Republic of the Philippines

BATANGAS STATE UNIVERSITY

Gov. Pablo Borbon Campus II, Alangilan Batangas City, Philippines 4200
College of Engineering, Architecture & Fine Arts
www.batstate-u.edu.ph Tel. No. (043) 425-0139 loc. 118

Chemical and Food Engineering Department

ChE 416: Physical Chemistry for Engineers 2

SURFACE CHEMISTRY
AND
COLLOIDS

ChE-4101

Engr. Angelica De Sagun

Intructor

NOVEMBER, 2016

Surface/ Interface: A boundary that separates two phases. Each surface possesses special properties that
differ from those of the phases themselves.
What is adsorption?
Adsorption is a surface phenomenon of accumulation of large number of molecular species at the
surface of liquid or solid phase in comparison to the bulk. In simpler terms, it refers to the attachment or
adhesion of particles (atoms, ions, or molecules) from a gas, liquid, or dissolved solid to a surface. It is a
process by which the molecules of a substance pass through the surface to become uniformly distributed
throughout the body of a solid or liquid absorbing medium. This process essentially happens at the surface of
the substance.

Desorption refers to the removal of the adsorbed substance from a surface. It is the reverse process of
adsorption. Sorption is the phenomenon in which adsorption and absorption occurs simultaneously.

Components of Adsorption
Adsorbate is the substance which is being adsorbed on the surface. Adsorbate gets
adsorbed.Adsorbent is the underlying material or substance on the surface of which adsorption takes place
(to which the adsorbate is attached). It can be a surface of a solid or liquid.
Adsorbate + Adsorbent = Adsorption

Causes of Adsorption
The process of adsorption takes place due to the unbalanced or residual forces of attraction or free
valencies present at the solid or liquid surface. These residual forces have the property to attract and retain the
molecules of a gas or a dissolved substance on to their surfaces with which they come in contact.
Examples of Adsorption
1. Acetic acid in solution and various gases are adsorbed by charcoal
2. Ammonia gas placed in contact with charcoal gets adsorbed on the charcoal.

Characteristics of Adsorption
1. Adsorption refers to the existence of a higher concentration of any particular component at the
surface of a liquid or a solid phase.
2. Adsorption is accompanied by decrease in the G (free energy change) of the system when G = 0.
The process is said to be spontaneous. On the basis of Gibbs Helmholtz equation, G = H - TS,
G can be negative if H has sufficiently high negative value and TS has positive value.
3. Adsorption is an exothermic process therefore H of adsorption is always negative.
4. When a gas is adsorbed, the freedom of movement of its molecules becomes restricted. On account
of it, the entropy of the gas decreases after adsorption, S is negative.

TWO MAIN TYPES OF ADSORPTION

PHYSICAL or VAN DER WAALS ADSORPTION: if the forces of attraction existing between adsorbate
and adsorbent are Van der Waals forces. This type is also known as physisorption. It can easily be
reversed by heating or decreasing the pressure.
The forces are of a physical nature and the adsorption is relatively weak. The forces correspond to
those considered by J. H. van der Waals in connection with his equation of state for gases and are
known as van der Waals forces. This type of adsorption is known as physical adsorption,
physisorption, or van der Waals adsorption. The heat evolved when a mole of gas becomes
physically adsorbed is usually small, of the order of 10,000 cal per mole of adsorbate. This type of
adsorption plays only an unimportant role in catalysis, except for certain special types of reactions
involving free atoms or radicals.
- characterized by low heat of absorption, of the order of 10000 cal or less per mole of adsorbate
- adsorption equilibrium is equilibrium and established rapidly
- observed in the adsorption of various gases in charcoal
 - forces responsible are of the same kind as are involved in deviations of gases from ideal and in
liquefaction
- may be found in all instances, although can be masked by stronger chemical type
- Weak interactions, characteristic of weak van der Waals forces, lead to physisorption
- adsorbed molecules remain unbroken
ex. Van der Waals principle

CHEMICAL OR ACTIVATED ADSORPTION: if the forces of attraction existing between adsorbate

particles and adsorbent are almost of the same strength as chemical bonds. This type of adsorption is
also called as chemisorption or Langmuir adsorption. This type cannot be easily reversed.
- accompanied by much higher heat changes (20,000-100,000cal)
- leads to a much firmer attachment of the gas to the surface
- more specific in nature
- found where there is a tendency toward compound formation between a gas and adsorbent

