Chapter 1

Introduction
History:
Throughout the history of civilization, the need for efficient washing of
skin and clothes pushed many inventors and scientist to create many
types of substances that facilitated that need. Because modern
detergents found their footing only after the rise of technology and
chemistry of 20th century, our ancestors focused their attention on
production of various soaps.

From ancient times, chemical additives were recognized for their ability
to facilitate the mechanical washing with water. The Italians used a mix
of sulfur and water with charcoal to clean cloth. Egyptians added ashes
and silicates to soften water. Soaps were the first detergents.

In 1916 the first synthetic detergent was developed in Germany (at
World War I), in response to shortages of soap. In the 1930s,
commercially viable routes to fatty alcohols were developed, and these
new materials were converted to their sulfate esters, key ingredients in
the commercially important German brand FEWA, produced by BASF,
and Dreft, the US brand produced by Procter and Gamble.

After World War II, new developments and the later conversion of
aviation fuel plants to produce tetrapropylene, used in household
detergents, caused a fast growth of domestic use in the late 1940s.
The use of enzymes for laundry was introduced in the early part of the
1900s by Otto Rohm. Only in the latter part of the century with the
availability of thermally robust bacterial enzymes did this technology
become main stream.

At the present time, soap has largely been displaced as the main
cleaning agent in developed countries. Soap is, by weight, relatively
ineffective, and it is highly sensitive to deactivation by hard water.

By the 1950s, soap had almost been completely replaced by branched
alkylbenzenesulfonates, but these detergents were found to be poorly
biodegradable. Linear alkylbenzenesulfonates (LABs), however, proved
to be both highly effective in cleaning and more biodegradable than the
branched relatives. LABs remain the main detergents used
domestically.

By 1953, sales of detergents had surpassed those of soap. Now
detergents have all but replaced soap-based products for laundering,
dishwashing and household cleaning.

Other detergents that have been developed include the linear
alkylsulfonates and olefinsulfonates, which also resist deactivation by
hard water. Both remain specialty products, for example only an
estimated 60 million kilograms of the sodium alkylsulfonates are
produced annually.

Detergents Time Line:

4800A.C The first proof of existence of detergents (soap) was found in
ancient Babylon.

2500A.C Soap cosmetics (Sumerians)

2000A.C Soap (Egypt)
1950s Creation of automatic dishwasher powders, Liquid laundry,
hand dishwashing and all-purpose cleaning products, Fabric softeners
(rinse-cycle added), Detergent with oxygen bleach.
1960s Prewash stain removers, enzyme presoaks.
1970s Liquid hand soaps, Fabric softeners (sheets and wash-cycle
added), Multifunctional products (e.g., detergent with fabric softener).
1980s Detergents with support for cold water washing, Automatic
dishwasher liquids, concentrated laundry powders.
1990s Ultra (super concentrated) powder and liquid detergents, Ultra
fabric softeners, Automatic dishwasher gels, Laundry and cleaning
product refills.
2000s Biodegradable and green friendly products, water conservation
washing machines, laundry detergent "all in one" tablets.

Synthetic Detergents
A detergent is a surfactant or a mixture of surfactants with "cleaning
properties in dilute solutions. These substances are usually
alkylbenzenesulfonates, a family of compounds that are similar
to soap but are more soluble in hard water, because the
polar sulfonate (of detergents) is less likely than the polar carboxyl (of
soap) to bind to calcium and other ions found in hard water. In most
household contexts, the term detergent by itself refers specifically
to laundry detergent or dish detergent, as opposed to hand soap or
other types of cleaning agents. Detergents are commonly available as
powders or concentrated solutions. Detergents, like soaps, work
because they are amphiphilic: partly hydrophilic (polar) and partly
hydrophobic (non-polar). Their dual nature facilitates the mixture of
hydrophobic compounds (like oil and grease) with water. Because air is
not hydrophilic, detergents are also foaming agents to varying degrees.


surfactant is a compound that lowers the surface tension of a liquid,
increasing the contact between the liquid and another substance. There
are a wide variety of these compounds that work with oil, water, and
an assortment of other liquids. Many companies manufacture a range
of surfactants for various purposes, ranging from soaps to inks. They
are also sometimes referred to as wetting agents.
Surfactants are a large group of surface active substances with a great
number of (cleaning) applications. Most surfactants have degreasing or
wash active abilities. They reduce the surface tension of the water so it
can wet the fibres and surfaces, they loosen and encapsulate the dirt
and in that way ensure that the soiling will not re-deposit on the
surfaces.
Surfactants have a hydrophobic (water repellent) part and a hydrophilic
(water loving) part. The hydrophobic part consists of an uncharged
carbohydrate group that can be straight, branched, cyclic or aromatic.
Surfactants are the active cleaning agents that perform three major
roles:
Penetrating and wetting fabric.
Loosening soils (assisted by the mechanical action of the washing
machine).
Emulsifying soils and keeping them suspended in the wash
solution.




