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Formulation Chemistry

• Book: ‘Chemical Formulation – an overview of

surfactant-based preparations used in everyday life’ –
T Hargreaves
• http://www.essentialchemicalindustry.org/materials-
and-applications/surfactants.html

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Formulation Chemistry
• Introduction
• Surfactants
• Surface tension
• Micelles
• Hydrotropes
• Emulsions
• Selecting surfactants for emulsions
• Solubilisation
• Foams
• Detergency
• Formulation of consumer products

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Formulation Chemistry
• The science and technology of formulation is about making
products from raw materials
• Simply put, formulation is the mixing of compounds which do
not react in order to get a mixture with the desired
characteristics.
• Hunter/gatherers from Mesolithic times ( 10000 BC) attached
flint arrow head by using a blend of plant resin and beeswax
• Formulation is all about designing the everyday products we
use: detergents, paints, cosmetics, pharmaceuticals, food and
fuel additives
• Chemical reactions – change one substance into another;
formulation based on mixing chemicals – do not change
structures of compounds
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Formulation Chemistry

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Ingredients

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Homework
For Friday (hand in):
- For any two products, give the name and the
ingredients of the product
- For each of the ingredients, give the function
of the ingredient (do some research).

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Formulation Chemistry
• Introduction
• Surfactants
• Foam/antifoam
• Emulsifiers
• Preservatives / Antioxidants
• Flavours
• Fragrances
• Formulation of personal care products
• Formulation of household products

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Surfactants
• Important constituent of detergents
• Added to remove dirt from skin, clothes and household
articles particularly in kitchens and bathrooms
• Also used extensively in industry
• Surface active agent = surfactant
• Lower the surface tension (or interfacial tension) between
two liquids or between a liquid and a solid
• Surfactants function by breaking down the interface between
water and oils and/or dirt
• They also hold these oils and dirt in suspension, and so allow
their removal.
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Surfactants
• Surfactants may act as detergents, wetting agents, emulsifiers,
foaming agents, and dispersants.
• World production of surfactants is estimated at 15 Million
ton/year, of which about half are anionic surfactants used as
detergents
• Surfactants are usually organic compounds that are
amphiphilic, meaning they contain both hydrophobic groups
(their tails, apolar) and hydrophilic groups (their heads, polar)

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Natural Surfactants
• The earliest surfactants (soaps) were prepared from plant and
animal fats
• Natural fats (lipids) consist of triglycerides = esters of glycerol
and long chain fatty acids.
• The glycerides are hydrolyzed by heating with sodium
hydroxide solution to form soaps, the sodium salts of the
acids, and propane-1,2,3-triol.
• Process is known as saponification.

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Natural Surfactants
• Long chain fatty acids:
• C12 lauric acid, (dodecyl) CH3(CH2)10COOH
• C14 myristic acid (tetradecyl)
• C16 palmitic acid (hexadecyl)
• C18 stearic acid (octadecyl)
• Saponification process
• NaOH = hard soaps, KOH = soft soaps
• Can also form salts with ammonia, ethanolamine

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Vegetable oils

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Fatty acids
OH O
10 9
18 16 14 12 7 5 3 1 OH
(CH2)7CH3 17 15 13 11 8 6 4 2

Ricinoleic acid
(CH2)11COOH

Erucic acid O
13 12 10 9 7
17
15
5 3 1
11 8 2
OH
14 6 4
18 16

Linoleic acid

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Surfactants
• Synthetic surfactants have one very important advantage
over soaps
– Because soaps form insoluble calcium and magnesium salts
with the calcium and magnesium ions in hard water and in the
clays which are present in dirt, much of the soap is wasted
forming an insoluble scum
• Scum do not form when using a synthetic surfactant
• For example, in the anionic surfactants, the carboxylate
group in soap is replaced by a sulfonate or sulfate group
as the hydrophilic component.
• The corresponding calcium and magnesium salts are
more soluble in water than the calcium and magnesium
salts of carboxylic acids.

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Surfactants
Surfactants are classified based upon the nature
of the hydrophilic "head-groups" as:
• Anionics
• Cationics
• Non-ionics
• Amphoterics

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Anionic Surfactants
• In these surfactants the hydrophilic group is negatively
charged.
• They are the most widely used type of surfactants for
laundering, dishwashing liquids and shampoos.
• They are particularly good at keeping the dirt, once
dislodged, away from fabrics.
• Four anionic surfactants are used:
– alkylbenzene sulfonates
– alkyl sulfates
– alkyl ether sulfates
– soaps

