LECTURE NOTES

CHI 2308 SURFACE AND COLLOID CHEMISTRY

GROUP: BSC INDUSTRIAL CHEMISTRY Y3S2

Purpose

To equip students with the physical and chemical adsorption process

Expected Learning Outcomes

At the end of this unit, the students should be able to:
1. Explain physico-chemical process of adsorption on solid surfaces
2. Predict chemical reactivity and equilibrium of nano- and macro-scale materials at varying
temperatures and pressures.
3. Determine surface and interfacial tensions and, thermodynamics of adsorption
4. Explain the phenomenon of rheology, viscosity, emulsions and colloidal stability.

Course Description

Adsorption of gases and vapours on solids: physical adsorption and chemisorption of gases and
vapours on solids; Classification of adsorption isotherms; Isotherm equations: Langmuir and
BET; Determination of solid surface areas; Adsorption energies for physical adsorption and
chemisorptions; Heterogeneous catalysis; Surface and interfacial tensions, thermodynamics of
adsorption; Gibbs equation, micelle formation monomolecular films; Contact angles and wetting
floatation, detergency and adsorption from solution; Charge of surface; electric layer;
Electrokinetics: electrophoresis, electro-osmosis, zeta potential, streaming current and steam
potential; Colloidal state: classification, preparation and purification of its systems; Kinetic
properties; Relative molecular masses of macromolecule: ultracentrifuge and osmotic pressure
methods; Optical properties: light scattering and macromolecular relative mass determination;
Rheology: phenomenon of rheology viscosity for molar mass determination; Colloidal stability:
coagulation and its kinetics; Emulsions: types, emulsifying agents, emulsion stability and breaking
of emulsions; Foams: stability and art foaming agents.

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1.0 INTRODUCTION

1.1 Colloidal state

 Colloid science entails systems in which one or more of the components has at least one
dimension ranging within the nanometre (10-9 m) to micrometre (10-6 m). The main,
systems contains large molecules and/or small particles.
 Microscopic particles of one phase dispersed in another are generally called colloidal
solutions or dispersions.
 Though there is no sharp distinction between colloidal and non-colloidal systems, the term
'microheterogeneous' is used to describe most colloidal systems.
 A colloid system is described as a stable dispersion of particles in a continuous medium of
a different composition which can be solid, liquid, or gas e.g. solid dispersions, emulsion,
foams, gels. The size of dispersed particles in a colloid system is between 1 and 1000 nm
(at least in one dimension), thus, colloid science has a huge overlap with nano-science and
nanotechnology.
 Colloid science covers systems occupying an intermediate position (with respect to particle
size) between true solutions of low molecular weight substances and suspensions.
 Surface Chemistry can be defined as the study of surface properties and reactions at
interfaces, which aims at surface modification to alter a wide range of surface
characteristics such as roughness, hydrophilicity/hydrophobicity, surface charge,
biocompatibility, and reactivity. It is closely related to Interface and Colloid science and
has a broad range of technological fields such as surfactants and self-assembly, surface
modification, heterogeneous catalysis, fuel cells, nano-technology, adsorption, etc.
 Colloid science and Surface Chemistry have many applications in the chemical industry,
pharmaceuticals, biotechnology, ceramics, minerals, nanotechnology, and microfluidics,
among others.
 There are several colloidal systems and processes where colloid surface chemical
phenomena involved are of practical importance. Examples of colloidal systems:
 Aerosols  Cosmetics  Fabrics
 Agrochemicals  Dyestuffs  Foams
 Cement  Emulsions  Foodstuffs

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  Ink  Pharmaceuticals  Soil
 Paint  Plastics
 Paper  Rubber
 Processes which rely heavily on the application of colloid/surface phenomena include

 Adhesion  Emulsion  Water evaporation

 Chromatography polymerisation control
 Detergency  Soil conditioning  Ion exchange
 Ore flotation  Food processing  Water repellency
 Precipitation  Sugar refining  Lubrication
 Road surfacing  Grinding  Wetting
 Electrophoretic  Water clarification  Oil-well drilling
deposition  Heterogeneous
 Sewage disposal catalysis

 The existence of matter in the colloidal state may be either desirable or an undesirable.
Consequently, knowledge on both constituting and destroying colloidal systems is vital.
 The factors which contribute most to the overall nature and characteristics of a colloidal
system are:
 Particle size
 Particle shape and flexibility
 Surface properties (surface area and surface charge density)
 Particle-particle interactions
 Particle-solvent interactions
 The stability of colloidal systems is determined by:

