DETERMINATION OF THE TOTAL FATTY MATTER CONTENT IN SELECTED SOAPS ON THE GHANAIAN MARKET (MAKOLA)

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Information about DETERMINATION OF THE TOTAL FATTY MATTER CONTENT IN SELECTED SOAPS ON THE...

Published on October 19, 2016

Author: RaphertTETTEH

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1. CHAPTER ONE BACKGROUND INFORMATION Soap is one of the most popular detergents in personal care. According to Roman Legend, soap was named after mount Sapo, an ancient site of animal sacrifices. After an animal sacrifices, rain would wash the animal fat and ash that collected under the ceremonial alters down the slopes to the banks of the Tiber River. Women washing clothes in the river noticed that if they washed their clothes in certain parts of the river after a heavy rain their clothes were much cleaner (Ahmed, 2002). A soap-like material found in clay cylinders during the excavation of ancient Babylon is evidence that soap making was known as early as 2800 B.C. Inscriptions on the cylinders revealed that fats were boiled with ashes, a soap making method. It is generally agreed that the Hebrew word “borith” which has been translated as soap, is a generic term for any cleaning agent. By the second century A.D, the Greek physician, Galen, recommended soap for both medicinal and cleansing purposes. In other words, it is a substance, that when dissolved in water removed dirt from dirty materials (Oghome et al, 2012). Historically, it has been claimed that the esteem of a country’s civilization is based on consumption of soap. In the 18th century, because of the shortage of some raw materials, soap was a highly priced luxury, and only wealthy people could afford it. It became handy to other people only after the manufacture of sodium carbonate was developed. At the end of the 19th century, the first soap powder for laundry was made using sodium silicate as a builder. Whereas the use of sodium or potassium carbonate leads to a hard or soft soap, respectively, the chemical nature of the lipophilic part of the soap plays by far the largest role in determining the performance of the finished soap (Anzene and Aremu, 2007) In the 1960’s, modern soap factories were established to meet the demand for high quality and affordable soaps in Ghana. These factories include Unilever Limited in Tema, Appiah Minkah soap in Kumasi and Lovable soap in Takoradi. Between 1984 and 1989, there was a steady rise in the production of both toilet and laundry soap in Ghana. Soap, is chemically a combination of Na+ or K+ ions and fatty acids. Over a hundred fatty acids are known to exist today. Out of these hundred and over, forty are known to occur widely,

2. Soap is produced via the saponification reaction (hydrolysis) of fatty acid triglycerides with a strong base (usually potassium or sodium hydroxides), producing soap (potassium or sodium salts of fatty acid) and glycerol. Soap quality depends on the composition of saponificated fatty acids, i.e. saturated fatty acid give light open foam bubbles and solid, hard consistency, while unsaturated fatty acids provide moisturizing, conditioning and nourishing properties (Strunz & Jopp, 2006). Fatty acids are merely carboxylic acids with long hydrocarbon chains. The hydrocarbon chains length may vary from 10-30 carbons (mostly12-18). The non-polar hydrocarbon alkane chain is an important counterbalance to the polar acid functional group. In acids with only a few carbons, the acid functional group dominates and gives the whole molecule a polar character. However, in fatty acids, the non-polar hydrocarbon chain gives the molecule a non-polar character. The oils use in making soaps occurs in many varieties. More than hundred (100) are known to exist. Unfortunately, not all these oils are suitable for soap production as many of them form fatty acids that cannot be saponified. Usually, combinations of oils are use in soap production to give a high quality product. Some components of these combinations may not undergo saponfication upon hydrolysis and maybe left out as unreacted fatty acids in the soap. Total Fatty Matter (TFM) is one of the most important characteristics describing the quality of soap . It is defined as the total amount of fatty matter, mostly fatty acids, that can be separated from a sample after splitting with mineral acid, usually hydrochloric acid. The fatty acids most commonly present in soap are oleic, stearic and palmitic acids and pure, dry, sodium oleate has TFM 92.8%, while top quality soap noodles now increasingly used for making soap tablets in small and medium size factories, are typically traded with a specification TFM 78% minimum, moisture 14% maximum. But besides moisture, finished commercial soap, especially laundry soap, also contains fillers used to lower its cost or confer special properties, plus emollients, preservatives etc., and then the TFM can be as low as 50%. Fillers, which are usually dry powders, also make the soap harder, harsher on the skin and with greater tendency to become 'mushy' in water and so low TFM is usually associated with hardness and lower quality (Viorica et al, 2011)

3. PROBLEM STATEMENT Total Fatty Matter (TFM) is one of the most important characteristics describing the quality of soaps and it is always specified in commercial transactions. When one says healthcare and wellness, we immediately think of food, nutrition and exercise. But what about external body care? How your soap affects your wellbeing? Higher TFM ensures that soaps are least harmful to the skin and do not cause dryness; in "bathing" bars. Less TFM means very harmful soap, that soap will grasp all the moisture present in the skin making it dry. As skin becomes dry it may become more sensitive and prone to rashes, infections and skin breakdown. This condition is sometimes referred to as xerosis. Bathing soaps are classified into three grades, Grade 1: soaps should have 76% minimum TFM, Grade 2: soaps should have 70% minimum TFM and Grade 3: 60% minimum TFM. For laundry soaps, they are classified in two grades. Grade 1: 62% minimum TFM and Grade 2: 50% minimum TFM according to Ghana Standards Authority (GSA, 2008). Simply put, higher the TFM of soap better is its cleansing ability. MAIN OBJECTIVE To determine the total fatty matter (TFM) content in selected soaps on the Ghanaian market.