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Anionic Surfactants
• In these surfactants the hydrophilic group is negatively
charged.
• They are the most widely used type of surfactants for
laundering, dishwashing liquids and shampoos.
• They are particularly good at keeping the dirt, once
dislodged, away from fabrics.
• Four anionic surfactants are used:
– alkylbenzene sulfonates
– alkyl sulfates
– alkyl ether sulfates
– soaps

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Alkylbenzene sulfonates
• The most common of the synthetic anionic surfactants are
based on the straight chain alkylbenzene sulfonates
• Benzene, in slight excess, is mixed with an alkene or
chloroalkane in the presence of an acid catalyst, usually a
solid zeolite (ion exchange), aluminium chloride (AlCl3) or
hydrofluoric acid (HF), to produce an alkylbenzene
(sometimes called detergent alkylate)

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Alkylbenzene sulfonates
• The alkylate is sulfonated using an air/sulfur trioxide mixture,
and the resulting sulfonic acid is then neutralised with an
aqueous solution of sodium hydroxide (often in situ), for
example:

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Alkyl sulfates
• Many detergent products, particularly liquids, contain other synthetic
anionic surfactants such as alkyl sulfates, esters of linear alcohols (C10-C18)
and sulfuric acid
• The alkyl sulfates are also used in personal care products such as
toothpaste and are manufactured by treating the alcohol with sulfur
trioxide. The product is then neutralised with aqueous sodium hydroxide
solution to form a sodium alkyl sulfate

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Alkyl sulfates
• The alcohols are either produced from carboxylic acids obtained from oils,
obtained naturally, for example from palm kernel oil or coconut oil, or
alternatively from long-chain alkenes, manufactured from ethene.
• Ethene  alpha-olefins  long-chain alcohols
• Ziegler process or SHOP process

• Common alkyl sulphate: sodium lauryl sulfate:

CH3(CH2)10CH2OSO3-Na+
• Can cause skin and eye irritation

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Alkyl ether sulfates

• Various types of sodium alkyl ether sulfates (SLES) are more widely used
than simple alkyl sulfates (e.g. sodium laureth sulfate, structure ??)
• In the manufacturing process, a primary alkyl alcohol (from a synthetic or
natural source and typically a blend based around dodecanol) is first
ethoxylated with 1 to 3 molar equivalents of epoxyethane
• The product is then sulfated using sulfur trioxide and neutralized with
alkali to form the alkyl ether sulfate
• These materials are preferred by product formulators for many
applications (dishwashing liquids, shower gels, shampoo, etc.) because
they are milder to the skin than alkyl sulfates. They also generate less
foam which is an advantage in the formulation of laundry machine
products.
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Soaps

• Disadvantage: pH>8
• Lose activity in hard water

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Soaps
• Modern plants have continuous processes.
• The oils are purified, blended and then mixed with sodium hydroxide
solution very rapidly.
• The mixture is passed into a heated reaction chamber where
saponification occurs.
• The glycerol is more valuable than the soap and most of it is
recovered. Some is left in the soap to make it smooth and soft.
• After saponification the soap and glycerol mixture is usually passed
on to a rotating disc contact or RDC where the mixture is passed
down a column and is washed with a counter-current of sodium
chloride solution.
• Soap is not very soluble in salt water and separates out. Glycerol
stays in solution which is known as lye. The washed soap is then
further treated with sodium chloride solutions and centrifuged to
give soap at the required concentration.

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Designing soaps
• In order to give those properties to the soap the public seek, it is
manufactured from a blend of animal fats (tallow) and vegetable oils
(coconut and palm kernel). Some pure vegetable soaps are available,
manufactured by substituting palm oil for tallow as the triglycerides
have sufficiently similar composition. These are most likely to be
manufactured in tropical countries where the vegetable oils are more
readily available than are animal fats.

• Some high quality soaps contain un-neutralised fatty acids. These

help to stabilise the lather and improve the feel of the soap on the
skin.

• Traditional bar soaps are being increasingly replaced, particularly in

developed markets, by liquid products such as shower gels, body
washes and 'liquid soaps' that are formulated using synthetic
surfactants rather than soaps.
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Cationic surfactants
• Hydrophilic head is positively charged.
• Although they are produced in much smaller
quantities than the anionics, there are several
types, each used for a specific purpose.

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Mono alkyl quaternary systems

• They are used as fabric softeners with anionic
surfactants, helping them to break down the
interface between the dirt/stain and the
water.

