 Generally, the term “detergents” is applied to materials and/or products that

provide the following functions:

1. Promote removal of material from a surface, e.g., soil from a fabric, food from
a dish, or soap scum from a hard surface.

2. Disperse and stabilize materials in a bulk matrix, e.g., suspension of oil droplets
in a mobile phase like water.

 The ability of a detergent to perform either of these functions depends on the

composition of the formulation, the conditions of use, the nature of the surfaces
being treated, the nature of the substance to be removed and/or dispersed, and the
nature of the bulk phase.

 Accordingly, detergent formulation is a complex process driven by the specific

needs of the end user, economics, environmental considerations, and the
availability of specific “actives” that can provide the required functionality.
 By far the most common and familiar detergents are those used in household
cleaning and personal care.

 These products can be grouped into four general categories:

1. Laundry detergents and laundry aids.
 These comprise mainframe laundry detergents in powder, liquid, tablet, gel,
and bar form, fabric conditioner products typically in liquid or sheet form,
and an array of specialty products like pretreaters (as sticks, gels, sprays,
bars), presoaks (liquids, powders), and bleaches (liquids, powders).

2. Dishwashing products.
 These include detergents for hand and machine dishwashing and are
typically provided in liquid, gel, powder, or tablet form.
 Hand dish wash products are formulated to remove and suspend food soils
from a variety of surfaces.
 They also must deliver long-lasting suds, even at high soil loads, and they
must be mild to skin.
3. Household cleaning products.
 Because no single product can provide the range of cleaning required on the
various surfaces found in the home a broad range of household cleaning
products are currently marketed.
 These are typically formulated either in liquid or powder form although gel,
solid, sheet, and pad products are also available.
 So-called “all-purpose” cleaners are designed to penetrate and loosen soil,
control water hardness, and prevent soil from redepositing onto clean
surfaces.

4. Personal cleansing products.

 These include products for hand and body washing as well as shampoos,
conditioners, and toothpastes.
 They are marketed primarily in bar, gel, and liquid forms.
 A major consideration in formulation of such products is the desired
consumer aesthetic such as lather, skin feel, rinsability, smell, and taste.
Major Components of detergents
 A detergent is a formulated product which is specially designed to promote the cleaning
action.
 Each individual component in the formulation has its own specific functions in the
washing process but it can also produce synergistic effect with other components.
 The major components can be categorized into:
a. Surfactants: A surfactant ( surface active agent) is a compound with a water soluble
oil-insoluble (hydrophilic) portion on one side and an oil-soluble water-insoluble
(hydrophobic) portion on the opposite side.

b. Builders: These are used to support detergent action and to deal with the problem of
water hardness caused by the presence of calcium and magnesium ions.
 They include alkalis, complexing agents and ion exchangers.

c. Bleaching agents: Bleaches increase the reflectance of visible light at the expense of
absorption.
 It involves the removal or change of dyes and soil by mechanical and/or physical means.
 Hydrogen peroxide is the main bleaching agent.
 Sodium perborate NaBO3 is incorporated in detergents as a source of hydrogen
peroxide.
 Con’t…d
 Surfactants have a characteristic molecular structure consisting of one structural
unit that has very little attraction for the solvent (lyophobic group) combined
with a group that has a strong attraction for the solvent (lyophilic group).

 This duality is known as an amphipathic structure.

 Surfactant molecules are typically depicted using a stick and ball representation.

 The polar head group of ionic detergents contain either a positive (cationic) or
negative (anionic) charge. 

 Depending on the charged nature of the head group, surfactants are classified as:
 Anionic detergents
 Cationic detergents
 Nonionic detergents
 Amphoteric detergents
 2.1. Anionic detergents

 The head group bears a negative charge.

 The negatively charged group is involved in cleansing in these detergents.
 These include alkylbenzene suphonates, fatty alcohol sulphates (alkyl sulphates)
and alkyl ether sulphates.

Linear Alkyl Benzene Sulfonate Paraffin sulfonate

Alkyl Ether Sulfate Methyl ester sulfonate

2.1.1. Manufacture of linear alkyl benzene (LAB)

 Linear alkylbenzenes (sometimes also known as LABs) are a family

of organic compounds with the formula C6H5CnH2n+1.
 Typically, n lies between 10 and 16, although generally supplied as a tighter cut,
such as C12-C15, C12-C13 and C10-C13, for detergent use.

