Topic 11

Soap, Shampoo And

Detergents
 Soap and Detergents

Raw materials
Fat (triglycerides)
- Tallow (Beef or mutton fats) and coconut oil, palm oils, palm kernel oil,
and their derivatives
- Greases (fats), obtained from hogs and smaller domestic animals.

• The soap from coconut oil is firm and foams well. It contains a large amount of the
desired glycerides of lauric (C12) and myristic acids (C14).
Na2CO3
Required chemicals in addition to fat KOH
• The caustic soda, salt, soda ash, caustic potash, sodium silicate (builder),
sodium bicarbonate (builder) , and trisodium phosphate (builder).
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 Chemistry of soaps

• Soaps are water-soluble sodium or potassium salts of fatty acids containing 8 to

22 carbon atoms.

• The fatty acids are generally a mixture of saturated and unsaturated moieties.
- Saturated soap: CH3(CH2)n COOM
- Mono-unsaturated soap: CH3(CH2)nCH2CH=CHCH2(CH2)m—COOM
- Poly-unsaturated soap: CH3(CH2CH=CH)xCH2(CH2)y—COOM
[M=Na, K, R4N+]

SOAP

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 Chemistry of soaps

• (1) The basic chemical reaction in the making of soap is saponification:

Caustic soda

The chemical reaction between any fat and sodium

hydroxide is a saponification reaction.
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 Chemistry of soaps

(2) The other method for making soap comprises fat splitting followed by the
neutralization process with sodium hydroxide.

• Sodium hydroxide, potassium hydroxide, sodium carbonate, and

triethanolamine are the most commonly used alkaline.
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 Chemistry of soaps
(3). Soap manufacture by the saponification of fatty methyl esters

- The methanolysis of triglycerides takes place in the presence of enzymes (lipase) as

catalysts to produce fatty methyl ester and glycerin. The fatty methyl ester undergoes
the saponification and forms the final product.

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 Classification of soaps

Toilet soap is usually made from mixtures of

tallow and coconut in the ratios 80 - 90:10 - 20.

Toilet soaps contain only 10 to 15 % moisture,

except for perfume and a fraction of a percent
of titanium dioxide used as a whitening agent.

Bar soap includes regular and super fatted

toilet soaps, deodorant and antimicrobial
soaps, floating soaps, and hard water soaps.

The super fatted soaps are also made from a

mixture of tallow and coconut oil in ratios 50 -
60:40 - 50.
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 Classification of soaps

• Laundry soap bars are precursors of the chip and the powder forms.

• They are generally made from tallow or a combination of tallow and coconut oil.

• Borax (sodium tetraborate (Na2B4O7·10H2O) and builders, such as sodium silicate

and sodium carbonate, are included to improve performance and help soften water.

• All soaps contain10 to 30 % water and also contain perfume to improve the original
soap odor.

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 Definition of Detergent

• A detergent is similar to a soap, but with a general structure R-SO4-, Na+, where
R is a long-chain alkyl group.

• They made from chemical compounds rather than fats and lye (potash or
potassium carbonate).

• They are not inactivated by hard water, and have wetting-agent and emulsifying
agent properties.

• A surface-active chemical such as an alkyl sulphonate, are widely used.

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 Principle groups of synthetic detergents

• Detergents are complex formulations that contain more than 25 different

ingredients that can be categorized into the following main groups:

1. Surfactants
2. Builders
3. Bleaching agents
4. Additives

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 Surfactants

• Surfactants are chemicals that comprise a hydrophobic group (a long alkyl

chain) attached to a hydrophilic group.

• The hydrophilic group is usually added synthetically to produce water soluble.

• When it dissolved in water or another solvent, orient themselves at the interface

between the liquid and a second solid, liquid, or gaseous phase and modify the
properties of the interface.

• Surfactants are not only important as the active constituent of soaps and
detergents but are also in the stabilization of emulsions, in fabric softening.

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Mechanism of Surfactants

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 Classification of surfactants

• There are four main groups of surfactants: anionic, cationic, nonionic,

and amphoteric.

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 Anionic Surfactants

Anionic surfactants

• In anionics the long hydrophobic alkyl chain is in the anionic part of the
molecule. The organic part is negative.

• Major anionics are

- soaps,
- linear alcohol sulfates (AS),
- linear alcohol ethoxysulfates (AES), detergents
- linear alkylbenzenesulfonates (LAS).

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 Anionic Surfactants
Soaps
• The first type of cleansing agent, used by humankind for centuries, was soap.

• Soaps are the sodium or potassium salts of certain fatty acids obtained from
the hydrolysis of triglycerides.

• The fats (triglycerides) used in soap manufacture come from diverse natural
sources. Animal tallows and coconut oil are the favoured sources of the
tryglycerides. Palm, olive, cottonseed, castor, and tall oil are other sources.

• Often mixtures from different sources are used to vary hardness, water
solubility, and cleansing action of the final product.

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 Anionic Surfactants
Soaps

• Disadvantages of soaps compared to synthetic detergents:

- They are more expensive,
- They compete with food uses for fats and oils, and
- Their calcium and magnesium salts formed in hard water are very
insoluble and precipitate onto the clothing being washed.
- They also tend to clog automatic washers.
- They deteriorate on storage and are unstable in acid solutions.

• Advantages of soaps include greater biodegradability and less toxicity.

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 Anionic Surfactants

• Many synthetic anionic detergents are based on straight chain primary

alcohols and -olefins.