1. The effect of the large surface area-to-volume ratio (e.g., 1000 m2 surface area
per gram of solid [active charcoal]).
2. The forces operating between the colloidal particles
3. Surface charges (varying from positive or negative or neutral surface charge) are
very important characteristics of such systems

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  Three fundamental forces that operate on fine particles dispersed in solution:
(1) A gravitational force, tending to settle or raise particles depending on their density
relative to the solvent;
(2) A viscous drag force, which arises as a resistance to motion, since the fluid has to
be forced apart as the particle moves through it;
(3) The ‘natural’ kinetic energy of particles and molecules, which causes Brownian
motion.
 Effect of the first two factors:
 A spherical particle of radius r, has terminal or limiting velocity, V, (for settling or
rising, depending on the particle’s density relative to water). This can be easily
calculated using gravitational force and viscous drag force. Under these conditions,
the viscous drag force must be equal the gravitational force. Thus, at a settling
velocity, V, the viscous drag force is given by:
Fdrag = 6πrVη = 4πr3g(ρp - ρw)/3 = Fgravity,

Where;
Fdrag is the viscous drag force
Fgravity is the gravitational force,
η is the viscosity of water
g is the strength of gravitational field
(ρp - ρw) is the density difference between particle and water .
 Various solutions made of particles of various sizes, ranging from 100 – 106 Å,
assuming a particle–water density difference of +1 gcm-3, we obtain following
limiting velocity, V, for each:

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  Clearly, from factors (1) and (2), small particles will take a very long time to settle
and so a fine dispersion will be stable almost indefinitely, even for materials denser
than water.
 Explaining factor (3):
 Each particle, independent of size, will have a kinetic energy, on average, of around
1ƦT. So the typical, random speed (v) of a particle (in any direction) will be roughly
given by:

Ʀ is Boltzmann constant
 Assuming that ρp = 2 gcm-3, then the results are:

 The values suggest that kinetic random motion will dominate the behaviour of small
particles, which will not settle and the dispersion will be completely stable.

NB: The kinetic energy in the small particles cause them to collide with each other
in the dispersion, with collision energies ranging up to at least 10Kt.
If there are attractive forces between the particles – as is the case since most
colloids initially formed via a vigorous mechanical process of disruption of a
macroscopic or large body – each collision might cause the growth of large
aggregates which will then settle out, and we will no longer have a stable
dispersion. The colloidal solution will coagulate and produce a solid
precipitate at the bottom of a clear solution.

 The motion of colloidal particles is the basis of the physical characteristics of the system
and thus, the Brownian motion of particles is a much studied field.
 The fractal nature of surface roughness is also important in determining the properties of
the colloidal system.
 The term Surface is used when one considers the dividing phase between:
 Gas–Liquid
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  Gas–Solid
 Interface is the term used when one considers the dividing phase:
 Solid–Liquid: (colloids)
 Liquid1–Liquid2: (oil–water emulsion)
 Solid1–Solid2: (adhesion: glue, cement)

 Surface tension may be considered to arise due to a certain well-defined degree of

unsaturation of bonds that occurs when a molecule resides at the surface and not in the
bulk. The term surface tension is used for solid–vapor or liquid–vapor interfaces while
interfacial tension (IFT) is more generally used for the interface between two liquids (oil–
water), two solids, or a liquid and solid. In a one-component system, the fluid is uniform
from the bulk phase to the surface. However, the orientation of the surface molecules will
be different from those molecules in the bulk phase in all systems.

1.2 The forces involved in colloidal stability

 Van der Waals forces act to coagulate dispersed colloids,

 The charge generated at the surface of the particles: it is possible to generate an opposing
repulsive force of comparable strength. This force arises because most materials, when
dispersed in water, ionize to some degree or selectively adsorb ions from solution and
hence become charged. Two similarly charged colloids will repel each other via an
electrostatic repulsion, which will oppose coagulation.
 The properties and stability of any colloidal dispersion is thus determined by the behaviour
of the surface of the particle via its surface charge and its short-range attractive van der
Waals force.
 The combination of these two forces, attractive van der Waals and repulsive electrostatic
forces, forms the fundamental basis for understanding the stability of colloidal solutions.
 Understanding of these forces helps to selectively control the electrostatic
repulsion, and so create a powerful mechanism for controlling the properties of
colloidal solutions. For instance, if we have a valuable mineral embedded in a
quartz rock, grinding the rock will both separate out pure, individual quartz and the
mineral particles, which can both be dispersed in water. The valuable mineral can

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 then be selectively coagulated, whilst leaving the unwanted quartz in solution. This
process is used widely in the mining industry as the first stage of mineral separation.

