at this moment the contact angle
=0o.
22
Wilhelmy-plate method
The principle involved in this method is the same as that in
the DuNouy-ring method.
L cos = F Wplate
where L = 2(l + t) is the wetted length, l and t are the length
and thickness of the plate, is the surface tension, is the
contact angle, and Wplate is the weight of the plate.
The surface tension can therefore be
expressed as
F W plate
=
L cos
If the plate is completely wetted by the
liquid, then = 0. Platinum plates are
often used for this purpose, since the
contact angle of most liquids against a
platinum plate is zero.
23
Gibbs adsorption equation

The Gibbs adsorption equation enables the extent of
adsorption at a liquid surface to be estimated from the surface
tension data.
Representation of an interface between bulk phase and
24
Gibbs Dividing Surface

The total volume V is
25
The Gibbs equation: experimental results
Typical variation of surface tension in aqueous solution

Curve 2: Positive slope negative
Inorganic electrolyte or highly hydrated
electrolyte.
Curve 1: un-ionized organic compounds
Curve 3: Surfactants
1 d
c 2 d
2 =
=
RT d ln c 2
RT dc 2
Slope
26
Contact Angle
27
Types of wetting
1. Spreading wetting
2. Adhesional wetting
3. Immersional wetting
28
Critical surface tension for solid surfaces

From spreading wetting:
Cos = -1 +2(Sd/ LG)1/2
Shouls decrease with decreasing LG, and become zero at a
Certain value of LG called critical surface tension c.
Fluorocarbon surfaces have characteristically low critical surface tensions and have well known
application in non stick surfaces
29
Factors affecting the contact angle and

wetting
Three types of wetting are summarised as:
-
Gspreading/A = S = SG - SL - LG
-
Gadhesional/A = Wa = SG - SL + LG
-
Gimmersional/A = SG - SL = LGcos
A reduction of SL facilitates all of these wetting processes but

reducing LG is not always helpful.
30
Advancing and Receding angle

Advancing contact angle:
An advancing contact angle is measured when the sessile drop has the maximum
volume allowable for the liquid-solid interfacial area, any addition will make the drop
expand and increase the liquid-solid interfacial area.
This can be thought of as the "wetting angle" because the drop is ready to wet
additional area.
The receding contact angle:
The receding angle is the opposite: if any liquid is removed from the drop, the liquidsolid interfacial area will decrease. This is the "de-wetting angle.
The advancing angle is the largest possible angle and the receding is the smallest
possible contact angle. Both are presumed to be measured at thermodynamic
equilibrium.
Advancing Angle (a) and the Receding Angle
(r). The tilting angle of a solid surface when the
droplet starts sliding downward is called the
Sliding Angle ().
31
Hysteresis of contact angle

The ends of the droplet show the hysteresis of contact angle variations by
increasing (or decreasing) volume. The angle formed while increasing
volume is called the Advancing Angle, likewise the angle while decreasing
volume is called the Receding Angle.
32
Surfactant adsorption and contact angle on

hydrophilic and hydrophobic surfaces
Young-Dupre equation: Wa = LG (1 + cos )

For hydrophilic surfaces: Due to adsorption of surface active molecules surface
become hydrophobic. Wa is decreased, since some of the glass-water interface is
replaced by hydrocarbon-water interface, hence fron Young-Dupre equation,
increases.
For hydrophobic surface: By addition of surfactants Wa is increased and LG is
decreased , as a result from the Young-Dupre equation, decreases.
33
Contact angle and oil removal

Complete removal
Incomplete removal
Solid surface
Removal of oil from a solid surface

by Roll-up mechanism (
> 90o)
Mechanism:
1. Wetting of solid surface
2. Low oil water interfacial tension
Removal of oil from a solid surface

< 90o)
by Necking mechanism (
Oil
OW
S
Water
SO
Solid surface
cos =
SW
SO
OW
34
Ultra water repellency (UWR)
Why lotus leaf have UWR?
Artificial UWR
35
Self cleaning property, Lotus effect
Water droplets are able to pick-up the dirt particles and remove them from the
surface, Lotus effect.
36
Application of UWR films
37
Superhydrophobic surfaces
Superhydrophobic materials have surfaces that are extremely difficult to wet with
water and therefore are of considerable interest for various industrial applications.
The Lotus Effect is based on this principle. Hydrophile on the other hand refers to a
physical property of a molecule that can transiently bond with water (H2O) through
hydrogen bonding, the exact opposite of hydrophobes
Superhydrophobic materials have surfaces that are extremely difficult to wet with
water and therefore are of considerable interest for various industrial applications.
Potential industrial applications are self cleaning windows and windshields, hard disks
and magnetic tapes
Surfaces with a contact angle between 150 and 180 are called superhydrophobic.
38
Wetting of Rough surfaces

