A COMPARISON OF IODINE VALUES OF SOME

COMMON VEGETABLE OILS

CHRISTOPHER, UNYIME EBONG

ABSTRACT

Vegetable oils are triglycerides extract from plants and made of up of fatty acid chains. The fatty
acids can be saturated or unsaturated depending on the number of carbon-carbon double bonds.
The degree of saturation/unsaturation is indicated by the iodine value of the oil. Hence this
research work was aimed at comparing the iodine values of five different vegetable oil
(groundnut oil, palm oil, olive oil, palm kernel oil and coconut oil) samples bought from Swali
market, Yenagoa, Bayelsa state in Nigeria. The vegetable oils were analyzed for their iodine
values and the following results were obtained: For groundnut oil, the iodine values were found
to be 86.00 g I2/100g, olive oil 81.01 g I2/100g, palm oil 53.91 g I2/100g, palm kernel oil 36.74 g
I2/100g, and coconut oil 10 g I2/100g. The iodine values of the five vegetable oil samples
analyzed follows the order: Groundnut oil > Olive oil > Palm oil > Palm kernel oil > Coconut oil.
Since their iodine values are lower than 100, they are considered to be a non-drying oil which
does not harden when it is exposed to air and therefore can be used industrially for the
production of hard soaps and are of good nutritional value, hence the oils pose no significant
health risks to consumers. Thus, the result of these findings shows that the iodine values obtained
were within the regulatory standard and did not exceed the permissible level.

1
TABLE OF CONTENT

2
 CHAPTER ONE

1.1 Introduction

Vegetables oils are derived from plant sources like soya beans, melon, groundnut, corn, oil palm,

shea butter, coconut, etc. The term "vegetable oil" can be narrowly defined as referring only to

substances that are liquid at room temperature (Odoemelam, 2005), or broadly defined without

regard to a substance's state of matter at a given temperature (Barku, et al., 2012). For this

reason, vegetable oils that are solid at room temperature are sometimes called vegetable fats.

Some of these vegetable oils are used for domestic (edible) and industrial purposes (Tautorus,

2006).

3
The domestic use of vegetable oil began in the early 1900s when new chemical processes

allowed them to be extracted. Unlike butter or coconut oil, these vegetable oils can not be

extracted just by pressing or separating naturally, they must be chemically removed, deodorized

and altered. Vegetable oils are composed of triglycerides which are the ester of one molecule of

glycerol and three molecules of fatty acids. Fatty acids are primary nutritional components found

in edible seed oils.

Vegetable oils are mainly classed as Oleic-Linoleic acid oils since they contain a relatively high

proportion of unsaturated fatty acids, such as the monounsaturated oleic acid and the

polyunsaturated linoleic acid (Nkafamiya, et al., 2010; Musa, et al., 2012). They are

characterized by a higher ratio of polyunsaturated fatty acids to saturated fatty acids. Vegetable

oils contain a very high concentration of Omega 6 fatty acids and polyunsaturated fats.

Nutritionally, vegetable oils are usually preferred to animal fat as evidence linking health

benefits to the consumption of vegetable oils continues to grow (Parry, et al., 2005) even when

recent researches (Wallstrom, et al., 2007; Crowe, et al., 2008; Sieri, et al., 2008; Alexander, et

al., 2009) disapproves this notion. Vegetable oils also contain additional health beneficial

phytochemicals such as saponin, phlobatanin, flavonoid, tanin, terpenoid, anthraquinone, etc.

Majority of the phytochemicals have been known to bear valuable therapeutic activities such as

insecticidals (Kambu, et al., 1982), antibacterial, antifungal (Lemos, et al., 1990),

anticonstipative, spasmolytic (Sontos, et al., 1998), antiplasmodial (Benoitvical, et al., 2001) and

antioxidant (Vardar-unlu, et al., 2003) activities etc. Vegetable oils also contain some metals;

some of these metals like Na, K, Ca, Mg, Fe, Cu, Zn and Mn are essential nutrients for human

growth while certain forms of these metals can be toxic. The presence of trace metals is an

important factor as far as the quality of edible oil is concerned.

4
Vegetable oils are a very important ingredient in many manufactured products. Vegetable oils

are used in various industrial applications such as emulsifiers, lubricants, plasticizers,

surfactants, plastics, solvents, and resins. Vegetable oils are reusable. They are used for animal

feed and pet food. More recently, waste vegetable oils have become known for their ability to be

refined into biodiesel, which can be used like conventional diesel fuel in diesel engines.

Vegetable and edible oils had made an important contribution to the diet of people in many

countries, serving as a good source of protein, lipid and fatty acids for human nutrition including

the repair of worn out tissues, new cells formation as well as a useful source of energy (Trease,

and Evans, 2005).

In Nigeria, the major sources of edible oils are groundnut, palm and coconut. Vegetable oils,

mostly groundnut oil is of high quality and can withstand higher temperature without burning or

breaking down. It has neutral flavour and odour. It does not absorb odours from other foods

(Passera, 2008; Musa et al., 2012). These make it the most preferred oil in most parts of Nigeria.

It is therefore necessary to analyze these vegetable oils that are preponderant in our market

places to determine its edibility, suitability for a given purpose and its overall impact on public

health.

1.2 Aims and Objectives

This research work is aimed at comparing the iodine values of some common vegetable oils. The

specific objectives are:

i. To examine the iodine values of groundnut oil, palm oil, palm kernel oil, olive oil and

coconut oil.

5
 ii. To compare the iodine values with a regulatory standard in order to ascertain their

edibility and industrial applications.

