SURFACE PHENOMENA

AND SURFACTANT

DR ENY KUSRINI, [Link].

Department of Chemical Engineering
Faculty of Engineering
Universitas Indonesia

1
 Interfaces
ü When phases exist together, the boundary
between two of them is known as an interface.

ü The properties of the molecules forming the

interface are often sufficiently different from
those in the bulk of each phase.

ü The term surface is used when referring to either

a gas–solid or a gas–liquid interface.
Types of interface
 Liquid Interfaces
Surface and Interfacial Tensions
• molecules in the bulk liquid are surrounded in all directions by
other molecules for which they have an equal attraction.

• molecules at the surface (i.e., at the liquid–air interface) can

only develop attractive cohesive forces with other liquid
molecules that are situated below and adjacent to them. They
can develop adhesive forces of attraction with the molecules
constituting the other phase involved in the interface,
although, in the case of the liquid–gas interface, this adhesive
force of attraction is small.
• The net effect is that the molecules at the
surface of the liquid experience an inward force
toward the bulk.

• Such a force pulls the molecules of the interface

together and, as a result, contracts the surface,
resulting in a surface tension.
• This “tension” in the surface is the force per unit length
that must be applied parallel to the surface so as to
counterbalance the net inward pull.
• Interfacial tension is the force per unit length existing
at the interface between two immiscible liquid phases.
• It is like surface tension has the units of dyne/cm or
N/m.
• The work required to increase the surface area by
unit area is termed the surface free energy.
• The units of surface and interfacial tensions have are
similar (dynes/cm or N/m).
• The surface tensions of most liquids decrease
almost linearly with an increase in temperature,
that is, with an increase in the kinetic energy of
the molecules.

• In the region of its critical temperature, the

surface tension of a liquid becomes zero.

• The surface tension of water at 0°C is 75.6, at

20°C it is 72.8, and at 75°C it is 63.5 dynes/cm.
 Surface Free Energy and Surface Tension

• The surface layer of a liquid possesses

additional energy as compared to the bulk liquid.

• This energy increases when the surface of the

same mass of liquid increases and is therefore
called surface free energy.
The work W required to create a unit area of surface is
known as SURFACE FREE ENERGY/UNIT AREA (ergs/cm2)
erg = dyne . cm
Its equivalent to the surface tension γ W=γ∆A
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.
 Measurement of Surface and Interfacial Tensions

1. Capillary Rise Method

2. The DuNoüy Ring Method

3. Drop weight method (Stalagmometer), bubble pressure,

pendent drop, sessile drop, Wilhelmy plate, and oscillating drop

The choice of the method for measuring surface

and interfacial tension depend on:

1. Whether surface or interfacial tension is to be determined.

2. The accuracy desired

3. The size of sample.

 Capillary Rise Method

• When a capillary tube is placed in a liquid

contained in a beaker, the liquid generally rises
up the tube a certain distance.

• By measuring this rise in a capillary, it is possible

to determine the surface tension of the liquid. It
is not possible, however, to obtain interfacial
tensions using the capillary rise method.
• Because of the surface
tension, the liquid continues to
rise in the tube, but because of
the weight of the liquid, the
upward movement is just
balanced by the downward
force of gravity.
Example:

• A sample of chloroform rose to a height of 3.67

cm at 20°C in a capillary tube having an inside
radius of 0.01 cm. What is the surface tension of
chloroform at this temperature? The density of
chloroform is 1.476 g/cm3.
 The DuNoüy Ring Method
• The DuNoüy tensiometer is widely used
for measuring surface and interfacial
tensions.

• the force necessary to detach a platinum–

iridium ring immersed at the surface or
interface is proportional to the surface or
interfacial tension.

• The force required to detach the ring in

this manner is provided by a torsion wire
and is recorded in dynes on a calibrated
dial.
• A correction factor is necessary because the
simple theory does not take into account certain
variables such as the radius of the ring, the
radius of the wire used to form the ring, and the
volume of liquid raised out of the surface.

• Errors as large as 25% may occur if the

correction factor is not calculated and applied.
 Spreading Coefficient
• When a substance such as oleic acid is placed on the surface of
water, it will spread as a film if the force of adhesion between the
oleic acid molecules and the water molecules is greater than the
cohesive forces between the oleic acid molecules themselves.

• The term film used here applies to a duplex film as opposed to a

monomolecular film. Duplex films are sufficiently thick (100 Å or
more) so that the surface (boundary between oleic acid and air) and
interface (boundary between water and oleic acid) are independent
of one another.
• The work of adhesion, is the energy required to
break the attraction between the unlike
molecules.

