BS 8th

Course Title : Nanoscience and technology

Course Code : PHY-608
Credit Hour : 3(3-0)

Delivered by Dr. Seemab Iqbal

Surface Physicochemical Phenomena Properties
Surface and interfaces
Surface chemistry and physics
 Outline of topics to be covered

1. Introduction
2. Amphiphilic Studies
3. Surface tension studies
4. Interfacial Studies
5. Contact Angle
6. Wetting Process
7. Detergency
8. Adsorption
9. Micelization
Applications or Uses of surface active agents
10. Solubilization
Intro. cont:

◼ This topic will be discussed under the concept of

Surface science.
◼ What is surface science? This is the study of
physical and chemical phenomena that occurs at the
surfaces or interfaces of two or more phases,
◼ These may include solid-liquid e.g. solutions,
suspensions, pastes etc solid-gas e.g aerosols, sprays
etc, solid-vacuum, and liquid-gas e.g aerosols, sprays
etc of interfaces.
◼ It includes the fields of surface chemistry and
surface physics.
Introduction continued:

◼ In other ways this aims to modify the

chemical composition of a surface by
incorporation of selected elements or
functional groups of the reactants that
exert and produce various desired
effects or improvements in the
properties of the surface or interface
for intended or desired outcome or
output.
Factorial considerations:
◼ The state of the surface e.g. liquid, solid etc
◼ The amount of surface area
◼ The presence of the catalyst may affect the rate of reaction
◼ Whether homogenous or heterogeneous reactional
surfaces
◼ the surface charges, dipoles, energies and their distribution
within the electrical double layer for solution based
reactions
◼ Thermodynamics of the reactions e.g. state functions,
temperature, reactional energy (chemical kinetics etc)
◼ Chemical affinities
 1. Amphiphilic Studies

◼ What is or how is an Amphiphile look

like?
◼ Amphiphile is a chemical compound
possessing both hydrophilic (water loving)
and hydrophobic (water hating)
properties.
◼ Such a compound is called an amphiphilic
or amphipathic substance.
Amphiphilic Studies -continued

◼ This is so because hydrophilic

properties are due to ionic form of the
ends of the molecule (anionic or
cationic ends)
◼ Hydrophobic properties are due to non
ionic form of the other end

Non ionic (-) or (+)

Structure and Properties
Structure and Properties - continued

◼ The hydrophobic group is typically a

large hydrocarbon moiety, such as a
long chain of the form CH3(CH2)n, with
n > 4.
◼ The hydrophilic group falls into one of
the following categories:
Structure and Properties - continued

◼ Anionic (negatively charged), with the

hydrophobic part of the molecule
represented by an R, can be:
o carboxylates: RCO2-;
o sulfates: RSO4-;
o sulfonates: RSO3-.
o Phosphates: RPO4- This is charged
functionality in phospholipids.
 Structure and Properties - continued

◼ Cationic. Examples:
o amines: RNH3+

◼ Polar, uncharged groups. Examples are

alcohols with large R groups, such as diacyl

glycerol (DAG), and oligo ethyleneglycols
with long alkyl chains.
Structure and Properties - continued

◼ Often, amphiphilic species have several

hydrophobic parts, several hydrophilic
parts, or several of both.
◼ Proteins and some block copolymers are
such examples.
Structure and Properties - continued

◼ Many other amphiphilic compounds may

strongly interact with biological
membranes by insertion of hydrophobic
part into the lipid membrane, while
exposing the hydrophilic part to the
aqueous medium, altering their physical
behaviour and sometimes disrupting
them e.g. wound cleaning with a
detergent.
Structure and Properties - continued

◼ Surfactants are an example group of

non biological amphiphilic chemical
compounds.
◼ Their polar region can be either ionic, or
non-ionic.
Structure and Properties - continued

◼ As already mentioned earlier, there are

also many biological amphiphilic
chemical compounds such as:
o phospholipids,
o cholesterol,
o glycolipids,
o fatty acids,
o bile acids,
o saponins, etc.
 2. Surface tension

◼ Surface tension is an effect within the

surface layer of a liquid that causes that
layer to behave as an elastic sheet.
◼ Surface tension, represented by the
symbol σ,γor T, is defined as the force
along a line of unit length, where the
force is parallel to the surface but
perpendicular to the line.
Surface tension (continued)