1.3 Classification of colloidal systems

 In general, based on composition, colloidal systems are classified into three distinct types:

1. In simple colloids, clear distinction can be made between the disperse phase and the
disperse medium, for example, simple emulsions of oil-in-water (o/w) or water-in-
oil (w/o).
2. Multiple colloids involve the coexistence of three phases of which two are finely
divided, for example, multiple emulsions (mayonnaise, milk) of water-in-oil-in-
water (w/o/w) or oil-in-water-in-oil (o/w/o).
3. Network colloids have two phases forming an interpenetrating network, for example,
polymer matrix.
 Based on stability, colloidal systems may be grouped into three general classifications:
1. Colloidal dispersions: these are thermodynamically unstable owing to their high
surface free energy and are irreversible systems in the sense that they are not easily
reconstituted after phase separation.
2. True solutions of macromolecular material (natural or synthetic): are
thermodynamically stable and reversible in the sense that they are easily
reconstituted after separation of solute from solvent.
3. Association colloids: are thermodynamically stable

1.6 Structural characteristics

 The experimental procedures for determining particle size and shape can roughly be
categorised, as follows:
1. Observation of the movement of particles in response to an applied force
2. Direct observation of particle images (microscopy and electron microscopy).
3. Observation of the response of particles to electromagnetic radiation.
4. Measurements which relate to the total surface area of the particles (gas adsorption
and adsorption from solution)

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1.6.1 Particle shape

 Particle asymmetry is considered in determining the overall properties (especially those of

a mechanical nature) of colloidal systems.
 Generally, colloidal particles can be classified according to shape as: corpuscular, laminar
or linear. The exact shape may be complex but, to a first approximation, the particles can
often be treated theoretically in terms of models which have relatively simple shapes
(Figure 1.1).

Figure 1.1: Some model representations for non-spherical particles

 Spheres: are the easiest model to treat theoretically and many colloidal systems contain
spherical or nearly spherical particles. Emulsions, latexes, liquid aerosols, etc., contain
spherical particles. Certain protein molecules are approximately spherical. The crystallite
particles in dispersions such as gold and silver iodide sols are sufficiently symmetrical to
behave like spheres.
 Corpuscular particles: deviate from spherical shape and are often treated theoretically as
ellipsoids of revolution. Many proteins approximate this shape. An ellipsoid of revolution
is characterised by its axial ratio, which is the ratio of the single half-axis ‘a’ to the radius
of revolution ‘b’. The axial ratio is greater than unity for a prolate (rugby-football-shaped)
ellipsoid, and less than unity for an oblate (discus-shaped) ellipsoid. E.g. iron(III) oxide
and clay suspensions systems containing plate-like particles.

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  High-polymeric material usually exists in the form of long threadlike straight or branched-
chain molecules. As a result of inter-chain attraction or cross-linking (arising from
covalent bonding, hydrogen bonding or van der Waals forces) and entanglement of the
polymer chains, these materials often exhibit considerable mechanical strength and
durability. This is not possible when the particles are corpuscular or laminar.
 In nature, thread-like polymeric material fulfils an essential structural role. Plant life is
built mainly from cellulose fibres. Animal life is built from linear protein material such as
collagen in skin, sinew and bone, myosin in muscle and keratin in nails and hair. The
coiled polypeptide chains of the so-called globular proteins which circulate in the body
fluids are folded up to give corpuscular particles.
 When particles aggregate together, many different shapes can be formed. These do not
necessarily correspond to the shape of the primary particles.

1.6.2 Flexibility

 Thread-like high-polymer molecules show considerable flexibility due to rotation about

carbon-carbon and other bonds. In solution, the shape of these molecules alters
continuously under the influence of thermal motion and a rigid rod model is therefore
unsuitable. .
 Theoretically, polymer molecules are treated as random coils. However, rotation about
bonds does not permit complete flexibility. Dissolved linear polymer molecules will tend
to be more extended than random coils due to steric and excluded volume effects that
oppose the formation of a truly random configuration.
 The relative magnitudes of polymer-polymer and polymer-solvent forces must also be
taken into account. If the segments of the polymer chain tend to stick to one another, then
a tighter than random coil and possibly precipitation, will result; whereas a looser coil
results when the polymer segments tend to avoid one another because of strong solvation
and/or electrical repulsion.

