Iodine value

In chemistry, the iodine value (IV; also

iodine absorption value, iodine number or
iodine index) is the mass of iodine in
grams that is consumed by 100 grams of a
chemical substance. Iodine numbers are
often used to determine the degree of
unsaturation in fats, oils and waxes. In
fatty acids, unsaturation occurs mainly as
double bonds which are very reactive
towards halogens, the iodine in this case.
Thus, the higher the iodine value, the more
unsaturations are present in the fat.[1] It
can be seen from the table that coconut oil
is very saturated, which means it is good
for making soap. On the other hand,
linseed oil is highly unsaturated, which
makes it a drying oil, well suited for
making oil paints.
Principle

An example of triglyceride occurring in the saponifiable fraction of oils with a saturated fatty acid residue, a
monounsaturated fatty acid residue and a triple unsaturated (polyunsaturated) fatty acid residue. The triple esterified
glycerol (marked black) can be seen in the center of the structure. Such a triglyceride has a high iodine value (approx. 119).
Below, the reaction product after the addition of four equivalents of iodine or bromine to the four C=C double bonds of the
unsaturated fatty acid residues.
The determination of iodine value is a
particular example of iodometry. A
solution of iodine I2 is yellow/brown in
color. When this is added to a solution to
be tested, however, any chemical group
(usually in this test −C=C− double bonds)
that react with iodine effectively reduce the
strength, or magnitude of the color (by
taking I2 out of solution). Thus the amount
of iodine required to make a solution retain
the characteristic yellow/brown color can
effectively be used to determine the
amount of iodine sensitive groups present
in the solution.
The chemical reaction associated with this
method of analysis involves formation of
the diiodo alkane (R and R' symbolize alkyl
or other organic groups):

The precursor alkene (RCH=CHR’) is

colorless and so is the organoiodine
product (RCHI−CHIR’).

In a typical procedure, the fatty acid is

treated with an excess of the Hanuš or
Wijs solution, which are, respectively,
solutions of iodine monobromide (IBr) and
iodine monochloride (ICl) in glacial acetic
acid. Unreacted iodine monobromide (or
monochloride) is then allowed to react
with potassium iodide, converting it to
iodine I2, whose concentration can be
determined by back-titration with sodium
thiosulfate (Na2S2O3) standard
solution.[2][3]

Methods for the

determination of iodine
value

Hübl method

The basic principle of iodine value was

originally introduced in 1884 by A. V. Hübl
as “Jodzahl”. He used iodine alcoholic
solution in presence of mercuric chloride
(HgCl2) and carbon tetrachloride (CCl4) as
fat solubilizer. [Note 1] The residual iodine is
titrated against sodium thiosulfate
solution with starch used as endpoint
indicator.[4] This method is now
considered as obsolete.

Wijs/ Hanuš method

J. J. A. Wijs introduced modifications in

Hübl method by using iodine monochloride
(ICl) in glacial acetic acid, which became
known as Wijs's solution, dropping the
HgCl2 reagent.[4] Alternatively, J. Hanuš
used iodine monobromide (IBr), which is
more stable than ICl when protected from
light. Typically, fat is dissolved in
chloroform [Note 2] and treated with excess
ICl/IBr. Some of the halogen reacts with
the double bonds in the unsaturated fat
while the rest remains.

Then, saturated solution of potassium

iodide (KI) is added to this mixture, which
reacts with remaining free ICl/IBr to form
potassium chloride (KCl) and diiodide (I2).

Afterward, the liberated I2 is titrated

against sodium thiosulfate, in presence of
starch, to indirectly determine the
concentration of the reacted iodine.[5]

IV (g I/ 100 g) is calculated from the

formula :

Where:
(B – S) is the difference between the
volumes, in mL, of sodium thiosulfate
required for the blank and for the
sample, respectively ;
N is the normality of sodium
thiosulfate solution in Eq/ L ;
 12.69 is the conversion factor from
mEq sodium thiosulfate to grams of
iodine (the molecular weight of iodine
is 126.9 g/mol) ;
W is the weight of the sample in
grams.

The determination of IV according to Wijs

is the official method currently accepted
by international standards such as DIN
53241-1:1995-05, AOCS Method Cd 1-25,
EN 14111 and ISO 3961:2018. One of the
major limitations of is that halogens does
not react stoichiometrically with
conjugated double bonds (particularly
abundant in some drying oils). Therefore,
Rosenmund-Kuhnhenn method makes
more accurate measurement in this
situation.[6]

Kaufmann method

Proposed by H. P. Kaufmann in 1935, it

consists in the bromination of the double
bonds using an excess of bromine and
anhydrous sodium bromide dissolved in
methanol. The reaction involves the
formation of a bromonium intermediate as
follows:[7]
Then the unused bromine is reduced to
−
bromide with iodide (I ).

Now, the amount of iodine formed is

determined by back-titration with sodium
thiosulfate solution.

The reactions must be carried out in the

dark, since the formation of bromine
radicals is stimulated by light. This would
lead to undesirable side reactions, and
thus falsifying a result consumption of
bromine.[8]
For educational purposes, Simurdiak et al.
(2016)[3] suggested the use of pyridinium
tribromide as bromination reagent which is
more safer in chemistry class and reduces
drastically the reaction time.

