Aim: To determine the iodine value of clove oil using Wij’s method

Introduction:

The most common methods used for iodine value determination are the Wij’s and Hanus methods. In
this experiment, the iodine value of the clove oil will be determined by using the Wij’s method.
Iodine value, also called the Iodine Number, in analytical chemistry, means the measure of the
degree of unsaturation of an oil, fat, or wax. It is defined as the percentage of iodine absorbed by the
oil under the test conditions. (Thomas, Alfred, 2002). Saturated oils, fats, and waxes will take up no
iodine; therefore, their iodine value is zero; but unsaturated oils, fats and waxes take up iodine. This
is because unsaturated compounds contain molecules with double or triple bonds, which are very
reactive toward iodine. (Thomas, Alfred, 2002) Unsaturated fatty acids undergo halogenation reaction
resulting in the addition of an iodine atom to one carbon of the double bond, producing di-
halogenated single bond. (Thomas, Alfred, 2002). Once 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. 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, fat, or wax.

The Wij’s method involves the addition of a solution of iodine monochloride in a mixture of acetic
acid and cyclohexane (Wij’s solution) to a test sample. (Brisbois, R. G. , 2004) After iodine addition
to the double bonds has occurred, the excess iodine monochloride is reduced to free iodine by
addition of potassium iodide solution and water. The liberated iodine is titrated with a standardized
solution of sodium thiosulphate with starch as indicator, then the amount of iodine remaining
unreacted is determined by titration. Results are expressed as the number of grams of iodine
absorbed by 100 g of the oil sample. (Brisbois, R. G. , 2004)

The formula to calculate the iodine value is:

ʹǤ Hʹ  H 䁞
Iodine value =
In this formula, the value of 12.69 which is a constant value represent the iodine value in each mL of
sodium thiosulphate solution. Whereas the N represent the exact amount of sodium thiosulphate
solution used. Next, the (V2- V1) means the volume sodium thiosulphate used in blank test minus the
solution used for determination. The symbol V2 is the volume of sodium thiosulphate solution used
in blank test while V1 is the volume of sodium thiosulphate used for determination. From V2- V1, we
can find the value of iodine that reacted with unsaturated fats. Lastly, w from the formula is the
weight of the sample portion in gram.

Procedure:

About 0.3g of oil sample was weighed and transferred into 250 mL Erlenmeyer flask. The samples
were done in triplicate. Then, 15 mL of CHCl3 was added into each flask and warmed slightly. The
mixture was cooled down for 10 minutes to dissolve the oil. 25 mL of Wij’s solution was added into
each flask and shaken gently. The flask was then allowed to stand for 30 minutes in dark place. 20
mL of KI solution was then added into each flask. After that, the solution was titrated with 0.1 N
sodium thiosulphate solution until the appearance of yellow colour. 1 mL of starch indicator was
then added and the solution was again titrated against sodium thiosulphate solution from the burette.
The end point of titration was indicated by the disappearance of blue colour. The procedures above
were repeated without sample oil to prepare a blank. This blank test was carried out simultaneously
under the same condition.

Results:

Table 1 shown the titration volume of 0.1N sodium thiosulphate for blank solution.
Total volume
Volume of
of 0.1N
Initial reading Final reading 0.1N sodium
Titration sodium Observation
(mL) (mL) thiosulphate
thiosulphate
titrated (mL)
titrated (mL)
Pale yellow
Without
0.00 27.50 27.50 with double
starch 30.90
layer
With starch 27.50 30.90 3.40 Colourless

Table 2 shown the titration volume of 0.1N sodium thiosulphate for Sample 1 solution.
Total volume
Volume of
of 0.1N
Initial Final reading 0.1N sodium
Titration sodium Observation
reading (mL) (mL) thiosulphate
thiosulphate
titrated
titrated (mL)
Pale yellow
Without
0.00 10.10 10.10 with double
starch
layer
Blue
12.40
precipitate
With starch 10.10 12.40 2.30 in dark
yellow
solution

Table 3 shown the titration volume of 0.1N sodium thiosulphate for Sample 2 solution.
Total volume
Volume of
of 0.1N
Initial reading Final reading 0.1N sodium
Titration sodium Observation
(mL) (mL) thiosulphate
thiosulphate
titrated
titrated (mL)
Pale yellow
Without
0.00 10.80 10.80 with double
starch
layer
12.90 Blue
precipitate
With starch 10.80 12.90 2.10 in dark
yellow
solution
 Table 4 shown the titration volume of 0.1N sodium thiosulphate for Sample 3 solution.
Total volume
Volume of
of 0.1N
Initial Final reading 0.1N sodium
Titration sodium Observation
reading (mL) (mL) thiosulphate
thiosulphate
titrated
titrated (mL)
Pale yellow
Without
0.00 11.20 11.20 with double
starch
layer
Blue
13.10
precipitate
With starch 11.20 13.10 1.90 in dark
yellow
solution

Calculation:

Average reading for samples:

ʹ pl e ʹ l e l t

=12.67 mL

Relative standard deviation (RSD) value = 2.82 %

ʹǤ Hʹ  H 䁞
Iodine value =
12.69 (constant) = iodine value in each mL of sodium thiosulfate solution
N= exact amount of sodium thiosulphate solution used
V2= the volume, in mL, of the sodium thiosulphate solution used for the blank test
V1= the volume, in mL, of the sodium thiosulphate solution used for the determination
W= Then the weight, in grams of the test portion

ʹǤ l N l l ʹ Ǥ7 ml
Iodine value=
l g
= 77.11

Theoretical value of iodine value in clove oil from literature = 122.08 M.O (Bello and A.A
Jimoh ,2012).