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1.6.3 Solvation

 Colloidal particles are usually solvated, often to the extent of about one molecular layer,
and this tightly bound solvent must be treated as a part of the particle.
 Sometimes much greater amounts of solvent can be immobilised by mechanical entrapment
within particle aggregates. This occurs when voluminous flocculent hydroxide precipitates
are formed. In solutions of long thread-like molecules the polymer chains may cross-link,
chemically or physically, and/or become mechanically entangled to such an extent that a
continuous three-dimensional network is formed. If all of the solvent becomes
mechanically trapped and immobilised within this network, the system as a whole takes on
a solid appearance and is called a gel.

1.6.4 Polydispersity and the averages

 The terms relative molecular mass and particle size can only have well-defined meanings
when the system under consideration is monodispersed - i.e. when the molecules or
particles are all alike.
 Colloidal systems are generally of a poly dispersed nature - i.e. the molecules or particles
in a particular sample vary in size. By virtue of their stepwise build-up, colloidal particle
and polymer molecular sizes tend to have skew distributions, as illustrated in Figure 1.2,
for which the Poisson distribution often offers a good approximation.
 Very often, detailed determination of relative molecular mass or particle size distribution
is impracticable and less perfect experimental methods, which yield average values, must
be accepted. The significance of the word average depends on the relative contributions
of the various molecules or particles to the property of the system which is being measured.

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Figure 1.2: Particle diameter distribution for a polydispersed colloidal dispersion expressed (a)
in histogram form, and (b) as a cumulative distribution

 Osmotic pressure, which is a colligative property, depends simply on the number of solute
molecules present and so yields a number average relative molecular mass:

Where n/ is the number of molecules of relative molecular mass Afrn.

 In most cases the larger particles make a greater individual contribution to the property
being measured. If the contribution of each particle is proportional to its mass (as in light
scattering), a mass-average relative molecular mass or particle mass is given:

 For any polydispersed system, Afr (mass average) > Mr (number average), and only when
the system is monodispersed will these averages coincide. The ratio MT (mass
average)/Afr (number average) is a measure of the degree of polydispersity.

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1.7 Surface tension and wetting

1.8 Wetting properties and their industrial importance

 A liquid will always try to form a minimum-surface-area shape, if no other forces are
involved. However, it can also interact with other macroscopic objects, such as a suitable
solid, to reduce its surface tension via molecular bonding to another material.
 Indeed, it may be energetically favourable for the liquid to interact and ‘wet’ another
material. The wetting properties of a liquid on a particular solid are determined solely by
surface properties.
 For example water on clean glass; water wets clean glass (Figure 1.3) because of the
favourable hydrogen bond interaction between the surface silanol groups on glass and
adjacent water molecules.

Figure 1.3: Water molecules form hydrogen bonds with the silanol groups at the surface
of clean glass.

 Exposure of glass to Me3SiCl vapour rapidly produces a 0.5 nm layer of methyl

groups on the surface. These groups cannot hydrogen-bond and hence water now
does not wet and instead forms high ‘contact angle’ (θ) droplets and the glass now
appears to be hydrophobic, with water droplet beads similar to those observed on
paraffin wax (Figure 1.4).

Figure 1.4: Water molecules can only weakly interact (by vdw forces) with a
methylated glass surface.

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 Figure 1.5: A non-wetting water droplet on the surface of methylated, hydrophobic
silica.
 Surface treatments offer a remarkably efficient method for the control of
macroscopic properties of materials.
 This dramatic macroscopic difference in wetting behaviour is caused by only a thin
molecular layer on the surface of glass and clearly demonstrates the importance of
surface properties. The same type of effect occurs every day, for instance;
o When dirty fingers coat grease onto a drinking glass
o When insecticides are sprayed onto plant leaves, it is vital that the liquid
wet and spread over the surface.
o The froth flotation technique, used by industry to separate ore. Whether
valuable mineral particles will attach to rising bubbles and be ‘collected’ in
the flotation process, is determined entirely by the surface properties or
surface chemistry of the mineral particle, and this can be controlled by the
use of low levels of ‘surface-active’ materials, which will selectively adsorb
and change the surface properties of the mineral particles. Very large
quantities of minerals are separated simply by the adjustment of their
surface properties.
o Latex paint technology
o Photographic emulsions
o Soil science
o Soaps and detergents
o Food science
o Mineral processing.