CHAPTER TWO

2.1 Literature Review

Ibrahim, et al., (2008), examined the physical and chemical characteristics of olive oils from

cooperatives for olive growers in the North of Morocco. Their study were aim at evaluating the

physical and chemical characteristics of olive oils (acidity, pH, peroxide values, saponification

number, Iodine value of all olive oils samples ranged from (79.44 - 91.38 g of iodine/100 g oil),

they were not exceeding limits that give very strong indication of degree of unstauration of a

molecule, ultraviolet spectrophotometric analysis (k232 and k270), refractive index), fatty acids

composition and total phenol content. The sample were also analyzed for fatty acids commonly

6
present in olive oils which are palmitic, palmitoleic, stearic, oleic, linoleic, linolenic, and

arachidic. Oliec acid were found in high percentage ranged from (64.80 to 72.80), followed by

palmitic, Linoleic, palmitoleic, stearic and linolenic. Arachidic acid was detected in all olive oil

samples but in low percentage. Total phenol contents expressed as gallic acid of olive oils values

ranged from (112 to 313 mg/kg). All olive oil samples were compared with International Olive

Oil Council (IOOC), were not exceed the limits and exhibited remarkable physicochemical

properties and could be useful as edible oils and industrial applications.

Atasie and Akinhanmi, (2009) reported the extraction, compositional studies and physico-

chemical characteristics of palm kernel oil. Proximate, physico-chemical and elemental analysis

of palm kernel nut were determined to contain fat/oil 42%, crude protein 7.01%, moisture 6.5%,

crude fibre 11.09% and carbohydrate (by difference) 33.40%. The elemental composition

(mg/100 g), included: Na (37.00±0.40, K (39.51±0.22), Mg (3.60±0.1), Ca (19.0±0.42), Fe

(20.04±0.28), Zn (2.82±0.30), P (3.4±0.00). The result of the physico-chemical properties of the

palm kernel oil were: saponification value (234.815 mg/KOH/g), refractive index (1.435), iodine

value (41.24g/100g), acid value (11.60 mg/KOH/g) and peroxide value (1.70meq/kg).

Amira, et al., (2014) investigated the physicochemical properties of palm oil and the following

results were obtained: Saponification value; 280.5±56.1 mgKOH/g, acid value; 2.7±0.3 mg

KOH/g, Free Fatty Acid (FFA); 1.35±0.15 KOH/g, ester value; 277.8±56.4 mgKOH/g, peroxide

value; 14.3±0.8 mEq/kg; iodine value; 50.08-58.90g I2/100g, mgKOH/g, Specific Gravity (S.G)

value; 0.904, refractive index; 1.412 and inorganic materials; 1.05%. Its odour and colour were

heavy burnt smell and burnt brown, respectively. These values were compared with those

obtained for groundnut and coconut oils. It was found that the physico-chemical properties of

7
palm oil are comparable to those of groundnut and coconut oils except for the peroxide value

(i.e., 14.3±0.8 mEq) which was not detectable in groundnut and coconut oils.

Musa, et al., (2012) examined the physicochemical properties of some commercial groundnut oil

products sold in Sokoto metropolis, Northwest Nigeria. The physicochemical properties of

commercial groundnut oils sold in Sokoto metropolis, Sokoto State, Northwest Nigeria were

investigated in their study. Four different groundnut oil products purchased from Sokoto main

market, Old market, Kara market and Mabera area within the metropolis and one extracted from

groundnut seeds in the laboratory were analysed. The oil from Mabera was found to have the

highest saponification value of 215.05 ± 1.36 mg KOH/g which is significantly high compared to

that extracted in the laboratory (175.78 ± 0.93). Iodine value was significantly higher at (pı 0.05)

in oil from the laboratory (95.87 ± 0.15 g/100 g) compared to oils from Sokoto main market

(43.72 ± 0.21) and Mabera area (45.12 ±0.35). Groundnut oil from Sokoto main market has the

highest acid value of 6.83 ± 0.15 which was above the cut-off value of 5.99, while the oil

extracted in the laboratory has the lowest acid value of 1.88 ± 0.15. There was no significant

difference at (pı 0.05) in the specific gravity of the different oil samples. The range was 0.900 –

0.918. The results show that the oils are of good nutritional value and are good for industrial

applications, hence the oils pose no significant health risks to consumers in Sokoto metropolis.

Sani, et al., (2014) evaluated the physicochemical properties, phytochemicals and mineral

composition of Cocosnucifera L. (Coconut) Oil. They determined the potential applications of

the coconut seed by investigating the physicochemical characteristics as well as the

phytochemical and mineral compositions of its extracted oil content. The oil was extracted using

Soxhlet apparatus, and the physicochemical characterization, together with the phytochemical

screening and determination of the mineral composition were carried out using standard

8
methods. The physicochemical parameters of the extracted oil were as follows: acid value

0.7963± 0.21 mg KOH/g, saponification value 7.74 ± 0.73mg KOH/g, iodine value 46.8±0.63

I2/100g, free fatty acid 20.49±1.46 (% oleic acid), peroxide value (mEq H 2O2/100g) 10.0 ± 5.0,

specific gravity(g) 0.95.0.05. The oil was observed to have clear white appearance, liquid at

room temperature and has a nutty smell when fresh and unpleasant when rancid. Cocosnucifera

L. seed kernel has low oil content of 26.61%. The phytochemical analysis of the seed oil

revealed the presence of saponins, alkaloids, flavonoids, steroids, and terpenoids, and absence of

cardiac glycosides, tannins, phenols, phlobatanins and anthraquinones. The result of the mineral

element analysis revealed that 1 L of the oil contains 3.67±0.59mg of sodium, 2.33±0.59mg of

potassium, 1.50±0.03mg of calcium, 0.28±0.03mg of magnesium, 0.17±0.06mg of manganese,

0.07±0.01mg of copper, 1.70 ±0.02mg of iron, 0.33 ±0.01mg of Zinc and 0.00mg of lead. These

results showed that the Cocosnucifera seed can be a good source of oil, and the extracted oil

contains an appreciable amount of phytochemicals and mineral elements. Therefore, Justification

of the use of the coconut oil for food, medicinal and cosmetic was expatiated

2.2 Iodine Value

The iodine value equals the number of grams of iodine required to saturate the fatty acids present

in 100 grams of the oil or fat. Technically it is the value of the amount of iodine, measured in

grams, absorbed by 100 grams of a given oil sample. Iodine values are often used to determine

the amount of unsaturation in fatty acids. This unsaturation is in the form of double bonds, which

react with iodine compounds. The higher the iodine number, the more C=C bonds are present in

the fat (Mbatchou and Kosoono, 2012).

