Chapter 2

Detergents
• Detergents are synthetic compounds that mimic the action of soaps.

• A special class of personal care product containing a surfactant or a mixture of surfactants with cleaning
properties in dilute solutions.

• Any synthetic chemical that cleans well and can be employed as a surface-active agent in both hard and soft
water.

• Synthetic detergents are not only used as cleaning materials but also have industrial applications in textiles,
pesticide industry as carriers, etc.

• Detergents can align at aqueous/non-aqueous interfaces, resulting in reduced surface tension, increased
miscibility, and stabilization of emulsions.
• Detergents are the potassium or sodium salts of a long alkyl chain ending with a sulfonate group.

• Synthetic detergents harm water since they aren’t totally biodegradable.

• Detergents are amphipathic molecules that contain charged hydrophilic or polar groups at the end of long
lipophilic hydrocarbon groups which is called the head and the long lipophilic hydrocarbon group is called the
tail.
• The chemical composition is different from soap , but the same mechanism by the soap, not adversely affected by
hard minerals in the water.

• Detergents tend to be more soluble in hard water than soap because the sulfonate of detergent doesn't bind
calcium and other ions in hard water as easily as the carboxylate in soap does.

Sodium salts of long-chain benzene sulphonic

acids are detergents.
• Detergents are also alkyl benzene sulfonates.
• A detergent is an effective cleaning product because it contains one or more surfactants.
 ❖ Cleansing Action of Detergents

• Cleaning with only water does not work effectively, as the surface tension is too high for cohesive forces to work

• Cleaning agents are compounds that are used to remove stains, dust, unpleasant odors, grime, and other
contaminants from surfaces. These are the chemicals that are used to reduce surface tension on planes so that
water can do its job effectively.

• Detergents are also called surface-active agents, or surfactants. Surface active molecules present in
detergents dissolve in water.

• Such surfactants are less sensitive than soap to the hardness minerals in water and most will not form a solid
mass. This properties makes the surfactant molecule a wetting agent.
• When a detergent is added to water that contains oil or other water-insoluble materials, the
detergent molecules surround the oil droplets.

• The oil or grease is “dissolved” in the alkyl groups of the molecules while the ionic end allows the micelle to
dissolve in water. As a result, the oil droplets are dispersed throughout the water (this is referred to as
emulsification ) and can be rinsed away.

• A detergent works similar to a soap, but does not form precipitates with metal ions, reducing the discoloration of
clothes due to the precipitated soap.
• The cleansing action of detergents is due to their capacity to reduce the surface tension of water,
emulsify oil or grease, and retain it in suspension in water. detergents have this potential due to their
structure.

• A detergent dissolves in water to produce detergent anions and sodium cations. The ionization of
sodium alkyl sulphate and sodium alkylbenzene sulphonate, for example,
• Critical micelle concentration (CMC): defined as minimum concentration of surfactant at which
micelle formation is first seen in the solution, spontaneously.

• CMC represent a transition point in the behavior of surfactant molecules in solution.

• Below CMC, surfactant exist as individual entities in the solution. However, as the concentration
increases, these molecules start associate and organize themselves into micelles.

• Above CMC, surfactant molecules primarily exist as micelles, and further increases in concentration
have minimal impact on micellar structure.
• The lower the CMC, the more stable the micelle and the more slowly molecules are incorporated
into or removed from the micelle.

• The CMC value associated with the detergent is a useful guide to hydrophobic binding strength.
Detergents with higher CMC values have weaker binding and are subsequently easier to remove.

• Detergents with low CMC values require less detergent in order to form micelles and solubilize
proteins or lipids.
➢ The average number of monomers in a micelle is the aggregation number.

• A description of the number of molecules present in a micelle once the critical micelle
concentration (CMC) has been reached.

• The CMC and aggregation number values are highly dependent on factors such as temperature, pH,
ionic strength, detergent homogeneity and purity.

• Aggregation number values are also shifted by concentration, since the number of detergent
molecules per micelle may increase if the concentration is above the CMC.
➢Another useful parameter when evaluating detergents for downstream removal is the micelle
molecular weight, which indicates relative micelle size.