Detergents Technique:

Surfactants have two domains within the one molecule: a polar, or
hydrophilic (water-loving) head group, and a non-polar, fatty or
hydrophobic (water-hating) tail. The basic principle at work is that
polar substances interact well with other polar substances, and non-
polar substances interact well with other non-polar substances.

Water has a high surface tension, that is, it resists distortion at its
surfaces (water-air, water-oil, water-solid).
When a detergent is added, surfactant molecules accumulate near the
surface of the water because the non-polar (hydrophobic) tail of the
surfactant wants to get away from the water. Since the surfactant
disrupts the bonding of water molecules, the water distorts and more
surfactant molecules fit near the surface. Because the water now has
reduced surface tension it can permeate previously non-wettable
surfaces, such as fabrics.












Detergents Classification:

There are four main classes of detergents, anionic, cationic, nonionic,
amphoteric (zwitterionic)

1- Anionic Detergents:

Anionic means a negatively charged molecule. 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.

2- Catonic Detergents:

Cation means positively charged. The detergency is in the cation, which
can be a substantially sized molecule. Strong acids are used, such as
Hydrochloric Acid to produce the Cl anion as the neutralising agent,
although in essence, no neutralisation takes place in the manufacturing
process.
A cationic detergent is most likely to be found in a shampoo or clothes
"rinse". The purpose is to neutralize the static electrical charges from
residual anionic (negative ions) detergent molecules. Since the negative
charges repel each other, the positive cationic detergent neutralizes
this charge.

3- Neutral or non-ionic Detergents:
As the name implies, no ionic constituents are present. They are
ionically inert.
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.
4- Amphoteric or 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.

Class Example Chemical Properties Uses



Anionic
CH
3
(CH
2
)
11
OSO
3
-
Na
+

sodium dodecyl sulfate
Usually contain either
a sulfate (SO
4
) head
widely used
due to cost
and
performance
-laundry
detergents
-dishwashing
liquids
-oven cleaners

CH
3
(CH
2
)
11
C
6
H
4
SO
3
-
Na
+

sodium
dodecylbenzenesulfonate
or
a sulfonate (SO
3
) head

Cationic CH
3
(CH
2
)
11
NH
3
+
Cl
-

dodecylamine hydrochloride
CH
3
(CH
2
)
15
N(CH
3
)
3
+
Br
-

hexadecyltrimethylammonium
bromide
Usually contain a
modified ammonium
ion as active site
which produces a
germicidal action.
More expensive than
anionic detergents.
-cleaning
plastics
-hair
shampoos
-nappy washes
-fabric
softeners and
conditioners

Non-
ionic
or
neutral
CH
3
(CH
2
)
14
COOCH
2
C(CH
2
OH)
3

pentaerythrityl palmitate
Contains polar parts,
eg, OH groups, to
provide water
solubility.
No ionic groups so no
reaction in hard
water.
Low lathering
prevents foam build
up in dishwashers.
-car shampoos
-dishwasher
detergents
-cosmetics




Detergents Ingredients:
additive Use
surfactants, wetting agents Small hydrocarbon chain length is a better
wetting agent than a long one, but long
hydrocarbon chain length is better for dirt
removal and dispersion.
A chain length of about C
12
is the best
compromise for most anionic detergents.

carboxymethylcellulose Forms a protective hydrated adsorbed layer
on cleaned fabric preventing redeposition of
dirt.

builders (pyrophosphates,
tripolyphosphates, silicates eg,
zeolites)
Form soluble complexes with Ca
2+
and Mg
2+

in hard water and act as deflocculating
agents preventing scum buildup.

abrasives To scour.

foaming agents To promote and stabilize foam formation.

oxidisers, eg, perborates Bleaching

pH modifiers To promote the effectiveness of some
ingredients.

enzymes To digest proteins, carbohydrates and fats.

optical whiteners
(fluorescent dyes)
Add brightness to fabrics by absorbing UV
light and emitting blue light which masks any
yellow tint which may develop in white
fabrics.

fragrances Enhance the odour of detergents.



Environmental Concerns:
The first detergents in use were highly branched
alkylbenzenesulfonates,
CH
3
CH(CH
3
)CH
2
CH(CH
3
)CH
2
CH(CH
3
)CH
2
CH(CH
3
)C

SO
3
-
Na
+

Microorganisms in septic tanks and sewage-treatment plants cannot
degrade branched chains.
To prevent buildup of detergents in rivers and lakes, modern-day
detergents are designed to be biodegradable.
Alkylbenzenesulfonates with a continuous chain, rather than a
branched chain are biodegradable.
Continuous chain alkysulfates, eg, CH
3
(CH
2
)
16
CH
2
OSO
3
-
Na
+
, are also
biodegradable.

Detergents Production:
Despite an unprecedented number of cleaning forms and line
extensions in the laundry detergent market, the same giants emerged
as the category's major players this year-in the same forms. Liquids, for
example, topped powders at $3 billion in sales vs. $1.8 billion for the 52
weeks ended Oct. 7, 2001, according to Information Resources, Inc.,
Chicago. And Procter & Gamble, Lever Brothers and Dial were Nos. 1, 2
and 3 respectively in liquid and powders, a repeat of last year's
performance