SOAPS and Detergents

History of Soap Manufacturing

 Used for more than 3000 years. Recorded that the Babylonians were making soap around 2800 B.C. The Purifying Oils were recorded on hebrew tablets in 400 B.C.

 In ancient times, soaps were made from ashes(remains) of plants which contain sodium carbonate and potassium carbonate. The ashes were boiled with lime (calcium oxide) to produce caustic potash (potassium hydroxide). Caustic potash is then boiled with animal fats to produce soap.

 The equation : - Ash + lime (K3CO3 ) (CaO)

boil

caustic potash (KOH)

boil

- Caustic potash + animal fats

soap

 In 1861, the Belgian chemist Ernest Solvay ( 18381922) discovered the process to make soda (sodium carbonate) from common salt (sodium chloride) and calcium carbonate. This process is known as the Solvay Process which produces sodium carbonate cheaply for industrial use. Sodium carbonate (often called soda or soda ash) is used for making glass, soaps and detergents.

 Michel Chevreul (1786-1889), a French chemist, was noted for his research in the composition of animal fats.

In 1816, he discovered that animal fats are composed of fatty acids(A carboxylic acid which is attached to a chain of at least eight carbon atoms) and glycerol. This discovery contributed to the rapid development of the soap and candle industry.

Soaps
1. Cleansing agents are chemical substances used to remove grease and dirt. 2. There are 2 types of cleansing agents: Soaps Detergents

 Soap is a cleansing agent produced by the reaction between sodium hydroxide/potassium hydroxide with animal fats/vegetable oils. This reaction is known as saponification. Fats and vegetable oils are large, naturally occuring ester molecules. When fats or oils are boiled with concentrated alkalis, such as sodium hydroxide or potassium hydroxide, saponification occurs and the ester molecules are broken down into soap and glycerol

Fats/ Vegetable Oils + Concentrated Alkalis

Soap + Glycerol Saponification is the alkaline hydrolysis of esters using alkali solutions. Alkaline hydrolysis is the use of alkali chemical in water to break down complex molecules (specifically, tissues) into their basic building blocks.

 From the chemistry aspect, soaps are sodium salts or potassium salts of long chain carboxylic acids (with 12 to 18 carbon atoms per molecule). Sodium stearate, C17H35COONA Sodium oleate, C17H33COONA

Sodium palmatate,

C15H31COONA

 Glyceryl tristearates are naturally occurring esters commonly found in animal fats and vegetable oils. When the ester is boiled with concentrated sodium hydroxide solution, sopanification (alkaline hydrolysis) occurs and a mixture of sodium stearate(soap) and glycerol is obtained.

 Additives such as perfume, coloring matter and sometimes antiseptic are added to soaps to enhance their marketability. The soap produced can be precipitated by adding common salt (sodium chloride) to the reaction mixture. The sodium chloride added reduces the solubility of soap in water. As a result, precipitation of soap occurs.

The properties of soap depend on:

The type of alkali used for saponification The type of animal fats or vegetable oils used.

 Soap produced from sodium hydroxide are hard Whereas soap produced from potassium hydroxide are soft. Animal fats (tallow) from cows and vegetable oils ( such as palm oil or olive oil) are used for making soap.

Preparation of soap

Steps to prepare soap

A) Preparation of soap 10cm3 of palm oil is measured out into a beaker. 50cm3 of concentrated (5 mol dm-3) sodium hydroxide solution is measured out and poured into the palm oil in a beaker. The mixture is heated until boiling. The solution is stirred with a glass rod throughout the heating process. The boiling is continued for about 5 minutes until the layers of oil disappear. The Bunsen flame is then turned off and the reaction mixture is left to cool.

B) To separate soap from the reaction mixture. 1. 3 to 4 spatula of sodium chloride is dissolved in about 100cm3 of water. 2. The salt solution is then added to the soap solution obtained in Section A. The mixture is boiled again for about 5 minutes 3. When the mixture is cooled, a white precipitate will formed, which floats on the surface of the mixture. 4. The mixture is filtered and washed with distilled water to remove excess alkali and salt.

 A small amount of the residue on the filter paper is examined by rubbing it on the hand and shaking it with water in a boiling tube. The white residue on the filter paper is soap because it has a slippery feel and produces foam on shaking with water. The soap produced in section A can be precipitated form the solution by adding sodium chloride and boiling the solution again. This process is called salting out. The salting out process occurs because sodium chloride reduces the solubility of soap in water and causes it to be precipitated.

The structure of soap molecule

When soap is dissolved in water, it will dissociate and produce sodium ions and carboxylate ions(RCOO- ). For example, sodium stearate dissolves in water to form sodium ions and stearate ions.

sodium stearate

stearate ions

The active substance in soap is the carboxylate ion, stearate ion. The stearate ion consists of two parts: the head and the tail. The head is negatively changed and the tail is a long hydrocarbon chain. The head contains the COO ion which dissolves readily in water (hydrophilic) but does not dissolve in oil. Conversely, the tail contains a long hydrocarbon chain which is insoluble in water (hydrophobic) but dissolves readily in oil.