Eliminating Ca2+ and Mg2+ ions

Linear Alcohol Sulfates (AS)

• Alcohol sulfates (AS) are usually manufactured by the reaction of a primary

alcohol with sulfur trioxide or chlorosulfonic acid followed by neutralization
with a base.
• These are high foam surfactants but they are sensitive to water hardness and
higher levels of phosphates are required.
• Sodium lauryl sulfate (R = C11) is a constituent of shampoos due to its high-foaming
properties.

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 Anionic Surfactants
Linear Alcohol Ethoxysulfates (AES)

• Alcohol ethoxysulfates (AES) are made by reaction of ethylene oxide with a linear
C12 - C14 primary alcohol to give a low molecular weight ethoxylate, followed
by the usual sulfonation.

• They have high foam for shampoos and are "kind to the skin.“

• They are also used in light duty products such as dishwashing detergents.

• It is the least sensitive of the anionics to water hardness and therefore has
benefited in the trend away from phosphates.

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 Anionic Surfactants
Linear Alkylbenzenesulfonates (LAS)

• n-alkanes (C10-C14) separated from the kerosene fraction of petroleum are used as
one source of the alkyl group.

• n-Alkanes can be dehydrogenated to -olefins, which then can undergo a Friedel -

Crafts alkylation with benzene followed by sulfonation and caustic treatment gives a
more linear alkylbenzenesulfonate (LAS) which is "soft" or biodegradable.

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 + +
H
H21C10 CH CH2 H21C10 CH CH3
electrophilic attack secondary
of catalyst carbocation

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 Cationic surfactants

Cationic surfactants

• In cationics the long hydrophobic alkyl chain is in the cationic portion of the
molecule.

• Another way, the organic part is positive.

• In the more general structure R1R2R3R4N+X-, R1 is a long alkyl chain, the other R's
may be alkyl or hydrogen, and X- is halogen or sulfate.

• Cationic surfactants are not very good for cleaning because most surfaces carry a
negative charge and cationic surfactants adsorb on the surface instead of
dissolving the grease.

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 Cationic surfactants
Fatty acids can be obtained through the hydrolyzation of naturally occurring fats.

The fatty acid is then converted into the "quat" by the following sequence of reactions.
Chloromethane

• Cationic surfactants are used for special effects:

- fabric softeners
- antistatic agents
- microbicides
• Also find use in the hair conditioners.
An antistatic agent is a compound used
for treatment of materials or their surfaces
in order to reduce or eliminate build up of
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static electricity.
 Nonionics

Nonionics

• In nonionics, the molecule has a nonpolar hydrophobic portion and a more polar,
but not ionic, hydrophilic part capable of hydrogen bonding with water.

Alcohol Ethoxylates (AE or AEO)

• These are polyoxyethylene derivatives of straight-chain primary or secondary

alcohols with C10-C18.

• These linear alcohol ethoxylate nonionics (AE or AEO) are biodegradable.

• They have better detergent properties than LAS.
• They require fewer phosphates and work well in energy-saving cooler wash
water.

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 Amphoteric surfactants
Amphoteric surfactants

• These surfactants carry both a positive and a negative charge in the organic part
of the molecule. They have a long hydrocarbon chain as the hydrophobic tail.

• They may behave as anionics or cationics depending on the pH. They are
derivatives of amino acids.

• These compounds have the characteristics of fabric softeners.

• They tend to work best at neutral pH, and are found in shampoos, skin
• cleaners, and carpet shampoos.

• They are very stable in strong acidic conditions. These surfactants are rarely
employed in laundry detergents due to expensive. 24
 Detergent Builders

Definition of Builders

• The calcium and magnesium ions in solution interfere with the dislodging of dirt
from the substrate, and the dirt-suspending power is affected because of their double
positive charge.

• A chemical must be added to the detergent to sequester or complex the ions.

These are called builders.

• 58 % (w/w) builders are found in a detergent, 36 % (w/w) in the surfactants.

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 Detergent Builders

• The first important commercial builder was sodium tripolyphosphate, Na5P3O10.

• Besides sequestering polyvalent metal ions, it prevents re-deposition of dirt,

buffers the solution to pH 9-10, kills bacteria, and controls corrosion and deposits in
the lines of automatic washers.

• Phosphates pass unchanged through sewage into rivers and lakes. Since they are
plant nutrients they cause blue-green algae to grow at a very fast rate on the
surface, causing oxygen depletion. This is called eutrophication. The search for
phosphate substitutes began since 1970.

sodium tripolyphosphate 26
 Detergent Builders

• Alternative builders

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 Detergent Builders

• Builders enhance the detergency action so that less can be used of the more
expensive detergents of high activity.

• The combination of builders and surfactants exhibits a synergistic effect to

boost total detergency and cleaning efficacy.

• Detergent-builders should have the ability to control water hardness and other
metal ions by eliminating calcium and magnesium ions that arise from the
water and soil.

• Phosphates have been replaced largely with zeolites and sodium carbonate,
with the aid of newer anti-deposition aids like acrylic polymers.

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 Detergent Builders

Sundry organic builders (Optical brighteners)

• They are organic compounds capable of converting a portion of the invisible

ultraviolet light into longer wavelength visible blue light.

• They are dyestuffs, which are absorbed by textile fibers, but are not easily rinsed
off.

• The reflection of the blue light makes the clothes look brighter than they actually
are.

• Optical brighteners are usually derivatives of coumarin, stilbene, distyrylbiphenyl,

and bis(benzoxazole).

• The optical brighteners binding occur through the formation of hydrogen bond to
the cotton fibers.
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