 The CnH2n+1 chain is unbranched.

 They are mainly produced as intermediate in the production of surfactants, for
use in detergent.

 General form examples

 Con’t…d

 Dehydrogenation of linear paraffin and production of olefins is another method.

 These olefins react with benzene and produce LAB in the presence of the HF
acid catalyst.
 Unreacted paraffin are returned to the beginning of the process after separation
by distillation.

 The HF acid is one of the suitable catalysts with high recovery capability for
alkylation reactions, but its disadvantage is that it is very corrosive and toxic.

The HF acts as a homogeneous catalyst and it dissociated in the solution to a

fluoride ion and a proton (positive ion of hydrogen), the H+ has the main part in the
catalytic alkylation reaction mechanism.
 Con’t…d

The Friedel-Crafts reaction mechanism in LAB production by HF catalyst.

2.1.2. Sulphonation of LAB – preparation of acid slurry

 Acid slurry or alkyl benzene sulphonate (LAS) is prepared by sulphonation of Linear

alkyl Benzene (LAB) with a suitable sulphonating agent.

 LAS is presently made predominantly by sulfonation with sulfur trioxide, although in

the past oleum and sulfuric acid were widely used and are still not completely obsolete
in this role.

 Sulfur trioxide is a very reactive sulfonating agent.

 The usual explanation for this paradox is that accompanying the main reaction with
overall stoichiometry:
R R

H2SO4
+ SO3

SO3H

 There is a side reaction producing LAS anhydride.

 When the reactor is fed with sulfur trioxide and LAB in a 1:1 molar ratio, then to
the extent that the side reaction occurs there will be residual LAB when all of the
sulfur trioxide has been consumed.

 This explains why the conversion at the base of the falling film reactor (FFR) is
relatively low.

 However, LAS anhydride and sulfuric acid together act as a slow sulfonating
agent, and in the ageing step they sulfonate the residual LAB to produce more
LAS, in a reaction with overall stoichiometry:

 As a final step in LAS manufacture it is customary to add a small amount of

water (typically about 1%) after ageing to hydrolyze any remaining LAS
anhydride.
 The chemistry underlying the effect of water addition does not appear to have
been fully investigated, but it is usually argued that residual LAS anhydride
could continue to sulfonate under uncontrolled conditions during storage, leading
to color formation.

 Another side reaction leads to formation of diaryl sulfones and sulfuric acid, the
overall stoichiometry being:

 To the extent that it occurs, sulfone formation limits the maximum achievable
conversion of LAB to LAS to a value below 100% and makes it impossible to
completely avoid the presence of sulfuric acid (typically at levels in the range 1-
2%) in the final sulfonation product.
 Con’t…d
 Sulfone levels in the final product depend on the ratio of sulfur trioxide to
LAB supplied to the reactor but are usually below 1%.

 After completion of the water-addition step the reaction mixture consists

predominantly of LAS and can be stored until required for further use or
transported to another location for use there.

 This material is often referred to as LAS, LAS acid, or LASH.

 In other contexts the term LAS is sometimes reserved for the neutralized
form (usually the sodium salt).
 This structure of a C12-LAS
is representative of the category.
2.2. Cationic detergents: examples and applications

 These surfactants are made up of a cationic head.

 They are used for special effects for example as antiseptic, fabric softening,
microbicides, antistatic agents, etc.

 Because cationics are antistatic agents, they perform well in removing static
charges associated with synthetic fabrics.

 Since cationics display behaviour opposite to that of anionics, the two are
incompatible.

 They are incompatible with anionic antibacterial agents like hexachlorophene but
are compatible with cationic germicides such as mercurials.

 Nonionic surfactants are more tolerant of cationics than anionics.

 Con’t…d
 There are many different types of cationic detergents.
 The following are common cationic detergents.
 Con’t…d

 Quaternary ammonium compounds (QAC), R’R”N(CH3) 2Cl are among the most
widely used cationic detergents.

 Quaternary ammonium compounds R’HN(CH3)2Cl having a single long aliphatic

chain possess bacteriological properties.

