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264 Journal of Food, Agriculture & Environment, Vol.

8 (3&4), July-October 2010


www.world-food.net
Journal of Food, Agriculture & Environment Vol.8 (3&4): 264-269. 2010
WFLPublisher
Science and Technology
Meri-Rastilantie 3 B, FI-00980
Helsinki, Finland
e-mail: info@world-food.net
Physico-chemical properties of palm oil from different palm oil local factories in
Nigeria
F. F. Akinola
1
, O. O. Oguntibeju
2*
, A. W. Adisa
1
and O. S. Owojuyigbe
3
1
Department of Biomedical Sciences, Ladoke Akintola University of Technology, Nigeria.
2
Department of Biomedical Sciences,
Faculty of Health & Wellness Sciences, Cape Peninsula University of Technology, Bellville, 7535, South Africa.
3
Department of
Science Laboratory Technology, School of Applied Sciences, Federal Polytechnic Ede, Nigeria.
*e-mail: oguntibejuo@cput.ac.za, bejufemi@yahoo.co.uk
Abstract
Physico-chemical properties of palm oil from different Nigerian oil palm local factories were determined at varying temperature. -carotene contents
were determined by spectrophotometric method using Spectronic 21D spectrophotometer (digital) at wavelength of 440 nm. Refractive index was
determined by using Abbe refractometer while saponification value, acid value, free fatty acid contents, ester value, iodine value and peroxide value
were determined by titrimetric method. Results showed that palm oil from Ogbomoso had the highest -carotene contents, while palm oil from Ile-
Ife had the least -carotene content, which was reduced progressively as the experimental temperature increased.
Key words: Palm oil, physical properties, chemical properties, stability, -carotene, Nigeria.
Received 17 July 2010, accepted 28 October 2010.
Introduction
Palm oil which is orange-red to brownish or yellowish-red in
colour is extracted from the mesocarp of fruits of oil palm tree
(Elaeis guineensis). The oil palm fruit, a drupe, prolate spheroid
in shape varies between 20 and 50 mm in length and could be as
large as 25 mm in diameter is found in bunches that are attached
to the crown of the tree through a stalk
1, 2
. The pericarp
comprises three layers, namely the exocarp (the skin), mesocarp
(the outer pulp containing palm oil) and endocarp (a hard shell
enclosing the kernel (the endosperm) which contains oil and
carbohydrate reserves for the embryo. Fruit development starts
at about two weeks after anthesis (WAA). Oil deposition in the
endosperm starts at about 12 WAA and is almost completed by
16 WAA
3
. It has been shown that during the 12 WAA, the
endosperm and endocarp slowly harden and by 16 WAA, the
endocarp is a hard shell enclosing a hard white endosperm (the
kernel). Oil deposition in the mesocarp is believed to start at
about 15 WAA and continues until fruit maturity at about 20 WAA.
The fruits on a bunch do not ripen simultaneously owing to slight
variation in the time of pollination. Fruits at the end of each
spikelet ripen first and those at the base last. Fruits outside of
the bunch are large and deep orange when ripe while the inner
fruits are smaller and paler
4
.
Palmitoleic and linolenic acids are present in significant amounts
in the early stages of lipid synthesis. These are typical chloroplast
and membrane fatty acids, reflecting a high ratio of chloroplast
and cellular synthesis to lipid synthesis and storage. However,
these fatty acids are undetectable after 16 WAA, possibly because
it is highly diluted by the accumulation of storage lipids. The
immature mesocarp contains large amounts of chlorophyll which
decline by about 17 WAA, followed by a massive accumulation
of carotenes as the fruit ripens. The immature green mesocarp
also contains large amounts of sterols. It has been reported that
as the fruit matures, the sterols decrease as a result of dilution by
the huge amount of triglyceride synthesised
5
.
Like all oils, triglycerides are the major constituents of palm oil.
More than 95% of palm oil consists of mixtures of triglycerides
(glycerol molecules), each esterified with three fatty acids. During
oil extraction from the mesocarp, the hydrophobic triglycerides
attract other fat- or oil-soluble cellular components which represent
the minor components of palm oil such as phosphatides, sterols,
pigments, tocopherols, tocotrienols and trace metals. Other
components in palm oil include monoglycerols, diglycerols and
free fatty acids. The fatty acids are any of the class of aliphatic
acids such as palmitic, stearic and oleic in animal and vegetable
fats and oils. The major fatty acids in palm oil are myristic, palmitic,
stearic, oleic and linoleic and most of the fatty acids are present as
triglycerides. It has been reported that palm oil has saturated and
unsaturated fatty acids in approximately equal amounts
5, 6
.