9
All fats and oils are composed of fat molecules known as fatty acids. The molecules can be

classified into three categories depending on their degree of saturation; saturated,

monounsaturated, and polyunsaturated fatty acids. No oil in nature is composed entirely of any

one of these three. All dietary oils contain a mixture. Soybean oil, for example, is referred to as a

polyunsaturated oil because that is the predominant fatty acid. It also contains 24 percent

monounsaturated fatty acids and 15 percent saturated fatty acids. Coconut oil is also a mixture. It

contains 92 percent saturated fatty acids, 6 percent monounsaturated fatty acids, and 2 percent

polyunsaturated fatty acids (Akububugwo and Ugbogu, 2007).

10
The terms saturated, monounsaturated, and polyunsaturated refers to the degree of hydrogen

saturation. A saturated fatty acid contains all the hydrogen atoms it possibly can. In other words,

it is fully saturated with hydrogen. A monounsaturated fatty acid contains all but one pair of

hydrogen atoms it can hold. Polyunsaturated fatty acids are lacking two or more pairs of

hydrogen atoms.

A fatty acid that is missing any hydrogen atoms is classified as being unsaturated. This includes

all monounsaturated and polyunsaturated fatty acids. Unsaturated fats have a lower melting point

and are more likely to be liquid at room temperature this is because as you increase the number

of double bonds in a fatty acid, you reduce that ability for oils to gain a conformation that would

make them solid, so they remain liquid. Saturated fats have a higher melting point and are more

likely to be solid at room temperature (Ramakrishna, et al., 2004).

11
Although the iodine value is used primarily in industry, it is of value to us because it gives an

indication of the oil’s stability and health properties and the higher the iodine value, the greater

amount of unsaturation (Akububugwo and Ugbogu, 2007).

2.3 Vegetable Oil

Vegetable oils are triglycerides extracted from plants. Such oils have been part of human culture

for millennia. Edible vegetable oils are used in food, both in cooking and as supplements. Many

oils, edible and otherwise, are burned as fuel, such as in oil lamps and as a substitute for

petroleum-based fuels. Some of the many other uses include wood finishing, oil painting, and

skin care.

There are several types of plant oils, distinguished by the method used to extract the oil from the

plant. The relevant part of the plant may be placed under pressure to extract the oil, giving an

12
expressed (or pressed) oil. The oils included in this list are of this type. Oils may also be

extracted from plants by dissolving parts of plants in water or another solvent. The solution may

be separated from the plant material and concentrated, giving an extracted or leached oil. The

mixture may also be separated by distilling the oil away from the plant material. Oils extracted

by this latter method are called essential oils. Essential oils often have different properties and

uses than pressed or leached vegetable oils. Finally, macerated oils are made by infusing parts of

plants in a base oil, a process called liquid-liquid extraction.

Figure 1: Olive oil Figure 2: Palm kernel oil

13
Figure 3: Palm oil

Figure 4: Groundnut oil

Figure 5: Coconut oil

14
2.3.1 Production of Vegetable Oils

To produce vegetable oils, the oil first needs to be removed from the oil-bearing plant

components, typically seeds. This can be done via mechanical extraction using an oil mill or

chemical extraction using a solvent. The extracted oil can then be purified and, if required,

refined or chemically altered.

2.3.2 Mechanical extraction

Oils can also be removed via mechanical extraction, termed "crushing" or "pressing." This

method is typically used to produce the more traditional oils (e.g., olive, coconut etc.), and it is

preferred by most health food customers in the United States and in Europe. There are several

different types of mechanical extraction: expeller-pressing extraction is common, though the

screw press, ram press, and Ghani (powered mortar and pestle) are also used. Oil seed presses

are commonly used in developing countries, among people for whom other extraction methods

would be prohibitively expensive; the Ghani is primarily used in India.

2.3.3 Solvent extraction

The processing of vegetable oil in commercial applications is commonly done by chemical

extraction, using solvent extracts, which produces higher yields and is quicker and less

expensive. The most common solvent is petroleum-derived hexane. This technique is used for

most of the "newer" industrial oils such as soybean and corn oils. Supercritical carbon dioxide

can be used as a non-toxic alternative to other solvents.

2.3.4 Sparging

In the processing of edible oils, the oil is heated under vacuum to near the smoke point, and

water is introduced at the bottom of the oil. The water immediately is converted to steam, which

15
bubbles through the oil, carrying with it any chemicals which are water-soluble. The steam

sparging removes impurities that can impart unwanted flavors and odors to the oil.

2.3.5 Hydrogenation

Oils may be partially hydrogenated to produce various ingredient oils. Lightly

hydrogenated oils have very similar physical characteristics to regular soya oil, but are more

resistant to becoming rancid. Hardening vegetable oil is done by raising a blend of vegetable oil

and a catalyst in near-vacuum to very high temperatures, and introducing hydrogen. This causes

the carbon atoms of the oil to break double-bonds with other carbons, each carbon forming a new

single-bond with a hydrogen atom. Adding these hydrogen atoms to the oil makes it more solid,

raises the smoke point, and makes the oil more stable (AOCS. 2007). .

A simple hydrogenation reaction is: H2C=CH2+H2 → CH3CH3

16
Hydrogenated vegetable oils differ in two major ways from other oils which are equally

saturated. During hydrogenation, it is easier for hydrogen to come into contact with the fatty

acids on the end of the triglyceride, and less easy for them to come into contact with the center

fatty acid. This makes the resulting fat more brittle than a tropical oil; soy margarines are less

"spreadable". The other difference is that trans fatty acids (often called trans fat) are formed in

the hydrogenation reactor, and may amount to as much as 40 percent by weight of a partially

hydrogenated oil. Hydrogenated oils, especially partially hydrogenated oils with their higher

amounts of trans fatty acids are increasingly thought to be unhealthy.