➢Smaller micelles are more easily removed and are usually desirable when protein-detergent
complexes are to be separated based on the molecular size of the protein.

➢The micelle molecular weight may be calculated by multiplying the aggregation number by the
monomer molecular weight.
 • The liquid detergent manufacturing process

• In addition to liquid laundry and dish-washing liquid detergents, household cleaners such as floor
cleaning liquids or glass cleaners are also classified as liquid detergents. All these detergents can be
produced in the same plant.

• Substantially, liquid detergents are powders mixed with water and chemical solutions called
solubilizers, making detergents dissolvable in water.

➢The first stage of the liquid detergent manufacturing process consists of neutralizing fatty acids with
either caustic soda or potassium hydroxide.
• After the chemical reaction and the premix step, ingredients such as thickeners and pH adjusters
are added to a homogeneous mixer. These balancing ingredients are essential to achieve desirable
viscosity, stability, and pH value.

• In the enzyme addition stage, powdered enzymes are added to the cooled mixture due to their delicate
nature.

• Lastly, liquidized detergents are pumped into bottles by a filling system, weighted on weighing
devices and sealed by a capping machine.
 • Types of Detergents

➢ The chemical structure of hydrophilic heads determines the type of detergent.

• Detergents are classified according to the electrical charge they carry as anionic, cationic, or non-ionic.

1. Anionic detergents: have a net negative electrical charge.

• The liver produces bile acids, which are anionic detergents the body uses to digest and absorb fats.

• Commercial anionic detergents are usually alkylbenzene sulfonates.

• They are very good in removing sebum and dirt; however, they are strong cleaners and may induce an
increase of the electrical negative charges on the hair surface, creating frizz and friction.

• Therefore, in order to reduce damages and to have a mild detergency, secondary surfactants such as nonionic
and amphoteric surfactants are usually added in the formulation.

• The most important anionic surfactants used in laundry detergents are

➢ Soaps

➢ Alkyl benzene sulfonates (mainly LABS)

➢ Alkyl sulfates (AS)

➢ Alkyl ether sulfates (AES)

➢ Secondary alkane sulfonates (SAS)

• LABS (Alkyl benzene sulfonates) show very good detergency performance and frequently used in formulations
for liquid detergent due to their high solubility.

• Like soap LABS are sensitive to water hardness as a result the detergency performance is reduced with increasing
water hardness.

• AS (Alkyl sulfates ) are mainly alcohol sulfates and are produced either from natural fatty alcohols or from
petrochemical substances. Their use has increased especially in concentrated products.

• Alkyl ether sulfates (AES) are ethoxy sulfates having a hydrophobic alkyl and a hydrophilic ethoxy chain. AES
show a low sensitivity to water hardness in comparison to alkyl sulfates, as well as high solubility and good
storage stability at low temperature in liquid formulations

• Commercial AES consist of alkyl ether sulfates and alkyl sulfates as the main components.
• AES led to intensive foaming and are thus well suited for the use in high-foam detergents for vertical-axis
washing machines.

• Because of their specific properties AES are preferred constituents of detergents for delicate or wool washables,
foam baths, hair shampoos, and manual dishwashing agents.

• SAS (Secondary alkane sulfonates) are seen as special anionic surfactants for consumer products. SAS include
high solubility, fast wetting properties, chemical stability and they are very similar to LAS in terms of
detergency properties and water hardness sensitivity.

• They are completely insensitive to hydrolysis, even at extreme pH values, a result of the presence of the
stable carbon–sulfur bond.
 Manufacture of linear alkyl Benzene (LAB)

• Linear alkyl benzenes (LABs) are the precursors of linear alkyl benzene sulfonates (LABSs).

• LABS is the world’s largest commodity biodegradable surfactant commonly used in cleaners, detergents, and
laundry powders .

• Commercially, LABs are produced from Friedel −Crafts alkylation between benzene and linear C10−C14
alpha olefins (i.e. 1-alkenes) using hydrogen fluoride (HF) or aluminum chloride (AlCl3 ) as a catalyst.

• The reaction mechanism proceeds with a two-step process: catalytic alkene protonation followed by benzene
alkylation
➢ Some Routes for the Production of LAB

• Linear paraffin's are chlorinated and mono chloro paraffin is formed and then an aluminum chloride catalyst is
used which causes alkylation of benzene with mono chloroparaffin , this method was used in the early 1960s.