The minor constituents can be categorised into two groups. The
first group consists of fatty acid derivatives, such as partial
glycerides (e.g monoglycerols), phosphatides, esters and sterols
while the second group comprises classes of compounds not
related chemically to fatty acids and they are the hydrocarbons,
aliphatic alcohols, free sterols, tocopherols, pigments and trace
metals. Most of the minor components found in the unsaponifiable
fraction of palm oil are sterols, higher aliphatic alcohols, pigments
and hydrocarbons. However, the other minor components such
as partial glycerides and phosphatides are saponifiable by alkaline
Journal of Food, Agriculture & Environment, Vol.8 (3&4), July-October 2010
265
hydroxide
7, 8
. The partial glycerides do not occur naturally in
significant amounts except in palm oil from damaged fruits and
such oils would have undergone partial hydrolysis resulting in
the production of free fatty acids, water and partial glycerides
9, 10
.
It should be noted that pigmentation of palm fruits is related
to their stage of maturity and two classes of natural pigments
occurring in crude palm oil are the carotenoids and the
chlorophylls. The carotenoids are highly unsaturated tetraterpenes
biosynthesized from eight isoprene units. Carotenoids are the
precursors of vitamin A with carotene having the highest
provitamin A activity. Palm oil has fifteen times more retinol
equivalents than carrot and three hundred times more than tomato.
Carotenes are sensitive to oxygen and light, and the oxidation of
carotenes is accelerated by hydroperoxides generated from lipid
oxidation, leading to discoloration and bleaching
7-9, 11
.
Over 90% of the world oil production is used as food. This has
necessitated that the nutritional, physico-chemical properties and
its fractions be adequately demonstrated. Also, since palm oil and
its products have desirable physical and chemical characteristics
for many food applications including margarine, it is therefore
important to examine the physico-chemical properties of palm oil
at different temperatures. This study was aimed at determining
the physico-chemical properties such as beta-carotene contents,
sapanification value, free-acid value, ester value, iodine value,
specific gravity, refractive index and melting point of Nigerian
palm oil obtained from different local factories in Ondo,
Ogbomosho, Ikirun, Ife and Ede in the south-west region.
Materials and Methods
Sample collection: Samples of palm oil were collected from
different palm oil processing units at Ile-Ife, Ikirun, Ede, Ogbomoso
and Ondo all in the western region of Nigeria. All chemicals and
solvents used were of analytical grade purchased from Merck,
Germany. Fatty acid methyl esters and triacylglycerol standards
were obtained from Sigma Chemical Company, USA.
Determination of saponification value: Saponification value is
the amount of alkali necessary to saponify a definite quantity of
the sample (oil). It is expressed as the number of milligrams of
potassium hydroxide (KOH) required for saponifying 1 g of the
sample. The smaller the saponification number, the larger the
average molecular weight of the tricylglycerol present in the oil
12
.
Triacylglycerol + 3KOH (Glycerol + 3 fatty acids + 3 molecule of
KOH) C
3
H
5
(C
17
H
35
COO)
3
+ 3KOH C
3
H
5
(OH)
3
+ 3C
17
H
35
COOK
Two g of oil was weighed accurately and put into a conical flask
containing 25 ml of 0.5 M alcoholic KOH. Reflux condenser was
fitted to the flask containing the ionic solution and heated in a
water bath for an hour swirling the flask frequently. Excess KOH
was titrated hot with 0.5 M HCI using 1 ml of phenolphthalein
(1%) solution. The saponification value was calculated from the
difference between the blank and the sample titration.
Saponification value = (b a) x 28.05/Weight of sample
where b = titre value of blank; a = titre value of sample; 28.05
= mg of KOH equivalent to 1 ml of 0.5 M HCI.
Determination of acid value and free acid content: The acid
value is the number of milligrams of the potassium hydroxide
necessary to neutralize the free acid in 1 g sample. The acid value
is often a good measure of the breakdown of the triacylglycerol
into free fatty acids, which has an adverse effect on the quality of
many fats
13
.
Ten ml of diethyl ether and 10 ml of n-propanol were mixed and
1 ml of phenolphthalein solution (1%) was added. Two g of oil
was dissolved in the solvent and titrated with aqueous 0.1 M KOH,
shaking constantly until a pink colour which persists for 15 s
was obtained. The amount of KOH used was recorded. The
procedure was repeated for the blank.
% Free fatty-acid = Acid value/2
Determination of ester value: Ester value is obtained by finding
the difference between the saponification value (SV) and acid
value (AV).
Determination of viscosity: For this study, specific gravity was
used to measure viscosity. Specific gravity is the ratio of the mass
of a given volume to the mass of an equal volume of water. The
specific gravity decreases with increased temperature and
decreases slightly as viscosity decreases for similar compositions.