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Esterquats
• The directly quaternised fatty acid surfactants described on previous slide
have been replaced for laundry applications by more complicated
structures in which there is an ester linkage between the alkyl chains and
the quaternary head-group as these are more biodegradable and less toxic
• They are known as esterquats
• Esterquats give detergents their fabric softening qualities

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Cationic surfactants
• Positive charge on nitrogen
• Surfaces of most materials carry negative charges
• Strong interaction with cationic surfactant – holds surfactant molecule in
place at specific chemical sites
• Chemisorption
• Properties of surface changed
• Widely used in hair care products – hair softer and silkier. Prevent static
electricity
• Also in skin preparations – when absorbed onto skin (protein), skin
acquires pleasing softness
• Fabric softener
• Some have bactericidal properties

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Nonionic surfactants
• These surfactants do not bear an electrical charge and are often used
together with anionic surfactants
• An advantage is that they do not interact with calcium and magnesium
ions in hard water
• They account for nearly 50% of surfactant production (excluding soap).
The major group of nonionics are the ethoxylates made by condensing
long chain alcohols with epoxyethane (ethylene oxide) to form ethers
• The long-chain alcohol can come from either a synthetic or natural source

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Nonionic surfactants
• Although they do not contain an ionic group as their hydrophilic
component, hydrophilic properties are conferred on them by the presence
of a number of oxygen atoms in one part of the molecule which are
capable of forming hydrogen bonds with molecules of water.

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Nonionic surfactants
• As the temperature of the surfactant solution is increased the hydrogen bonds
gradually break causing the surfactant to come out of solution.
• This is commonly referred to as the cloud point and is characteristic for each
nonionic surfactant.
• Nonionics are more surface active and better emulsifiers than anionics at
similar concentrations.
• They are less soluble than anionics in hot water and produce less foam
• They are also more efficient in removing oily and organic dirt than anionics.
• Depending on the type of fibre, they can be active in cold solution and so are
useful in countries which lack hot water supplies and in developed countries
where there is a desire to lower the wash temperatures either to save energy
or because of the type of fabric being washed.
• Nonionics are used in fabric washing detergents (both powders and liquids), in
hard surface cleaners and in many industrial processes such as emulsion
polymerization and agrochemical formulations.

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Amphoteric surfactants
• Amphoteric (or zwitterionic)
surfactants are so called because
the head-group carries both a
negative and positive charge.
• A range of methods is used to
produce such materials, almost all
of which contain a quaternary
ammonium ion (a cation).
• The negatively charged group can
be carboxylate, -CO2-, sulfate, -
OSO3- or sulfonate, -SO3-.
• One such well-used class is the
alkyl betaines which have a
carboxyl group.
• Betaines are neutral compounds
with a cationic and an anionic
group which are not adjacent to
one another

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Amphoteric surfactants
• Good detergency, high foaming capacity, mild action on skin
• Baby shampoo, shower gel
• Frequently used shampoo where they act as secondary
surfactant, the primary one being an anionic such as sodium
lauryl ether sulphate
• Properties depend on pH of water in which they are dissolved
– Low pH, behave as cationic molecule

• Coco imidazole betaine Cold water detergent

• Cocoamido sulfo betaine Acid metal cleaners
• Oleo amido propyl betaine Skin care products
• Tall oil imidazoline Industrial detergent

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• Coconut oil
– 48% lauric acid (C12 saturated)

• Tall oil fatty acids

– Obtained from wood pulp of pine trees
– Mostly oleic acid

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Surface Tension

• Duck: do not get wet

• Water spider – can run on surface of water

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Surface Tension
• In liquid, there are forces between the individual molecules
(forces in H2O?)
• Each molecule experience forces in all three directions from
neighbouring molecules
• A molecule on the surface is deficient of the ‘upward’ force
but strength of other forces remain the same
• Consequently there is a net downward pull that creates a
tension at the surface which results in a skin-like property
on the surface of the water
• All liquids have surface tension, but it is more pronounced
in water
• Surface tension becomes a problem when you want to mix
certain liquids such as oil (dirt) and water

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Surface Tension

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Surface Tension
• When dissolved in water, some substances increase
its surface tension whereas other substances have
the opposite effect.

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Adsorption
• When a surfactant is mixed with water, its
hydrophilic part is strongly attracted to water but
the lipophilic part is not
• Surfactant molecules prefer a place on the
surface where its lipophilic part orients itself
away from the water
• Concentration of molecules on surface is called
adsorption
• As consequence of adsorption, only a small
amount of surfactant is necessary to have a
significant effect on the surface tension
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Adsorption

• Low concentrations random orientation; at higher concentrations

surfactant of surface more ordered
• Adsorption also occurs at other interfaces – solid/gas, solid/liquid,
liquid A/liquid B

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Micelles
• When concentration of surfactant is increased, molecules are
forced to agglomerate to form larger particles called micelles
• Concentration at which molecules in solution no longer exist
as discrete particles but start to aggregate is known as the
Critical Micelle Concentration (CMC)
• As the lipophilic chain of surfactant increases in length, its
water solubility is lower which corresponds to lower CMC

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Micelles

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Micelles
• If concentration of surfactant in water is increased, it will
reach a stage where surface is packed full with surfactant
molecules
• Surface tension is at minimum
• Surface has effectively changed from water surface (high
surface tension) to hydrocarbon surface (low surface tension)
• What happens if concentration of surfactant is increased?