• First, linear paraffin's are chlorinated and then hydrogen is dechlorinated, in which case olefins are formed.
Finally, hydrochloric acid is employed as a catalyst for the alkylation of benzene with linear olefins.

❖ Cracking waxes are formed by the oligomerization of ethylene or separating larger olefins.

• Alkylation of these olefins with benzene in the presence of a hydrochloric acid catalyst results in the production of
LAB, which has been used by Shell and Amco Company.

❖ Dehydrogenation of linear paraffin's 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's
are returned to the beginning of the process after separation by distillation.
• The alkylation process typically in a homogeneous catalytic system using acids as catalysts causes problems
including toxicity, corrosion of equipment, problems during transportation, low selectivity, difficulty separating
the product and economically coasty and production of waste materials.

• Thus, the use of solid and environmentally friendly catalysts as an alternative to these acidic compounds has been
considered.

• Currently, solid catalysts is developing to replace HF acid units slowly to guarantee environmental safety and
expand the economy.

• Many materials such as clays, zeolites, aluminum chloride and various types of metal oxides, have been appraised
for this process as solid acid catalysts.
 • Sulphonation of LAB – preparation of acid slurry

• Acid slurry or alkyl benzene sulphonate is prepared by sulphonation of Linear Alkyl Benzene (LAB) with a
suitable sulphonating agent.

➢ Sulphonation can be done by the following processes:

• Batch sulphonation with either diluted SO2 gas or concentrated sulphuric acid or a mixture of 20% oleum and
98% sulphuric acid or oleum alone.

• Continuous sulphonation with 20% oleum.

• Continuous sulphonation with SO3

 Different ingredients in the formulation of detergent powders

• Detergents are complex formulations that contain different ingredients, which can be categorized into the
following main groups:

1. Surfactants

2. Builders

3. Bleaching agents

4. Additives(colorant, perfume, enzymes, foam stabilizer , medical agents etc.)

• 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

• Some components are added to

➢ aid or improve efficiency of the production process
➢ while others are added to improve the appearance, activities of other ingredients and odour of the product
Liquid detergents: foam boosters, alpha olefin sulphonates (AOS)

• Alpha olefin sulphonate (AOS) is the best foaming agent for any industry.

• This surfactant has a wide range of uses has primarily used in Cleaning and detergent industry as foam booster.
For some extent it has capacity to soften the water for synergetic cleaning action.

• Foam boasters are blowing agent that can reduce surface tension of the liquid and produce a large amount of
uniform and stable foam by mixing with pressurized air.

• Sodium laurate sulphate(SLS),Ammonium laurate sulphate(ALS), Coco-glycoside and sodium laurate ether
sulphate (SLES) are the most common foam booster.

• Generally, petroleum-based active substances such as linear alkyl benzene sulfonate (LABS) and alpha olefin
sulfonate (AOS) are used in heavy and light duty liquid detergent formulations
 ❖ What is the meaning of “detergent powder?
• Powder detergent is used for removing stains, typically from various kinds of fabric. It’s a popular and
affordable option for cleaning fabrics, available in recyclable, eco-friendly packages such as
cardboard boxes.

• By definition, it’s a powder that is used to wash clothes, sheets, towels, and fabrics in general. It can
be used in a washing machine or for manual washing.

• Powder detergent is one of the more traditional washing solutions, with two key
advantages: affordability and power against heavy stains.
• Powder detergent pros
• Affordability
• Recyclable packages
• Excellent for removal of heavy stains
• Brightening and whitening properties
• Specific optional ingredients such as oxygen bleach

• Powder detergent cons

• Dosing can be tricky and messy
• Lower quality formulas can leave residue or dissolve only partially on low temperatures
• The package is sensitive to water and tear
• Not the best solution for pre-treatment of stains
 • Detergent powder ingredients

• Modern powder detergent formulas comprise several different types of ingredients.

1. Builders

• Builders are the ultimate component of any detergent base powder. They enhance the efficiency of
the surfactant, while also affecting minerals in hard water to prevent precipitation.