4. CHAPTER TWO The traditional way of making soap from ash-derived alkalis has been an age-old craft in Ghana, Nigeria and many West African countries (Nwoko, 1982). Ash derived alkalis offer inexpensive alternatives to imported ones such as potassium and sodium hydroxide, etc. Agricultural wastes such as plantain peels, cocoa pods, maize cobs, cassava peels and numerous others contain high levels of potash. According to Onyegbado et al. (2002), when they are burnt in air, the resulting ashes contain oxides of potassium and sodium which when dissolved in water yields the corresponding hydroxides according to the following equations: Na2O + H2O -------->2NaOH (1) K2O +H2O -------->2KOH (2) In soap making the properties of the fats and oils are important; the fatty acid composition in oil determines its properties (Nwoko, 1982). The acids may be distributed at random in the triglycerides. In the soap making, it is the fatty acid content that matters the most. The chain length (C number) is usually cited and helps describe the molecule’s properties in relation to others in its same series. Saturated fatty acids contain no double bonds. They are stiff molecules which tend to increase the melting point of oils. Oil and alkali based soap making involves the hydrolysis of the triacyl glyceride molecule of the fat into fatty acids and glycerol and the subsequent saponification of the fatty acids by the alkali to form soap. The various methods adopted in soap making may be thus classified: 1. Boiling the fats and oils in open kettles by open steam with indefinite quantities of caustic alkali solutions until the finished soap is obtained ordinarily named full boiled soaps. These may be sub-divided into (a) hard soaps with sodium hydrate as a base, in which the glycerine is recovered from the spent lye; (b) hard soaps with soda as a base, in which the glycerine remains in the soap, e. g., marine coconut oil soaps; (c) soft potash soaps, in which the glycerine is retained by the soap (Webb, 1926).

5. 2. Combining the required amount of lye for complete saponification of a fat therewith, heating slightly with dry heat and then allowing the saponification to complete itself. This is known as the cold process. 3. Utilizing the fatty acid, instead of the neutral fat, and combining it directly with caustic alkali or carbonate, which is incorrectly termed carbonate saponification, since it is merely neutralizing the free fatty acid and thus is not a saponification in the true sense of the word. In the methods outlined the one most generally employed is the full boiled process to form sodium soap. The stock, strength of lye, heat, amount of salt or brine added, time of settling, etc., are all influencing factors (Webb. 1926). The total fatty matter determination is crucial in the soap development process since it defines the quality of the soap and helps in soap grading. It is the water-insoluble fatty material obtained by decomposing the soap with a mineral acid under the specified conditions or the total amount of fatty matter, mostly fatty acids, that can be separated from a sample after splitting with mineral acid, usually hydrochloric acid. Poor quality soaps can cause skin discomforts such as acne, eczema, hives, rashes, skin irritation and possibly lead to cancer (Butler, 1997).Although soap is effective in removing grime and is relatively inexpensive, alkaline soaps or those with high content of percentage free alkali can cause skin irritation, dryness and scaling which can predispose the skin to fungal attacks (Butler, 1997). This is because the excess alkali will saponify the fats and oils, normally found on the skin as a protective coat, to form soluble soap and therefore get washed away, thereby rendering the skin dry. FATTY ACIDS The basic structure of fats was established nearly a century and one-half ago when Chevreul found that they were –composed of fatty acids and glycerol. A little later Gusserow separated saturated from unsaturated acids by differential solubilities of their lead salts. Fats are essential constituents of all forms of plant and animal life, and are consequently widely distributed. However, the plants and animals that produce oils and fats in sufficient quantity to constitute a significant source are few. The largest of these comprises the annual plants sucli as flax, soybean, cotton, peanut and castor bean. These grow in temperate climates requiring cultivation and production can be varied. The second source of vegetable oils is the oil bearing trees such as coconut, palm, olive, and tung. These grow in the warm or temperate climates. The commercial

6. land animal fats come largely from hogs, sheep and cattle. (Gardner, 1931) Milk fats are nearly all used for food. The sea contributes a considerable volume of oil. Among the most important sources are sardine, menhaden, herring and whale, including sperm whale. The natural fatty acids are generally aliphatic compounds with a carboxyl group at the end of a straight carbon chain. Nearly all of them have an even number of carbon atoms. The acids differ from one another in the number of carbon atoms and the number and position of the double or unsaturated bonds (Von Mikusch and Fraeier, 1941) Lauric and all longer chain acids are solids at room temperature. The most widely distributed and the most commercially important are palmitic and stearic acids. Commercial stearic acid in its different grades consists of roughly equal parts of these two acids (Peter and Mark, 1950) The unsaturated acids differ from one another in the number of carbon atoms, the number of double bonds, the position of the double bonds, and the geometry of the double bonds. All of the unsaturated acids, with the exception of elaidic, are liquid at room temperature (Peter and Mark, 1950) FATTY ACIDS IN SOAPS Soap is a function of acids and fatty acids are functions of fats and oil. In the simplest sense, oils that are solid at room temperature are hard whereas those that are liquid at room temperature are soft. The degree of hardness and softness differs according to their sources and other parameters. Oils that are hard contributes to hardness and/or lather in soap. Oils that are soft contribute to conditioning. The main conditioning fatty acids are oleic (1 unsaturated bonds), linoleic (2 unsaturated bonds) and linolenic (3 unsaturated bonds). The more unsaturated bonds, the better the conditioning and the more easily it is absorbed by the skin, but the softer the oil is in soap, the more prone to oxidation. Making soap therefore means choosing a combination of oils with different degrees of hard/soft, conditioning and lather, to get the particular product that fits best and provides the best result (Oghome et al., 2012). According to Oghome et al., (2012), the chief fatty acids in soap making are lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. They are obtained from mutton tallow, beef tallow (animal fats), palm oil, and palm kernel oil. Lauric acid is a saturated fatty acid whose single bond helps in soap hardening. It also has good cleansing agent and supports foaming. As they increase in size from lauric to stearic, the melting point of the oil