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  Surface energy of a liquid actually gives rise to a ‘surface tension’ i.e. force acting
to oppose any increase in surface area. Thus, we have to ‘blow’ to create a soap
bubble by stretching a soap film.
 A spherical soap bubble is formed in response to the tension in the bubble surface
 If we stretch a soap film on a wire frame, we find that we need to apply a significant,
measurable force, F, to prevent collapse of the film (Figure 1.6). The magnitude of
this force can be obtained by consideration of the energy change involved in an
infinitesimal movement of the cross-bar by a distance dx, which can be achieved
by doing reversible work on the system, thus raising its free energy by a small
amount Fdx.
 If the system is at equilibrium, this change in (free) energy must be exactly equal
to the increase in surface (free) energy (2dxlγ) associated with increasing the area
of both surfaces of the soap film. Hence, at equilibrium:
Fdx = 2dxlγ 2.1
Or γ = F/2l 2.2
 It is precisely this, that work has to be done to increase a liquid’s surface area, that
makes the surface of a liquid behave like a stretched skin, hence the term ‘surface
tension’.

Figure 1.6: Diagram of a soap film stretched on a wire frame.

1.9 Methods for determining the surface tension of liquids

 The equilibrium curvature of a liquid surface or meniscus depends on: its surface
tension, its density and the effect of gravity.

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  The variation in curvature of a meniscus surface is due to hydrostatic pressure
differences at different vertical points on the meniscus. If the curvature at a given
starting point on a surface is known, the adjacent curvature can be obtained from the
Laplace equation and its change in hydrostatic pressure Δhργ.
 In practice the liquid droplet, say in air, has a constant volume and is physically
constrained at some point, for example when a pendant drop is constrained by the
edge of a capillary tube (Figure 1.7).

 Figure 1.7: Photograph and diagram of a pendant liquid drop at the end of a glass
capillary tube.
 Thus we would expect water to ‘climb’ up the walls of a clean (i.e. water-wetting)
glass vessel for a few millimetres but not more, and we would expect a sessile water
droplet to reach a height of several mm on a hydrophobic surface, before the droplet
surface is flattened by gravitational forces. The curved liquid border at the perimeter
of a liquid surface or film is called the ‘Plateau border’ after the French scientist who
studied liquid shapes after the onset of blindness, following his personal experiments
on the effects of sunlight on the human eye.
 Methods of measuring the surface energy of liquids:

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 o Observation of a pendant drop in measuring surface and interfacial energies
of liquids: the drop can be photographed and the profile digitized or
published tables can be used to obtain γ from only the drop volume and the
minimum and maximum widths of the drop.
o Using a capillary tube: In this method the height to which the liquid rises,
in the capillary, above the free liquid surface is measured. This situation is
illustrated in Figure 1.8. Using the Laplace equation the pressure difference
between points A and B is given simply by ΔP = 2γ/r, if we assume that the
meniscus is hemispherical and of radius r. However, this will be accurate
only if the liquid wets the walls of the glass tube. If the liquid has a finite
contact angle θ with the glass as in Figure 1.9, then from simple geometry
(again assuming the meniscus is spherical)

Figure 1.8: Schematic diagram of the rise of a liquid that wets the inside walls of a capillary
tube.

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Figure 1.9: Schematic diagram of the shape of a meniscus for wetting and non-wetting liquids.

 Note that if θ > 90° (e.g. mercury on glass), the liquid will actually fall below the reservoir
level and the meniscus will be curved in the opposite direction.
 The pressure difference between points A and B must be equal to the hydrostatic pressure
difference hργ (where r is the density of the liquid and the density of air is ignored). Thus,
we obtain the result that:

 Thus, measurement of the capillary rise and the contact angle gives the surface tension
of the liquid. This phenomenon occurs because the interfacial energy of the clean
glass–water interface is much lower than that of the glass–air interface. The amount
of energy released on wetting the glass surface and the potential energy gained by the
liquid on rising in a gravitational field, must be minimized at equilibrium.

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