Soap and Detergents Introduction 1. Cleansing agents are chemical substance used to remove grease and dirt. 2.

Th ere are two type of cleansing agents : a) Soaps b) Detergents 3. Soaps are sodiu m or potassium salt of fatty acids that contains 12 to 18 carbon atoms per molec ule. 4. Soaps are cleansing agents made from animal fats or vegetable oil by sap onification. Soap is a salt of a compound known as a fatty acid. A soap molecule consists of a long hydrocarbon chain (composed of carbons and hydrogens) with a carboxylic a cid group on one end which is ionic bonded to a metal ion, usually a sodium or p otassium. The hydrocarbon end is nonpolar and is soluble in nonpolar substances (such as fats and oils), and the ionic end (the salt of a carboxylic acid) is so luble in water. The structure of a soap molecule is represented below: O || CH3-CH2-CH2- CH2-CH2-CH2-CH2- CH2-CH2- CH2-CH2- CH2-CH2- CH2-CH2- C-O Na+ Non-polar hydrocarbon chain ionic end (Soluble in nonpolar substances) (Soluble in water) Detergents are structurally similar to soaps, but differ in the watersoluble portion. Three examples of detergents are shown below. a sodium alkyl sulfate a sodium alkylbenzene sulfonate Heonhsleonhs@hotmail.com

Soap The History of Soap Manufacturing 1. Soap have been used for more than 3000 years. It was recorded that the Babylo nians were making soaps around 2800 B.C. 2. The Purifying Oils were recorded on He brew tablets in 4000 B.C. 3. In ancients time, soap made from ashes of plants wh ich contain sodium carbonate and potassium carbonate. The ashes were boiled with lime (calcium oxide) to produce caustic potash (potassium hydroxide). Caustic p otash is then boiled with the animal fats to produce soap. a) Ash + Lime boiled (CaO) Caustic Potash (KOH) (K2CO3) b) Caustic Potash + Animal Fats boiled Soap 4. In 1861, the Belgian Chemist Ernest Solvay (1838-1922) discovered the process to make soda (sodium carbonate) from common salt (sodium chloride) and calcium carbonate. 5. This process is known as the Solvay Process which produces sodium carbonate cheaply for industrial use. Sodium carbonate (often called soda or sod a ash) is used for making glass, soaps and detergents. 6. Michel Chevreul (17861889), a French chemist, was noted for his research in the composition of animal fats is composed of fatty acids and glycerol. This discovery contributed to the rapid development of the soap and candle industry. Heonhsleonhs@hotmail.com

Preparation of soap by saponification 1. Soap is a cleansing agents produced by the reaction between sodium hydroxide and potassium hydroxide with animal fats or vegetable oils. This reaction is kno wn as saponification. 2. Fats and vegetable oils are large, naturally occurring ester molecules. When fats or oils are boiled with concentrated alkalis, such as sodium hydroxide, saponification occurs and the ester molecules are broken down into soap and glycerol. Fats or vegetable oils + concentrated alkalis soap +gly cerol 3. Saponification is the alkaline hydrolysis of ester using alkali solutions. Fr om the chemist aspect, soaps are sodium salts or potassium salts of long chain c arboxylic acids (with 12 to 18 carbon atoms per molecule). 4. Some examples of s oaps are shown below. a) Sodium palmitate, C15H31COONa b) Sodium oleate, C17H33C OONa c) Sodium stearate, C17H35COONa Additives such as perfume, colouring matter and sometimes antiseptics are added to soaps to enhance their marketability. 5. Glyceryl tristearates are naturally occurring esters commonly found in animal f ats and vegetable oils. When the ester is boiled with concentrated sodium hydrox ide solution, saponification (alkaline hydrolysis) occurs and mixture of sodium stearate (soap) and glycerol is obtained. Heonhsleonhs@hotmail.com