• The work of cohesion, required to separate the

molecules of the spreading liquid so that it can
flow over the sublayer,
• The term (Wa - Wc) is known as the spreading
coefficient, S;

• if it is positive, the oil will spread over a water

surface.

• S= γS – (γL + γLS)
• γS is the surface tension of the sublayer liquid,
• γL is the surface tension of the spreading liquid,
• γLS is the interfacial tension between the two
liquids.
• Spreading occurs (S is positive)
when the surface tension of the
sublayer liquid is greater than the
sum of the surface tension of the
spreading liquid and the interfacial
tension between the sublayer and
the spreading liquid.

• If (γL + γLS) is larger than γS, the

substance forms globules or a
floating lens and fails to spread
over the surface. An example of
such a case is mineral oil on
water.
Example:

• If the surface tension of water γS is 72.8

dynes/cm at 20°C, the surface tension of
benzene, γL, is 28.9 dynes/cm, and the
interfacial tension between benzene and
water, γLS, is 35.0 dynes/cm, what is the initial
spreading coefficient?

• Following equilibration, γS′ is 62.2 dynes/cm

and γL′ is 28.8 dynes/cm. What is the final
spreading coefficient?
 The applications of spreading coefficients

1. The surface of the skin is bathed in an

aqueous–oily layer having a polar–nonpolar
character similar to that of a mixture of fatty
acids.

2. For a lotion with a mineral oil base to spread

freely and evenly on the skin, its polarity and
hence its spreading coefficient should be
increased by the addition of a surfactant.
 Adsorption at Liquid Interfaces
1. Certain molecules and ions, when dispersed in
the liquid, move of their own accord to the
interface.

2. the surface free energy and the surface tension

of the system are automatically reduced.

3. Molecules and ions that are adsorbed at

interfaces are termed surface-active
agents or surfactants. An alternative term
is amphiphile,
 SURFACE ACTIVE AGENTS

A surfactant molecule is depicted schematically as a

cylinder representing the hydrocarbon (hydrophobic)
portion with a sphere representing the polar
(hydrophilic) group attached at one end.
The hydrocarbon chains are straight because rotation around
carbon-carbon bonds bends, coils and twists them.

Sodium
Lauryl
Sulfate
molecule
 Surface-Active Agents

ü It is the amphiphilic nature of surface-active agents that

causes them to be absorbed at interfaces
ü Thus, in an aqueous dispersion of amphiphile, the polar
group is able to associate with the water molecules. The
nonpolar portion is rejected
ü As a result, the amphiphile is adsorbed at the interface.
ü The situation for a fatty acid at the air–water and oil–water
interface:
ü At the oil–water interface, the lipophilic chains are directed
upward into the air;
ü at the air–oil interface, they are associated with the oil
phase.
• For the amphiphile to be concentrated at the interface, it must be balanced
with the proper amount of water- and oil-soluble groups.

• If the molecule is too hydrophilic, it remains within the body of the aqueous
phase and exerts no effect at the interface.

• if it is too lipophilic, it dissolves completely in the oil phase and little appears at
the interface
 Systems of Hydrophile–Lipophile
Classification

• The higher the HLB of an agent, the more

hydrophilic it is.

• The Spans, sorbitan esters , are lipophilic and

have low HLB values (1.8–8.6);

• The Tweens, polyoxyethylene derivatives of the

Spans, are hydrophilic and have high HLB
values (9.6–16.7).
Micelles and the Critical Micelle Concentration

• When present in a liquid medium at low

concentrations, the amphiphiles exist separately.

• As the concentration is increased, aggregation

occurs. These aggregates, which may contain
50 or more monomers, are called micelles

• The concentration of monomer at which micelles

form is termed the critical micelle
concentration(CMC).
• (a) spherical micelle
in aqueous media,

• (b) reversed micelle in

nonaqueous media,

• (c) laminar micelle,

formed at higher
amphiphile
concentration, in
aqueous media.
• The surface tension decreases up to the CMC .
• When the surface tension, γ, of a surfactant is
plotted against the logarithm of the surfactant
activity or concentration, log c2, the plot takes on
the shape shown in Figure.

• The initial curved segment A–B is followed by a

linear segment, B–C, along which there is a
sharp decrease in surface tension as
log c2 increases.
• The point C corresponds to the critical micelle
concentration (CMC), the concentration at which
micelles form in the solution.
• Beyond the CMC, the line becomes horizontal
because further additions of surfactant are no
longer being accompanied by a decrease in
surface tension.
• is the ability of the micelles to increase the
solubility of materials that are normally insoluble,
or only slightly soluble, in the dispersion medium
used.
• This phenomenon, known as solubilization,
Adsorption at Solid Interfaces
• solid–gas adsorption:
• the removal of objectionable odors from rooms
and food,
• the operation of gas masks,
• the measurement of the dimensions of particles
in a powder.

