DETERGENTS

By: Eunice G. Pacifico

Introduction

A detergent (as a noun; detersive means

cleaning or having cleaning properties;
adjective detergency indicates presence or
degree of cleaning property) is a material
intended to assist cleaning.
Today, detergent surfactants are made from
a variety of petrochemicals (derived from
petroleum) and/or oleochemicals (derived
from fats and oils)
Description

When soap is used in hard water, a white solid

precipitate we call scum forms. This is because
charged calcium and magnesium ions present in
the hard water react with soap to form an
insoluble substance.
Like soap, detergent molecules have a long
chain of carbon and hydrogen atoms, but at the
end of the molecule there is this group -SO3 -
called sulphonate instead of the -COO -
carboxylate group present in soap.
The calcium salt of a sulphonate is soluble in
water unlike the calcium salts of the
carboxylate.
HISTORY
Detergents and Surfactants
Greasy stains do not mix with water because the main
interactions between water molecules are hydrogen
bonding and those between molecules of oils and fats
(which constitute grease) are van der Waals forces.
To get water and grease to mix we use molecules called
surfactants or detergents.
WHAT MAKES A DETERGENT
WORK
&
FACTORS THAT AFFECT
CLEANING

8
THE CHEMISTRY OF CLEANING
In the process of cleaning there are a lot of technical words and terms used to
describe the contents of the cleaning chemical formulations and their actions.
Most detergents contain several different components, which can usually be placed
into groups having similar functions. The groups of chemicals used in detergent
formulations are:

SURFACTANTS - Wetting agents that help wet the surface.

ACIDS & ALKALIS
SEQUESTRANTS - Mop up hard water ions and facilitate the
surfactant.
SOLVENTS - Dissolve oils & greases to help the
surfactant work.

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 SURFACTANTS
The word surfactant is a shortened, easy to remember name for
surface active agent - surfactants act on surfaces.

SURFACTANT ACTIONS
Wetting
Emulsification
Solubilisation
Solubilisation versus Emulsification
Foaming / Defoaming
Dispersion

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SURFACTANT STRUCTURE
Surfactants have a chemical structure comprising:
an oil-loving tail and a water-loving head and may be considered as looking something
like a tadpole. This structure gives surfactants the ability to align themselves at surfaces
between water and oil and / or air.

The water-loving head protrudes into the water phase and the oil-loving tail protrudes into the
oil phase or air (or even onto a solid surface). In all cases, the oil-loving tail tries to escape
from being in the water phase. This property is used extensively in detergent formulations to
impart specific actions.

IN BRIEF: The oil-loving head sticks to the grease and the surfactant acts as a glue between
the oil and the water and makes the oil soluble in water

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SURFACTANT TYPES
The major types of surfactants used in detergents are:
Anionic (neg-charge) 90% Detergents etc
Cationic (pos-charge) 10% Polishes/Finishes
Non-ionic
The charges on the different surfactant types place restrictions on blending of
different surfactant types in formulations.
Opposite charges attract and, if anionic and cationic surfactants are blended
together - neutralize one another.
This results in no surface activity and no cleaning ability.
Balance of cost of cleaning versus cleaning performance. Many products
have a great cost but dont perform very well
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SURFACTANT ACTIONS
Wetting
At water / air surfaces, the alignment of surfactants with their oil-
loving tails out of the water surface breaks down the
surface tension of the water
the skin on the surface of water that allows insects to walk on water and
that pulls water droplets into beads on oily surfaces.

The ability of surfactants to reduce the surface tension of water

allows water droplets to spread and wet oily surfaces, hence the
other common name for surfactants wetting agents.

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SURFACTANT ACTIONS
Emulsification
When oil droplets are dispersed in water the oil quickly floats to the surface to form
a continuous oil film. When surfactants are added to the water:
the surfactants adsorb onto the surface of the oil droplets
with their oil-loving tails in the oil droplet
with their water-loving heads extending into the water.
This gives the surface of the oil droplets a water-loving skin which allows the droplets to
remain dispersed in the water.
This property of surfactants, to keep oil droplets dispersed, is called
emulsification
The stable dispersion of oil droplets in the water is called an emulsion
When oil droplets are dispersed in a continuous water phase, the emulsion formed is called an oil
in water emulsion, frequently shortened to o/w emulsion.