Contact angle can be represent at the solid liquid interface by Wenzels law
cos
* = r cos
* = is resulting contact angle at the rough surface, = contact angle at equivalent

flat surface
r is the ratio of the real surface area divided by the projected flat surface area
and is therefore always larger than 1.
The equation shows roughness drives the contact angle away from 90, either
toward complete wetting if < 90 or to nonwetting if > 90.
R = 5, = 100 ; * = 150 ; R = 5, = 80 ; * = 30
Ref.: Langmuir 20 (2004) 2405

39
Water repellency in textile
Treatment with long chain cationic surfactants

Pressure required to force water through the fabric depends on
Surface tension
Inversely proportional to fiber spacing
40
Emulsion/Microemulsion
Emulsion: An emulsion is a mixture of two immiscible (unblendable) substances. One
substance (the dispersed phase) is dispersed in the other (the continuous phase).
The emulsion is normally called macroemulsion.
Size range: Macroemulsion are usally seze between 0.1 m to 10 m.
Microemulsion: Microemulsion is defined as a thermodynamically stable phase
consists of ternary mixtures of oil-surfactant-water or quaternary mixtures of oilsurfactant-cosurfactant-water.
Size range: Their average particle size may fall in the range of 5-100 nm.
A surfactant mixed with a cosurfactant in a certain proportion is most often
convenient.
Cosurfactants: Lower alkanols like butanol, pentanol and hexanol, and amines like
butylamine, hexylamine.
Role of cosurfactant: their presence in the interface between water and oil imparts
flexibility, in addition to lowering the interfacial tension causing easier surface
bending to energetically favored dispersion.
41
Schematic presentation of reverse

micelle and microemulsion
Water in oil microemulsion
Reverse micelle
Normal micelle
Oil in water microemulsion

42
Difference in Emulsion and microemulsion
Emulsion: ~ 1 m, emulsion is milky; 1-0.1 m, blue white; 0.1-0.5 m, gray and semi
transparent; less than 0.5 m, Transperent.
Normal emulsion: Kinetically stable
Microemulsion: Thermodynamicallt stable
43
Change in free energy

Gm = G1 + G2 + G3-T
S
Gm = Free energy change for microemulsion formation
G1 = Free energy change due to increase in total surface area
G2 = Free energy change due to interaction between droplets
G3 = Free energy change due to adsorption of surfactants at
oil/water interface from bulk oil or water
S = increase in entropy due to dispersion of oil as droplet
44
Different phases
1. Dispersion of oil in water (o/w) in contact with essentially oil Winsor I;
2. Dispersion of water in oil (w/o) in contact with essentially water Winsor II;
3. Both o/w and w/o dispersions are simultaneously present in the same domain
in mixed state in separate contacts with both oil and water Winsor III;
4. A homogeneous single phase of dispersion either o/w or w/o not in contact
with any other phase Winsor IV .
45
Ternary Phase Diagram
A comprehensive ternary phase diagram showing probable interal

structures: (a) o/w microemulsion; (b) w/o microemulsion; (c)
bicontinuous dispersion; (d) isolated and aggregated o/w dispersion; and
(e) isolated and aggregated w/o dispersion.
46
Ternary Phase Diagram
Schematic ternary phase diagram of wateroilsurfactant mixtures representing

L1, a single phase region of normal micelles or oil-in-water (o/w) microemulsion;
L2, reverse micelles or water-inoil (w/o) microemulsions; D, anisotropic lamellar
liquid crystalline phase.
47
Application of Microemulsion
Enhanced oil recovery (EOR): Roughly 20% of the unrecoverable
underground oil can be obtained by the EOR process. The oil remains
trappedin the reservoir because of high interfacial tension (about 2025
mN/m) between the crude oil and reservoir brine. If the interfacial tension
can be reduced to around 103 mN/m, a substantial fraction of the residual
oil in the porous media in which it is trapped can be
mobilized.
Microemulsions in detergency: Microemulsions are promising systems for
detergency purposes over traditionally-used organic solvents, as they can
solubilize polar (e.g., salt, pigment, protein) and non-polar soil components
(e.g., grease, oil).
Microemulsions in cosmetics: In many cosmetic applications such as skin
care products, emulsions are widely used with water as the continuous
phase.
48
Application of Microemulsion
Microemulsions in agrochemicals:
Microemulsions in environmental remediation and detoxification:
Microemulsion in pharmaceuticals:
49
Factors determining stability of