◼ Surface tension is therefore measured in forces per unit

length.
◼ Its SI unit is newton per metre but the ergs unit of dynes
per cm is most commonly used.
◼ An equivalent definition, one that is useful in
thermodynamics, is work done per unit area.
◼ Surface tension is caused by the attraction between the
molecules of the liquid by various intermolecular forces as
follows:
• o In the bulk of the liquid each molecule is pulled equally
in all directions by neighboring liquid molecules, resulting
in a net force of zero.
 Surface tension (continued)
◼ Applying Newtonian physics
to the forces that arise due
to surface tension
accurately predicts many
liquid behaviors that are so
commonly placed that most
people take them for
granted.
Usual occurrence of Surface tension

◼ Some examples of the effects of surface

tension seen with ordinary water:
o Beading of rain water on the surface of a waxed automobile.
o Formation of drops occurs when a mass of liquid is
stretched.
o Floatation of objects denser than water.
o Separation of oil and water.
o Tears of wine.
o Soap bubbles have very large surface areas with very little
bulk.
o Emulsions are a type of solution in which surface tension
plays a role.
 3. Interfacial Phases

◼ In pharmacy, an interface is defined as a

surface forming a common boundary
among two different phases, such as
outlined above, i.e. the boundary between
any two phases.
◼ Among the three phases—gas, liquid, and
solid—five types of interfaces are possible:
gas-liquid, gas-solid, liquid-liquid,
liquid-solid, and solid-solid.
Interfacial Phases (continued)

Contact angle at interface of three phases.

 Interfacial Phases (continued)

◼ The abrupt transition from one phase to

another at these boundaries, even though
subject to the kinetic effects of molecular
motion, is statistically a surface only one or
two molecules thick.
◼ The importance of the interface depends on
which type of system is being treated: the
bigger the quotient area/volume, the more
effect the surface phenomena will have.

◼ Therefore interfaces will be considered in systems with

big area/volume ratios, such as colloids.
 4. Surface energy

◼ A unique property of the surfaces of the

phases that adjoin at an interface is the
surface energy which is the result of
unbalanced molecular fields existing at the
surfaces of the two phases as earlier alluded
to
◼ Thomas Young described surface energy as
the interaction between the forces of
cohesion and the forces of adhesion which, in
turn, dictate if wetting occurs.
Surface energy (continued)

◼ If the surface is hydrophobic then the contact

angle of a drop of water will be larger.
◼ Hydrophilicity is indicated by smaller contact
angles and higher surface energy.
◼ Water has high surface energy by nature; it's
polar and forms hydrogen bonds.
◼ If wetting occurs, the drop will spread out
flat.
 5. Contact Angle

◼ The contact angle is the angle at

which a liquid/vapor interface may meet
the solid surface.

A contact angle of a liquid sample

Contact Angle (continued)

◼ The contact angle is specific for any given

system and is determined by the interactions
across the three interfaces.
◼ Most often the concept is illustrated with a
small liquid droplet resting on a flat horizontal
solid surface.
◼ The shape of the droplet is determined by
the Young-Laplace equation.
Contact Angle (continued)

◼ The theoretical description of contact

may arise from the consideration of a
thermodynamic equilibrium between
the three phases:
◼ the liquid phase of the droplet (L),
◼ the solid phase of the substrate (S),
◼ the gas/vapor phase of the ambient (V)
(which will be a mixture of ambient
atmosphere and an equilibrium concentration
of the liquid vapor).
Contact Angle (continued)

◼ An equation has been derived from

such parameters that must be satisfied
in equilibrium and is known as the
Young Equation:

θis the experimental contact angle

Contact Angle (continued)

◼ Thus the contact angle can be used to

determine an interfacial energy (if other
interfacial energies are known).
◼ This equation can be rewritten as the
Young-Dupré equation:

ΔWSLV is the adhesion energy per unit area

of the solid and liquid surfaces when in
the medium V
Contact Angle (continued)

◼ The contact angle plays the role of a

boundary condition.
◼ Contact angle is measured using a
contact angle goniometer (see below).
◼ The contact angle is not limited to a
liquid/vapour interface; it is equally
applicable to the interface of two liquids
or two vapours.
Contact Angle (continued)