CH2COOC17H35 CH2OH CHCOOC17H35 + 3NaOH (heating) CHOH CH2COOC17H35 Glyceryl tristearate 3C17H35COONa Sodium stearate (soap) + CH2OH Glycerol 6. The soap produced can be precipitated by adding common salt (sodium chloride) to the reaction mixture. 7. The sodium chloride added reduced the solubility of soap in water. As a result, precipitation of soap occurs. 8. The properties of soap depend on : a) The type of alkali used for saponification b) The type of an imal fats or vegetable oils used. 9. Soaps produced from sodium hydroxide are ha rd, whereas soaps produced from potassium hydroxide are soft. 10. Animal fats (t allow) from cows and vegetable oils (such as palm oil or olive oil) ae used for making soap. The structure of soap molecule 1. When soap is dissolved in water, it will dissociate and produce sodium ions a nd carboxylate ions (RCOO-). For example, sodium stearate dissolves in water to form sodium ions and stearate ions. Heonhsleonhs@hotmail.com

C17H35COONa (s) + water sodium stearate C17H35COO- (aq) stearate ions + Na + (aq) 2. The active substance in soap is the carboxylate ion, for example, stearate io n. The stearate ion consist of two parts : the head and the tail. The head id negative ly charged and the tail is a long hydrocarbon chain. O 3. The head contains the -C-O- ions which dissolves readily in water (hydrophilic) but does not dissolve in oil. Conversely, the tail contains a long hydrocarbon ch ain which is insoluble in water (hydrophobic) but dissolves readily in oil. 4. S oaps made from palmitic acid are known as sodium palmitate. Figure 5.2 shows the structure of the palmitate ion in soaps. 5. The figure 5.3 9a) shows the molecu lar model of palmitate ion and Figure 5.3 (b) shows the simple representation of the structure of the palmitate ion. (a) The molecular model of the palmitate ion. (b) The diagrammatic representation of the soap ion. Heonhsleonhs@hotmail.com

Detergents 1. Detergents are synthetic cleansing agents made from hydrocarbons obtained fro m petroleum fractions. Thus, detergents are petrochemicals. 2. Detergents can be classified into three main types, depending on the charge on the detergent ion. a) Anionic detergents where the head of the detergent particle contains a negat ively charged ion. Negatively Example: R O SO3 Na (Sodium alkyl sulphate) + charged ion b) Cationic detergents where the head of the detergent particle contains a posit ively charged ion. Positively Example: R N (CH3)3+BRcharged ion c) Non ionic detergents Example: R O CH2CH2OH 3. There are two types of anionic detergents : a) Detergent molecule with a benz ene ring such as sodium alkylbenzene sulphonate. Heonhsleonhs@hotmail.com

Where R represents a long hydrocarbon chain. We can represent the detergent ion, alkylbenzene sulphonate ion, more simply as : b) Detergent molecule without a benzene ring such as sodium alkyl sulphate. We c an represent the detergent ion, alkyl sulphate ion as: R OSO3Preparation of detergents 1. The detergent, sodium alkyl sulphate can be prepared from alcohols with chain lengths of 12 to 18 carbon atoms in two steps. Steps 1: Reaction with concentrated sulphuric acid Heonhsleonhs@hotmail.com

Step 2: Neutralisation with sodium hydroxide solution. 2. An example of a long chain alcohol is didecan 1 ol, CH 3(CH2)10CH2OH. The dete rgent prepared from dodecan -1 ol is called sodium dodecyl sulphate (IUPAC name) or sodium lauryl sulphate (common name). CH3(CH2)10CH2O-SO3-Na+ . 3. Sodikum alk ylbenzene sulphinates, were first used in 1940s. It can be prepared in three ste ps. The starting materials for making this detergents in a long chain alkene, RC H = CH2 , obtained from the cracking of petroleum. a) Step 1 : Alkylation Alkylation is the introduction of the alkyl group to an organic molecule. Heonhsleonhs@hotmail.com

b) Step 2 : Sulphonation Alkylbenzene produced the react with concentrated sulph uric acid acid to form alkylbenzene sulphonic acid. Sulphonation is the introduction of the sulphonic acid group, -SO3H to an organi c molecule to form sulphonic acid. c) Step 3 : Neutralisation Alkylbenzene sulphonic acid produced reacted with sod ium hydroxide to form sodium alkylbenzene sulphonate, the detergent Heonhsleonhs@hotmail.com