14
SAPONIFICATION
When animal and vegetable fats and oils are reacted with a strong
alkali such as caustic soda (sodium hydroxide), the fatty acid groups
are split off and neutralized by the alkali to make soap the salt of
the fatty acid.
NOTE: Animal and vegetable fats and oils all belong to the same
chemical family. The only difference between them are that at
room temperature:
fats are solid
oils are liquid

15
pH
No discussion on acids and alkali would be complete without reference to pH.
The pH scale is a measure of the amount of acidity or alkalinity in water.
Due to the mathematical nature of the pH scale
each one-unit decrease in pH, requires a tenfold increase in the
hydrogen ion concentration.
each one-unit increase in pH, requires a tenfold decrease in the
hydrogen ion concentration, brought about by a tenfold increase in the
hydroxide ion concentration
This means that a liquid with a:
pH of 9.0 is ten times more alkaline than a liquid with a pH of 8.0
pH of 10.0 is 100 times (10x10) more alkaline than a liquid with a pH
of 8.0
The same works in reverse for Acids pH 4.0 is ten times more Acidic
than pH 5.0
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 pH pictorial examples

Source: Wikipedia http://en.wikipedia.org/wiki/PH

17
ALKALINITY IN CLEANING
In general detergents are formulated to be either:
neutral
alkaline.
Many soils will be acidic therefore alkalinity in the detergent assists
in their removal by neutralizing them to make soluble salts.
Functions of the alkalinity in the detergent include :
saponifying fats and oils
breaking down and solubilising proteins
neutralizing acids present in soils
removal of acidic metal oxides from surfaces
alkalinity also assists in wetting of surfaces and dispersing and
suspending solid soils
18
ACIDS IN CLEANING
Acids, in general will attack and dissolve many:
metals, basic metal oxides and alkaline metal salts
concrete, mortar and grout.

The most frequently encountered examples of basic metal oxides and alkaline
metal salts are:
iron oxides rust
calcium / magnesium carbonate water scale

The specific type and concentration of acid used and the presence of corrosion
inhibitors and other additives will all affect the degree of acidic attack.

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SEQUESTRANTS
Sequestrants are special chemicals added to detergent formulations to:
prevent dissolved metal ions present in the cleaning solution from causing scaling and from
reacting with, and inactivating, other cleaning chemicals.

Sequestrants do this by preferentially reacting with the problem metal ions to

prevent their interaction with the other chemicals.
The major source of dissolved metal ions is the water used to prepare the
cleaning solution.
The main metal ions in the water are:
calcium and magnesium hardness
but can also contain iron, manganese, copper, and minor levels of other metals ions.
Dissolved metal ions can also be introduced into the detergent formulation or
cleaning solution, as contaminants of other cleaning chemicals.

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SOLVENTS
When the word solvent is mentioned, most people immediately
think of petroleum solvents like paraffin and white spirit or
chlorinated solvents like methylene chloride and trichloroethylene.
However, a solvent is simply a liquid that dissolves another
substance.
The range of solvents that are employed in cleaning processes is
extensive. Some of the many types include:
hydrocarbons
chlorinated solvents
natural oils
alcohols
ketones, esters, ethers, glycols and glycol ethers

21
SOIL TYPE
Identifying the soils to be removed is a major consideration in selecting an
appropriate detergent formulation for a cleaning application.
Most soils tend to be combinations of different soil types and compromises are
often required in selecting an optimum formulation, based on:
relative levels of soil types present
the type of surface being cleaned and method of cleaning to be used.

SOIL TYPE HOW TO REMOVE

Animal & vegetable fats & oils surfactant; alkali; solvent
Petroleum (mineral) oils & grease surfactant; solvent
Protein acid; alkali
Starch acid neutral detergent
Water-soluble salts water
Mineral deposits (incl. water hardness) acid
Metal oxides typically acid (e.g. for rust, aluminium oxide)but
alkali can be used in some applications
Metals (deposited, plating, etching) acid
Paint solvent; alkali

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WATER HARDNESS
A detergent formulation to be used in hard water areas will require higher levels of
sequestrants than a similar detergent for use in soft waters.
These higher levels are necessary to handle the higher levels of:
calcium
magnesium present in the water.