7. increases. Saturated fatty acids in soap have good cleaning properties. Unsaturated fatty acids are liquids. They tend to have good cleaning power, but lather poorly. These fatty acids also tend to make milder soaps (Web, 1926) The percentage of palmitoleic acid is between 0.00-2.20 percent. This acid is unsaturated. It makes soap to be mild, have good cleaning power but foams poorly (Oghome et al., 2012). Lauric Acids Lauric acid, or dodecanoic acid, is a saturated fatty acid with the molecular formula CH3 (CH2)10COOH. It is the main acid in coconut oil and in palm kernel oil, and is believed to have antimicrobial properties. It is also found in human milk (5.8% of total fat), cow’s milk (2.2%), and goat milk (4.5%). "Approximately 50% of the fatty acids in coconut fat are lauric acid (Linstrom and Mallard, 2014). Lauric acid is a medium chain fatty acid (MCFA), which has the additional beneficial function of being formed into monolaurin in the human or animal body. Monolaurin is the antiviral, antibacterial, and antiprotozoal monoglyceride used by the human or animal to destroy lipid coated viruses such as HIV, herpes, cytomegalovirus, influenza, various pathogenic bacteria including listeria monocytogenes and heliobacter pylori, and protozoa such as giardia lamblia. Some studies have also shown some antimicrobial effects of the free lauric acid. (Gunstone, 2007) Steric Acids Stearic acid is a waxy crystalline solid melting at 69.6o C. It is practically insoluble in water [0.00029 g / 100 g of water at 20o C], fairly soluble in chloroform [0.5g / 100ml] and decreasingly soluble in CS2, C6H6, CCl4, CH3CH2OH and CH3 – O – CH3. It has melting point of 69.30o C, boiling point of 3830o C, and specific gravity of 0.847 and neutralization value of 197.23 Stearic acid occurs in most fruit flesh and seed fats and in marine animal oils. It has also been reported to comprise more than 1% of carnabua wax. Palm oil contains 2 to 6% of this acid; Most so called yellow oils (Cotton seeds, Corn, Soyabean, Peanut, Sesame, Sunflower, Kapole) contain 2 to 8%, milk fats – 5 to 15%) lard 10 to 12%, tallows – 14 to 30%, Cocoa and Shea butters – 30 to 35%. (Gunstone et al, 2007). It is a principal constituent of most commercially hydrogenated gats and constitutes as much as 90% of completely hydrogenated corn and

8. soyabean oils. Also used as plasticizer, softener, water – proofing agent, polishing agent and oiling agent, antisatatic agent in textile industry, lubricant in metal machining, mold releasing agent in tile making and used as addictive for Polyethylene, Polypropylene, and PVC etc. Potassium salts of fatty acids with excess stearic acid give a slow drying lather for shaving soap. Derivations of stearic acid are used in manufacture of soaps, Metallic salts, Stearoyl chlorides, Bromide, Steramide, Stearonitrile, Stearyl alcohol. (Beare-Rogers, et al, 2001) Myristic acid Myristic acid, also called tetradecanoic acid, is a common saturated fatty acid with the molecular formula CH3 (CH2)12COOH. Molecular weight: 228.37092 [g/mol]. In purified form it is white solid insoluble in water, with melting point at 53.9 °C and boiling point at 250 °C at 100 mmHg. A myristate is a salt or ester of myristic acid. Myristic acid is named after the nutmeg Myristic. Besides nutmeg, myristic acid is also found in palm kernel oil, butter fat and is a minor component of many other animal fats (IUPAC, 2001). In fruit, it is present in high amounts only in dried and fresh coconut 9.5 g . It is present in small quantities in a few cereals (corn, with a 0.28 g/100 g of edible portion, is the richest source). It is used as ingredient in soaps, cosmetic and shaving creams, often in the form of the ester isopropyl myristate. (Akoh and Min, 2008) . Oleic acids Oleic acid is a fatty acid that occurs naturally in various animal and vegetable fats and oils. It is odorless, colorless oil, although commercial samples may be yellowish. In chemical terms, oleic acid is classified as a monounsaturated omega-9 fatty acid. It has the formula CH3 (CH2)7CH=CH (CH2)7COOH (Thomas, 2000). Fatty acids like oleic acid occur as their esters, commonly triglycerides, which are the greasy materials in many natural oils. Triglycerides of oleic acid compose the majority of olive oil, although there may be less than 2.0% (Grossi, 2014), as free acid in virgin olive oil, with higher concentrations making the olive oil inedible. Oleic acid (in triglyceride form) is included in the normal human diet as a part of animal fats and vegetable oils. Oleic acid as its sodium salt is a major component of soap as an emulsifying agent. It is also used as an emollient. Small amounts of oleic acid are used as an excipient in

9. pharmaceuticals, and it is used as an emulsifying or solubilizing agent in aerosol products (Smolinske and Susan 1992). Oleic acid is also used to induce lung damage in certain types of animals, for the purpose of testing new drugs and other means to treat lung diseases. (Julien et al, 1986) Palmitic Acids Palmitic acid, or hexadecanoic acid in IUPAC nomenclature, is the most common fatty acid (saturated) found in animals, plants and microorganisms (Gunstone, 2007). Its chemical formula is CH3 (CH2)14COOH. As its name indicates, it is a major component of the oil from palm trees (palm oil), but can also be found in meats, cheeses, butter, and dairy products. Palmitate is a term for the salts and esters of palmitic acid. Palmitic acid is used to produce soaps, cosmetics, and release agents. These applications utilize sodium palmitate, which is commonly obtained by saponification of palm oil. Because it is inexpensive and adds texture to processed foods (convenience food), palmitic acid and its sodium salt find wide use including foodstuffs. Sodium palmitate is permitted as a natural additive in organic products (Anneken, 2006.) Hydrogenation of palmitic acid yields acetyl alcohol, which is used to produce detergents and cosmetics. RAW MATERIAL FOR SOAP MAKING Alkalis Sodium hydroxide (caustic soda) is the strongest of the alkalis and inexpensive. It has excellent dissolving properties, is a very strong saponifier and has added advantage of being strongly bactericidal. It is, however, highly corrosive to metals especially aluminium and extreme care must be taken when handling as it can cause severe burns to the skin (Oghome et al., 2012). Sodium metasilicate, although a strong alkali, is non-caustic and therefore much less corrosive than sodium hydroxide. Trisodium phosphate (TSP) is a good emulsifier and saponifier has strong dispersive properties and has the ability to soften water by precipitating the salts. Although somewhat corrosive, it is often incorporated in soaps (Thomsson, 1922). Soap formed using soda and potash is soluble in water, unlike those from the other bases and they constitute the soap of commerce. These reagents are always used in sufficient quantity to combine with the whole of the fatty acids contained in an oil or fat, though doubtless, by the use

