ChE 311: Industrial Chemistry for Chemical Engineering

CHEMISTRY OF SURFACTANTS

What is Surfactant?
 A Surfactant is an organic chemical that when added to liquid, changes the properties of that liquid
at a surface or interface. The word surfactants stand for “SURFace ACTive AgeNT”.
 Two Parts of Surfactants:
Hydrophobic Tail
-Straight Chain, Long Alkyl Groups
-Branch Chain, Long Alkyl Groups
-Long-Chain Alkyl + Benzene
-High MW Propylene Oxide Polymers
Hydrophilic Head
-Anionic
-Cationic
-Nonionic
-Amphoteric
 Surfactants are one of the major components of cleaning products and can be regarded as the
‘workhorses’.
 There are four main types of surfactants used in laundry and cleaning products.
1. Anionic
2. Cationic
3. Non-ionic
4. Amphoteric/ zwitterionic

SOAPS
History
 The origin of the word “soap” is traced to sacrificial Mount Sapo of ancient Roman legend where
animals were sacrificed. The mixture of fat and wood ashes that reacted to form soap was carried
by rain to the banks of the Tiber River ad was found as a clay deposit useful for cleaning clothes.
 The washing industry, usually known as the soap industry, has roots over 2000 years in the past, a
soap factory having found in the Pompeii Excavations.
 Soap itself was never actually “discovered”, but instead graudally evolved from crude mixtures of
alkaline and fatty materials.
1811 – Michel Eugene Chevreul, a French chemist, showed that soap formation was
actually a chemical reaction. Domeier completed his research on the recovery of glycerine from
saponification mixtures in this period.
1791 – Nicholas Leblanc(French Chemist) important discovery of so called SODA ASH
PROCESS. Producing lower-priced sodium carbonate from sodium chloride, the alkali required was
obtained by the crude leaching of wood ashes or from the evaporation of naturally occuring
alkaline waters, e.g., the Nile River
Mid-1800’s – Ernest Solvay (Belgian Chemist) – the ammonia process, which used common
table salt, or sodium chloride, to make soda ash.
 The raw materials shortage of WW1 led the Germans to develop “synthetic soaps” or detergents.
And during the 1960’s the requirement of biodegradability became important and caused to return
to linear long chains, because only the linear chains can be easily biodegraded.

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Definition
Soap is a cleansing agent created by the chemical reaction of a fatty acid with an alkali metal hydroxide.
It has the general formula of RCOOX.
The modern definition of soap relates to cleansing agents derived from fats, oils, and other fatty
derivatives; the soaps are alkali and ammonium salts of fatty acids containing from 8 to 22 carbon atoms.
 Two types of chemical reactions which are utilized in the manufacture of soap:
A. Saponification of triglycerides (fats and oils)
B. Neutralization of fatty acids
-fatty acids are produced from the triglycerides by a variety of methods, most notably splitting or
hydrolysis of fats and oils with steam under high pressure.

Components of Soap
The three main components of soap by both cost and volumes are oils, caustic, and perfumes.
Tallow Soaps: Coconut oil
40-45% Oleate 45-50% various C12 carboxylates
25-30% Palmitate 16-20% various C14 carboxylates
15-20% Stearate 8-10% various C16 carboxylates
5-6% oleate
10-15% various C12 or shorter
carboxylates

A soap molecule has two ends with different properties:

1. A long HYDROCARBON part which is hydrophobic (i.e. it dissolves in hydrocarbon.
2. A short IONIC part containing COO-Na+ which is hydrophilic (i.e. it dissolves in water)

Manufacture of Soap
Raw Materials
 Fats and Oils - used in soap-making come from animal or plant sources. Each fat or oil is made up
of a distinctive mixture of several different triglycerides.
In a triglyceride molecule, three fatty acid molecules are attached to one molecule of glycerine.
There are many types of triglycerides; each type consists of its own particular combination of fatty
acids. Fatty acids are the components of fats and oils that are used in making soap. They are weak
acids composed of two parts: A carboxylic acid group consisting of one hydrogen (H) atom, two
oxygen (O) atoms, and one carbon (C) atom, plus a hydrocarbon chain attached to the carboxylic
acid group. Generally, it is made up of a long straight chain of carbon (C) atoms each carrying two
hydrogen (H) atoms.
 Alkali - An alkali is a soluble salt of an alkali metal like sodium or potassium. Originally, the alkalis
used in soap-making were obtained from the ashes of plants, but they are now made commercially.
Today, the term alkali describes a substance that chemically is a base and that reacts with and
neutralizes an acid.
The common alkalis used in soap-making are sodium hydroxide (NaOH), also called caustic soda;
and potassium hydroxide (KOH), also called caustic potash.