 Benzalkonium chloride (BAC), also known as alkyldimethylbenzylammonium

chloride (ADBAC) and by the trade name Zephiran, is a type of cationic
surfactant.

 It has two aliphatic chains are used as textile softeners for both household and
industrial use.

 Benzalkonium Chloride is a powerful antiseptic for pharmaceutical applications

and a cationic surfactant.
 2.3. Non-ionic detergents

 Non-ionic detergents contain molecules with head groups that are uncharged.
 The following are the common nonionic detergents. epoxide ring of
ethylene oxide opens and combines with an active
hydrogen atom contained in a functional group present
in the compound with which it is being condensed
to form a hydroxyethyl to produce surface-active agents.
 2.4. Amphoteric detergents
 In amphoteric/ zwitterionic detergents the head group has either a positive or
negative charge depending on solution pH.
 Examples:
 2.5. Mechanism of action of detergents
 The cleaning action of detergents are the same as soap’s mechanism action.
 A detergent dissolves in water to produce detergent anions and sodium cations.
 The ionisation of sodium alkyl sulphate and sodium alkylbenzene sulphonate, for
example, is seen in the chemical equations below.
 Con’t…d
 Similarly, the anion element of a detergent has a hydrophobic and a hydrophilic
component.
 Because soap or detergent lowers the surface tension of water, the cloth’s surface
gets fully wetted.
 In grease, the hydrophobic components of soap or detergent anions dissolve.
 The hydrophilic portions of anions are water-soluble. 
 2.6. Comparison of soaps and detergents
 People frequently misunderstand these two cleansers and use them interchangeably since
they are both used for cleaning. However, there are major differences between soaps and
detergents in reality.
Soaps Detergents

Soaps are sodium or potassium salts of a long chain of Detergents are ammonium or sulfonate salts of long chains
carboxylic acids. of carboxylic acids.

Soaps do not clean well in hard, acidic and saline water. They are effective in hard, saline and acidic water as well.

They form scum with hard water. They form lather with hard water.

They are made from natural compounds such as fatty acids

or vegetable or animal fats. Detergents are synthetically derived from chemicals.

Soap is generally prepared from plant and animal fats Petroleum (Petrochemicals) was found to be a plentiful
through saponification.  source for the manufacture of detergent.

Detergents may be cationic, anionic, or non-ionic in

Soaps are not ionic in nature. nature.

Examples: Sodium Stearate Examples: Sodium lauryl sulphate

2.7. Biodegradation – environmental effects of detergents
 Biodegradation means the microbial degradation of organic substances.

 Depending on the degradation result, biodegradation with respect to surfactants is

defined as follows.

 Primary biodegradation means the structural change (transformation) of a

surfactant by microorganisms resulting in the loss of its surface-active properties
due to the degradation of the parent substance and consequential loss of the surface-
active property.

 Ultimate biodegradation means the level of biodegradation achieved when the

surfactant is totally used by micro-organisms resulting in its breakdown to inorganic
end-products such as carbon dioxide, water and mineral salts of any other elements
present (mineralization) and new microbial cellular constituents (biomass).

 Ready aerobic biodegradability is an arbitrary classification of surfactants which

have passed certain specified screening tests for ultimate biodegradability; these
tests are so stringent that it is assumed that such compounds will rapidly and
completely biodegrade in aquatic environment under aerobic conditions.
 Con’t…d
 The natural environment is predominantly aerobic, which for a long time has led
to a focus on the biodegradation behavior of chemicals under aerobic conditions.

 Nevertheless there are a few environmental compartments with absence of free

oxygen and more or less anaerobic conditions such as river sediments and sub-
surface soil layers, as well as anaerobic sludge digesters of wastewater
treatment plants.

 Anaerobic biodegradation means the microbial degradation of organic

compounds under conditions free of molecular oxygen.

 In opposite to aerobic biodegradation pathways, where organic compounds often

are mineralized by one type of microorganisms, the anaerobic biodegradation of
a substance up to inorganic end-products always requires the co-operation of
different types of microorganisms.
 Con’t…d
 The biodegradation is influenced by several factors:
 number of microorganisms capable of metabolizing the organic
compound
 growth factors such as
 temperature,
 pH,
 nutrients,
 water content and
 bioavailability of the organic substrate

 In biodegradation tests and technical biodegradation processes, the reaction can

be started with an initial supply of microorganisms which are adapted to;

 the special conditions (e.g. aerobic or anaerobic) and/or

 the special compound used as substrate source.