10. of considerably smaller quantities, under pressure, complete resolution of the fatty matter into fatty acids and glycerol could be accomplished. They are, by far, the most important saponifying agents employed in the soap manufacturing processes over a long period of time (Oghome et al., 2012) Oils The type of oil or fat that is used has a significant and direct influence on the finished characteristics and qualities of the detergent product. Some fats and oil are better for bubbles and others are better for cleaners. Examples of fats and oils that are suited for the traditional soap making process are: neem, coconut, tallow, palm oil, palm kernel, ground pea nut, Shea butter, and cocoa butter (Ekpa and Ekpe, 1995) Besides the various physical properties of oils and fats, such as color, specific gravity, melting point, solubility, etc., they may be distinguished chemically by a number of chemical constants. These are the iodine number, the acetyl value, saponification number, Reichert-Meissl number for volatile acids, and Hehner number for insoluble acids. These constants, while they vary somewhat with any particular oil or fat, are more applicable to the edible products and form criteria where any adulteration of fat or oil is suspected (Thomssen, 1922). The various oils used in detergent and soap making have similarities and differences that make them exhibit unique chemical and physical properties. Due to the triglyceride composition, the oils used in soap making exhibit a steep melting curve and melt below body temperature. Their low degree of unsaturation gives them a high oxidative stability. The characteristics exhibited by oils used in soap making are due to their high content of saturation (Webb, 1926). Coconut Oil Desiccated coconut contains about 69% coconut fats. Approximately 50% of the fatty acids in coconut fat are lauric acid. Some studies have shown some antimicrobial effects of free lauric acid. It is a medium chain fatty acid, which has the added beneficial function of being formed into monolaurin in the human or animal body (Hautfenne, 1982)

11. Palm Oil Palm kernel oil is manufactured from the kernel of the oilseed palm. It is very similar in composition to coconut oil. Palm kernel and coconut oils are known as lauric fats (Pantzaris and Ahmad, 2004). Lauric fats, Capric acid and Caprylic acid, are known for their natural antifungal and antimicrobial properties. Among the 17 major oils and fats in world trade, there are only two lauric oils: coconut oil and palm kernel oil and they are called lauric because lauric acid is the major fatty acid in their composition at about 50%, while no other major oil contains more than about 1% (Ekwenye and Ijeomah, 2005). Other oils employed in soap making There are other oils that can equally be used in soap manufacturing but they offer different characteristics to the final soap formed based on chemical constants of the oils such as its saponification value, iodine number, peroxide value etc. The various and most important oils and fats used in the manufacture of soap are, tallow, coconut oil, palm oil, olive oil, poppy oil, sesame oil, soya bean oil, cotton-seed oil, corn oil and the various greases. Besides these the fatty acids, stearic, red oil (oleic acid) are more or less extensively used. These oils, fats and fatty acids, which vary from time to time and as to their colour, odour and consistency can readily be distinguished by various physical and chemical constants (Thomssen, 1922). Tallow is the name given to the fat extracted from the solid fat or "suet" of cattle, sheep or horses. The quality varies greatly, depending upon the seasons of the year, the food and age of the animal and the method of rendering. The better quality is white and bleaches whiter upon exposure to air and light, though it usually has a yellowish tint, a well-defined grain and a clean odor. It consists chiefly of stearin, palmitin and olein. Tallow is by far the most extensively used and important fat in the making of soap (Thomssen, 1922). According to Mak-Mensah and Frempong (2011), neem oil has been used in the manufacture of natural cosmetics, soap, toothpaste, hair and skin care products, emulsions, liquors, ointments and medicinal cosmetics. However neem oil can be produced mechanically (hot or cold press) or chemically (solvent extraction) from dried neem seeds. The best quality neem oil with a majority of phytoconstituents intact is obtained through cold press. In cold press the oil is lighter in colour and has a milder odour. Moreover potential residual solvents in chemical extracted oil that may

12. pose health hazards to consumers are eliminated since solvents are not used in the pressing techniques. TYPES OF SOAPS Soaps are of different forms and types, depending on their uses, application and material composition. Examples of the types include laundry soap, toilet soap, toilet soap and medicated soaps. These could either be in liquid mousse, solid tablets or bars. Laundry soaps Laundry soaps, or washing soaps, is a type of soap (cleaning agent) that is used for cleaning laundry, while soaps are still sold in solid form; powdered detergents have been taking major market shares in many countries since their introduction in the 1960s (Anamuah-Mensah, 1999). Laundry cleaning products are to meet a variety of stain and soil removal, bleaching, fabric softening and conditioning and disinfectant requirements under varying water, temperature, and usage conditions. These products are either general purpose or light duty cleaning agents suitable for washing all types of fabrics and clothes. These cleansing products contain different ingredients that are used to improve their cleaning performance. The surfactant play an important role in improving the cleansing action by reducing the surface tension of wash liquid thereby improving the wet ability of washable fabric. Some of the important laundry soaps ingredients are surfactants, brightening agents, synthetic fragrances, colors, and more. (Cavitch and Miller, 1994) Bathing soaps Bathing soap is typically made up of moisturizers and cleansing agents that work together to soften skin and clean it. Depending on the brand, there can be more cleansing agents than moisturizers or vice versa. Checking the individual labels can let you know what soap additives are included in that particular soap. Bathing bars contain low TFM (total Fatty Matter). Today, 85 percent of soaps available in the consumer market are bathing bars. (Benn and Charles 2002) The bathing bars are nothing but entry level soaps. Some main ingredients in bathing soaps are; Sodium laureth sulfate is a cleanser with high-foaming properties that make it useful for those with hard water. It adds