- strong interactions, characteristic of covalent bonding, lead to chemisorption

- adsorbed molecules may or may not be broken up

Comparison between Physical Adsorption and Chemical Adsorption

Physical Adsorption
Takes place at low temperature and decreases
with increasing temperature.
It is related to the case of the liquefaction of
the gas.
It forms multimolecular layers.
It does not require any activation energy.
High pressure is favorable. Decrease of
pressure causes desorption.
It is not very specific.
Chemical Adsorption
It takes place at high temperature.
It is not related.
It forms monomolecular layers.
It requires high activation energy.
High pressure is favorable. Decrease of
pressure does not cause desorption.
It is highly specific.

FACTORS WHICH AFFECT THE EXTENT OF ADSORPTION

1. Nature of the adsorbate and adsorbent.
a. In general, easily liquefiable gases, e.g. CO2, NH3, Cl2 and SO@2,etc, are adsorbed to a greater
extent than the elemental gases , e.g. H2, O2. N2, H2, etc (while chemisorption is specific in
nature).
b. Porous and finely powdered solid adsorb more as compared to the hard non-porous materials.
2. Surface area of the solid adsorbent.
a. The extent of adsorption depends directly upon the surface area of the adsorbent.
Ex: The larger the surface area of the adsorbent, greater is the extent of adsorption.
b. Surface area of a powdered solid adsorbent depends upon its particle size. The smaller the particle
size, greater is its surface area.
3. Effect of temperature
a. As adsorption is accompanied by evolution of heat, so according to the Le Chateliers
principle, the magnitude of adsorption should decrease with rise in temperature.
A physical adsorption isobar shows a decrease in x/m ( where m is the mass of the
adsorbent and x that of adsorbate) as the temperature rises.
What is Adsorption Isotherm?
The process of Adsorption is usually studied through graphs known as adsorption isotherm. It is the graph
between the amounts of adsorbate (x) adsorbed on the surface of adsorbent (m) and pressure at constant
temperature. Different adsorption isotherms have been Freundlich, Langmuir and BET theory.
Basic Adsorption Isotherm
In the process of adsorption, adsorbate gets adsorbed on adsorbent.

According to Le-Chatelier principle, the direction of equilibrium would shift in that direction where the stress can
be relieved. In case of application of excess of pressure to the equilibrium system, the equilibrium will shift in
the direction where the number of molecules decreases. Since number of molecules decreases in forward
direction, with the increases in pressure, forward direction of equilibrium will be favored.

Basic Adsorption Isotherm

From the graph, we can predict that after saturation pressure Ps, adsorption does not occur anymore. This can
be explained by the fact that there are limited numbers of vacancies on the surface of the adsorbent. At high
pressure a stage is reached when all the sites are occupied and further increase in pressure does not cause
any difference in adsorption process. At high pressure, Adsorption is independent of pressure.
Freundlich Adsorption Isotherm
In 1909, Freundlich gave an empirical expression representing the isothermal variation of adsorption of a
quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This equation is known as Freundlich
Adsorption Isotherm or Freundlich Adsorption equation or simply Freundlich Isotherm.

Where x is the mass of the gas adsorbed on mass m of the adsorbent at pressure p and k, n are constants
whose values depend upon adsorbent and gas at particular temperature. Though Freundlich Isotherm correctly
established the relationship of adsorption with pressure at lower values, it failed to predict value of adsorption
at higher pressure.
Langmuir Adsorption Isotherm
In 1916 Langmuir proposed another Adsorption Isotherm known as Langmuir Adsorption isotherm. This
isotherm was based on different assumptions one of which is that dynamic equilibrium exists between
adsorbed gaseous molecules and the free gaseous molecules.

Where A(g) is unadsorbed gaseous molecule, B(s) is unoccupied metal surface and AB is Adsorbed gaseous
molecule.
Based on his theory, he derived Langmuir Equation which depicted a relationship between the number of
active sites of the surface undergoing adsorption and pressure.