◼ On extremely hydrophilic surfaces, a

water droplet will completely spread (an
effective contact angle of 0°).
o This occurs for surfaces that have a

large affinity for water (including

materials that absorb water).
◼ Theoretically, surface with contact

angle larger than 90° will be

hydrophobic.
Contact Angle (continued)

◼ And, surface with contact angle lower

than 90° will be hydrophilic.
◼ On many highly hydrophilic surfaces,
water droplets will exhibit contact
angles of 0° to 30°.
◼ On highly hydrophobic surfaces the
surfaces have water contact angles as
high as 150° or even nearly 180°.
Contact Angle (continued)

◼ On these surfaces, water droplets

simply rest on the surface, without
actually wetting to any significant
extent (These surfaces are termed
superhydrophobic)
 6. Wetting Process

Wetting of different fluids. A shows a fluid with very

high surface tension (and thus little wetting), while C
shows a fluid with very low surface tension (more
wetting action.) A has a high contact angle, and C
has a small contact angle while B is in between.
Wetting (continued)

◼ Wetting is the contact between a fluid

and a surface, when the two are
brought into contact.
◼ When a liquid has a high surface
tension (strong internal bonds), it will
form a droplet, whereas a liquid with
low surface tension will spread out over
a greater area (bonding to the surface).
Wetting (continued)

◼ The primary measurement to determine

wettability is a contact angle
measurement.
◼ This measures the angle between the
surface and the surface of a liquid
droplet on the surface. For example, a
droplet would have a high contact
angle, but a liquid spread on the
surface would have a small one.
 Wetting (continued)

◼ The contact angle and the surface

energies of the materials involved are
related by the Young–Dupré equation

γ is the surface tension between two substances

S, V, and L correspond to the solid, vapor, and liquid substances
 7. Detergency

◼ A detergent is a substance used to enhance

the cleansing action of water.
◼ Soap, the sodium salt of long-chain acids,
was the principal detergent until superseded
in 1954 by synthetic detergents (syndets)
which, unlike soap, do not form insoluble
products with the calcium in hard water.
◼ Most syndets are of the anionic type, that is,
sodium salts of alkyl sulfates or sulfonates.
 Composition of detergents
◼ Detergents, especially those made for use
with water, often include different
components such as:
◼ Surfactants to 'cut' grease and to wet surfaces
◼ Abrasive to scour
◼ Substances to modify pH or to affect performance
or stability of other ingredients, acids for descaling
◼ caustics to breakdown organic compounds
◼ Water softeners to counteract the effect of
"hardness" ions on other ingredients
 8. Adsorption (Definitions)
◼ This is a process in which atoms or molecules
move from a bulk phase (that is, solid, liquid,
or gas) and are attached physically or
chemically onto a solid or liquid surface.
◼ Examples include the following:
o purification by adsorption where impurities are
filtered from liquids or gases by their adsorption
onto the surface of a high-surface-area solid such
as activated charcoal or TST for water cleaning.
Desorption
The process of removal of an adsorbed substance from the surface on
which it is absorbed
General Introduction (continued) Adsorption vs absorption
 Adsorbent Materials

• Activated Carbon

• Activated Alumina

• Silica Gel

• Molecular Sieves (Zeolites)

• Polar and Non-polar adsorbents

 Activated carbon

• "Activation" is the process that produces the porous structure

essential for effective adsorption by oxidation of carbon with
water vapor or CO2.
• An activation level sufficient for useful application may be
attained solely from high surface area; however, further
chemical treatment often enhances adsorption properties.

• Activated carbon attracts non-polar molecules such as

hydrocarbons.

• Typical surface areas are 300 to 1500 m2/g.