13. softness to the skin and has been deemed safe to add to products by the Cosmetic Ingredient Review expert panel. It can also function as a surfactant, which creates a smooth surface for the product to glide over. This surfactant action makes it a better cleanser because it enables the soap to have continuous coverage. Sodium palmitate is both a cleanser and an emulsifier, according to the Environmental Working Group's Skin Deep database of cosmetic ingredients. Emulsifiers make oil and liquid ingredients blend well together. It states that sodium palmitate is the salt of palmitic acid and creates lather and cleanses well, but it could also dry out your skin. Sodium lauroyl isethionate works as a cleansing agent, an emulsifier and a wetting agent. It could be a drying ingredient. It is made through the sulfation of lauryl alcohol with a neutralization of sodium carbonate, and, while a good cleanser and degreaser, it may prove irritating to some sensitive skins. Sodium cocoate is a soap detergent cleansing agent that is used in many shampoos and bar soaps. While it makes for a good lather and cleans well, it can also be a skin irritant and drying to some who have sensitive (Garzena, 2004) Toilet soaps Toilet soap contains more fatty material. Toilet soaps are categorized into 3 grades based on their TFM values. The higher TFM present in soap contributes better cleansing action. An ideal fat to bases ratio of 5:1 makes a TFM of 83.3%. However, it is disappointing to note that you will not find such ideal toilet soap in the market. Due to the increasing awareness towards health and hygiene, toilet soaps have now become a necessity for people in modern life. Urbanization and developments in the industry has led to the increase in demand as well as improvement in quality of products. With the advent of new technologies and sophisticated manufacturing practices, the development processes have improved and as a result of which, the markets are flooded with a variety of soaps that vary in both the physical as well as functional attributes. Toilet soaps can be broadly categorized into several types of soaps, such as: Oily Skin Soap, Dry Skin Soap, Sensitive Skin Soap, Normal Skin Soap, Baby Soap, Antibacterial Soap, Glycerin Soap, Olive Oil Soap, Herbal Soap. These different types of toilet soaps are designed and manufactured on the basis of several factors, such as weather conditions, skin type, lifestyle and preferences of people. Toilet soaps come in several sizes for different purposes and requirements, such as -

14. • Small toilet soaps - Small toilet soaps generally come in weight of 10 gm to 30 gm and are specially designed for hotel industries and travel requirements. • Normal toilet bath bar soap - The normal toilet bath bar soap come in weight of 75 gm to 100 gm that are usually developed for mass consumption. Along with fats and oils, toilet soaps are made using a variety of ingredients, which depends on the type of soap and properties required. Some most common ingredients that are used in making toilet soaps are fats, alkalis, essential oils, fragrances, glycerin, blends, distilled water, cocoa butter, and more. Function and applications of some ingredients, which are used in soapmaking, are - • Pearlizing agents are added to opacify the formula and give it a more pleasing appearance • Fragrances are added to mask the odor of the base and increase consumer appeal • Thickeners are added to increase the viscosity of product • Colorants may also be included to improve the appearance of product • Primary surfactants are added foam and cleansing, while secondary surfactants are added to give the foam more creaminess and improve the skin feel Medicated soaps Medicated soaps are simply soaps that have ingredients which can cure one or the other problems such as acne and other skin problems like black heads, clogged pores, pimples, body itching, bacterial or fungal infections etc. There are many types of medicated soaps that can be helpful to us such as anti-bacterial soap that generally helps to relieve various skin problems. Then there are anti-fungal soaps having therapeutic effects that reduce the discomfort and relieve the symptoms caused by various fungal infections. One of the very popular types of medicated soaps includes the anti-acne soap that helps in getting rid from acne and pimples. The anti- cellulite soap are the medicated soaps for reducing cellulites that are the dimpled skin in such areas of body as hips, thighs and buttocks as a result of deposition of fat. The anti-mosquito soap is used to dispel mosquitoes, mostly in mosquitoes-infested areas.

15. There are certain medicated soaps that not only have therapeutic effects but are beauty treatments too such as anti-aging soap that are useful for both cleansing the outer body as well as to slow down the signs of aging. There are many other types of medicated soaps like sensitive skin soap which is gentle to the skin and maintains it properly. Anti-itch soap is for relieving skin problem of itching. Anti-chlorine soap is used while swimming to keep the harmful effects of chlorine at bay. Although the basic ingredients of soaps are similar, there are certain added ingredients of medicated soaps through which the all the problems are tried to be solved.  Antibacterial soap- The medicated antibacterial soaps contains antibacterial chemicals such as triclosan which is alcohol. Apart from triclosan, triclocarban/trichlorocarbamide and PCMX/chloroxylenol, tetrasodium EDTA are generally used for antibacterial effect in these soaps. However, it must be remembered that since there are various types of bacteria, effectiveness against any given type of bacterium does not ensure that it is effective against other unrelated types too. The ingredients of antibacterial soaps are generally only contained at preservative level unless the product is marked antibacterial, antiseptic, or germicidal. (Aiello et al, 2007)  Antifungal soap- Antifungal soaps are made by adding organic medicinal plant extracts, vitamin E, essential oils, natural glycerin, sulphur and zinc oxide, tea tree oil (melaleuca alternifolia) etc. into the soap.( Amen and Mahreen,2010)  Medicated soaps for skin problems- Medicated soaps for different skin problems have different ingredients. For example, exfoliating soaps for unclogging skin pores sometimes have oatmeal, pine and eucalyptus. Oatmeal opens the pores and deep cleans and removes excess dirt and oil. Pine and eucalyptus cleanse, moisturize and fragrance the skin. Anti-cellulite soaps have many natural ingredients, main being seaweeds that can be used alone or in combination with other agents like ivy extract, juniper, aminophylline, coffee bean extract, fennel seed extract, aloe, hyaluronic acid, ginko biloba, horse chestnut, bentonite etc. Many anti-acne soaps or oily skin soap have natural ingriedients like neem leaves (azadirachta indica) for extra care and protection for oily skin that mostly suffer from acne and pimples (Wilson, et al, 2004). The best medicated soaps are those that have the exact ingredients that target at the problem for which they are made or bought.