emulsion
Stability: Resistence of emulsions to the coalescence of their dispersed
droplets.
1. Physical Nature of the Interfacial Film: The droplets of dispersed
liquid in an emulsion are in constant motion, and therefore there
are frequent collisions between them. The mechanical strength of
the interfacial film is therefore one of the prime factors
determining macroemulsion stability. For maximum mechanical
stability, the interfacial film resulting from the adsorbed
surfactants should be condensed, with strong lateral
intermolecular forces, and should exhibit high film elasticity.
An example of an oil-soluble surfactant and a water-soluble
surfactant that are commonly used together as the emulsifying
agent for many applications.
2. Existence of an Electrical or Steric Barrier: The presence of a
charge on the dispersed droplets constitutes an electrical barrier
to the close approach of two particles to each other. This is
believed to be a significant factor only in O/W emulsions.
50
Factors determining stability of

emulsion
3. Viscosity of the Continuous Phase: An increase in the viscosity of the
continuous phase reduces the diffusion coefficient D of the droplets,
since, for spherical droplets,
k = Boltzmann constant, a = radius of the droplet
kT
D=
6a
As the diffusion constant is reduced, the frequency of collision of the

droplets and their rate of coalescence are reduced. The viscosity of
the external phase is increased as the number of suspended particles
increases, and this is one of the reasons that many emulsions are
more stable in concentrated form than when diluted. The viscosity of
the external phase in emulsions is often increased by the addition of
special ingredients for this purpose.
4. Temperature: Rate of coalesence of the particles, and thus the
stability of the emulsion can be expressed as
dV 4VkT E / KT
=
e
dT
3
51
Effect of contact angle on emulsion type
WE = OE + OWcos
; WE > OE;
<90, cos < 1
W/O emulsion formed
OE = WE + OWcos
; OE > WE
<90, cos < 1
O/W emulsion formed
If, at the contact between oil, water, and emulsifier, the oil contact
angle (the contact angle, measured in the oil phase) is less than 90,
then the oil surface is concave toward the water, producing a W/O
water
emulsion.
On the other hand, if at the same oilwateremulsifier contact, the
water contact angle is less than 90, then the water surfact is concave
toward the oil, producing an O/W emulsion.
52
Effect of contact angle on emulsion type

However, that if the oil contact angle is < 90, then WE > OE (i.e., the
emulsifier is more hydrophobic than hydrophilic).
If the water contact angle is < 90, then OE > WE, and the emulsifying agent
is more hydrophilic than hydrophobic.
Thus, whereas those with mainly hydrophobic character produce W/O
emulsions, emulsifying agents with mainly hydrophilic character produce
O/W emulsions.
53

Colloid and Interfacial Engineering Slides Part 02

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Electrical Double Layer

Distance from the charged surface, x

Electrical double layer:

Fixed charge: The surface charges are

Distance from the charged surface, x

Interfacial Science and Engineering

Charge reversal due to adsorption of

Interfacial Science and Engineering

Work of Adhesion and Cohesion

AB = Interfacial tension or Interfacial free energy

Interfacial Science and Engineering

Surface Wetting vs. Adhesive and

Interfacial Science and Engineering

Surface tension and Contact angle

Surface tension: Property of the interface between two phases

Interfacial Science and Engineering

Interfacial Science and Engineering

Thermodynamics of surfaces: Surface tension as

Work is a path dependent process in thermodynamics, how much work

Thermodynamics of surfaces: Surface

Thermodynamics of surfaces: Surface

* Surface tension is the increment of Gibbs free energy per unit

Interfacial Science and Engineering

Surface tension for Curved interfaces:

Interfacial Science and Engineering

Surface tension for Curved interfaces:

From the geometry of a triangle

Which is Young-Laplace equation

Surface tension for Curved interfaces:

Interfacial Science and Engineering

Examples with liquid films

Effect on vapor-liquid equilibria: Kelvin

VL molar volume of the liquid

Measurement of surface tension

Interfacial Science and Engineering

where Pg(h) is the gas pressure at point A, Pl(h) is

Due to cylindrical symmetry,

Interfacial Science and Engineering

where a2 = hr/ cos is called the capillary constant.

Interfacial Science and Engineering

If the liquid does not wet the

Interfacial Science and Engineering

In practice, however, a correction factor is

Interfacial Science and Engineering

As the film is stretched a maximum force is

Interfacial Science and Engineering

Interfacial Science and Engineering

Gibbs adsorption equation

Representation of an interface between bulk phase and

Interfacial Science and Engineering

Gibbs Dividing Surface

Interfacial Science and Engineering

The Gibbs equation: experimental results

Typical variation of surface tension in aqueous solution

Interfacial Science and Engineering

Interfacial Science and Engineering

Interfacial Science and Engineering

Critical surface tension for solid surfaces

Factors affecting the contact angle and

A reduction of SL facilitates all of these wetting processes but

Interfacial Science and Engineering

Advancing and Receding angle

Hysteresis of contact angle

Interfacial Science and Engineering