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Micelles

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Micelles

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Micelles
• Get different type of micelles, each depending on the
proportion of the surfactant molecules relative to the water
molecules
• Very low concentration: unassociated surfactants
(‘monomer’)
• Simplest micelle: spherical aggregates of surfactants with
lipophilic tails to the inside of the sphere and the hydrophilic
heads to the outside.

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Micelles
• Spherical micelles: Approximate diameter = twice lipophile
length
• Lipophilic tails are attracted to each other by van der Waal’s
forces
• Anionic heads repel each other as a result of anionic head
groups
• No hole in centre – core completely filled with lipophile
• Number of molecules involved in spherical micelle (aggregate
number) depends on particular surfactant and temperature of
system
• Equilibrium exists between surfactant molecules in spheres
and unassociated ones

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Micelles
• When proportion of surfactant molecules to water increases
well above CMC, micelles become cylindrical rods (sphere to
rod transition)
• Solution with spherical micelles is slightly more viscous than
one composed of unassociated surfactants
• When sphere-to rod transition takes place, the cylinders have
a line of contact resulting in a big increase of viscosity
• Further increase lead to situation where water molecules are
less likely to occupy spaces between cylinders – get close
hexagonal packing of cylinders
• Final stage (almost neat surfactant) – form a layer structure

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Micelles
• Presence of electrolytes in aqueous phase has profound effect
on micelle structure
• e.g. a dilute solution of anionic surfactant has low viscosity
because surfactant forms spherical micelles
• Addition of NaCl dramatically increases viscosity – ions forces
hydrophilic heads to pack closer together in micelles, resulting
in lower CMC causing more aggregation – lead to more
sphere-to-rod transition, more hexagonal packing, increase in
viscosity

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Micelles
• Opposite effect observed when a second surfactant with a
short lipophilic chain is present
• it becomes wedged into the micelles, preventing it from
undergoing sphere-to-rod transition
• Stabilise spherical arrangement
• Such surfactants are known as hydrotropes
• Keep viscosity down, even with dissolved salts and surfactants
at high levels

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Micelles
• Many commercial surfactants consists of mixtures with
different lengths of lipophilic chains
• Get mixed micelles
• In formulation, mixed micelles often gave better performance,
e.g. for surface tension reduction and for producing stable
emulsions

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Hydrotropes
• Many formulations are made in concentrated form to
minimize space demands in storage and transport,
reduce packaging waste
• E.g. formulation used for heavy degreasing/cleaning
required in some industrial processes
• Get a product that can be diluted to different
strengths for different demands
• In concentrated solutions it is common to have high
electrolyte contents (phosphates, silicates, etc.) and
maximum levels of surfactants
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Hydrotropes
• Preparing a concentrated formulation poses
problems of how to obtain a stable solution
and keep water to a minimum
• Surfactant concentration is much higher than
CMC
• Micelles in layered phase, solution high
viscosity
• Use hydrotrope to overcome problem

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Hydrotropes
• In hydrotope the lipophilic chain is relatively small
compared to hydrophilic head (In surfactants opposite
applies)
• Hydrotrope aggregate with surfactant molecules and
become part of micelle structure
• Large hydrophilic head relative to small lipophilic tail gives
them a wedge-like shape
• Enable them to force their way between surfactant
molecules in micelle
• Destabilize micelle structure
• Formulation of large micelles are prevented
• Viscosity is kept at low value

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Hydrotropes
• Examples: Sodium toluenesulfonate, sodium
cumenesulfonate, sodium xylenesulfonate
• Structures?
• Most hydrotropes are poor surfactants

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Hydrotropes

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Emulsification
• Emulsions are dispersions of two immiscible
liquid phases, usually oil and water
• Preparation of emulsions are often
problematic
• Emulsions are energetically unstable systems
and are constantly under influences trying to
make them revert to their component parts
• Some will break down in seconds; others have
half life of years
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Emulsification
• Oil/water emulsions can have two different
forms
– Oil-in-water (o/w): oil is dispersed (dispersed
phase) as small particles in water (continuous
phase)
– Water in oil (w/o): opposite

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Emulsification

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Emulsification
• Surface activity is at heart of emulsions
• Place 50 cm3 of oil and 50 cm3 of water in a 6 cm
diameter jar – get layer of oil floating on water
with well-defined oil/water interface
– What is the surface area of the interface?
• Add few drops of emulsifier and shake so that oil
become dispersed as tiny droplets
• If droplets have typical diameter of emulsions of
0.0001 cm
– What is the surface area of the interface?