16. IMPORTANCE OF SOAPS The skin is bombarded daily with foreign influences such as scorching sun, drying winds, biting cold weather, bacteria and dirt, our distant ancestors learned quickly that preserving the health of skin is a way for better and longer life. As our civilization slowly evolved from Stone Age into modern times, advancements in technology, chemistry and medicine enabled the rise of soap - multipurpose cleaning tool of skin, clothes and the area that we live in. Created from the countless variation of ingredients, all soaps have two main components - animal oils or fats and alkaline solution that enables the process of saponification. During the last few thousand years, process of soap creation received numerous upgrades and tweaks, mostly by adding natural additives of color and smell, but in modern times also many new industrial substances that increase soap's performance in cleaning and lubrication. The existence of first soap like material that can be proven in 4800 year old archeological digs of ancient Babylon, but scientist are speculating that those material consisting of boiled animal fats and ashes were used as a hair gel. More detailed accounts of soap use came from 3500 year old Ancient Egypt, where soaps and aromatic oils were not only used for washing but also as important medical cure for many skin and muscle diseases. The tradition of using soaps continued to live in Roman civilization, where several medicinal instruction books clearly stated that use of soap is beneficiary for health and long life. Sadly, after fall of Roman civilization tradition of personal, living quarters and eating hygiene was abandoned (except in Asia, where hygiene remained respected and enforced by tradition). Benefits of soap finally managed to appeal to wide European population in 17th century, and since then tradition of maintaining high personal hygiene experienced only constant growth. Advancements in technology and science enabled soaps to become more useful in cleaning and received many more medicinal uses as time went by. Sadly, introduction of heavily industrialized and mass produced soaps and detergents brought many unhealthy substances into soaps, which had a potential to cause skin irritation and other harmful effects on human body. As the era of environment friendly and natural products is sweeping around the world, many international manufacturers of solid and liquid soaps try to shift their production in a direction that will satisfy all modern customers who demand safe, biodegradable and cheap products

17. By general definition, “soap” is a substance that cleans off dirt when used in the presence of water. In its most common forms, it will produce bubbles, feel slippery, and remove oils, odors, and smudges from our skin. It leaves us feeling “clean” and often smells nice to boot. Specifically, how people would classify soap would depend on what it’s made of. Collectively consider anything commonly used for washing hands, whether liquid or bar, commercially produced or home-made, to be “soap”. We do most of our eating with our fingers not our palms. As a matter of fact, we rely on our fingers’ dexterity for a lot of important things (counting out money, opening doors, dialing, writing, and typing etc.), so it is safe to assume that they need more soapy attention than our palms most of the time. The next issue is the matter of thoroughness. The time and energy spent on washing do pay dividends. The lather of soap breaks up the oily dirt and other unwanted stuff and allows it to be rinsed away. ACTION OF SOAPS When used for cleaning, soap allows insoluble particles to become soluble in water, so they can then be rinsed away. For example: oil/fat is insoluble in water, but when a couple of drops of dish soap are added to the mixture, the oil/fat solubilizes into the water. The insoluble oil/fat molecules become associated inside micelles, tiny spheres formed from soap molecules with polar hydrophilic (water-attracting) groups on the outside and encasing a lipophilic (fat- attracting) pocket, which shields the oil/fat molecules from the water making it soluble. Anything that is soluble will be washed away with the water. ENVIRONMENTAL CONCERN ON SOAPS Soap is designed as a product to be used once and then flushed down the drain, so as expected, the environmental implications of soap manufacturing process are not nearly as important as its several other chemical processes. The two prime areas of concern include • Safe transport and containment of the raw materials • Minimization of losses during production Therefore, it becomes a prime responsibility of all soap manufacturers that not only they use natural and/or such ingredients that are not harmful to environment but also take care while transporting these raw materials as well as minimize their ill effects during soap manufacturing

18. process. The three prime soaps ingredients by volume & cost are perfumes, caustic and oil. Oils & perfume are insoluble in water and if spilled can create problems, although the oils do solidify at room temperature. These products are transported through trained carriers, and the equipment and systems for pumping from the truck are designed carefully. Perfumes are bought in lined steel drums that are adequately robust, and flammable perfumes are not used in the manufacturing of soaps. All the storage tanks are surrounded by bunds to catch the contents of the tank, in case it ruptures or valves get failed. When the storage systems are designed, the different safety features (like access to tank and valve) are designed in, as well as processes to deal with the product in case it end up in the bounded area. Inside the plant, all the process and operational areas are also bounded, and the trade waste is piped to an interception tank before draining to the council's trade waste system. The contents of the interception tank are consistently monitored for alkalinity or acidity, and are designed to maintain solids or light phase chemicals in right amount. If in the case, a spill is observed in the plant itself, a part of the interception tank can be isolated off and the consequences of the spill neutralized before the waste is dumped. In various cases and applications, however, potential problems can be detected and stopped before they actually happen. At times, an off-spec product can be recycled and blended rather than dumped, and even the wastewater can be reprocessed minimize the discharges from the plant. In some cases, the manufacturing method itself can be closely monitored to ensure that any losses or wastes are kept to a minimum. Consistent measurement of key characteristics, like - electrolytic levels and the moisture both assure that the end product is being designed to specifications and the technique is functioning properly as it was designed to. Hence by following these simple tips, losses in the plant can indirectly be minimized by monitoring the process. Many soap and manufacturers now make environmental friendly products, Apart from natural soaps; there are biodegradable soaps that can be called ecofriendly cleaning product. In recent times, there has been seen a strong move among the soap manufacturers to use biodegradable ingredients in place of environmentally hazardous ingredients used in the past. The Soap manufacturers can contribute to the enhancement of human health and quality of life