Rosenmund-Kuhnhenn method

This method is suitable for the

determination of iodine value in
conjugated systems (ASTM D1541). It has
been observed that Wijs/ Hanuš method
gives erratic values of IV for some sterols
(i.e. cholesterol) and other unsaturated
components of insaponifible fraction.[9]
The original method uses pyridine
dibromide sulfate solution as halogenating
agent and an incubation time of 5 min.[10]

Other methods

Measurement of iodine value with the

official method is time-consuming
(incubation time of 30 min with Wijs
solution) and uses hazardous reagents
and solvents.[3] Several non-wet methods
have been proposed for determining the
iodine value. For example, IV of pure fatty
acids and acylglycerols can be
theoretically calculated as follows:[11]
Accordingly, the IVs of oleic, linoleic, and
linolenic acids are respectively 90, 181,
and 273. Therefore, the IV of the mixture
can be approximated by the following
equation :[12]

in which and are, respectively,

the amount (%) and the iodine value of
each individual fatty acid f in the
mixture.

For fats and oils, the IV of the mixture can

be calculated from the fatty acid
composition profile as determined by gas
chromatography (AOAC Cd 1c-85; ISO
3961:2018). However this formula does
not take into consideration the olefinic
substances in the unsaponifiable fraction.
Therefore, this method is not applicable
for fish oils as they may contain
appreciable amounts of squalene.[13]

IV can be also predicted from near-

infrared, FTIR and Raman spectroscopy
data using the ratio between the intensities
of ν(C=C) and ν(CH2) bands.[14][15] High
resolution proton-NMR provides also fast
and reasonably accurate estimation of this
parameter.[16]
Significance and limitations
Although modern analytical methods (such
as GC) provides more detailed molecular
information including unsaturation degree,
the iodine value still widely considered as
an important quality parameter for oils and
fats. Moreover, IV generally indicates
oxidative stability of the fats which directly
depend on unsaturation amount. Such a
parameter have a direct impact on the
processing, the shelf-life and the suitable
applications for fat-based products. It is
also of a crucial interest for lubricants and
fuel industries. In biodiesel specifications,
the required limit for IV is 120 g I2/100 g,
according to standard EN 14214.[17]

IV is extensively used to monitor the

industrial processes of hydrogenation and
frying. However it must be completed by
additional analyses as it does not
differentiate cis/trans isomers.

G. Knothe (2002) [12] criticized the use of

IV as oxidative stability specification for
fats esterification products. He noticed
that not only the number but the position
of double bonds is involved in oxidation
susceptibility. For instance, linolenic acid
with two bis-allylic positions (at the
carbons no. 11 and 14 between the double
bonds Δ9, Δ12 and Δ15) is more prone to
autoxidation than linoleic acid exhibiting
one bis-allylic position (at C-11 between
Δ9 and Δ12). Therefore, Knothe introduced
alternative indices termed allylic position
and bis-allylic position equivalents (APE
and BAPE), which can be calculated
directly from the integration resultas of
chromatographic analysis.

Iodine values of various oils

and fats
Iodine value helps to classify oils
according to the degree of unsaturation
into drying oils, having IV > 150 (i.e.
linseed, tung), semi-drying oils IV : 125 –
150 ( soybean, sunflower) and non-drying
oils with IV < 125 (canola, olive, coconut).
The IV ranges of several common oils and
fats is provided by the table below.
 Fat Iodine value (gI/ 100g)

Beef t allow[18] 42 – 48

Beeswax[19] 7 – 16

But t er[20] 25 – 42

Canola oil[21] 110 – 126

Cast or oil[22] 81 – 91

Cocoa but t er[22] 32 – 40

Coconut oil[22] 6 – 11

Cod liver oil[23] 148 – 183

Corn oil[22] 107 – 128

Cot t onseed oil[22] 100 – 115

Fish oil[1] 190 – 205

Grape seed oil[22][24] 94 – 157

Hazelnut oil[24] 83 – 90

Jojoba oil[25] 80 – 85

Kapok seed oil[22] 86 – 110

Lard[18] 52 – 68

Linseed oil[24][22][26] 170 – 204

Olive oil[22] 75 – 94

Oit icica oil[24][27] 139 – 185

Palm kernel oil[24][22] 14 – 21

Palm oil[24] 49 – 55

Peanut oil[20] 82 – 107

Pecan oil[28] 77 – 106

Pist achio oil[24] 86 – 98

Poppyseed oil[29] 140 – 158

Rapeseed oil[21] 94 – 120

Rice bran oil[22] 99 – 108

 Fat Iodine value (gI/ 100g)

Safflower oil[22][30] 135 – 150

Sesame oil[24] 100 – 120

Sunflower oil[22][30] 110 – 145

Soybean oil[30] 120 – 139

Tung oil[24] 160 – 175

Walnut oil[28] 132 – 162

Wheat germ oil[24] 115 – 128

Related methods of analysis

Acid number
Amine value
Argentation chromatography
Bromine number
Epoxy value
Hydroxyl value
Peroxide value
Saponification value
Notes
^ The interaction between mercuric
chloride and iodine chloride is supposed
to produce the active agent of
halogenation, the ICl as follows : HgCl2 +
I2 → HgClI + ICl [31]
^ Chloroform is replaced in modern
protocols by less hazardous and more
available solvents such as cyclohexane
and 2,2,4-trimethylpentane (ASTM
D5768).

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