• Apart from that, builders can emulsify fat, turning it into washable tiny globules.

• Builders such as sodium silicate prevent corrosion inside washing machines, ensuring that the
formula is safe to use.

• These chemicals are modern versions of traditional washing agents, fatty acids, lye, and ash
• The best powder detergents are lightweight puffed powders with excellent free-flowing properties.

• Their average bulk density ranges between 250-500 g/l, comprising hollow particles with dimensions
of 0.2-2.5mm.

• The spray drying tower is the most dependable way to obtain a mass with such properties.

• It’s necessary for products that need to be compatible with the pH levels of human skin.

• Powdered laundry detergents, on the other hand, belong to the same spectrum as bar soaps with a pH
in the alkali range.
• Alkaline builders are, essentially, soluble salts that neutralize acids. Combined with surfactants, they make a
base of laundry detergent suitable for stain removal.

2. Surfactants

• Surfactants or foamers – such as LABSA (Linear Alkyl Benzene Sulphonic Acid) are added to alkalis as a
second principal component to promote their washing ability.

• Surfactants or foamers : key role is to enhance the foaming ability.

• However, surfactants also work to break up stains further, disbanding the components that don’t dissolve in
water easily.
3. Colorful additives: brightening agents are visual enhancers, while oxygen bleaches improve the
detergency of the mixture.

• Finally, processing aids such as sodium sulfate are added to prevent caking and standardize product
density.

• Perfumes or fragrances are primarily used to cover chemical scents and dirt odors. Each supporting
ingredient adds or enhances specific properties, and defines a unique product.
➢ Powder detergent spray drying process
• Modern powder detergents comprise a lightweight, free-flowing, puffed mass.

• Spray drying delivers a superior product: lightweight, almost perfectly dehydrated, with minimal
risk of issues such as caking of the final product.

1. Handling raw materials

• Before anything, it’s necessary to handle raw materials properly, and that includes storage and
transport.

• Most solid ones come in powdered form, packed in woven bags, such as Soda Ash , while liquids
like LABSA or Caustic lye are commonly stored in tanks
2. Detergent manufacture by the spray drying

➢ Step 1 - Slurry making

• The solid and liquid raw ingredients are fed into a large tank known as a slurry mixer or clutcher.

• As the ingredients are added the mixture heats up as a result of two exothermic reactions: the hydration of sodium
tripolyphosphate and the reaction between caustic soda and linear alkylbenzene sulphonic acid.

• The mixture is then further heated to 85oC and stirred until it forms a homogeneous slurry

➢ Step 2 - Spray drying

• The slurry is deaerated in a vacuum chamber and then separated by an atomizer into finely divided droplets.

• These are sprayed into a column of air at about 425oC, which dries them instantaneously.
• The resultant powder is known as ’base powder’ from which other products are made.

• Step 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 and agglomeration is takes place
• The method of spray-drying: is the most common method for the manufacture of washing powder, or foam

• Diagrammatical representation of spry drying tower

➢ Cationic surfactants

• have a positively charged hydrophilic end

• used mainly as conditioners, being able to balance hair negative charges after washing, reducing frizz.

• Cationic surfactants in detergent formulations are used as fabric softener in washing processes

• The most important ones are: quaternary nitrogen compounds: Mono or di-alkyl quaternary compounds eg.
Ditallow dimethyl ammonium chloride (DTDMAC), Esterified mono- or di-alkyl quaternary compounds
(esterquats), Imidazoline derivatives, trimethylalkylammonium chlorides etc.

• The first surfactant developed in this category was DTDMAC, introduced in 1949 as a fabric softener for cotton
diapers.
• DTDMAC has been largely replaced by esterquats

• Esterquats possess favorable Eco-toxicological and toxicological properties.

• Are highly biodegradable compounds and are natural fatty acids functionalized with quaternary ammonium
cationic head and weak ester bonds.

• At the present time, Alkylated imidazoline derivatives are also used as fabric softeners and, due to
dermatological compatibility, as body care products.

• Amphoteric surfactants

• possess both anionic and cationic groups in the same molecule even in aqueous solution. are characterized by the
charge control through the solution pH values

• They are anionic or cationic surfactants in alkaline or acid solutions, respectively.