 Example: Sodium Lauryl Ether Sulfate (SLES) Biodegradation by Nitrate-reducing Bacteria

 The surfactant sodium lauryl ether sulfate (SLES) is widely used in the
composition of detergents and frequently ends up in wastewater treatment plants
(WWTPs).

 The average concentration of anionic surfactants in domestic wastewater can vary

between 0.4 and 12 mg L−1, although higher concentrations are frequently present
in industrial wastewater.

 SLES can be degraded by different aerobic bacteria, namely Citrobacter

braakii and a consortium of Acinetobacter calcoacetiacus, Klebsiella oxytoca,
and Serratia odorifera.

 The scheme of possible SLES cleavage mechanisms for complete degradation to

CO2 and biomass formation has been shown in the next slide.

 The general molecular structure of SLES is shown, where n is the mean of ethoxy
units (n = 2–3 in commercial products), and R is the alkyl group (12 to 18 carbons).
Con’t…d
2.8. ISO specifications/limits

 Among the many ISO specifications/limits, let’s consider limitations on the

content of phosphates and of other phosphorus compounds.
Detergent Limitations Date as of which the
limitation applies

1. Consumer Shall not be placed on the market if the total 30 June 2013
laundry detergents content of phosphorus is equal to or greater than
0.5 grams in the recommended quantity of the
detergent to be used in the main cycle of the
washing process for a standard washing machine
load;
- for water of hard water hardness
- for ‘normally soiled’ fabrics in the case of
heavy-duty detergents,
- for ‘lightly soiled’ fabrics in the case of
detergents for delicate fabrics,

2. Consumer Shall not be placed on the market if the total 1 January 2017
automatic content of phosphorus is equal to or greater than
dishwasher 0.3 grams in the standard dosage
detergents
Chapter Three: Shampoos
3.1. Introduction
 Definition: A shampoo is a preparation of a surfactant (i.e. surface active material)
in a suitable form
 liquid,
 solid or
 powder which when used under the specified conditions will remove
surface grease, dirt, and skin debris from the hair shaft and scalp without
adversely affecting the user.

 Shampoos have the following requirements:

1. It should effectively and completely remove dust or soil, excessive sebum or other
fatty substances and loose corneal cells from the hair.

2. It should produce a good amount of foam to satisfy the psychological requirements

of the user.

3. It should be easily removed on rinsing with water.

 Con’t…d
4. It should leave the hair non‐dry, soft, lustrous with good manage ability and
minimum fly away.

5. It should impart a pleasant fragrance to the hair.

6. It should not cause any side‐effects/irritation to skin or eye.

7. It should not make the hand rough and chapped.

3.2. Different Kinds of Shampoo

 Shampoos are of the following types:
A. Dry/ Powder Shampoo
B. Liquid shampoo
C. Lotion Shampoo
D. Cream Shampoo
E. Jelly Shampoo
F. Aerosol Shampoo
G. Specialized Shampoo
 Conditioning Shampoo
 Anti‐dandruff Shampoo
 Anti-lice shampoo
 Baby Shampoo
 Herbal Shampoo
 Two Layer Shampoo

3.3. Ingredients and functions

The raw materials used in the manufacture of shampoos are:
1. Principal surfactants: Provide detergency and foam.
2. Secondary surfactants: Improve detergency, foam and hair condition and
3. Other additives
3.3.1. Surfactants
 Surfactant is substance which tends to reduce the surface tension of a liquid in
which it is dissolved.

 Surfactants are the main component of shampoo.

 Anionic surfactants are mostly used (good foaming properties).

 The hydrophilic portion carries a negative charge which results in superior

foaming, cleaning, and end result attributes.

 Non‐ionic surfactants have good cleansing properties but do not have sufficient
foaming power.

 Amphoteric, being expensive, are generally not used.

 However, they are mainly used as secondary surfactants and good hair
conditioners.
3.3.2. Additives

 Conditioning agents: Lanolin, mineral oil, herbal extracts, egg derivatives.