19. by adopting responsible formulations and through the production and sale of environment friendly cleaning products & ingredients. Some initiatives, which soap manufacturers can take for environment / health sustainability, are - • To only market products, which have proved to be safe for humans and the environment • While production, the manufacturers should carefully consider the potential health and environmental effects, exposures and releases, which will be associated with the production, transportation, use and disposal of different cleaning products • To encourage and promote transparent communication of safety and handling information • To facilitate basic research to resolve uncertainties around human and environmental safety when they arise • To follow the spirit and intent of all national laws and regulations

20. CHAPTER THREE CHEMICALS AND REAGENTS Water Methyl orange Sulfuric acid Ethyl ether Acetone Anhydrous sodium sulphate APPARATUS Analytical balance (BOECO BAS 31 plus) Rotary Evaporator (RE200B) Hot air oven (Labcon 5016LC) Steam bath (Labcon WBE001) 250ml Beaker 100ml conical flask Stirrer Pipette Burette Standard flask Separating funnel Desiccators

21. Funnel SAMPLE SIZE Twenty (20) samples group into four different categories was analyzed in triplicate making a total of forty (40) samples analyzed. PROCEDURE The soap was weighed into a beaker and dissolved completely in 100ml of hot distilled water. The solution was then transferred into a separating funnel and the beaker was washed with small quantities of hot water and the washings transferred to the contents of the separating funnel. A few drops of methyl orange indicator were added and from a burette, a quantity of the sulphuric acid prepared was added to it. The sulphuric acid was added until the color of the solution turned pink. An excess of 5ml of the acid was added. The solution was allowed to cool to room temperature and 100ml of ethyl ether added. The separating funnel was shaken several times with the release of the stopper intermittently to release the pressure. The shaken repeated until the aqueous layer had become clear and allowed to stand. The aqueous layer was run into a second separating funnel and extracted with 50ml of ethyl ether. Another 50ml ethyl ether was used to extract the fatty acid from the aqueous layer. The three ether extracts were combined in the first separatory funnel. The ether extracts were washed by shaking with three successive sessions of 50ml distilled water until the washings were neutral to methyl orange indicator. The ether extracts were filtered with dry filter paper covered with anhydrous sodium sulphate into a weighted flask. The separatory funnel was washed out with small quantities of ether extracts and added to the weighted flask. The ether solution was distilled slowly on a rotary evaporator on steam bath. 5ml of acetone was then added to the residue in the flask and warmed on the steam bath for about one minute. The flask was shaken at an angle of about 40° to direct a current of dry air into it to remove the acetone. The flask was then placed in an oven at a temperature of 90°C for 10 minutes. It was removed from the oven and blown with air for 15s and was cooled in the desiccator and reweighted. The drying procedure was repeated until the difference in consecutive weighing was less than 0.005gm. The fatty matter left was then calculated.

22. CHAPTER FOUR RESULTS Table 1: Total fatty matter content of the selected bathing soaps SAMPLE CODES MASS OF FATTY ACIDS(gm) TOTAL FATTY MATTER (%) BS001 2.514 25.125 BS002 3.513 35.098 BS003 4.429 44.286 BS004 8.906 89.030 BS005 3.064 30.639 Table 2: Total fatty matter content of the selected laundry soaps SAMPLE CODES MASS OF FATTY ACIDS(gm) TOTAL FATTY MATTER (%) LS001 2.754 27.531 LS002 3.008 30.077 LS003 4.504 45.017 LS004 3.330 33.293 LS005 3.597 35.956 Table 3: Total fatty matter content of the selected medicated soaps SAMPLE CODES MASS OF FATTY ACIDS (gm) TOTAL FATTY MATTER (%) MS001 5.623 56.206 MS002 4.565 45.626 MS003 4.359 43.569 MS004 4.845 48.422 MS005 4.220 42.231 Table 4: Total fatty matter content of the selected toilet soaps SAMPLE CODES MASS OF FATTY ACIDS(gm) TOTAL FATTY MATTER (%) TS001 6.531 65.271 TS002 7.379 73.750

23. TS003 5.898 58.94 TS004 4.264 42.614 TS005 4.044 40.428 CHARTS Figure 1: A graph of the total fatty matter content for the selected bathing soaps Figure 2: A graph of the total fatty matter content for the selected laundry soaps Figure 3: A graph of the total fatty matter content for the selected toilet soaps. Figure 4: A graph of the total fatty matter content for the selected toilet soaps. DISCUSSION From the results obtained it was realized that all the soaps contains amounts of fatty matter in them though some of the soaps total fatty matter fall below the minimum accepted values as prescribed by the standard authority. The various total fatty matters of the soaps were determined according to how it is use in our everyday life. The bathing soaps with identical codes; BS001,BS002,BS003,BS004 and BS005 was determine to have 25.125%, 35.098%, 44.286%, 89.030% and 30.639% total fatty matter respectively, comparing with the accepted standard by the Ghana standard Authority, only the soaps with identical code BS004 meet the minimum accepted standard and hence can be classified as grade three (3) soaps. The remaining soaps (BS001, BS002, BS003 and BS005) total fatty matter was lower and hence did not meet the