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Soap is produced industrially in four basic steps:

1. Saponification
- A mixture of tallow (animal fat) and coconut oil is mixed with sodium hydroxide and heated. The soap
produced is the salt of a long chain carboxylic acid.
*Saponification - process of making soap by the hydrolysis of fats and oils with alkalies
2. Glycerine Removal
-Glycerine is more valuable than soap, so most of it is removed. Some is left in the soap to help
make it soft and smooth. Soap is not very soluble in salt water, whereas glycerine is, so salt is added to the
wet soap causing it to separate out into soap and glycerine in salt water.
3. Soap purification
-Any remaining sodium hydroxide is neutralized with a weak acid such as citric acid and two thirds
of the remaining water removed.
4. Finishing
-Additives such as preservatives, colour and perfume are added and mixed in with the soap and it
is shaped into bars for sale.

Examples of Soap:
 Sodium stearate (Chemical formula: C17H35COO-Na+)

 Sodium palmitate (Chemical formula: C15H31COO-Na+)

 Sodium oleate (Chemical formula: C17H33COO-Na+)

Classifications of Soap:
Cheaper Toilet Soaps Mercury Soap
Run and Glued Up Soaps Castile Soap
Curd Soap Eschweger Soap
Cold made toilet soaps Transparent Soap
Medicinal Soap Shaying Soap
Sulphur Soap Pumice/ Sand Soap
Tar Soap Liquid Soap
Carbolic Soap Textile Soap
Peroxide Soap Wool Throwers

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Advantages
 Very effective as a bactericide
 It will form gels, emulsify oil and lower the
surfaces tension of water
 Excellent everyday cleaning agent
 Good biodegradability
Disadvantages
 Oils and perfume are immiscible in water
and if spilled create havoc, although the
oils do solidify at room temperature
 When used in hard water, soap can
produce a scum.

DETERGENTS
History
 The chemistry of soap manufacturing stayed essentially the same until 1916, when the first
synthetic detergent was developed in Germany in response to a World War I-related shortage of
fats for making soap.
 Known today simply as detergents, synthetic detergents are washing and cleaning products
without soap, "synthesized" or put together chemically from a variety of raw materials.
 Household detergent production in North America began in the early 1930s, but did not really take
off until after World War II.
 The first detergents were used chiefly for hand dishwashing and fine fabric laundering.
 The breakthrough in the development of detergents for all-purpose laundry uses came in 1946,
when the first "built" detergent (containing a surfactant/builder combination) was introduced in
the United States.
 By 1953, sales of detergents in the United States had surpassed those of soap. Now detergents
have all but replaced soap-based products for laundering, dishwashing and household cleaning.
Detergents (alone or in combination with soap) are also found in many of the bars and liquids used
for personal cleansing.

Definition
Detergents differ from soap in their action in hard water. Soaps form insoluble compounds with
the calcium and magnesium ions present in hard water. These insoluble compounds precipitate out and
reduce foaming and cleaning action.
Detergents may react with the hard water ions, but resulting products are either soluble or remain
colloidally dispersed in the water
What is a detergent?
 Detergents are the sodium salts of long chain benzene sulphuric acids.
 Uses a synthetic surfactant in place of the metal fatty acid salts used in soaps
 Both in powder and liquid form, and sold as laundry powders, hard surface cleansers, dish washing
liquids, fabric conditioners etc.
 Primarily surfactants, which could be produced easily from petrochemicals. *Surfactants lower the
surface tension of water, essentially making it 'wetter' so that it is less likely to stick to itself and
more likely to interact with oil and grease.
Detergents are divided into four main groups:
a) Anionic
b) Cationic
c) Nonionic

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d) Amphoteric

Manufature of Detergents
Raw materials
 ADDITIVES
- Corrosion inhibitors, such as sodium silicate, protect metal and washer parts, utensils, and
dishes from the action of detergents and waters.
- Carboxymethyl cellulose has been used as an antiredeposition agent.
- Tarnish Inhibitors carry on the work of the corrosion for inhibitor and extend protection to
metals such as German silver. Benzotriazole has been used for this purpose.
- Fabric Brighteners are flourescent dyes which make fabrics look brighter because of their
ability to convert ultraviolet light to visible light.
- Bluings improve the whiteness of fabrics by counteracting the natural yellowing tendency.
- Antimicrobial agents includes carbanilides, salicylanilides, and cationics.