• They are considered very mild and thus dermatologically compatible.

• Furthermore, they have a good foaming, detergent and wetting properties. For these reasons, they are used to
reduce the aggressiveness of anionic surfactants.

• Among amphoteric, the betains are economic importance classes. Betains are insensitive to water hardness, are
only slightly toxic and compatible with the skin. They are mainly used in manual dishwashing and body care
products.

• The most important types of amphoterics are: Alkyl betaine, Alkylamidopropyl betaine, Betaines derived from
imidazolines, Alkylamphoacetates.
• Non-ionic detergents

• Are not exhibit electric charge in aqueous solutions due to the absence of hydrophilic dissociable groups.

• They are less aggressive than other surfactants and, thanks to their eudermic properties, are widely used as
emulsifiers and solubilizers in cosmetic formulations.

• They are often derived from plants, such as glucosides, citrates, sulfosuccinates and hydro lysates proteins.

• Production and use of these has been increasing steadily since the 1970s.

• This is due to ethoxylates of fatty alcohols, oxo-alcohols, and secondary alcohols obtained by reaction of the
corresponding alcohols with ethylene oxide. Ethylene oxide condensate are one of well known from this group.
• The most important nonionic surfactants are: Alcohol ethoxylates (AE), Alkyl phenol ethoxylates (APE), Fatty
acid alkanol amides (FAA) , Alkyl amine oxides (AO), N-Methyl glucamides (NMG) and Alkyl poly glycosides
(APG).
• AE are the most important nonionic surfactants in detergent formulations. By varying the length of carbon chain
and the degree of ethoxylation, these nonionic surfactants can be tailor-made with respect to the washing
temperature.
• Difference between soap and detergents
• The key differences between soaps and detergents are tabulated below.
 Environmental effects
• Detergents become part of human life and consumed for different aims especially hygienic purposes.

• Among the different contaminants, detergent as an important pollutant has serious risks to natural

ecosystems and affect fauna and flora directly and indirectly.

• Detergent components can enter to soil and water bodies from different sources.

• Therefore, production of environment-friendly detergent is an important issue around the world.

 ❖ Chemical Effects

• Laundry detergent is far more than just a basic cleansing soap. It contains a huge number of harmful
chemicals that have a serious impact on our environment. Some of the most concerning ones are:

1. Phosphates - linked to cardiovascular (heart) disease as well as osteoporosis. These toxins are

particularly damaging to the marine environment when dispersed in wastewater from your wash.

2. Bleach - often used to brighten whites, its toxic fumes cause respiratory distress and on contact with

skin and eyes it is able to cause caustic burns

3. Formaldehyde - A chemical usually associated with the preservation of dead bodies. This toxic
ingredient as classified by the EPA , is a class B1 probable carcinogen. This means it has been linked
with an increased risk of cancer.

4. Ammonium Sulfate and Ammonium Quaternary Sanitizers - harsh cleansing agents that are
corrosive and toxic. They can cause eye, skin and lung damage even with minimal exposure.

5. Dioxane (1,4 Dioxane/ Diethylene Dioxide/ Diethylene Ether/ Dioxan) is quite possibly one of the
worst additives. Dioxane is also a carcinogen and has been known to pose a combustion risk. Exposure
to this toxin can damage your kidneys, lungs, central nervous system, eyes, skin and respiratory
function.
• Many laundry detergents contain approximately 35-75% phosphate salts. Phosphates can cause a variety of water
pollution problems. For example, phosphate tends to inhibit the biodegradation of organic substances.

• Synthetic surfactants reduce the tension of the water’s surface, making it susceptible to pollutants such as car
exhaust and pesticides. This further impacts the aquatic environments

• Surfactants damage the protective layers of fish, leaving them vulnerable to parasites, bacteria and other
pollutants.

• Another problem caused by a standard surfactant was foam creation in the nation’s waterways. It was caused by
ABS (alkyl-benzene sulfonate). Nowadays, manufacturers replaced ABS with LAS (linear alkylate sulfonate),
which biodegrades faster than ABS.
ISO specification of detergents and quality testing procedure
(Reading assignment )
This is the great task for chemists!

Thank you!!!