2.4 Reactions of Fats and Oils

2.4.1 Rancidification

When oils are exposed to sunlight, photosynthesis tend to occur which is disrupted leading to

release of the hydrogen ions that reacts with molecular oxygen to form loosely combined

hydrogen peroxide. The unstable peroxide unites with unsaturated bond of triacylglyceride to

form a glyceride peroxide which in turn splits into an aldehyde and forms the rancid compound

that can be detected through sensory evidence. Three pathways for rancidification are recognized

(Freeman, 2000):

- Hydrolytic rancidity: Hydrolytic rancidity refers to the odor that develops when

triglycerides are hydrolyzed and free fatty acids are released. This reaction of lipid with

water sometimes requires a catalyst, but results in the formation of free fatty acids and

salts of free fatty acids. In particular, short-chain fatty acids, such as common butter fats,

are odorous. Rancidity in foods may be very slight, indicated by a loss of freshness to

very severe, indicated by objectionable odors and/or flavors.

17
 - Oxidative rancidity: Oxidative rancidity is associated with the degradation by

oxygen in the air. Via a free radical process, the double bonds of an unsaturated fatty acid

can undergo cleavage, releasing volatile aldehydes and ketones. Oxidation primarily

occurs with unsaturated fats. For example, even though meat is held under refrigeration

or in a frozen state, the poly-unsaturated fat will continue to oxidize and slowly become

rancid. The fat oxidation process, potentially resulting in rancidity, begins immediately

after the animal is slaughtered and the muscle, intra-muscular, inter-muscular and surface

fat becomes exposed to oxygen of the air. This chemical process continues during frozen

storage, though more slowly at lower temperature. The process can be suppressed by the

exclusion of oxygen or by the addition of antioxidants. Thus, airtight packaging will slow

rancidity development.

- Microbial rancidity: Microbial rancidity refers to a process in which

microorganisms, such as bacteria or molds, use their enzymes such as lipases to break

down fat. This pathway can be prevented by sterilization.

Consuming rancid food products is unlikely to cause immediate illness or harm. Rancidification

can reduce the nutritional value of food, and some vitamins are highly sensitive to degradation.

In addition, rancidification can produce potentially toxic compounds associated with long-term

harmful health effects concerning advanced aging, neurological disorders, heart disease, and

cancer. Hydrogenated oils have been shown to cause what is commonly termed the "double

deadly effect", raising the level of low density lipoproteins (LDLs) and decreasing the level of

high density lipoproteins (HDLs) in the blood, increasing the risk of blood clotting inside blood

vessels. A high consumption of omega-6 polyunsaturated fatty acids (PUFAs), which are found

in most types of vegetable oil (e.g. soyabean oil, corn oil– the most consumed in USA, sunflower

18
oil, etc.) may increase the likelihood that postmenopausal women will develop breast cancer. A

similar effect was observed on prostate cancer in mice. Plant based oils high in monounsaturated

fatty acids, such as olive oil, peanut oil, and canola oil are relatively low in omega-6 PUFAs and

can be used in place of high-polyunsaturated oils.

2.5 Uses of Triglyceride Vegetable Oil

The following are some of the uses of vegetable oils:

i. Culinary uses: Many vegetable oils are consumed directly, or indirectly as ingredients

in food – a role that they share with some animal fats, including butter and ghee.

ii. Industrial uses: Vegetable oils are used as an ingredient or component in many

manufactured products. Many vegetable oils are used to make soaps, skin products,

candles, perfumes and other personal care and cosmetic products. Some oils are

particularly suitable as drying oils, and are used in making paints and other wood

treatment products. Dammar oil (a mixture of linseed oil and dammar resin), for example,

is used almost exclusively in treating the hulls of wooden boats. Vegetable oils are

increasingly being used in the electrical industry as insulators.

iii. Pet food additive: Vegetable oil is used in production of some pet foods. In some
poorer grade pet foods though, the oil is listed only as "vegetable oil", without specifying

the particular oil.

iv. Fuel: Vegetable oils are also used to make biodiesel, which can be used like

conventional diesel. Some vegetable oil blends are used in unmodified vehicles but

straight vegetable oil, also known as pure plant oil, needs specially prepared vehicles.

v. Margarine: Margarine is a semi-solid emulsion composed mainly of vegetable fats

and water. While butter is derived from milk fat, margarine is mainly derived from plant

19
 oils and fats and may contain some skimmed milk. In some locales it is colloquially

referred to as oleo, short for oleomargarine. Margarine, like butter, consists of a water-in-

fat emulsion, with tiny droplets of water dispersed uniformly throughout a fat phase

which is in a stable crystalline form. Margarine has a minimum fat content of 80%, the

same as butter, but unlike butter reduced-fat varieties of margarine can also be labelled as

margarine. Margarine can be used both for spreading or for baking and cooking. It is also

commonly used as an ingredient in other food products, such as pastries and cookies, for

its wide range of functionalities.