ʹʹ l877
Percentage error (%) = ll = 36.84%
ʹʹ l8
Discussion:

As mentioned in the introdcution, we have used Wij’s method to determine the iodine value in clove
oil. Wij’s solution is an interhalogen compound with chemical formula of ICl. It is a reddish-
brown chemical compound that has melting point nearly to the room temperature. Due to the
difference of electronegativity between iodine and chlorine, ICl is therefore a highly polar molecule
and behaves as a source of I-. (Puja, 2018)

Wij’s solution is producedby reacting the halogens (Cl and I) in a 1:1 molar ratio. The preparation
can be represented by the equation below (Wan, 1939):

I2 + Cl2 → 2 ICl

When chlorine gas, Cl2 is passed through iodine crystals, the brown vapor of iodine monochloride is
seen. Dark brown iodine monochloride liquid is ten collected by condensation. Excess chlorine
converts iodine monochloride into iodine trichloride in a reversible reaction (Wan, 1939):

ICl + Cl2 ⇌ ICl3

In the very beginning of the experiment, clove oil was treated with trichloromethane, CHCl3. CHCl3
is an organic solvent that act as used to dissolve clove oil as the hydrogen attached to carbon in
chloroform participates in hydrogen bonding. (Susan &Richard, 2015)

Then the solution is left in the dark while the reagents are reacting as the solution is now light
sensitive.
After the reaction is complete, the amount of iodine that has reacted is determined by adding a
solution of potassium iodide to the reaction product. This causes the remaining unreacted ICl to form
molecular iodine.
ICl + KI → KCl + I2

The liberated I2 is then titrated with a standard solution of 0.1 N sodium thiosulphate. At the
beginning of the titration, the solution appeared to be reddish-brown due to the high concentration f
I2, the intensity of the colour gradually decrease upon titration as I2 was used to react with Na2S2O3,
forming Na2S2O4. The end point was indicated as the solution turned to pale yellow. The equation
below summarized the titration process.
I2 + 2 Na2S2O3 → 2 NaI + Na2S2O4
However, the end-point for the complete titration should be indicated by a colourless solution. But,
the transition of pale yellow to colourless is not obvious. Therefore, to improve the accuracy of the
result, starch indicator is added into the solution to detect the presence of I2 by turning the solution
into blue-black colour.
I2 + I- → I3-
I3- + starch → dark blue complex
The blue-black solution was titrated again with 0.1 N sodium thiosulphate until the solution turns
colorless.

From the result above, we have concluded that the iodine value in clove oil used in this experiment is
77.11, which is slightly different from the literature value of 122.08.
Conclusion:

The calculated iodine value for clove oil is 77.11 Whereas the theoretical value of iodine value in
clove oil from literature is 122.08. Percentage error for this experiment is 36.84%. As the degree of
iodine value indicates that the content of unsaturated fatty acid in certain fatty acid. Hence, it also
indicates the healthiness of the oil. The higher the unsaturated fatty acid content, the healthier the oil
is. (Charlotte & Kathleen, 2017)

References:

Puja, P 2018, Determination Of Iodine Value Of Fats And Oil, Discover Food Tech, [online]
https://discoverfoodtech.com/iodine-value-of-fats-and-oil/

Charlotte, WP, Kathleen, C 2017, Essential Biochemistry, 4th end, John Wiley & Sons, Inc.

Wan, S, W 1939, The Reaction of Wij’s Solution With Tung Oil, Journal of the American Chemical
Society, [online] https://pubs.acs.org/doi/pdf/10.1021/ja01878a004

Susan M. Barlow, Richard K. Miller 2015, Chloroform (trichloromethane), Drugs During Pregnancy
and Lactation (Third Edition)

Brisbois, R. G.; Wanke, R. A.; Stubbs, K. A.; Stick, R. V. "Iodine Monochloride" Encyclopedia of
Reagents for Organic Synthesis, 2004 John Wiley & Sons

Thomas, Alfred (2002). "Fats and Fatty Oils". Ullmann's Encyclopedia of Industrial Chemistry.
Weinheim: Wiley-VCH

M.O Bello and A.A Jimoh (2012). “Nutrients composition of seed, chemical characterisation and
fatty acid composition of oil of syzygium aromaticum”. Applied
Chemistry.[https://www.elixirpublishers.com/articles/1350135502_42%20(2012)%206065-6068.pdf]