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Emulsification
• Surface activity is at heart of emulsions
• Place 50 cm3 of oil and 50 cm3 of water in a 6
cm diameter jar – get layer of oil floating on
water with well-defined oil/water interface
• What is the surface area of the interface?
• Area = πr2
• r=?
• Area = 28.3 cm2
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Emulsification
• Add few drops of emulsifier and shake so that
oil become dispersed as tiny droplets
• If droplets have typical diameter of emulsions
of 0.0001 cm, the volume of each one is
V = (4/3)πr3 = 523 x 10-15 cm3
• Number of oil particles in 50 cm3 is N = 0.0956
x 1015
• Total surface area = 4πr2N = 3 000 000 cm2

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Emulsification
• In general, for o/w emulsions, the dispersed
phase (oil) amounts between 5% and 60%
• For w/o emulsions the dispersed phase
(water) may be as high as 70%
• Example of emulsion: mayonnaise
– Tiny drops of vegetable oil in water (vinegar = 4%
acetic acid in water)
– Require emulsifier (a surfactant) = egg yolk

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Stability of emulsions
• Emulsions can break down into two phases as a result of
inherent instability
• Can also undergo inversion from o/w to w/o and vice versa
(inversion)
• E.g. preparation of butter: churning of cream (o/w emulsion)
is changed to butter (w/o emulsion)

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Stability of emulsions
• For reasonable stable emulsion, the surfactant used
(emulsifier) must produce an interface that is highly
elastic
• E.g. it needs to withstand mechanical action when a
droplet of the disperse phase migrates in the
continuous phase and collide with other dispersed
droplets
• A weak interface would be ruptured by such a collision
resulting in the onset of separation
• An emulsion with large particles of the dispersed phase
will be less stable than a similar composition with
smaller dispersed phase particles

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Stability of emulsions
• Improvements to stability of emulsions can be
made by using two structurally different
surfactants
• A mixture produced an elastic adsorped layer
as a result of different shaped lipophiles
becoming entangled or interwoven
• Less easily separated than orderly
arrangement of lipophiles of same shape

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Stability of emulsions
• Viscosity also play a role
• Increasing viscosity reduce impact energy and
frequency of collision
• Decrease particle rupture
• Higher viscosity achieved by incorporating
thickeners

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Stability of emulsions
• Temperature increases affect stability of
emulsions
– Changing solubility of emulsifying agent
– Reducing viscosity of the phases, especially of
continuous phase
– Causing greater rate of diffusion and agitation
between phases along with more collisions
between particles

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Selecting surfactant for emulsion

• Can be difficult task
• HLB numbers: hydrophile lipophile balance
• Confined to non-ionic surfactants
• Gave values between 0 and 20 to indicate relative strength of
hydrophilic and lipophilic parts of surfactant molecule
• HLB number is calculated on basis of molecular structure and
is normally provided with other technical data by
manufacturer
• Can also obtain HLB number by comparing unknown with
surfactant with known HLB number in emulsification of
known oil.
• Can obtain HLB number of anionic surfactants by this way
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Selecting surfactant for emulsion

• Low HLB value (0 – 10) = weak hydrophile, strong
lipophile
• Oil soluble. Useful as w/o emulsifier
• High HLB value (10 – 20) = water soluble, used for
o/w emulsifiers
• Most of HLB data available is for preparation of w/o
emulsifiers
• HLB values can also be used for best performance in
wetting and detergency

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Selecting surfactant for emulsion

• First task in preparing stable emulsion is to find a
surfactant system that have same HLB number as
value for proposed oil/water blend
• Find HLB value of oil if oil is single compound
• If mixture – then calculate

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Selecting surfactant for emulsion

HLB values for surfactants cannot be measured directly as
for example the density of a liquid. However, an
approximate indication of HLB range may be obtained by
observing how the surfactant behaves when mixed with
water followed by thorough agitation:

HLB 1-4 Does not disperse and readily separates

HLB 3-6 Disperse with difficulty
HLB 6-10 Forms a milk
HLB 10-13 Cloudy to clear dispersion
HLB 13-20 Solution
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Selecting surfactant for emulsion

HLB values give an indication of the main function as shown
below. Typical values found for nonylphenol ethoxylates (EO =
ethylene oxide)

Water-in-oil emulsifier (1-3 EO) HLB 3 to 6

Wetting agent HLB 7-9
Oil-in-water emulsifier (4-6 EO) HLB 8 to 15
Detergent (7-12 EO) HLB 12 to 15
Hydrotrope (12 & over EO) HLB 15 to 18

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Selecting surfactant for emulsion -

Example
You need to prepare a skin cream based on o/w
emulsion in which an oil and two waxes are emulsified
in water. Assume that the oil phase must comprise 80%
liquid paraffin, 12% cetostearyl alcohol, 8% lanoline.
Which surfactant will you use to form the skin cream as
an emulsion in water?