Where the number of sites of the surface which are covered with gaseous molecule, P represents pressure
and K is the equilibrium constant for distribution of adsorbate between the surface and the gas phase. The
basic limitation of Langmuir adsorption equation is that it is valid at low pressure only.
 At lower pressure, KP is so small, that factor (1+KP) in denominator can almost be ignored. So, Langmuir
equation reduces to
= KP
At high pressure KP is so large, that factor (1+KP) in denominator is nearly equal to KP. So, Langmuir equation
reduces to

BET adsorption Isotherm

BET Theory put forward by Brunauer, Emmett and Teller explained that multilayer formation is the true picture
of physical Adsorption.
One of the basic assumptions of Langmuir Adsorption Isotherm was that adsorption is monolayer in nature.
Langmuir adsorption equation is applicable under the conditions of low pressure. Under these conditions,
gaseous molecules would possess high thermal energy and high escape velocity. As a result of this less
number of gaseous molecules would be available near the surface of adsorbent.
Under the condition of high pressure and low temperature, thermal energy of gaseous molecules decreases
and more and more gaseous molecules would be available per unit surface area. Due to this multilayer
adsorption, would occur. The multilayer formation was explained by BET Theory. The BET equation is given as

Another form of BET equation is

Where Vmono be the adsorbed volume of gas at high pressure conditions so as to cover the surface with a
unilayer of gaseous molecules,

the ratio is designated C. K1 is the equilibrium constant when single molecule adsorbed per vacant site and KL
is the equilibrium constant to the saturated vapor liquid equilibrium.
Type of Adsorption Isotherm
Five different types of adsorption isotherm and their characteristics are explained below.
Type I Adsorption Isotherm

Type I Adsorption Isotherm

The above graph depicts Monolayer adsorption.
This graph can be easily explained using Langmuir Adsorption Isotherm.
If BET equation, when P/P0<<1 and c>>1, then it leads to monolayer formation and Type I Adsorption
Isotherm is obtained.
Examples of Type-I adsorption are Adsorption of Nitrogen (N2) or Hydrogen (H) on charcoal at
temperature near to -1800C.

Type II Adsorption Isotherm

 Type II Adsorption Isotherm
Type II Adsorption Isotherm shows large deviation from Langmuir model of adsorption.
The intermediate flat region in the isotherm corresponds to monolayer formation.
In BET equation, value of C has to be very large in comparison to 1.

Examples of Type-II adsorption are Nitrogen (N2 (g)) adsorbed at -1950C on Iron (Fe) catalyst and
Nitrogen (N2 (g)) adsorbed at -1950C on silica gel.

Type III Adsorption Isotherm

Type III Adsorption Isotherm

Type III Adsorption Isotherm also shows large deviation from Langmuir model.
In BET equation value if C <<< 1 Type III Adsorption Isotherm obtained.
This isotherm explains the formation of multilayer.
There is no flattish portion in the curve which indicates that monolayer formation is missing.
Examples of Type III Adsorption Isotherm are Bromine (Br2) at 790C on silica gel or Iodine (I2) at 790C
on silica gel.

Type IV Adsorption Isotherm

Type IV Adsorption Isotherm

At lower pressure region of graph is quite similar to Type II. This explains formation of monolayer
followed by multilayer.
 The saturation level reaches at a pressure below the saturation vapor pressure. This can be explained
on the basis of a possibility of gases getting condensed in the tiny capillary pores of adsorbent at pressure
below the saturation pressure (PS) of the gas.
Examples of Type IV Adsorption Isotherm are of adsorption of Benzene on Iron Oxide (Fe2O3) at 500C
and adsorption of Benzene on silica gel at 500C.

Type V Adsorption Isotherm

Type V Adsorption Isotherm

Explanation of Type V graph is similar to Type IV.
Example of Type V Adsorption Isotherm is adsorption of Water (vapors) at 1000C on charcoal.
Type IV and V shows phenomenon of capillary condensation of gas.

Chemical Reactions on Surfaces

Molecularity - number of reactant molecules that come together during the course of reaction.
Unimolecular Reaction - reactions involving a single reacting substance.
Bimolecular Reaction - reactions involving two reacting substances.