• solid–liquid adsorption:
• decolorizing solutions,
• adsorption chromatography,
• detergency, wetting.
 The Solid–Gas Interface

• the adsorbent : the material used to adsorb the

gas)
• the adsorbate: the substance being adsorbed

Types of adsorption:
1. Physical adsorption
• Associated with van der Waals forces
• Reversible
• The removal of the adsorbate from the adsorbent
being known as desorption. A physically adsorbed
gas can be desorbed from a solid by increasing the
temperature and reducing the pressure.
2. Chemical adsorption or chemisorption
• the adsorbate is attached to the adsorbent by
primary chemical bonds,
• irreversible unless the bonds are broken.
The degree of adsorption of a gas by a solid depends
on:
ü the chemical nature of the adsorbent and
the adsorbate
ü the surface area of the adsorbent
ü the temperature
ü the partial pressure of the adsorbed gas.
• The relationship between the amount of gas
physically adsorbed on a solid and the equilibrium
pressure or concentration at constant temperature
yields an adsorption isotherm when plotted.
• The number of moles, grams, or milliliters, x, of gas
adsorbed on, m, grams of adsorbent at standard
temperature and pressure is plotted on the vertical
axis against the equilibrium pressure of the gas in
mm Hg on the horizontal axis.
 Freundlich isotherm

• x is the mass of gas adsorbed

• m is the mass of adsorbent,
• y is x/m
• k and n are constants that can be evaluated
from the results of the experiment.
• the logarithmic form,

• which yields a straight line when plotted.

• The constant, log k, is the intercept on the
ordinate,
• 1/n is the slope of the line.
 Langmuir isotherm

• based on the theory that the molecules or atoms

of gas are adsorbed on active sites of the solid
to form a layer one molecule thick (monolayer)
• A plot of p/y against p should yield a straight line,
and Ym and b can be obtained from the slope
and intercept.

• Ym is the quantity of vapor adsorbed per unit

mass of adsorbent when the surface is covered
with a monomolecular layer.
 BET equation

• derived by Brunauer, Emmett, and Teller.

 The Solid–Liquid Interface

• Drugs such as dyes, alkaloids, fatty acids, and

even inorganic acids and bases can be
absorbed from solution onto solids such as
charcoal and alumina.

• Isotherms that fit one or more of the equations

mentioned previously can be obtained by
substituting solute concentration for the vapor
pressure term used for solid–gas systems.
• Langmuir equation:

• c is the equilibrium concentration in milligrams of

alkaloidal base per 100 mL of solution,
• y is the amount of alkaloidal base, x, in
milligrams adsorbed per gram, m, of clay
(i.e., y = x/m)
Adsorption of strychnine on various clays
• Data for adsorption of timolol from aqueous
solution onto kaolin.
• Adsorption isotherm
• Calculate

x/m (mg/g) C (mg/100 mL)

3.1 20
2.8 17
1.8 9
0.84 3
 Wetting

• Adsorption at solid surfaces is involved in the

phenomena of wetting and detergency.
• When a liquid comes into contact with the solid,
the forces of attraction between the liquid and
the solid phases begin to play a significant role.
• In this case, the behavior of the liquid will
depend on the balance between the forces of
attraction of molecules in the liquid and the
forces of attraction between the liquid and the
solid phases.
• In the case of mercury and glass, attractive
forces between molecules of mercury and glass
are much smaller than the forces of attraction
between molecules of mercury themselves.
• As a result, mercury will come together as a
single spherical drop.
• In contrast, for water and glass (or mercury and
zinc), attractive forces between the solid and
liquid molecules are greater than the forces
between molecules of liquid themselves, and so
the liquid is able to wet the surface of the glass.
• The contact angle is the angle between a liquid
droplet and the surface over which it spreads.

• the contact angle between a liquid and a solid

may be 0° signifying complete wetting, or may
approach 180°, at which wetting is insignificant.
• The most important action of a wetting agent is
to lower the contact angle between the surface
and the wetting liquid.