2.4.2 Soap Industry: Soap is a salt of a fatty acid. Soaps are mainly used as surfactants for

washing, bathing, cleaning, in textile spinning and are important components of

lubricants. Soaps for cleansing are obtained by treating vegetable or animal oils and fats

with a strongly alkaline solution. Fats and oils are composed of triglycerides; three

molecules of fatty acids are attached to a single molecule of glycerol. The alkaline

solution, which is often called lye, (although the term "lye soap" refers almost exclusively

to soaps made with sodium hydroxide) brings about a chemical reaction known as

saponification. In saponification, the fats are first hydrolyzed into free fatty acids, which

then combine with the alkali to form crude soap. Glycerol (glycerin) is liberated and is

either left in or washed out and recovered as a useful byproduct, depending on the

process employed. When used for cleaning, soap allows otherwise insoluble particles to

become soluble in water and then be rinsed away. For example: oil/fat is insoluble in

water, but when a couple drops of dish soap are added to the mixture the oil/fat

apparently disappears. The insoluble oil/fat molecules become associated inside micelles,

tiny spheres formed from soap molecules with polar hydrophilic (water-loving) groups on

20
 the outside and encasing a lipophilic (fat-loving) pocket, which shielded the oil/fat

molecules from the water making it soluble. Anything that is soluble will be washed

away with the water. Synthetic detergents operate by similar mechanisms to soap. The

type of alkali metal used determines the kind of soap produced. Sodium soaps, prepared

from sodium hydroxide, are firm, whereas potassium soaps, derived from potassium

hydroxide, are softer or often liquid. Historically, potassium hydroxide was extracted

from the ashes of bracken or other plants. Lithium soaps also tend to be hard these are

used exclusively in greases. Typical vegetable oils used in soap making are palm oil,

coconut oil, olive oil, and laurel oil. Each species offers quite different fatty acid content

and, hence, results in soaps of distinct feel. The seed oils give softer but milder soaps.

Soap made from pure olive oil is sometimes called Castile/Marseille soap, and is reputed

for being extra mild. The term "Castile" is also sometimes applied to soaps from a

mixture of oils, but a high percentage of olive oil. Fats containing a high percentage of

lower and unsaturated fatty acids give soaps that are readily soluble in cold water, that

have good foaming properties even in cold solutions and they are not readily salted out.

Although Palm oil, which contains high percentage of long chain saturated acids are used

in soap production, as general rule, mixtures of different fats are used to impart optimum

properties to the soap for every specific use (FAO, 1993). Detergents are produced from

long chain alcohols gotten from fats by converting them into salts of alkyl hydrogen

sulfates.

vi. Biodiesel production: Biodiesel production is the process of producing the

biofuel/biodiesel, through the chemical reactions: transesterification and esterification.

21
This involves vegetable or animal fats and oils being reacted with short-chain alcohols

(typically methanol or ethanol).

CHAPTER THREE

3.0 MATERIALS AND METHODS

22
3.1 Sample Collection

The vegetable oils (palm oil, groundnut oil, olive oil, castor oil and palm kernel oil) to be

analyzed were bought in neat bottles from Swali market, Yenagoa Bayelsa State, Nigeria. The

samples were labeled 1-5 and were stored at room temperature in fume cupboard to prevent

exposure to light which could also altered the oil properties.

3.2 Apparatus/Instruments Used

- Burette (25 ml)

- Retort stand and clamp

- 100 ml measuring cylinders

- 100 ml beakers

- 10ml measuring cylinder

- 100ml volumetric flask

- Stoppered bottle (250 ml)

- Analytical balance

3.3 Materials

- 5g of palm oil

- 5g of groundnut oil

- 5g of olive oil

- 5g of castor oil

- 5g of palm kernel oil

- Wij’s reagent (ICl 0.2M)

- Sodium thiosulphate (Na2S2O3 0.1M)

- Potassium Iodide (KI 10g/l)

23
 - Starch indictor (1g/l)

- Chloroform (10 ml)

3.4 Methods

Iodine value were determined according to the titrimetric method of Pearson (1970). 5g of the

vegetable oil sample were weighed into 250 mL conical flask and 10 mL of chloroform were

added to dissolve the oil sample, 25 mL of the Wijs reagent (ICl) were added. The flasks were

sealed, shaken thoroughly and placed in a fume cupboard for 11 hours. After the 11 hours, 10

mL of 10% potassium iodide (KI) were added to the sample solution. The sample solution were

immediately titrated with 0.2M sodium thiosulphate (Na 2S2O3). The samples were titrated to a

yellow straw colour and then 1 mL of the 1% starch solution were added to the solution which

results to a dark-blue colouration of the solution and titration continues until the dark-blue colour

disappears leaving behind a clear solution with thorough shaking of the conical flask throughout

the titration process in order to ensure that all the iodine were removed from the chloroform

layer.

At the same time, a blank solution were set up containing only 25 ml of Wij’s reagent and 10ml

of chloroform titrated with 0.2M sodium thiosulphate until a clear solution were observed. The

titration processes were repeated with the other four oil samples.

The volume of the sodium thiosulphate in the burette were recorded in a data table. One blank of

each trial and one test sample of each trial were utilized. The difference between the blank (B)

and test (T) reading (B-T), gives the number of ml of 0.2M sodium thiosulphate needed to react

with the equivalent volume of iodine.

24
The iodine value from the above experiment were calculated from the average titre volume of

sodium thiosulphate (Na2S2O3) used in the titration of both the sample and the blank and were

plugged into the relation (Singh et al., 1981).

Iodine Number = M (B- T) (12.69)

Where “M” = Molarity of the standard sodium thiosulphate solution,

Where “T” = the volume of sodium thiosulphate required to titrate the test solution containing

the oil samples.

W = the weight in grams of the sample

Where “126.9” is the molecular weight of iodine per 100g of the oil sample

25
 CHAPTER FOUR

4.0 RESULTS AND DISCUSSION

The results of this research work are summarized using tables as shown below:

Table I: Titration values of Groundnut oil

Titration Blank 1 2 3
Final Burette Reading (ml) 170.00 0.60 0.50 0.60
Initial Burette Reading (ml) 0.00 0.00 0.00 0.00
Titre (ml) 170.00 0.60 0.50 0.60
0.60+0.50+0.60 1.70
Average titre = 3
= 3 = 0.57± 0.06 ml

Table II: Titration values of Olive oil

Titration Blank 1 2 3
Final Burette Reading (ml) 170.00 10.40 10.30 10.50
Initial Burette Reading (ml) 0.00 0.00 0.00 0.00
Titre (ml) 170.00 10.40 10.30 10.50
10.40+10.30+10.50 31.20
Average titre = 3
= 3 = 10.40± 0.10 ml