Hint: calculate HLB values (HLB values for components

can be obtained in tables).

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Selecting surfactant for emulsion -

Example
Liquid paraffin HLB 10 80% of 10 = 8
Cetostearyl alcohol HLB 15 12% of 15 = 1.8
Lanolin HLB 9 8% of 9 = 0.72
HLB requirement 10.52

To choose surfactant, application need to be taken into

account. Sorbitan monosterates are used in skin
preparations

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Selecting surfactant for emulsion -

Example
A mixture of surfactants is often needed the get to the required HLB:

Sorbitan monostearate (20EO) HLB 14.9

Sorbitan monostearate HLB 4.3

Mixture 1:1 HLB 9.6

What must the ratio of the tow surfactants be to get a HLB of 10.52?

Amount of mixture to use is normally around 2-5% with oil 30% and
water (containing surfactant) 70%

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Solubilisation
• Another way in which surfactant molecules in
aqueous solution can emulsify an oil is by
solubilisation
• Result in liquid, called microemulsions, in which oil is
held within surfactant micelle structure
• Normally spherical micelles have a diameter of twice
length of lipophile and this is capable of some
expansion as other lipophilic material, e.g. an oil,
dissolves within the micelle

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Solubilisation
• Although micelles are swollen it is still colloidal
• Particles are too small to scatter light and are transparent
or slight bluish opalescence unlike regular emulsions
(macro emulsions) with larger particle sizes (white
opacity)
• E.g. if essential oils (e.g. eucalyptus) (immiscible in water)
is mixed with about three times its mass with a non-ionic
ethoxylate and then added to water, the result is a clear
solution (a colloid dispersion of swollen micelles)
• If the oil and water is mixed in presence of small amount
of same ethoxylate, a milky suspension is formed.

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Foaming
• A foam is a dispersion of a gas in liquid
• E.g. shaving foam
• Usually liquid is an aqueous solution and gas is air
• In aerosol dispensed foams , the dispersed gas is the
propellant such as propane/butane
• Foam forms as a result of huge amount of interfacial
area between water/gas
• Study of foams similar to emulsions and involves
understanding of adsorption of surfactants at
water/gas interface

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Foaming

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Foaming
• Liquid tend to drain downwards as a result of gravity (or
bubbles float to top)
• Bubbles move closer together until polyhedral gas cells form
• Drainage may not proceed further and relatively stable foam
results
• If liquid continues to drain, the thin film will rupture and foam
collapse
• For a stable foam, the thin aqueous film needs cell walls with
correct surface properties, namely elasticity and capacity to
resist continuous drainage
• With right surfactant these surface properties can be achieved

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Foaming
• Liquid tend to drain downwards as a result of gravity (or
bubbles float to top)
• Bubbles move closer together until polyhedral gas cells form
• Drainage may not proceed further and relatively stable foam
results
• If liquid continues to drain, the thin film will rupture and foam
collapse
• For a stable foam, the thin aqueous film needs cell walls with
correct surface properties, namely elasticity and capacity to
resist continuous drainage
• With right surfactant these surface properties can be achieved

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Detergency
• Largest consumption of surfactants is in detergent products
• Anionic surfactants important
• Sodium alkylbenzene sulfonates and sodium lauryl sulfates are
popular in washing-up liquids and machine clothes wash
preparations
• Usually blended with other surfactants such as amphoterics and
non-ionics
• Most soils encountered in detergency comprise of a mixture of dust
particles such as finely divided minerals (silica, brick, coal, cement,
soot, metals) and organic substances (smoke, fats, protein, food).
• Nearly all these are acidic materials or contain groups that yield
acidic substances during hydrolysis
• Will be water soluble if it reacts with right base

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Detergency
• pH during washing plays an important role
• Alkali and hot water can go a long way to clean soiling
• Oven cleaners, drain cleaners consist solutions of strong bases
such as NaOH
• However, it is too severe for most household uses, especially
if in contact with skin
• Alkaline conditions also suppress solubility of water hardness
salts such as calcium salts, which can form scum and react
with anionics to bridge hydrophilic heads and reduce their
effectivity as surfactants, react with soil to form insoluble
compounds
• Problem of calcium ions can be tackled by addition of
chelating agents