UNIMOLECULAR REACTIONS

Surface reactions involving one molecule may be treated in terms of the Langmuir Adsorption
Isotherm. In the simplest case the rate of reaction is proportional to is thus

(Eq. 1)

This equation is of the same form as the Michaelis-Menten equation but we should note that it has
been derived on the assumption of a rapid adsorption equilibrium followed by slow chemical reaction.

At sufficiently high concentrations the rate is independent of the concentration, which means that the
kinetics are zero order. At low concentrations, when K[A] = 1, the kinetics are first order. A good example of
this type of behavior is the decomposition of ammonia into nitrogen and hydrogen on a tungsten surface.

Sometimes a substance other than the reactant is adsorbed on the surface, with the result that the
effective surface area, and therefore the rate, are reduced. Suppose that a substance A is undergoing a
unimolecular reaction on a surface and that a nonreacting substance I, known as an inhibitor or a poison, is
also adsorbed. If the fraction of the surface covered by A is and that covered by I is i ,

(Eq. 2)

where K and Ki are the adsorption constants for A and I. The rate of reaction, equal to k is thus
 (Eq. 3)

In the absence of inhibitor this equation reduces to Eq. 1.

A case of special interest is when the surface is only sparsely covered by the reactant but is fairly fully covered
by the inhibitor. In other words,

Ki[I]>>1+K[A]
and the rate is then

(Eq. 4)

A good example of Eq. 4 is provided by the decomposition of ammonia on platinum, the rate law for
which is

Since hydrogen is a product of reaction, there is progressive inhibition as reaction proceeds. There is no
appreciable inhibition by the other reaction product, nitrogen.

BIMOLECULAR REACTIONS

When a solid surface catalyzes a bimolecular process, there are two possible mechanisms. One of these,
first suggested by Langmuir and further developed by Hinshelwood, involves reaction between two
molecules adsorbed on the surface. Such a mechanism may be formulated as follows.

In the first step the two molecules A and B

become adsorbed on neighboring sites on the surface. Reaction then takes place, by way of an activated
complex, to give the reaction products.

When this Langmuir-Hinshelwood mechanism applies, the rate is proportional to the probability that A and B
are adsorbed on neighboring sites, and this is proportional to the product of fractions of the surface, A and B,
covered by A and B. These fractions were given in

and the rate of reaction is therefore

v = k A B = (Eq. 5)

An alternative mechanism for a bimolecular surface process is for the reaction to occur between a
molecule that is not adsorbed (e.g., A) and an adsorbed molecule (B). Such a mechanism was also considered
by Langmuir and was further developed by the British physical chemist Sir Eric K. Rideal (18901974). This
mechanism may be represented as

The adsorption of A may occur; it is simply postulated, in this

mechanism, that an adsorbed A does not react.

Not many ordinary chemical reactions occur by a Langmuir-Rideal mechanism. There is evidence,
however, that radical combinations on surfaces sometimes occur in this way. The combination of hydrogen
atoms, for example, is sometimes a first-order reaction, and it appears to
occur by the mechanism

In 1912, and later, Langmuir made important investigations on the production of hydrogen atoms at hot
tungsten surfaces, such as used in tungsten-filament incandescent lamps. The rate is proportional to the
square root of the hydrogen pressure, and the mechanism is believed to be the reverse of that just given,
namely

Surface Heterogeneity in treatment of adsorption and of chemical

reactions on surfaces is assumed that all the surface sites are of the
same character. The Langmuir adsorption isotherm, is based on
this assumption of surface homogeneity. In reality, as H. S. Taylor first pointed out, surfaces are never
absolutely smooth, and we have to take account of variations in surface activity. Various lines of experimental
evidence provide evidence for the inherent heterogeneity of surfaces.

In view of the fact that surfaces show such variability, it may at first seem surprising that fairly simple kinetic
laws often apply to surface-catalyzed reactions. The reason is that because of the exponential term in the
rate equation a reaction will occur predominantly on the most active surface sites.

Aside from an inherent heterogeneity, resulting in a true variation in surface sites, there can also be an
induced heterogeneity resulting from the interactions between adsorbed molecules. Suppose, for example,
that there is a significant repulsion between molecules that are adsorbed side by side on a surface. The result
will be that as the substance is progressively adsorbed, the
first molecules will not be close together, but
subsequent molecules will necessarily be close to other The high surface tension of water
molecules and will be adsorbed less strongly. The meniscus explains why various small
adsorption behavior is thus very similar to that insects are able to skate across the
occurring when the surface is inherently surface of a pond.
heterogeneous; the first molecules will be attached more
strongly than the later ones. The heat evolved on
chemisorption usually falls as the surface is
progressively covered. This can be due to inherent heterogeneity, to induced heterogeneity, or to a
combination of the two.