 Silica gel

➢Silica gel is a granular, vitreous, porous form of

silicon dioxide made synthetically from sodium silicate.
➢Silica gel is tough and hard; it is more solid than
common household gels like gelatin or agar.
➢It is a naturally occurring mineral that is purified and
processed into either granular or beaded form.
➢As a desiccant, it has an average pore size of 2.4
nanometers and has a strong affinity for water
molecules.
 9.Micellization

◼ The process of forming micellae is known as

micellization and this forms part of the phase behaviour
of many lipids according to their polymorphism.
◼ A micelle (rarely micella, plural micellae) is an
aggregate of surfactant molecules dispersed in a liquid
colloid.
◼ A typical micelle in aqueous solution forms an aggregate
with the hydrophilic "head" (blue cycles) regions in
contact with surrounding solvent, sequestering the
hydrophobic (red lines) tail regions in the micelle
centre.
Micellization (continued)
 Micellization (continued)

◼ Other phases, including shapes such as ellipsoids,

cylinders, and bilayers are also possible.
◼ The shape and size of a micelle is a function of
the molecular geometry of its surfactant
molecules and solution conditions such as
surfactant concentration, temperature, pH, and
ionic strength.
 Uses (continued)

▪ Other uses such as:

o Detergents;
o Fabric softener ;
o Emulsifiers;
o Paints;
o Adhesives;
o Inks;
o Anti-fogging;
o Soil remediation;
o Wetting;
 Uses (continued)

o Ski Wax;
o Snowboard Wax;
o Foaming;
o Defoaming;
o Laxatives;
o Agrochemical formulations (Herbicides, Insecticides);
o Quantum dot coating;
o Biocides (Sanitizers);
o Hair Conditioners (after shampoo); Spermicide (Nonoxynol
9);
o Used as an additive in 2.5 gallon fire extinguishers
 Applications or Uses of surface active
agents

◼ There is a wide spectrum of applications or

use of surface active agents including the
following:
o Pharmaceutical
o Medical
o Biological
o Industrial / Environmental
o etc
 Medical Uses

◼ Laxatives in digestive pathophysiological

incidences e.g.
o Methylcellulose as bulk forming agent
o Docusate as stool softening agent
o Mineral oil as lubricating agent
o Magnesium Citrate as osmotic agent
o Castor oil as irritating agent
o Hypromellose as artificial tears
 Industrial / Environmental use

◼ They have cidal effects on a wide range of

living organisms e.g.

o Pyrethrum, chlorinated hydrocarbons, as an

insecticides
o Pyrethroid as a pesticide
o Sodium lauysulphate as detergent
 Pharmaceutical Use
o Binders include synthetic or natural resins
such as acrylics, polyurethanes, polyesters,
melamine resins, epoxy, or oils for
suspensions / pastes or granulation
manufacturing or processing.
o Organic solvents such as petroleum distillate,
alcohols, ketones, esters, glycol, and the like
as liquid / solvent system thickeners e.g.
creams, gels, ointments, suspension, etc
o Emulsifying agents in emulsions
o Methylcellulose as lubricating agent in saliva
and tears deficiencies
 10. Solubilization

◼ By definition, this is the process by which

water insoluble or partly soluble substances
are brought into solutions by incorporation
into a micellar structure.
◼ The site of solubilization within the micelle is
closely related to the chemical nature of the
solubilizate
 Solubilization (continued)

◼ Some of these aggregates are known as micelles.

◼ The concentration at which surfactants begin to
form micelles is known as the critical micelle
concentration or CMC.
◼ When micelles form in water, their tails form a core
that can encapsulate an oil droplet, and their
(ionic/polar) heads form an outer shell that
maintains favorable contact with water.
It is generally accepted that non-polar solubilizates
(aliphatic hydrocarbons, for example) are dissolved in
the hydrocarbon core as shown above
Water-insoluble compounds containing polar groups
are orientated with the polar group at the surface of
the ionic micelle among the micellar charged head
groups, and the hydrophobic group buried inside the
hydrocarbon core of the micelle
Slightly polar solubilizates without a distinct
amphiphilic structure partition between the
micelle surface and the core
Solubilization in non-ionic polyoxyethylated surfactants
can also occur in the polyoxyethylene shell (palisade
layer) that surrounds the core
 Pharmaceutical applications of solubilization

◼ A wide range of insoluble drugs have been

formulated using the principle of solubilization,
some of which will be considered here:
◼ Phenolic compounds such as cresol,
chlorocresol, chloroxylenol and thymol are
frequently solubilized with soap to form clear
solutions which are widely used for disinfection