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Detergency
• Detergent effect of surfactant comes into effect when
surfactant molecules present themselves for absorption
at the soil/water, soil/substrate and substrate/water
interface
• Molecules on water/air interface not directly involved in
cleaning action but form foams which indicates when
detergent has been used up
• Rate at which surfactant molecule arrives from bulk
liquid at interface depends on concentration of monomer
(unassociated molecule)
• Surfactants with high CMC values are effective
detergents (that is why anionics are mainly used)

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Formulation Case Study: Shampoo

Ingredients on label
Aqua Polyquarternium
Sodium laureth sulfate Formaldehyde
Sodium chloride Tetrasodium EDTA
Cocoamide DEA Methyl paraben
Coco amido propyl betaine Propyl paraben
Perfume C1 47005 & 74260
Citric acid

– Amounts of ingredients not listed

– Trade secret
– Must list ingredients in order of amount present starting with
greatest proportion

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Formulation Case Study: Shampoo

Aqua
– Aqua = water

– Large amounts of water is necessary to get correct

properties for the product
– Usually filtered and deionized water

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Formulation Case Study: Shampoo

• Sodium laureth sulfate
• Anionic surfactant
• Sodium lauryl ether sulfate
– CH3(CH2)10CH2(OCH2CH2)nOSO3Na
– n = 2 or 3
– Remove natural greases that have built up and which bind
particles of dust and dirt
– Concentration important: too strong and it will gel when added
to water; too weak and user will need to use large volume to be
effective
– Typical concentration used 11%
– Above CMC level
– Most surfactant molecules associated as spherical micelles

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Formulation Case Study: Shampoo

• Sodium laureth sulfate
– Shampoo cannot be too thin
– A greater concentration of sodium laureth sulfate
would achieve this but when a highly
concentrated surfactant solution come in contact
with water, especially tap water with electrolytes,
a rigid gel may form
– To get a greater viscosity, it is necessary to
increase number of large micelles such as
cylindrical and hexagonal arrays of them

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Formulation Case Study: Shampoo

Sodium chloride
– Effect of electrolyte is to promote sphere-to-rod transition
of surfactant
– Cause a marked increase in viscosity
– Careful control of amount of salt added will result in right
amount of viscosity increase giving liquid greater staying
power
– Only small amounts of NaCl added (3%)
– Larger concentration may cause surfactant molecules into
the lamella structure which produces low viscosity as
layers slip easily under an applied force

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Formulation Case Study: Shampoo

Coconut diethanol amide

– Non-ionic surfactant which function is to improve foam

stability by changing coarse bubbles into fine ones
– Also increase viscosity by promoting larger micelle
arrangements

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Formulation Case Study: Shampoo

• Coco amido betaine

– Amphoteric surfactant – improving degreasing action without

increase in irritancy
– Low irritancy to skin and eyes

• Fragrance
– Small amounts added to mask smell of chemicals
– Provide pleasant odour

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Formulation Case Study: Shampoo

• Citric acid
– Control acidity
– Mild enough that slight excess will not make product
hazardous (pH 5-6)
– Can also use lactic acid. Lactic acid helps make skin soft
and smooth

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Formulation Case Study: Shampoo

• Quaternary cationic
– Cationics can react by means of ionic bond formation with
anionic surfactants to produce large hydrophobic molecule
with no surfactant activity
– However, some quaternized protein molecules are
compatible with sodium lauryl ether and can be used as
conditioners – they bond to hair shaft and leave hair with
shine and a silky feel

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Formulation Case Study: Shampoo

• Tetrasodium EDTA
– Bind to metals and prevent them from having adverse
reactions with other ingredients

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Formulation Case Study: Shampoo

• Formaldehyde
– Gas at room temperature
– Hydrated in aqueous solution (Formalin – 37% aq sol)
– Preservative
– Kills large number of micro-organisms; cheap
– However, concerns over health and safety

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Formulation Case Study: Shampoo

• Methyl paraben, propyl paraben

– Preservative in cosmetics and pharmaceutical producrs
– Broad spectrum antimicrobial, antifungal
– Preservatives such as these can be used in low concentrations
– Necessary for acceptable product life time

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Formulation Case Study: Shampoo

• Colour
– Needs to produce attractive product
– Colourant identified by Colour Index (CI) number
– Present only in trace amounts
– C147005 = quinoline yellow, a bright greenish yellow dye (food
dye)
– C174160 = copper phthalocyanine = blue insoluble complex

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Ingredients of washing powders

• Surfactants
• Buffering agents - to keep the pH at the appropriate value
• Structurants - to give shape to the fabric being washed
• Sequestrants - to react with free metal ions which might
otherwise cause problems with appearance or scum
formation
• Optical brighteners - to make the fabrics look brighter and
whiter
• Antifoaming agents
• Enzymes - to remove specific stains: proteases (to remove
proteins), amylases (to remove starches), lipases (to remove
fats)
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Ingredients of washing powders