Many surface catalysts are much more efficient if they are promoted. A promoter is a substance that in itself
has little or no catalytic power but which when added to a catalyst greatly improves its performance.
Promoters bring about their action in a variety of ways. Some of them act mainly by changing the structure of
the surface, with an increase in the surface area. Promoters also act by producing surface regions, such as
phase boundaries, which have a greater catalytic activity than other parts of the surface.

Fritz Haber (18681934) won the 1918 Nobel Prize for chemistry for the synthesis of ammonia from the
elements; he brought hydrogen and nitrogen together at high pressure in the presence of a promoted iron
catalyst.
Most catalysts are easily poisoned by substances that are strongly adsorbed at the active centers on the
surface. Since the proportion of active centers may be small, minute amounts of poison can cause a very
considerable decrease in the effectiveness of a solid surface.

SURFACE TENSION
Surface tension is the tendency of liquids to reduce their exposed surface to the smallest possible
area. A single drop of water such as a rain drop tries to take on the shape of a sphere. We attribute this
phenomenon to the attractive forces acting between the molecules of the liquid. The molecules within the liquid
bulk are attracted equally from all directions, but those near the outer surface of the droplet experience
unequal attractions, which cause them to draw in toward the centre of the droplet a phenomenon
experienced as a tension. (Monk, 2004)
Surface tension is a contractive tendency of the surface of a liquid that allows it to resist an external
force. It is shown, for example, in the floating of some objects on the surface of water, even though they are
denser than water. This property is caused by cohesion of similar molecules and is responsible for many of the
behaviours of liquids.

Surface tension has the unit of force per unit length , or of energy per unit of area. The two units are
equivalent. However, when we refer to energy per unit of area, we use the term surface energy, which is more
general in that it applies to solids as well as liquids.

CAPPILARY ACTION
Capillary action, or capillarity, is the ability of a liquid to flow in narrow spaces without the assistance of,
and in opposition to, external forces like gravity. The effect can be seen in the drawing-up of liquids between
the hairs of a paintbrush, in a thin tube, in porous materials such as paper, in some non-porous materials such
as liquefied carbon fiber, and in a cell. It occurs because of intermolecular attractive forces between the liquid
and solid surrounding surfaces. If the diameter of the tube is sufficiently small, then the combination of surface
tension (which is caused by cohesion within the liquid) and adhesive forces between the liquid and the
container act to lift the liquid.

Adhesion of water to the surface of a material will cause an upward force on the liquid at the edges and
result in meniscus which turns upward. The surface tension acts to hold the surface intact. Capillary action
occurs when the adhesion to the surface material is stronger than the cohesive forces between the water
molecules. The height to which capillary action will take water in a uniform circular tube is limited by surface
tension. Acting around the circumference, the upward force is
The height h to which capillary action will lift water depends upon the weight of water which the surface tension
will lift:

The height to which the liquid can be lifted is given by

In the case of a glass tube inserted in water with openings at both ends, as the edges of the tube are
brought closer together, such as in a very narrow tube, the liquid will be drawn upward in the tube. The more
narrow the tube, the greater the rise of the liquid. Greater surface tension and increased ratio of adhesion to
cohesion also result in greater rise.

In plants and trees

The capillary action is enhanced in trees by branching; evaporation at the leaves creating
depressurization; probably by osmotic pressure added at the roots; and possibly at other locations
inside the plant, especially when gathering humidity with air roots.