The structure of detergent molecule When a detergent is dissolved in water, it dissociates to form sodium ions (Na+) and detergent ions. The detergent ions have the same basic structure as the soa p ions, that is consist of two parts : a) The head is the sulphate group (-OSO3-) , which is negatively charged and hydrophilic (dissolves readily in water but no t in oils and grease). b) The tail is the long hydrocarbon chain, which is neutral and hydrophobic (dissolves readily in oils and grease, but not in water). alkyl sulphate ion Alkylbenzene sulphonate ion Heonhsleonhs@hotmail.com

The cleansing of soap and detergent 1. The cleansing action of soap or detergent depends on their chemical bonding a nd structures. a) The ionic head (negatively charged) is soluble in water (hydroph ilic) but insoluble in oily layer. b) The long hydrocarbon tail (neutral) is insol uble in water (hydrophobic) but soluble in oily layer. 2. Oil cannot be washed a way from clothing with water because oil (a covalent molecult0 is insoluble in w ater. 3. Lifting greasy dirt from the surface cloth. When soap or detergent is a dded to the dirty surface of a piece of cloth covered with a layer of oil or gre ase. a) The negatively charged head (hydrophilic) of soap ions or detergent ions d issolves in water. b) The hydrocarbon tail (hydrophobic) of soap or detergent ions dissolves in the layer of grease. 4. I the water is agitated slightly, the grea se begins to be lifted off the surface. This cause by the forces of attraction b etween the water molecules and the negatively charged heads. Heonhsleonhs@hotmail.com

The cleansing action of soap 5. On further agitation during washing, the greasy dirt is lifted from the surfa ce. 6. Emulsifying dirt in water a) Soaps and detergents can act as emulsifying agents to emulsify oils and grease. b) The process of emulsification breaks larg e drops of grease into smaller droplets that floats in water. The greasy droplet s repel on another because they carry the same charge. As a result, the grease i s suspended in the solution. c) When the cloth is rinsed with the water, the dro plet will be carried away. d) The cleaning process become more efficient in the water containing the soap or detergent solution is stirred Heonhsleonhs@hotmail.com

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Additives in detergents 1. Modern detergents used for washing clothes usually contains a few types of ad ditives to : a) Increase their cleaning power. b) Make them attractive and salea ble. 2. Only about 20% of the substances in a detergent are cle4ansing agents (s odium alkyl sulphate or sodium alkylbenzene sulphonate). The other substances ar e additives. The examples of addictives and their functions are described as fol lows : 3. Builders : Sodium tripolyphosphate (Na5P3O10) a) Sodium tripolyphospat he is usd to soften hard water. In the presence of sodium tripolyphosphate, Ca2+ ions and Mg2+ ions are removed. b) Sodium tripolyphosphate increases the pH val ue of water. In this way, muddy dirt can be removed. 4. Whitening / bleaching ag ents : sodium perborate Heonhsleonhs@hotmail.com

a) Bleaches (bleaching agents) remove coloured stains by oxidation process. When coloured stanis are oxidized, the colour will disappear. b) The whitening (blea ching) agents commonly used in detergent are sodium perborate (NaH2BO43H2O). Sod ium perborate decomposes in hot water to release oxygen (an oxidising agent) whi ch is responsible for the whitening (bleaching) action. c) Unlike chlorine, oxyg en does not bleach the colour of dyes are not damaging to fabrics. When properly used, the perborate bleaches make fabrics whiter than chlorine bleaches and the colourful dyes of the fabrics do not fade when dirty stains are removed. d) Bes ides sodium perborate, sodium hypochlorite, (NaCIO) can also be used as bleaches in detergents. The IUPAC name of sodium hypochlorite is sodium chlorate (I). e) Sodium hypochlorite releases chlorine that bleaches with dirty stains. However, high concentrations of chlorine can be quite damaging to fabrics. These bleache s do not work well on synthetic fabrics (polyster fabrics), often causing a yell owing rather than the desire whitening. Also chlorine causes the dyes on fabrics to fade. 5. Biological enzymes : Amylase, lipase, and protease a) Protein stain s such blood, milk, and tomato sauce cannot be removed by the ordinary detergent s because these types of stains are insoluble in water. b) Biological enzymes in detergents can break down fat and protein molecules in food stains. The fatty a cids, glycerol and amino acids produced are soluble in water and are removed dur ing washing. 6. Brighteners a) Figure below shows the action of brighteners. The brighteners absorb the invisible ultraviolet and re-radiate it as blue light. Brightener Cloth Heonhsleonhs@hotmail.com