Table III: Titration values of Palm oil

Titration Blank 1 2 3
Final Burette Reading (ml) 170.00 63.60 63.80 64.00
Initial Burette Reading (ml) 0.00 0.00 0.00 0.00
Titre (ml) 170.00 63.60 63.80 64.00
63.60+63.80+64.00 191.40
Average titre = 3
= 3 = 63.80± 0.20 ml

26
 Table IV: Titration values of Palm Kernel oil

Titration Blank 1 2 3
Final Burette Reading (ml) 170.00 97.10 98.00 97.80
Initial Burette Reading (ml) 0.00 0.00 0.00 0.00
Titre (ml) 170.00 97.10 98.00 97.80
97.10+98.00+ 97.80 292.90
Average titre = 3
= 3 = 97.63± 0.47 ml

Table V: Titration values of Coconut oil

Titration Blank 1 2 3
Final Burette Reading (ml) 170.00 150.30 150.10 150.50
Initial Burette Reading (ml) 0.00 0.00 0.00 0.00
Titre (ml) 170.00 150.30 150.10 150.50
150.30+ 150.10+150.50 450.90
Average titre = 3
= 3 = 150.30± 0.20 ml

Table VI: Showing the Iodine Values of Five Different Vegetable Oils

Vegetable oils Iodine value (g I2/100g) Food Safety and Standards Authority of India

(FSSAI 2011)
Groundnut oil 86.00 85 - 99
Olive oil 81.01 75 - 94
Palm oil 53.91 45 - 56
Palm kernel oil 36.74 10 - 23
Coconut oil 10.00 7.5 - 10

27
 Pie Chart Showing the iodine values of five vegetable oils

Groundnut oil
Olive oil
palm oil
palm kernel oil
coconut oil

4.2 Discussion

The iodine value equals the number of grams of iodine required to saturate the fatty acids present

in 100g of the oil. Oils rich in saturated fatty acids have low iodine values, while oils rich in

unsaturated fatty acids have high iodine values (Bennion, 1995).

In the above experiment, iodine is gradually added to a fixed volume of the oil sample dissolved

in chloroform. As long as double bonds are available, the colour of iodine does not appear in the

solution as the iodine is absorbed by the double bonds. When all the double bonds are saturated,

the colour of iodine appears in the solution.

Iodine monochloride (Wijs reagent) reacts with the unsaturated bonds to produce a di-

halogenated single bond, of which one carbon bond to an atom of iodine.

28
 After the reaction is complete, the amount of iodine that has reacted is determined by adding a

solution of potassium iodide (KI) to the reaction product.

                              ICl + KI     KCl + I2

This causes the remaining unreacted ICl to form molecular iodine. The liberated iodine (I2) is

then titrated with a standard solution of 0.2 M sodium thiosulphate.

                   I2 + 2 Na2S2O3    2 NaI + Na2S2O4

Starch is used as the indicator for this reaction so that the liberated iodine will react with starch

to give purple coloured product and thus the endpoint can be observed.

The iodine value is an important characteristic of oils as it indicates the proportion of unsaturated

fatty acids present.

The iodine values of groundnut oil from the above experiment were found to be 86.00g I2/100g.

These values are lower than that obtained by Musa, et al., (2012) with iodine values of 95.87±

0.15g I2/100g.

29
The iodine values of palm oil were found to be 53.91g I2/100g. These values are comparable to

that of Amira, et al., (2004) with iodine values ranging from 50.08-58.90g I2/100g. The iodine

values of palm oil obtained are lower than that of groundnut oil.

The iodine values of palm kernel oil were found to be 36.74g I2/100g. These values are lower

than that obtained by Atasie and Akinhanmi (2009) with iodine values of 41.24g I 2 /100g. The

iodine values of palm kernel oil obtained are lower than that of groundnut oil and palm oil.

The iodine values of olive oil were found to be 81.01g I2/100g. These values obtained are

comparable to that of Ibrahim, et al., (2008) with iodine values ranging from 79.44-91.38g

I2/100g. The iodine values of olive oil obtained are higher than that of palm kernel oil and palm

oil but lower than that of groundnut oil.

The iodine values of coconut oil were found to be 10g I 2/100g. The value obtained was lower

than that of Sani, et al., (2014) with iodine value of 46.8± 0.63g I2/100g. The iodine values of

coconut oil obtained are lower than that of groundnut oil, palm oil, palm kernel and olive oil.

This difference arises principally from the differences in fatty acid composition of these oils

(Akinhanmi and Atasie, 2008).

High iodine value justifies utilization of the oil in soap and shampoo productions (Hassan, et al.,

2007). Groundnut oil is an example of nondrying oils whose iodine numbers are less than 100

(Kochhar, 2007), they have the advantage of not undergoing oxidation to form a film, hence are

useful in the manufacture of soaps (Kochhar, 2007). The coconut oil has a very low iodine value

because of the saturated fatty acids present. The blend has a moderately high iodine value which

makes it suitable for soap making but does not make a soft soap because of the presence of

coconut oil. The higher the number for an oil, the greater the percentage of these acids, and thus

the softer the soap produced from the oil. The soft oils have high iodine numbers and are readily

30
oxidized. The iodine value thus indicates the hardness of the soap, the lower the number, the

harder the soap produced. The variation in colours is due to the degree of unsaturation of the

fatty acids. Increase in double bonds causes increase in intensity of colour.

CHAPTER FIVE

5.0 CONCLUSION AND RECOMMENDATION

5.1 Conclusion

Based on findings and result so far, it is evidently clear that iodine value of oil determines how

the oil is defined, its uses and applications. Iodine value is an indicator of the presence of double

bonds in the molecular structure of fats and oils, which influences the long term stability

properties of the oil (i.e. important for storage). It has been reported that oil with low iodine

value improves the stability and good yield of the liquid oil (Tan et al., 2002).