Water hardness salts become less soluble as the alkalinity level increases and
start to precipitate at pH greater than 7.6, unless appropriate sequestrants are
present in solution to prevent this from occurring.
In multi-stage cleaning processes this can present problems:
carryover of alkalinity into the rinse water will rapidly increase the pH above this threshold
whilst there will be insufficient sequestrant carryover to maintain the water hardness salts in
solution
resulting in scaling problems in the rinse area.

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Classification of Detergents

There are four main classes of detergents

1. Anionic detergents
2. Cationic detergents
3. Non-ionic
4. zwitterionic detergents (amphoteric)
Anionic Detergents
Anionic means a negatively
charged molecule. In the early
days always remembered this by
anionic (a negative). The
detergency of the anionic
detergent is vested in the anion.
The anion is neutralised with an
alkaline or basic material, to
produce full detergency.
Cationic Detergents:

Another class of
detergents have a positive
ionic charge and are called
"cationic" detergents. In
addition to being good
cleansing agents, they also
possess germicidal
properties which makes
them useful in hospitals.
Most of these detergents
are derivatives of
ammonia.
Neutral or non-ionic detergents:

Nonionic detergents are

used in dish washing
liquids. Since the
detergent does not have
any ionic groups, it does
not react with hard water
ions. In addition, nonionic
detergents foam less than
ionic detergents. The
detergent molecules must
have some polar parts to
provide the necessary
water solubility.
 Amphoterics (zwitterionic
detergents )
These have the characteristics of both anionic detergents
and cationic fabric softeners. They tend to work best at
neutral pH, and are found in shampoos, skin cleaners and
carpet shampoo. They are very stable in strong acidic
conditions and have found favour for use with
hydrofluoric acid.

3-[(3-Cholamidopropyl)dimethylammonio]-
1-propanesulfonate (CHAPS)
 Bile Salts - Intestinal Natural
Detergents:
Bile acids are produced in the liver and
secreted in the intestine via the gall
bladder. Bile acids are oxidation
products of cholesterol. First the
cholesterol is converted to the
trihydroxy derivative containing three
alcohol groups. The end of the alkane
chain at C # 17 is converted into an
acid, and finally the amino acid,
glycine is bonded through an amide
bond. The acid group on the glycine is
converted to a salt. The bile salt is
called sodiumglycoholate. Another
salt can be made with a chemical
called taurine.
Bleach

Bleach refers to a number of chemicals which

remove color, whiten or disinfect, often by
oxidation.
Chlorine is the basis for the most commonly used
bleaches, for example, the solution of sodium
hypochlorite, which is so ubiquitous that most
simply call it "bleach", and calcium hypochlorite, the
major compound in "bleaching powder".
Oxidizing bleaching agents that do not contain
chlorine most often are based on peroxides, such as
hydrogen peroxide, sodium percarbonate and
sodium perborate.
Colors in most dye and pigments are produced by
molecules which contain chromophores, such as
beta carotene. Chemical bleaches work in one of two
ways:

An oxidizing bleach works by breaking the

chemical bonds that make up the chromophore.
This changes the molecule into a different
substance that either does not contain a
chromophore, or contains a chromophore that
does not absorb visible light.
A reducing bleach works by converting double
bonds in the chromophore into single bonds. This
eliminates the ability of the chromophore to
absorb visible light.
Manufacturing
Manufacturing
Technical Analyses
Technical Analyses

Qualitative Analysis
Hydrophilic Groups
Linking Groups
Hydrophobic Groups

Paper Chromatography
Technical Analysis

Quantitative Analysis By Solvent Extractions

Light Petroleum
Ethyl Ether
Chloroform
Alcohol
Ion-Exchange Resins
Comprehensive Scheme of Analysis
Technical Analysis

Quantitative Analysis By Solvent Extractions

Comprehensive Scheme of Analysis
Colorimetric Determination
The Anionic-Cationic Titration
End-point detection
Standardisation
Miscellaneous Factors
The Single Phase Titration
THE END