• Fragrance
• Anti-redeposition agents - to prevent dirt being redeposited on fabrics
• Skin conditioning agent - to help to keep the skin in good condition
• Softness extender - to help keep the clothes 'soft'
• Emulsifier - to help keep immiscible liquids as an emulsion
• Colorant
• Domestic automatic machine laundry liquids are formulated using blends
of anionic, nonionic and soap surfactants and various other functional
substances. Bleach systems are not compatible with the higher water
temperature and cannot be used above ca 315 K.
• For hand washing (used for delicate fabrics such as wool or silk), foam-
stabilisers are included, to maintain foam. The customer equates the
quantity of foam produced with the detergent cleansing action. For the
quantity of foam produced the order is:
– anionics > soap > nonionics > cationics

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Ingredients of dishwashing
liquids/powders
• Machine dishwashing powders and tablets

The products used in dishwashers are usually powders and contain

builders (90-95%), a nonionic surfactant (1-5%), bleach agents with
an activator and enzymes. They are formulated with sodium
carbonate and sodium silicate to create a very alkaline
environment that helps to denature (break down) the fats and
proteins left on the used dishes and utensils.

• Washing up liquids

These formulations contain between 13-40% of surfactants which

are predominantly alkyl ether sulfates but also include nonionics
and amphoterics (betaines).

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Dish-wash liquid

• In contact with skin – mildness important

• Viscosity important – squeeze bottle
• Needs good foam, must lasts throughout process
• Needs to be environmentally friendly

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Ingredients
• Shampoos and shower gels
– These tend to be based on alkyl ether sulfates and usually
contain small amounts of other surfactants (most typically
amphoterics) which help protect the skin from irritation
and also condition the hair.

• Hair conditioners and fabric softeners

– These products are formulated using cationic surfactants
(sometimes combined with small amounts of non-ionic
surfactants). These are not cleansing products and the
cationic surfactant is deposited onto the slightly negatively
charged hair or cotton fibre surface, thus giving a
lubrication benefit.

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Formulation of Pharmaceuticals
• Apart from bio-active substance, pharmaceutical
preparations contain other chemicals that is essential for
effective application
• Surfactants as wetting, solubilizing, and emulsification agents
• Some surfactants are active components, e.g. cetylpyridinium
chloride used for antibacterial in mouth washes for oral
hygiene; benzalkonium chloride
(alkyldimethylbenzylammonium chloride) for eye wash liquid

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Formulation of Pharmaceuticals
• Currently much research into different ways in which drugs
can be delivered to precise location where it is needed
• Bio-molecule must arrive intact
• Surfactants can play a role – drug molecule can be locked in a
micelle until destination is reached where micelles break
open and releases drug.

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Formulate your own products

• Decide which product you want to make

• Do some research on internet on formulation
• Find out price and availability of raw materials
• Plan finances – can you make a profit?
• Marketing?
• Internet: Resources for entrepreneurs

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Formulate your own cosmetics

Website: http://chemistscorner.com/
Google ‘chemist corner’

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Tutorial Problem:
Comment on each of the structure and role of each
ingredient in the following formulation for toothpaste:

Water 21.5 (%)

Glycerol 25
Sodium carboxymethylcellulose 1
Sodium monofluorophosphate 0.8
Sodium saccharin 0.2
Dicalcium phosphate dihydrate 50
Sodium lauryl sulfate 1.5
Flavour
Preservative

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Toothpaste
• Water
• Glycerol
• Sodium carboxymethylcellulose
• Sodium monofluorophosphate
• Sodium saccharin
• Dicalcium phosphate dehydrate
• Sodium lauryl sulfate
• Flavour
• Preservative

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Toothpaste
• Water
• Glycerol
• Sodium carboxymethylcellulose
– Thickener, binder, prevent polishing agent from settling out
• Sodium monofluorophosphate
– Fluoride is beneficial for enamel by converting apatite to fluoroapetite

• Sodium saccharin
– Artificial sweetener
• Dicalcium phosphate dehydrate
– Polishing agent
• Sodium lauryl sulphate
– Surfactant. Wetting agent. Emulsification agent to remove grease and food residues
from the teeth
• Flavour
• Preservative

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Tutorial Problem
Comment on each of the structure and role of each
ingredient in the following formulation for dish-wash
liquid:

Water make up to 100

Sodium dodecylbenzene sulfonate 11.7
Coconut diethanolamide 1.0
Sodium lauryl ether sulfate (27%) 6.6
Sodium chloride qs
Perfume, colour, preservative qs

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