The more iodine is attached, the higher is the iodine value, and the more reactive, less stable,

softer, and more susceptible to oxidation and rancidification is the oil.

The iodine values of the five vegetable oil samples analyzed were less than 115, therefore they

are considered to be non-drying, and at such they can be used for soap making (hard soaps) and

in food products. Non-drying oil is oil which does not harden when it is exposed to air. This is

as opposed to a drying oil, which hardens (through polymerization) completely, or semi-drying

oil, which partially hardens. Oils with an iodine number of less than 115 are considered non-

drying (Ned, et al., 1995). The result of these findings shows that the oils are of good nutritional

value and are good for industrial applications; hence the oils pose no significant health risks to

consumers Also, the iodine values of the oil samples did not exceed the permissible level

prescribed by Food and Safety Standard Authority of India (2011).

5.2 Recommendation

31
It is therefore recommend that a more efficient extraction processes should be employ in the

extraction of these vegetable oils from its source.

REFERENCES
Atasie, V.N and Akinhanmi, T.F. (2009). Extraction, compositional studies and physic-chemical
characteristics of palm kernel oil. Pakistan Journal of Nutrition 8(6):800-803.

Amira, P. O., Babalola, O.O., and Oyediran A. M. (2014). Physicochemical properties of palm
kernel oil. Current Research Journal of Biological Sciences 6(5): 205-207

Akububugwo, I.E. and Ugbogu, A.E. (2007).“Physicochemical studies on oils from five selected
plant seeds”. PakistanJ Nutritn.; 6: 75-78.

AOCS, (2007). Sampling and Analysis of Commercial Fats and oils American Oil Chemists
Society Official Methods. AOCS Press, Champaign, Illinois, USA.

Alexander, D.D., Cushing, C.A., Lowe, K.A., Sceurman B. and Roberts, M.A. (2009) Meta-
analysis of animal fat or animal protein intake and colorectal cancer. American Journal of
Clinical Nutrition.

Applewhite, T. H. (1978). Fats and Fatty Oils: Encyclopedia of Chemical Technology, (3rd
Edition). New York: John Wiley and Sons Inc.

Barku, V.Y., Nyarko, H.D. and Dordunu P. (2012). Studies on the Physicochemical
Characteristics, Microbial Load and Storage Stability of Oil from Indian Almond Nut
(Terminalia catappa L.). Food Science and Quality Management. 8: 9-17.

Benoitvical, F., Valentin, A., Mallic, M. and Bassierc, J.M. (2001). Antiplasmodial activity of
Colchlospermum planchonii and C. tinctorium tubercle essential oils. J. Essent. Oil Res., 13: 65-
67.

Bennion, M. (1995). Introductory Foods, (10th Edition). New Jersey: Prentice-Hall Inc.

Bligh, E.G and Dyer, W.J. (2007).“A rapid method of total lipid extraction and purification”.
Journal of Biochemical Physiology.37: 911-917.

32
Crowe, F.L., Key, T.J. and Appleby, P.N. (2008) Dietary fat intake and risk of prostate cancer in
the European Prospective Investigation into Cancer and Nutrition. American Journal of Clinical
Nutrition.

Dunn, R. O. (2005). Effect of Antioxidants on the Oxidative Stability of Methyl Soyate

(Biodiesel). Fuel Proc. Technol. 86: 1071—1085.

Food and Agriculture Organization of the United Nation, 1993.

Freeman, I. P. (2000). "Margarines and Shortenings". Ullmann's Encyclopedia of Industrial

Chemistry.

Frega, N., Mozzon, M. and Lercker, G. (1999). Effects of Free Fatty Acids on Oxidative
Stability of Vegetable Oil. J. Am. Oil Chemists’ Soc. 76 (3): 325-329.

Gertz, C., Klostermann, S. and Kochhar, S. P. (2000). Testing and. Comparing Oxidative
Stability of Vegetable Oils and Fats at Frying Temperature. Eur. J. Lipid Sci. Technol. 102(8-9):
543-541.

Hassan, L.G, Osoba, O., Umar, K.J and Inuwa, M. (2007). Physico-chemical Analysis of
Cyperusesculentus oil. Yauri Journal of Arts and Science 1(4).

Ibrahim, H. A., Khaddor, M., Boussab, A., Garrouj, A.D. and Souhial, B. (2008). Physical and
Chemical Characteristics of Olive Oils from Cooperatives for Olive Growers in the North of
Morocco. International Journal of Basic & Applied Sciences, 14(02).

Kambu, K., Di Phenzu, N., Coune, C., Wauter, J.N. and Angenot, L. (1982). Plants Medicine ET
Phytotherapie, p. 34. 87(5):1405-13.

Kochhar, S.L. (2007). Economic Botany in the Tropics 2nd edition. Macmillan India Ltd.
Khanahmadi, M. and Janfeshan, K. (2006). Study on Antioxidation Property of Ferulago
angulata Plant. Asian J. Plant Sci. 5(3): 521-526.

Lemos, T.L.G., Matos, F.J.A., Alencar, J.W., Crareiro, A.A., Clark, A.M. and Chesnary, J.D.
(1990). Antimicrobial activity of essential oils of Brazilian plants: Phytopther. Res., 4: 82-84.

Musa, M. S., Bello, I., Itumoh, J. E., Bello, K., Bello, A. M. and Arzika, A. T. (2012).
Physicochemical Properties of Some Commercial Groundnut Oil Products Sold in Sokoto
Metropolis, Northwest Nigeria. Journal of Biological Science and Bioconservation 4: 17-24

33
Mbatchou, V. C., and Kosoono, I. (2012). “Aphrodisiac activity of oils from
AnacardiumoccidentaleL. seeds”.Phytopharmacology- International Journal of Phytotherapy
Bioactivities of Natatural Product 2: 81 -91.