Examples
Capillary action is essential for the drainage of constantly produced tear fluid from the eye. Two
canaliculi of tiny diameter are present in the inner corner of the eyelid, also called the lacrimal ducts;
their openings can be seen with the naked eye within the lacrymal sacs when the eyelids are everted.
Wicking is the absorption of a liquid by a material in the manner of a candle wick. Paper towels
absorb liquid through capillary action, allowing a fluid to be transferred from a surface to the towel. The
small pores of a sponge act as small capillaries, causing it to absorb a large amount of fluid. Some
textile fabrics are said to use capillary action to "wick" sweat away from the skin. These are often
referred to as wicking fabrics, after the capillary properties of candle and lamp wicks.
Capillary action is observed in thin layer chromatography, in which a solvent moves vertically up
a plate via capillary action. In this case the pores are gaps between very small particles.
Capillary action draws ink to the tips of fountain pen nibs from a reservoir or cartridge inside the
pen.
With some pairs of materials, such as mercury and glass, the intermolecular forces within the
liquid exceed those between the solid and the liquid, so a convex meniscus forms and capillary action
works in reverse.
In hydrology, capillary action describes the attraction of water molecules to soil particles.
Capillary action is responsible for moving groundwater from wet areas of the soil to dry areas.
Differences in soil potential drive capillary action in soil.

Liquid Films on Surfaces

Stilling the Waves, Oil on Water: Benjamin Franklin (1757)
while traveling by ship to England, noticed that oil on a stormy sea has the effect of stilling the waves. On
arriving in England he made a number of demonstrations of the effect by pouring a teaspoonful of oil on
various bodies of water, including a pond at Clapham Common and Derwent Water in the Lake District. It is
possible from his rough data to calculate the thickness of his layers of oil to be a few ngstroms

From 1880 until 1933 Agnes Pockels (18621935)

(Brunswick, Lower Saxony)
She first studied the relationship between the area occupied by a film and the surface tension and found that
the behavior was different above and below a certain critical area.
1891 (through the intervention of Lord Rayleigh) -first paper was published

"The surface balance technique Pockels developed became useful in physical chemistry for determining the
size and shape of organic molecules at a time when X-ray diffraction was not yet available. Her surface film
balance technique is the basis for the method later developed by Langmuir and often referred to as a Langmuir
trough. This technique is still used by surface chemists. "

"Pockel introduced water-insoluble compounds to the water surface by dissolving them in an organic solvent,
applying drops of the solution, and then allowing the solvent to evaporate is now the standard technique used.
Clean surfaces are a major problem for surface experimentation The technique she developed for ensuring a
clean surface has become standard procedure."

"Observations of the so-called Pockel's point, the minimum area occupied by a monomolecular surface film,
about 20 angstroms."

1917 Irving Langmuir began to use a film balance, which was a technical improvement over the apparatus
used by Agnes Pockels.Langmuirs apparatus, measures the surface pressure, s, of the film, which is the
force, F, exerted on it divided by the length of the edge along which the force is exerted. Unit N m1 = kg s2
Surface films
Studies of the relationship between the surface area and the surface pressure have shown that two-
dimensional monolayers can exist in states that are analogous to the solid, liquid, and gaseous states of three-
dimensional matter.
2 General Kinds
1. Coherent Films- there is a critical area per molecule; at larger areas the pressure is quite small, but
when the critical area is reached there is little further decrease in area with increase in pressure.
2. Noncoherent Films. For noncoherent films there is no critical area. Such films obey, to a good
approximation, the equation
sA= kBT
where s is the surface pressure and A is the area per molecule adsorbed. This equation is the two-
dimensional analog of the ideal gas equation, and noncoherent films therefore behave like a two-
dimensional gas; they are often called gaseous films. There are not many examples of gaseous films,
which tend to occur at higher temperatures; the molecular energies are then too high to permit the
formation of the condensed phase.

Definition
The solid-liquid interface is that between a solid (phase ) and a liquid (phase ). The solid can be
polar (high surface energy solid such as an oxide), semipolar (intermediate surface energy solid such as
cellulose acetate), or nonpolar (low surface energy solid such as hydrocarbon solid or
poly(tetrafluoroethylene).
The liquid can be polar (such as water or alcohol) or nonpolar (such as hydrocarbon oil). One can
define the solid/liquid interfacial tension as the energy per unit area in mJm 1, which depends on the nature
of the solid and the liquid. For a polar solid dispersed in a polar liquid, charge separation may take place
resulting in the formation of an electrical double layer. A surface charge o can be defined that is compensated
by unequal distribution of counterions and co-
ions. The diffuse double layer charge d is equal in
magnitude but opposite in sign to o.