• A wetting agent is a surfactant that, when

dissolved in water, lowers the advancing contact
angle, aids in displacing an air phase at the
surface, and replaces it with a liquid phase.
 Application of wetting

• the displacement of air from the surface of sulfur, charcoal,

and other powders for the purpose of dispersing these
drugs in liquid vehicles;
• the displacement of air from the matrix of cotton pads and
bandages so that medicinal solutions can be absorbed for
application to various body areas;
• the displacement of dirt and debris by the use of detergents
in the washing of wounds;
• the application of medicinal lotions and sprays to the
surface of the skin and mucous membranes.
• Wettability of tablet surfaces influences disintegration and
dissolution and the subsequent release of the active
ingredient(s) from the tablet.
• The influence of tablet binders on wettability of
acetaminophen tablets
 Electric Properties of Interfaces
• Particles dispersed in liquid media may become charged mainly in one
of two ways:
1. the selective adsorption of a particular ionic species present in solution.
• This may be an ion added to the solution or, in the case of pure water, it
may be the hydronium or hydroxyl ion.
• The majority of particles dispersed in water acquire a negative charge
due to preferential adsorption of the hydroxyl ion.

2. charges on particles arise from ionization of groups (such as COOH) that

may be situated at the surface of the particle. In these cases, the
charge is a function of pK and pH.
• A third, less common origin for the charge on a particle surface is
thought to arise when there is a difference in dielectric constant
between the particle and its dispersion medium.
 The Electric Double Layer

• Consider a solid surface in contact with a polar

solution containing ions, for example, an aqueous
solution of an electrolyte.
• suppose that some of the cations are adsorbed onto
the surface, giving it a positive charge.
• Remaining in solution are the rest of the cations plus
the total number of anions added.
• These anions are attracted to the positively charged
surface by electric forces that also serve to repel the
approach of any further cations once the initial
adsorption is complete.
• In addition to these electric forces, thermal motion
tends to produce an equal distribution of all the ions in
solution.
• As a result, an equilibrium situation is set up in
which some of the excess anions approach the
surface, whereas the remainder are distributed
in decreasing amounts as one proceeds away
from the charged surface.

• At a particular distance from the surface, the

concentrations of anions and cations are equal,
that is, conditions of electric neutrality prevail.
• the system as a whole is electrically neutral,
even though there are regions of unequal
distribution of anions and cations.
• aa′ is the surface of the solid.
• The adsorbed ions that give the surface its positive charge
are referred to as the potential-determining ions.
• Immediately adjacent to this surface layer is a region of
tightly bound solvent molecules, together with some
negative ions, also tightly bound to the surface.
• The limit of this region is given by the line bb′ .
• These ions, having a charge opposite to that of the
potential-determining ions, are known
as counterions or gegenions.
• In the region bounded by the lines bb′ and cc′, there is
an excess of negative ions.
• The potential at bb′ is still positive because, as
previously mentioned, there are fewer anions in the
tightly bound layer than cations adsorbed onto the
surface of the solid.
• Beyond cc′, the distribution of ions is uniform and
electric neutrality is obtained.

Thus, the electric distribution at the interface is

equivalent to a double layer of charge:
1. the first layer (extending from aa′ to bb′) tightly
bound
2. a second layer (from bb′ to cc′) that is more diffuse.

The so-called diffuse double layer therefore extends

from aa′ to cc′.
 Nernst and Zeta Potentials

• The changes in potential with distance from the surface for

the various situations:

• The potential at the solid surface aa′ due to the potential-

determining ion is the
electrothermodynamic (Nernst) potential, E is defined as
the difference in potential between the actual surface and
the electroneutral region of the solution.
• The potential located at the shear plane bb′ is known as
the electrokinetic, or zeta, potential, ζ.

• The zeta potential is defined as the difference in potential

between the surface of the tightly bound layer (shear
plane) and the electroneutral region of the solution.
• the potential initially drops off rapidly, followed by a
more gradual decrease as the distance from the surface
increases.
• This is because the counterions close to the surface act
as a screen that reduces the electrostatic attraction
between the charged surface and those counterions
further away from the surface.
• The zeta potential has practical application in
the stability of systems containing dispersed
particles because this potential governs the
degree of repulsion between adjacent, similarly
charged, dispersed particles.

• If the zeta potential is reduced below a certain

value (which depends on the particular system
being used), the attractive forces exceed the
repulsive forces, and the particles come
together. This phenomenon is known
as flocculation
 Effect of Electrolytes

• As the concentration of electrolyte present in the system is

increased, the screening effect of the counterions is also
increased.
• As a result, the potential falls off more rapidly with distance
because the thickness of the double layer shrinks.
• A similar situation occurs when the valency of the
counterion is increased while the total concentration of
electrolyte is held constant.
• The overall effect frequently causes a reduction in zeta
potential.