b) Brighteners make fabrics appear whiter and brighter because the blue light ca n hide any yellowing on the fabrics. Blue light added to the yellow light reflec ted on old fabrics make them look white. 7. Drying agents ; Sodium sulphate and sodium silicate Anhydrous sodium sulphate and sodium silicate (Na2S2O3) are used as drying agents to ensure that the dete rgent in powdered firm is always in a dry condition. 8. Stabilisers a) The funct ions of stabilizers is to prevents the formation of foam. b) In an automatic was hing machine, excessive foam can stop the pump working. So, washing powders for automatic washing machine are made using detergents that are good at removing an d emulsifying grease, but do not produced foam. 9. Perfumes Perfumes are added t o make clothes smell fresh and clean. Heonhsleonhs@hotmail.com

The effectiveness of soaps and detergents as cleansing agents Advantages of soaps 1. Soaps are effective cleansing agents in soft water, that is water does not co ntain Mg2+ and Ca2+ ions. 2. Soaps do not cause pollution problems to the enviro nment. This is because soaps are made from chemical found in animals and plants. This means that soaps are biodegradable, that is they can be composed by the ac tion of bacteria. Disadvantages of soaps 1. Soaps are ineffective in hard water, that is, water that contains magnesium a nd calcium salts. 2. In hard water, soaps will react with Mg2+ and thus, soaps d o not lather in hard water. 3. Scum is grey solid that is insoluble in water. It consists of magnesium stearate and calcium stearate. 4. Soaps are not also effe ctive in acidic water, for example rainwater containing dissolves acids. H + ion s from acids will react with soap ions to produce carboxylic acids molecular siz e that are insoluble in water. 5. Stearic acids and other carboxylic acids do no t act as cleansing agents because they exist mainly as molecules and do not anio nic hydrophilic ends (head) that dissolves in water. Advantages of detergents 1. Detergents are cleansing agents that are effective in soft water as well as h ard water. This is because detergents do not form scum with Mg+ and Ca2+ ions fo und in hard water. 2. The detergents ions (R O SO3- and R SO3- )react with Mg+ an d Ca2+ ions in hard water. However, the magnesium salts and calcium salts which are formed are soluble in water. Hence, the scum is not formed and the detergent s are still active in hard water and lathers easily. Heonhsleonhs@hotmail.com

3. Detergents are synthetic cleansing agents. This means that the structure of t he hydrocarbon chain can be modified to produce detergents with specific propert ies. Nowadays, different types of detergents have been synthesised for specific uses such as shampoos and dish cleaner. 4. Furthermore, detergents are also effe ctive in acidic water because H+ ion is acidic water do not combined with deterg ents ions. Disadvantages of detergents 1. Most detergents have branched hydrocarbon chains and are non-biodegradable, t hat is, they cannot decomposed by bacteria. As a result, non-biodegradable deter gents cause water pollution. 2. Phosphates in detergents act as fertilizers and promote the growth of water plants and algae. When the plants die and decay, the y will used up the oxygen dissolves in water. This will decrease the oxygen cont ent in water and kill fishes and other aquatic lives. 3. Detergents produce a lo t of foam in water. The layer of foam that covers the water surface will prevent s oxygen from dissolving in water. This condition will cause fish and other aqua tic life ti die from oxygen starvation. 4. Additives such as sodium hydrochlorit e (bleaching agents) releases chlorine gas in water that is acidic. Chlorine gas is highly toxic and kills aquatic life. Heonhsleonhs@hotmail.com