Soaps made from palmitic acid are known as

sodium palmitate.

Advantages of soaps
Soaps are effective cleansing agents in soft water, that is, water that does not contain Mg 2+ and Ca2+ ions. Soaps do not cause pollution problems to the environment. This is because soaps are made from chemicals found in animals and plants. This means that soaps are biodegradable, that is, they can be decomposed by the action of bacteria.

Disadvantages of soaps
Soaps are ineffective in hard water, that is, water that contains magnesium and calcium salts. In hard water, soaps will react with Mg 2+ and Ca2+ ions to from a precipitate called scum. Scum is a grey solid that is insoluble in water. It consists of magnesium stearate and calcium stearate.

stearate ion(soap ion) magnesium sterate(scum)

stearate ion(soap ion)

calcium sterate(scum)

 Soaps are also not effective in acidic water, for example, rainwater containing dissolved acids. H+ ions from acids will react with soap ions to produce carboxylic acid molecules of large molecular size that are insoluble in water.
stearate ion stearic acid

Stearic acids and other carboxylic acids do not act as cleansing agents because they exist mainly as molecules and do not have anionic hydrophilic ends (heads) that dissolve in water.

The cleansing action of soap and detergent

The cleansing action of soap or detergent depends on chemical bonding structure
Ionic head Negatively charge Long hydrocarbon tail Neutral

Hydrophilic ( soluble in water)

Insoluble in oily layer

Hydrophobic ( insoluble in water)

Soluble in oily layer

Emulsifying the water

a. Soaps and detergents can act as emulsifying agents to emulsify oils and grease. b. The process of emulsification breaks large drops of grease into smaller droplets that float in water. c. These greasy droplets repel one another because they carry the same charge. d. When clothes is rinsed with water, the droplets will be carried away. e. The cleaning process becomes more efficient with 2 steps Stirring Washing at high temperature.

Detergent

Definition
Detergent are synthetic cleaning agents made from hydrocarbons obtained from petroleum fractions.
Thus, detergents are petrochemicals.

Structure of detergent molecule

When a detergent is dissolved in water, it dissociate to form Na and detergent ions. The detergent ions have the same basic structure as soap ions, it consists of 2 parts:
Hydrocarbon tail , dissolves in oil and grease Ionic head (-OSO) or (-SO) which is negatively charged, dissolve in water.

3 main types
With a benzene ring

1. Anionic detergents 2. Cationic detergents 3. Non-ionic detergents

Without a benzene ring

Anionic detergents
where the head of the detergent particle contains a negatively charged ion.

Eg: R-O-SO Na (sodium alkyl sulphate)

negatively charged ion

Most detergents have a negative ionic group

Anionic detergents with a benzene ring

Anionic detergents without a benzene ring

Alkyl group

Sulphonate group

Sulphate group

Sodium alkylbenzene sulphonate

Sodium alkyl sulphate

 Sulphonate group contains 3 oxygen atoms (-SO)

A Sulphate group contains 4 oxygen atoms (-OSO)

Cationic detergents
where the head of the detergent particle contains a negatively charged ion. Eg: R-N(CH) Br
Positively charged ion

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.

Non-ionic/ neutral detergents

Eg: R-O-CHCHOH 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.

Preparation of detergents

 Sodium alkylbenzene sulphonate, R

SONa

1st

step

Alkylation RCH=CH +
alkene

Introduction of the alkyl gp to an organic molecule.

Ralkylbenzene
Introduction of the sulphonic acid gp, SOH to an organic molecule to form sulphonic acid.

benzene

2nd

step
R-

Sulphonation

+ HO-SOH R(HSO)

-SOH+ HO

alkylbenzene

Alkylbenzene sulphonic acid

3rd

step

Neutralisation

R-

-SOH + NaOH R-

- SONa + HO

Sodium alkylbenzene sulphonate

Whereas
Sodium alkyl sulphate can be prepared from alcohols with chain length of 12-18 carbon atoms in 2 steps. Step1: Reaction with conc. sulphuric acid

R-O-H+ H-

-H Rconc. sulphuric acid alkyl hydrogen sulphate

H + HO

Step 2: Neutralisation with NaOH solution R-H + NaOH RNa + HO

Additives in detergents
Modern detergents used for washing clothes usually contain a few types if additives to: 1. Increase their cleaning power 2. Make them attractive and saleable Only 20% of the substances in a detergent are cleansing agents (sodium alkyl sulphate or sodium alkylbenzene sulphonate). The other are additives.

Example of additives
1. Alkaline builders: Sodium tripolyphosphate (Na5P3O10) - to bind dissolved metal ions (Ca and Mg) and support emulsification. - Increase pH value of water to remove muddy dirt. - were preferred because of low cost and high cleansing effectiveness.

2. Whitening/bleaching agents: sodium perborate (NaHBO.3HO) Bleaches- remove coloured stains by oxidation process Whitening agents- sodium perborate decompose in hot water to release oxygen which is responsible for the whitening action.