Ten ml of distilled water was weighed on weighing balance and
the weight was recorded as W1. Ten ml of the oil sample was
also weighed on the weighing balance and the weight was
recorded as W2.
Determination of iodine value: The iodine value of an oil or fat
is defined as the weight of iodine absorbed by 100 g of the oil or
fat. The glycerides of the unsaturated fatty acids (particularly of
the oleic acid series) unite with a definite amount of halogen and
the iodine value is therefore a measure of the degree of
unsaturation. It is consistent for a particular oil or fat, however,
the exact figure obtained depends on the particular technique
employed. The greater the degree of unsaturation (i.e. the higher
the iodine value), the greater the likelyhood that the oil or fat will
become rancid by oxidation. The iodine value was determined by
Wijs method.
Palm oil was added and suitably weighed in a dry glass
stoppered bottle. The appropriate weight in gram of the palm oil
to be used was calculated by dividing 20 by the highest expected
iodine value, the stopper was inserted (previously moistened with
potassium iodide solution) and allowed to stand in the dark for 30
min. Of potassium iodide (10%) 15 ml was added and mixed with
100 ml water. The solution was titrated with 0.1 ml thiosulphate
solution using starch indicator just before the endpoint (titration
= a ml). Blank was treated at the same time commencing with 100
ml of carbon tetrachloride (titration = b ml).
Acid value =
Weight of sample used
Titre value x 5.61
Specific gravity =
W1
W2
Iodine value =
(b a) x 1.269
Weight of sample
266 Journal of Food, Agriculture & Environment, Vol.8 (3&4), July-October 2010
Determination of beta-carotene: Two g of each oil sample was
weighed into refine flask to form a paste. Of alcoholic KOH solution
25 ml was added and the mixture was heated in boiling water bath
for 1 hour while shaking frequently. The mixture was cooled rapidly
and 30 ml of water was added. The product obtained was
transferred into a separation funnel. The solution was extracted
three times with 25 ml of chloroform. Two g of anhydrous Na
2
SO
4
was added to the extract to remove any traces of water. The mixture
was then filtered into 100 ml volumetric flask and made up to mark
with chloroform. Standard solution of beta-carotene, vitamin A of
0-50 Ug/ml was prepared by dissolving 0.003 of standard beta-
carotene in 100 ml of chloroform. Gradient of different standard
preparations was determined with reference to the absorbance
from which average gradient was taken to calculate vitamin A
from beta-carotene (Ug/100g). Absorbance of sample and standard
were read spectrophotometrically at a wavelength of 440 nm.
Conversion:
6 Ug of beta-carotene = 1 retinol equivalent
12 Ug of other biological active cartenoids = 1 retinol equivalent
1 retinol equivalent of vitamin A activity = 1 Ug of retinol
1 retinol equivalent = S. I (International Unit)
Determination of refractive index: Refractive index of oil samples
was determined in triplicates at room temperature, 40C and 60C
using Abbe refractometer.
Determination of peroxide value: One g of oil sample was
weighed and poured into a dry 250 ml stoppered conical flask,
flushed with inert gas. Ten ml of chloroform was added and the oil
was dissolved by swirling. 15 ml of glacial acetic acid and 1 ml of
fresh saturated aqueous potassium iodide solution were added.
The flask was stoppered, shaken for 1 min and placed for 1 min in
the dark. Thereafter 75 ml of water was added, mixed and the freed
iodine was titrated with 0.002 M sodium thiosulphate solution
using soluble starch solution (1%) as an indicator. The titre value
was recorded as V. Blank determination (Vo) was also recorded.
where T = exact molarity of sodium thiosulphate solution.
Results and Discussion
Crude palm oil is a complex mixture consisting principally glycerides
that represent the major component while carotenoids, tocopherols,
tocotrienols, phytosterols and phosphatides represent the minor
components. Red palm oil is produced from crude palm oil through
a milder refining process that enables the retention of most of the
carotenes and vitamins in the refined oil
14
. Thus, red palm oil is
considered as one of the richest plant source of carotenes which
are precursor of vitamin A and vitamin E
15
. Therefore, carotenes
and vitamin E play important roles as antioxidants that may provide
oxidative stability to the oil. The stability of oil depends partly on
the extent of deterioration during heating or storage. It is known
that in living tissues, lipid constituents such as unsaturated fatty
acids are sufficiently stable by natural antioxidants and enzymes
that prevent lipid oxidation. However, once living tissues are
removed from plant or animal materials, lipids deteriorate readily
16
.
Common quality deteriorations that may occur during oil
processing are oxidation and hydrolysis. Criteria for assessing
the extent of deterioration are necessary not only for scientific
and industry interest but also because of health implications
17
.