 Foam builders: Lauroyl monoethanolamide, sarcosinates

 Viscosity modifiers:
 Electrolytes –NH4Cl, NaCl
 Natural gums –Gum Karaya, tragacanth, alginates
 Cellulose derivatives –Hydroxyethyl cellulose, methyl cellulose
 Carboxy vinyl polymers –Carbopol 934
 Others –PVP, phosphate esters.

 Sequestering agents: EDTA

 Opacifying agents: Alkanolamides of higher fatty acids, propylene glycol, Mg,

Ca and Zn salts of stearic acid, etc.
 Clarifying agents:
 Solubilizing alcohols –ethanol, isopropanol
 Phosphates –
 Non‐ionic solubilizers–polyethoxyatedal cohols and esters.
 Perfumes: Herbal, fruity or floral fragrances.

 Preservatives: Methyl and propyl paraben, formaldehyde (most effective).

 Anti‐dandruff agents: In order to be effective the active ingredient must work in

the oil‐water environment of the scalp and must be readily substantive to the scalp
for continuing activity.

 Example:
 Selenium sulfide,
 zinc pyrithone, and
 salicylic acid.
3.4. Manufacture of sodium lauryl sulfate (SLS)
 Sodium lauryl sulphate (SLS), better known as sodium dodecyl sulphate or SDS,
is an example of a synthetic organic compound.

 It is an anionic surfactant that is used in several cleaning and hygiene products.

 This molecule is a type of organosulphur, as well as salt.

 It is composed of a 12-carbon tail attached to a sulphate group, that is, the sodium
salt of dodecyl hydrogen sulphate, the ester of dodecyl alcohol, and sulphuric acid.

 Its hydrocarbon tail joined with a polar head group gives the compound
amphiphilic properties to make it useful as a detergent.

 Being extracted from a component of mixtures manufactured from inexpensive

coconut and palm oils, sodium lauryl sulphate is a common component of several
domestic cleaning, personal hygiene and cosmetic, pharmaceutical, and food
products, as well as of commercial cleaning and product formulations.
 Con’t…d
 Sodium lauryl sulphate is synthesized by treating lauryl alcohol and sulphur
trioxide gas, oleum, or chlorosulphuric in order to make hydrogen lauryl sulfate.

 Lauryl alcohol can be used in pure form as well as be derived from either coconut
or palm kernel oil through hydrolysis.

 The end product (hydrogen lauryl sulfate) is then neutralized through the addition
of sodium hydroxide or sodium carbonate.
3.5. Manufacture of sodium lauryl ether sulfate (SLES)

 SLES and SLS are among the most common anionic surfactants found in a wide
range of commercial products for different purposes.

 SLES is considered to irritate much less than SLS and consequently consumer
products containing SLES should presumably be milder, while nevertheless
maintaining the same characteristics.

 SLES has a lot of synonyms among them sodium laureth sulphate is the common
one.
 Production of sodium laureth sulfate involves three major steps:
 The reaction is called ethoxylation.
 Con’t…d
 1,4-dioxane is a common byproduct of the ethoxylation process.
 As mentioned earlier, the first step of SLES synthesis consists of a reaction between
lauryl alcohol and numerous ethylene oxide molecules.

1,4-dioxane

 Ethylene oxide is reacted with the alcohol, adding a C2H4O group to the end, which
increases the molecule’s solubility in water.

 Although 1,4-dioxane is not among the main ingredients of household cleansers or

cosmetics, it can be found in extremely small amounts as contamination.

 1,4-dioxane is carcinogenic, therefore, it must be removed from SLES.

 The United States Food and Drug Administration (FDA) recommends that levels of
1,4-dioxane be monitored carefully, and at the same time, encourages manufacturers
to remove this hazardous byproduct.
3.5. ISO specifications and testing procedures

 Performance characteristics
A. Foam and foam stability
B. Detergency and cleaning action
 Effect of water hardness
 Surface Tension and wetting
 Surfactant content and analysis
C. Rinsing
D. Conditioning action
 Softness
 Luster
 Lubricity
 Body, texture and set retention
 Irritation and toxicity
 Dandruff control
 Con’t…d
E. Microbiological assay
F. Eye irritancy test

 Product characteristics
 Fragrance

 Color

 Consistency

 Package