Structure of Solid Liquid Interface

 Fig. 1 Schematic model of atomic/molecular interaction
at solid/liquid interface [Source: www.jst.go.jp]

A model of the liquid/solid interface with examples of specific and non-specific adsorption
(a) The structure of the Helmholtz layer and a pure solvent
(b) Potential drop across the interface in case of nonspecific ion adsorption

Potentials inside the metal, in the electrolyte, and at the outer Helmholtz plane are shown
For nonspecifically adsorbing ions:
-linear potential drop across the interface
For specific adsorbing ions:
-a stepper potential gradient

(a)
(b)

Fig. 2&3 Stern Model of liquid/solid interface [Source: Kolb D.M., Surf. Sci 500 (2002)]

Four regions in the liquid/solid system

1. The bulk liquid
2. The bulk solid
3. The surface of the solid along with its adsorbate
4. The region just above the adsorbed layer that is different from the bulk liquid

Langmiur-Blodgett Films
Amphiphile molecule: molecules with both polar (hydrophilic) and nonpolar (hydrophobic) ends
The polar head group of the amphiphile molecule interacts with the liquid through hydrogen bonding or
electrostatic interactions; by aligning and tilting, the tail groups maximize their attractive interactions

Fig. 4 [Source: www.biolinscientific.com]

Young equation
Contact angle
L , S surface free energy of liquid and solid
SL interface energy or tension

Fig.5 &
6[Source.w
w w.physics.u
wo.ca]

Surface tension exerts force along surface at line of intersection

At equilibrium: L cos = S - L (Youngs eq.)

Sticking Coefficient in Solution

Similar to gas/solid case, the sticking coefficient is defined as :

The collision frequency in solution is given by z w = csol ( )2, where csol is the the concentration in molecules

per m3.
COLLOIDAL SYSTEMS

Colloids
The word colloid (Greek kolla, glue; -oeides, like) was introduced in 1861 by the Scottish chemist
Thomas Graham (18051869) to refer to substances that diffused slowly and would not pass through
parchment.
Colloids are systems which consist of media with dissolved or dispersed particles ranging from 1 m up
to several microns in size.
Colloids occupy then, an intermediate position between solutions of relatively low molecular weight
substances on the one hand, and coarse mixtures on the other. Coarse mixtures are dispersions with
particles larger than several microns.

Colloidal Systems
In colloidal systems, colloidal dispersions are considered to be heterogeneous, with the medium as one
phase and the dispersed substance as the other.
The medium in which the dispersion takes place is called the dispersion medium, the substance
dispersed the disperse phase, while the complete colloidal solution is referred to as disperse system.
The term disperse phase is used to refer to the particles that are present in the dispersion medium.
Both the disperse phase and the dispersion medium may be solid, liquid, or gaseous. Since gases are
always completely miscible, we cannot have a gas-in-gas colloidal dispersion.

Types of Colloidal Systems

Dispersion Medium Disperse Phase Name of System Examples

Gas Liquid Aerosol Fog, mist, clouds
Gas Solid Aerosol Smoke
Liquid Gas Foam Whipped cream
Liquid Liquid Emulsion Milk, mayonnaise
Liquid Solid Sol Gold in water
Solid Liquid Gel Jelly
 Solid Solid Gel Ruby glass, gold in
glass
Solid Gas Solid foam Pumice, styrofoam

Lyophobic and Lyophilic Sols

Colloidal dispersions of solids in liquids (i.e., sols) can be roughly divided into two types:

1. Lyophobic Sols. From the Greek lysis, loosening, dissolving; phobia, fear of. Lyophobic therefore
literally means fear of dissolving or solvent fearing. These can be called hydrophobic sols if the
dispersion medium is water. The term hydrophobic was first used in 1905 by the French physicist Jean
Baptiste Perrin (1870 1942) to denote a disperse phase, such as gold or arsenic sulfide, which has a
low affinity for water; it is now applied more generally in surface chemistry to refer also to water-
repellent surfaces.

2. Lyophilic (liquid-loving) Sols. These are sols in which there is a strong affinity between the disperse
phase and the molecules comprising the dispersion medium.

Methods of Preparing Colloidal Dispersions

1. Condensation Methods. The materials are initially in true solution. Chemical reactions are used to
produce the sol; care is takenby controlling concentrations, for exampleto prevent the growth of the
particles and consequent precipitation.