Powder detergent manufacturing

1. Slurry making
The solid and liquid raw ingredients are dropped into a large tank known as a slurry mixer. As the
ingredients are added the mixture heats up as a result of two exothermic reactions: the hydration of sodium

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tripolyphosphate and the reaction between caustic soda and linear alkylbenzenesulphonic acid. The
mixture is then further heated to 85oC and stirred until it forms a homogeneous slurry.
2. Spray Drying
The slurry is deaerated in a vacuum chamber and then separated by an atomiser into finely divided
droplets. These are sprayed into a column of air at 425 oC, where they dry instantaneously. The resultant
powder is known as 'base powder', and its exact treatment from this point on depends on the product
being made.
3. Post dosing
Other ingredients are now added, and the air blown through the mixture in a fluidizer to mix them
into a homogeneous powder. Typical ingredients are listed in Table 3.

Liquid detergent manufacturing

1. Soap Premix Manufacture
Liquid detergent contains soap as well as synthetic surfactants. This is usually made first as a
premix, then other ingredients are blended into it. This step simply consists of neutralizing fatty acids
(rather than fats themselves) with either caustic soda (NaOH) or potassium hydroxide.
2. Ingredient mixing
All ingredients except enzymes are added and mixed at high temperature. The ingredients used in
liquid detergent manufacture are typically sodium tripolyphosphate, caustic soda, sulphonic acid, perfume
and water. The functions of these ingredients has been covered above.
3. Enzyme addition
The mixture is cooled and milled, and the enzymes added in powder form.
4.

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 To determine the safety of a cleaning product ingredient, industry scientists evaluate the
toxicity of the ingredient.
Number of Factors Affecting Exposure:
- duration and frequency of exposure to the ingredient
- the concentration of the ingredient at the time of exposure
- the route and manner in which the exposure occurs

Four General Categories:

 Personal Cleansing – include bar soaps, gels, liquid soaps and heavy duty hand cleaners.
 Laundry – available as liquids, powders, gels, sticks, spray pumps, sheets and bars
 Dishwashing – include detergents for hand and machine dishwashing as well as some specialty
products. (liquids, gels, powders, solids)
 Household Cleaning – available as liquids, gels, powders, sheets and pads for use on painted,
plastic, metal, porcelain, glass and other surfaces, and on washable floor coverings.

Soap and detergents industry in the Philippines

 The origins of the chemical industry in the Philippines can be traced back during the 19th century.
This mainly involved the small-scale and rudimentary production involving some chemical
processes.
 As early as the 1950s, leather for slippers, harness, and soles were already being produced in
Meycauayan, Bulacan, with the leather being tanned through the use of vegetable oil tannin extract
from guamachili tree, or 'kamachile'.
 Shortly after, around 1875, soap making as a trade -- involving the mixing of coconut oil with alkali
(lye) obtained from leaching wood ashes in small iron pots -- started in the country.
 It was not until the early 20th century that more significant and advanced chemical activities began
to take place.
 In 1911, the first modern soap factory was built, followed quickly by others. Intensive sales and
advertising drives developed the Philippines market for soap.
 By the time World War II broke out, there were already 135 soap establishments in the country,
with only three processors using modern methods.

Comparison
Soap Detergent
They are metal salts of long chain higher fatty These are sodium salts of long chain hydrocarbons
acids. like alkyl sulfates or alkyl benzene sulfonates.
Prepared from vegetable oils and animal fats. Prepared from hydrocarbons of petroleum or coal.
Cannot be used effectively in had water as they Do not produce insoluble precipitates in hard
produce scum. water. They are effective in soft, hard or salt water.
More soluble in water.
Stronger cleansing action