24. minimum total fatty mater accepted to be in bathing soaps. However, dry skin needs soap which is high in total fatty matter. This re-hydrates the skin making it smooth and additionally the high oil content in the soap act as a lubricant throughout the day. The laundry soaps with identical codes; LS001, LS002, LS003, LS004 and LS005 total fatty matter content were 27.531%, 30.077%, 45.017%, 33.296% and 35.956% respectively, comparing with the accepted standard the minimum total fatty matter for laundry should be 50%, implying that the soaps did not meet the accepted total fatty matter that should be in laundry soaps. The total fatty matter for the medicated soaps with identical codes; MS001, MS002, MS003, MS004 and MS005 were 56.206%, 45.626%, 48.422%, 48.422% and 42.231% respectively. The total fatty matter of the toilet soaps with identical codes; TS001, TS002, TS003, TS004 and TS005 were 65.271%, 73.750%, 58.943% 42.614% and 40.427% respectively. The total fatty matter content of the toilet soaps is appreciably accepted according to the purpose to be used.

25. CHAPTER FIVE CONCLUSION From the result obtained from the analysis, it can be concluded that most of the soaps analyzed did not meet the standard set by the Ghana standard Authority and can therefore be classified as sub-standard soaps. RECOMMENDATIONS i. Different and further studies or analysis should be conducted on the similar soaps to established the soap quality ii. Further studies should be conducted on different parameters in soaps which determine the quality.

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28. Gibson, L.L., Rose, J.B., Haas, C.N., Gerba, C.P. & Rusin, P.A. (May 2002). "Quantitative assessment of risk reduction from hand washing with antibacterial soaps". Journal of Applied Microbiology 9(2), 136S–143S. doi:10.1046/j.1365-2672.92.5s1.17.x. PMID 12000622. Grossi, M., Di Lecce, G., Gallina Toschi, T. & Riccò, B. (2014). "Fast and accurate determination of olive oil acidity by electrochemical impedance spectroscopy". IEEE Sensors Journal 14(9), 2947–2954. doi:10.1109/JSEN.2014.2321323. Ghana Standards Authority. (2008). Code on standards for detergents and soaps (GSA code 132) Gunstone, F. D., John, L., Harwood, D. & Albert, J. (2007). The Lipid Handbook with Cd-Rom. (3rd ed). Boca Raton: CRC Press. ISBN 0849396883 | ISBN 978-0849396885 Hautfenne, A. (1982). Standard methods for the analysis of oils, fats and derivatives. Applied chemistry division commission on oils, fats and derivatives Julien, M., Hoeffel, J. & Flick, M. (1986). "Oleic acid lung injury in sheep". Journal of Applied Physiology 6(2), 433–40. PMID 3949648 Linstrom, P.J. & Mallard, W.G. (2014) NIST Chemistry WebBook, NIST Standard Reference Database Number 69. National Institute of Standards and Technology, Gaithersburg MD. Retrived from http://webbook.nist.gov on 9th May,2016 Mak-Mensah, E. E. & Firempong, C. K. (2011). Chemical characteristics of toilet soap prepared from neem (Azadirachta indica A. Juss) seed oil, pp.3- 5. McMurry, J. (1999). Organic Chemistry (5th Ed.). Brooks/Cole Pub Co, Salt Lake City, Utah, United States, pp 889-893. Nwoko, V.O. (1980). Chemical processing Development Proceedings of the 10th Annual Conference of the Nigerian Society of Chemical Engineers, 8(1) 40-53.

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31. APPENDICES Appendix A TABLE OF RESULTS Table 3: Comprehensive results of the selected bathing soaps SAMPLE CODES MEAN MASS OF SAMPLE(g) MEAN MASS OF TOTAL FATTY MATTER(g) PERCENTAGE TOTAL FATTY MATTER (%) BS001 10.0005 2.5594 25.5925 BS002 10.0006 3.5277 35.2745 BS003 10.0205 4.6006 45.9120 BS004 10.0205 8.9246 88.3055 BS005 10.1000 3.0506 30.2067 Tables 4: Comprehensive result of the selected laundry SAMPLE CODES MEAN MASS OF SAMPLE(g) MEAN MASS OF TOTAL FATTY ACID(g) PERCENTAGE TOTAL FATTY MATTER (%) LS001 10.0341 2.7388 27.2939 LS002 10.0279 3.0142 30.0590 LS003 10.0271 4.4840 44.7193 LS004 10.0515 3.3080 32.9100 LS005 10.0717 3.6014 35.7595 Tables 5: Comprehensive results of the selected medicated soaps SAMPLE CODES MEAN MASS OF MEAN MASS OF PERCENTAGE TOTAL

32. SAMPLE(g) TOTAL FATTY ACID(g) FATTY MATTER (%) MS001 10.0370 5.6373 56.1656 MS002 10.0638 4.5591 45.3020 MS003 10.1038 4.5959 45.4963 MS004 10.0116 5.0292 50.2323 MS005 10.1140 4.4104 43.5830 Tables 6: Comprehensive results of the selected toilet soaps SAMPLE CODES MEAN MASS OF SAMPLE (g) MEAN MASS OF TOTAL FATTY ACID (g) PERCENTAGE TOTAL FATTY MATTER (%) TS001 10.0246 6.7786 67.6253 TS002 10.1273 7.3863 72.9206 TS003 10.0406 5.8498 58.2573 TS004 10.0186 4.2564 42.4820 TS005 10.0670 4.0654 40.4052 APPENDIX B FORMULA FOR CALCULATION Percentages Total Fatty Matter (%TFM) = Mass of flask and fatty acid- Mass of flask / Mass of sample x 100

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