The extent of physical and chemical changes occurring in palm
oil is usually measured by chemical procedures that measure
the primary and secondary products of lipid oxidation as peroxide
value and carotene content. Free fatty acid content is measured
because this is still one reliable parameter for food quality and
it is used as indication of hydrolysis. It is also important to evaluate
thermal stability of palm oil
14
.
In this study, it was observed that -carotene content of palm
oil decreased with increase in temperature and palm oil from
Ogbomoso has the highest -carotene content at the various
temperatures of the experiment when compared with palm oil
from other locations (Table 1). Palm oil from Ile-Ife has the
least beta-carotene contents. This outcome is in agreement with
Chen et al.
18
, Lin and Chen
19
and Alyas et al.
14
who observed
that beta-carotene content declined following increase in
temperature. The difference in -carotene content between palm
oil from Ogbomoso and other locations reflect that palm oil from
Ogbomoso is more stable and may thus be of a better quality.
The primary products of lipid oxidation are hydroperoxides,
therefore, the result of peroxide value gives a clear indication
of oxidation
20
. The peroxide value of palm oil at 120C was less
than the peroxide value at lower temperatures of the experiment
(Table 2). The reduction of peroxide value at higher temperature
could be attributed to the rapid decomposition of hydroperoxide
to secondary oxidation product
21
. It was observed that palm oil
sample from Ondo has the highest peroxide value while sample
from Ikirun has the least one. Peroxide value of various palm oil
samples increased with increase in storage time. This is in line
with the findings of Aidos et al.
22
and Skara et al.
23
who reported
a significant increase in peroxide value with increasing storage
time in different oils. By implication, it could be said that the
peroxide value of the different palm oil samples reflected the
state of oxidation and therefore the stability and quality of the
oil.
Oil samples from Ikirun had the highest iodine value at various
temperatures while sample from Ogbomoso has the least iodine
value (Table 3). Iodine value increased with increase in
temperature. It has been reported that lowering the iodine value
improves the stability and good yield of the liquid oil
21
.
Samples from Ondo had the highest specific gravity, while
samples from Ikirun had the least specific gravity at various
temperatures (Table 4). Specific gravity of the various palm oil
samples decreased with increase in temperature. Sample from Ondo
was greatly viscid.
The amount of free fatty acid in palm oil is an indicator of the
quality of the palm oil, and high level of free fatty acid is a presage
of lipid oxidation
14
. Table 5 shows that sample from Ondo has
the highest free-fatty acid value while sample from Ile-Ife has
the least free fatty acid value. Free-fatty acid value of the various
Gradient =
Concentration of standard
Absorbance of standard
Peroxide value =
(V Vo) T
M
x 10
3
mEq/kg
Beta-carotene equivalent =
(Ug/100 g)
Absorbance Gradient Dilution factor
Weight of sample
1
Journal of Food, Agriculture & Environment, Vol.8 (3&4), July-October 2010
267
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268 Journal of Food, Agriculture & Environment, Vol.8 (3&4), July-October 2010
palm oil samples increase with increased temperature and agrees
with the report of Alyas et al.
14
Saponification number is an indication of the amount of fatty
saponifiable material in oil or fat. It gives information concerning
the character of the fatty acids of the oil or fat and in particular
regarding the solubility of their soaps in water. The higher the
saponification number of the oil, the more soluble the soap that
can be made from it
14
. We reported that samples from Ondo had
the highest saponification number or value while samples from
Ikirun required least amount of alkali to saponify and thus would
be adequate for soap making (Table 6). The saponification value
for the various oil samples decreased with increased temperature,
this implies that soaps are formed easily with increase in
temperature.
Table 7 shows that samples from Ondo had the highest ester
value, while samples from Ikirun had the least ester value. Ester
value of the various palm oil samples decreased with increased
temperature.
Table 8 shows that samples from Ondo had the highest melting
point while samples from Ikirun had the least melting point. Our
results also show that samples from Ondo had the highest refractive
index at various temperatures (Table 9). Refractive index decreased
with increased temperature of experimentation.
Conclusions and Recommendations
This study showed that palm oil produced at different local
factories in Western Nigeria display varied physico-chemical
properties which tend to reflect the stability and quality of the
palm oil. It also showed that temperature affects the physico-
chemical properties of palm oil and -carotene contents decreased
with increasing temperature. This confirms that heating destroys
the beta-carotene contents of palm oil and reduces its nutritive
value as source of vitamin A. Heating of the various palm oil
samples accelerated the formation of peroxide and this increased
with prolonged heating.
We did not assess the relationship between storage time and
physico-chemical changes of the different palm oil samples. The
study was limited to the Western part of Nigeria, therefore the
outcome of the study cannot be said to be a true representative of
palm oil from all parts of Nigeria.
Further studies that will investigate the effects of storage and
processing procedures on the components of palm oil are
recommended.
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269
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