2. Dispersion Methods. Material originally in massive form is disintegrated into particles of colloidal
dimensions. In one procedure, known as peptization (Greek pepticos, promoting digestion), the
disintegration is brought about by the action of a substance known as a peptizing agent.

Methods of Purification of Sols

1. Dialysis. In dialysis, the sol is purified by permitting the electrolyte to diffuse through a porous
membrane, such as parchment, cellophane, or collodion, which is permeable to molecules of solvent
and low molecular weight solutes, but not to colloidal particles.

2. Electrodialysis. In electrodialysis the dialyzing process is accelerated by applying a potential difference

across the membrane.

3. Ultrafiltration. It is a process similar to filtration of an ordinary precipitate, except that a membrane is

used which will permit passage of electrolytes and medium but not of colloid.

Light Scattering by Colloidal Particles

When colloidal particles are present, however, some of the light is

scattered, and the incident beam passes through with weakened
intensity. The first investigation of this phenomenon was made in
1871 by the British physicist John Tyndall (18201893), and the
 scattering is known as the Tyndall effect; the path of light through the medium, made visible as a result
of the scattering, is known as the Tyndall beam.

The proportion of incident light that is scattered increases with an increase in the number and size of
the particles. If the intensity of the incident radiation is Io and l is the length of the light path through the
scattering medium, the intensity of the transmitted radiation is given by:

Where is known as the turbidity.

Ultramicroscope
Ultramicroscope is invented in 1903 by the Austro-German chemist
Richard Adolf Zsigmondy (18651929) and his physicist
colleague H. Siedentopf.
In this instrument a beam is passed through the colloidal system,
and individual particles can be seen under the microscope as flashes
of scattered light.
Particles detected in an ultramicroscope undergo continuous and
rapid motion in all directions, and this is known as Brownian
movement, named after the Scottish botanist Robert Brown (1773
1858), who first observed it in pollen grains seen under an ordinary microscope.

Electrical Properties of Colloidal Systems

Electrophoresis
Migration of colloidal particles
Both lyophobic and lyophilic sols undergo electrophoresis.

The stability of a hydrophobic sol, for example, is very much dependent on the charges on the surface of
the particles; repulsion between particles carrying the same charges prevents them from approaching one
another and forming larger particles that will precipitate out.
Added electrolytes influence the stability of colloidal particles by affecting their charges. Again the behavior
is different for lyophobic and lyophilic sols. Usually lyophobic particles are easily coagulated, with the formation
of a visible precipitate, by the addition of electrolytes.
Lyophilic sols differ from lyophobic sols in that much larger amounts of electrolytes are required to bring
about precipitation. The reason is that lyophilic particles are to some extent protected by a layer of bound water
molecules.

Gels
A semirigid jellylike mass that includes the whole of the liquid present in the sol
There are two types, elastic gels and nonelastic gels.

Elastic Gels
Partial dehydration of an elastic gel leads to the formation of an elastic solid from which the original sol
can be regenerated by the addition of water.
 If an elastic gel such as gelatin is placed in water, it swells, water having been imbibed by the gel; the
process is known as imbibition.

Non-Elastic Gels
Dehydration of a nonelastic gel, on the other hand, leads to a glass or powder, which has little elasticity.
Nonelastic gels, on the other hand, may take up solvent but they do not swell; the liquid enters the
pores of the gel but, since the walls are rigid, the volume of the gel does not change.

Emulsions
Consists of droplets of one liquid dispersed in another liquid.
Emulsions are generally unstable unless a third substance, known as an emulsifying agent or a
stabilizing agent, is present.

Micelle
(Latin micella, small crumb, diminutive of the Latin
mica, crumb) was used by the Canadian-
American chemist James William McBain (1882 1953)
and the American chemist William Draper Harkins
(18731951) to refer to particles that are
stabilized by emulsifying agents

Emulsifying agents
The action of emulsifying agents is to reduce the interfacial tension between the two phases.

An emulsion with no stabilizing agent has properties similar to those of lyophobic sols; for example,
they are easily coagulated by electrolytes. Stabilized emulsions, on the other hand, behave more like lyophilic
sols and are only affected by electrolytes at high concentrations.