3. Biological enzymes: amylase, lipase and protease Protein stains (blood, milk, tomato sauce) cannot be removed by the ordinary detergents as these types of stains insoluble in water. Biological enzymes can break down fat and protein molecules in food stains.

4. Brighteners It absorbs the ultraviolet light and re-radiate it as a blue light. Make fabrics appear whiter and brighter because blue light can hide any yellowing.

5. Drying agents sodium sulphate and sodium silicate (NaSO) - To ensure that the detergent in powdered form is always in a dry condition. 6. Stabilizers -prevent the formation of foam- stop pump working Good powders for automatic washing machinesgood at removing and emulsifying grease, but not produce foam. 7. Perfumes- make clothes smell fresh and clean

In short,
Chemical names and its functions
Sodium sulphate and sodium silicate - to keep the

powder dry. Sodium triphosphate/tripolyphosphate - to make the solution alkaline. ( helps to remove dirt and also soften water.) Carboxy methyl cellulose to keep the dirt particles removed are kept suspended in the solution. sodium perborate (bleaching agent) - for obtaining sparkling white clothes,

Advantage of detergents
Detergents are effective in soft water as well as hard water. It do not form scum with Ca and Mg ions found in hard water.
2R-O-SO + Mg (R-O-SO)Mg
Alkyl sulphate ion (detergent) Magnesium alkyl sulphate (dissolves in water)

2R-O-SO + Ca (R-O-SO)Ca
Calcium alkyl sulphate (dissolves in water)

 Detergents are synthetic agents. The structure of the hydrocarbon chain can be modified to produce detergents with specific properties. Different types of detergents have been synthesized for specific uses such as shampoos and dish cleaner.
Furthermore, detergents can be also effective in acidic water as H ions in acidic water do not combine with detergent ions.

Disadvantages of detergents
Most detergents have branched hydrocarbon chains- non-biodegradable= cannot decomposed by bacteria cause water pollution. Phosphate in detergents acts as fertilisers, promote growth of water plants and algae. When plants die and decay, they use up the oxygen in water kill aquatic life.

 Foam in detergents- covers the water surfaceprevent oxygen from dissolving in water aquatic life threaten. Sodium hypochlorite(bleaching agent) release chlorine gas in water that is acidic. Chlorine gas is highly toxic and kill aquatic life.

Comparison of Soaps and Detergents

1. Soaps cannot be used in hard water 1. Synthetic detergents can be used in hard water

2. Soap is made from vegetable oil 2. Synthetic detergents made from or edible oils byproducts of petroleum industry ( to conserve edible oil)

3. Soaps cannot be used in acidic 3. Synthetic detergents can be used medium ( otherwise precipitate the in any medium including acidic. fatty acids)
4. Soaps have weak cleansing action 5. Soaps are not very soluble in water 6. Soaps are biodegradable and do not cause pollution 4. Synthetic detergents have strong cleansing action. 5. Synthetic detergents are highly soluble 6. Synthetic detergents are not biodegradable and cause water pollution

Uses of Soaps

 Soaps are excellent cleansing agents and have good biodegradability.

Soaps are also effective as mild antiseptics and ingestible antidotes for mineral acid( inorganic acid-release hydrogen ions when dissolved in water. For example, sulfuric acid, hydrochloric acid and nitric acid) or heavy metal poisoning.

 Special metallic soaps, made from soap and heavier metals, are used as additives in polishes, inks, paints, and lubricating oils.

 Soap is an excellent cleanser because of its ability to act as an emulsifying agent. An emulsifier is capable of dispersing one liquid into another immiscible liquid. This means that while oil (which attracts dirt) doesn't naturally mix with water, soap can suspend oil/dirt in such a way that it can be removed.

Uses of Detergents

All-Purpose Cleaner : Either form of detergent can be used to clean tiles, floors, counters, tubs and toilets. Mix 3/4 of a cup of bleach, 1 cup of detergent and 1 gallon of hot water together and pour it into spray bottles for a supply of all-purpose cleaner.

Moss Killer : Sprinkle powdered detergent on moss that is growing in the cracks of your steps, sidewalk or driveway. Give it a few days to turn brown, then brush it from the cracks with a broom. Oil Spills : Powdered detergent can absorb oil that's spilled on a garage floor or on the street.

Carpet Cleaning Both types of cleaner can be added to carpet steam cleaners to make the carpet smell fresher and boost the appliance's cleaning power.
Drains Instead of buying Drano to clean out a drain, put 1/4 cup of liquid detergent into the drain, then pour in a boiling pot of water after a minute to flush out to blockage.

Bubbles If your kids like to make bubbles with wants or play with bubble-making guns, make the bubble solution yourself by mixing liquid detergent with water. Soap-Detergent Sprays Control of plant pests.

 Detergents are used at three essential steps in biochemistry of proteins: extraction, storage, and analysis : -In solution: detergents help to keep molecules in solution by dissociating aggregates, increasing solubility, and unfolding proteins.