Nkafamiya, I. I., Maina, H. M., Osemeahon, S.A and Modibbo, U. U. (2010). Percentage oil
yield and physiochemical properties of different groundnut species (Arachis hypogaea). African
Journal of Food Science. 4 (7), 418 – 421.

Ned, A. P., Sarah, E. C. and Karen, A. (1995). "Mechanisms of free radical oxidation of
unsaturated lipids", 30, pp.277-290.

Njoku, O. U., Boniface, J. A. E., Obitte, N. C., Odimegwu, D. C. and Ogbu, H. I. (2010). “Some
nutriceutical potential of beniseed oil”. International Journal of Applied Research Natural
Product, 2(4): 11-19.

Odoemelam, S. A. (2005). Proximate Composition and Selected Physicochemical Properties of

th seeds of African Oil Bean (Pentaclethra marcrophylla). Pakistan Journal of Nutrition. 4(6):
382-283.

Oyedeji, F. O. and Oderinde, R. A. (2006). Characterization of Isopropanol Extracted Vegetable

Oils. Journal of Applied Science, 6(11): 2510-2513.

Parry, J., Su, L., Luther, M., Zhou, K., Yurawecz, P., Whitaker, P. and Yu, L. (2005). Fatty acid
composition and antioxidant properties of cold-pressed marionberry, boysenberry, redraspberry,
and blueberry seed oils. Journal of Agriculture and Food Chemistry, 53:566-573.

Passera, L. S. (2008) Oxidation of Lipids. Plant Food and Human Nutrition, 31: 77-83.

Ramakrishna, G., Prasad, N.B.L. and Azeemoddin, G. (2004). Cold processing neem seed,
JNTU, Oil Technological Research Institute, Proceedings of the World Neem Conference,
Bangalore, India. 24 –28.

Sani, I., Owoade, C., Abdulhamid, A., Isah, M. and Fakai, F. B. (2014). Evaluation of
Physicochemical Properties, Phytochemicals and Mineral Composition of Cocosnuciferal.
(Coconut) Oil. International Journal of Advanced Research in Chemical Science 1(8) , pp 22-30

Sieri, S., Krogh, V. and Ferrari, P. (2008) Dietary fat and breast cancer risk in the European
Prospective Investigation into Cancer and Nutrition. American Journal of Clinical Nutrition
88(5):1304-12.

34
Sontos, F.A., Rao, V.S.N. and Silveria, E.R. (1998) Investigations on the antinociceptive effect
of Psidium guajava leaf essential oil and its major constituents. Phytotherarapy of Research, 12:
24-27.

Tautorus, C. L., and McCurdy, A. R. (2006). Effect of Randomization on Oxidative Stability of

Vegetable Oils, at Two Different Temperatures. Journal of American Oil Chemistry Society.
67(8): 525-530.

Toshiyuki, C. (1999). Prediction of Oxidative Stability Based in Various Chemical Properties for
Refined Vegetable Oils. Journal of Japan Oil of Chemical Society 48(8):781-786.

Trease, G.E., and Evans, W.C. (2005). Pharmacology. 15thg Edn. Saunders Publishers, London.
Pps 42-44, 221-229, 246-249, 303-306, 331-332, 391-393.

Tan, C. P., Cheman, Y. B., Jinap, S., and Yousie, M. S. A. (2002). Effect of microwave heating
on the quality characteristics and thermal properties of RBD palm olein. Innovat. Food Science
and Emergence Technology 3:157-163.

Ullah, J., Hamayoun, M., Ahmad, T., Ayub, M., and Zarafullah, M. (2003). Effect of Light,
Natural and Synthetic Antioxidants on Stability of Edible Oil and Fats. Asian Journal of Plant
Science 2(17-24): 1192-1194.

Vardar-unlu, G., Cadan, F., and Sokmen, A. (2003). Deferera, Polissiou, M. Sokmen, M.
Donmez, E and tap bektas, Journal of Agriculture in Food Chemistry, pp. 51-63.

Wallstrom, P., Bjartell, A., Gullberg, B., Olsson, H., and Wirfalt, E. (2007) A prospective study
on dietary fat and incidence of prostate cancer (Malmo, Sweden). Cancer Causes Control
18(10):1107-21.

35
 APPENDIX

Calculations

Iodine Number = M (B- T) (12.69)

Where “M” = Molarity of the standard sodium thiosulphate solution,

Where “T” = the volume of sodium thiosulphate required to titrate the test solution containing

the oil samples.

W = the weight in grams of the sample

Where “126.9” is the molecular weight of iodine per 100g of the oil sample

For Groundnut Oil

B = 56.80 ml, T = 14.50 ml, w = 5g, M Na2S2O3 = 0.2M

(56.80−14.50)×0.2 ×126.9 ×100 107357.4

= = =21.47
( 1000)(5) 5000

For Olive Oil

B = 56.80 ml, T = 11.51 ml, w = 5g, M Na2S2O3 = 0.2M

(56.80−11.51)× 0.2× 126.9× 100 114946.02

= = =23
(1000)(5) 5000

36
For Palm Oil

B = 56.80 ml, T = 33.17 ml, w = 5g, M Na2S2O3 = 0.2M

(56.80−33.17)× 0.2× 126.9× 100 59972.94

= = =11.99
(1000)(5) 5000

For Palm Kernel Oil

B = 56.80 ml, T = 17.40 ml, w = 5g, M Na2S2O3 = 0.2M

(56.8 0−17.40)×0.2 ×126.9 ×100 99997.2

= = =20
(1000)(5) 5000

For Coconut Oil

B = 56.80 ml, T = 15.33 ml, w = 5g, M Na2S2O3 = 0.2M

(56.80−15.33)×0.2 ×126.9 ×100 105250.86

= = =21.05
( 1000)(5) 5000

37
 APPENDIX II

- Wij’s reagent (ICl 0.2M)

- Sodium thiosulphate (Na2S2O3 0.1M)

- Potassium Iodide (KI 10g/l)

- Starch indictor (1g/l)

Chloroform (10 ml

38