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SAMPLINC AND ANALYSIS OF COMMERCIAL FATS AND OILS

AOCS Official Method Cd 1d-92


Reapproved 1 997

lodine Value of Fats and Oils


Cyclohexane-Acetic Acid Method
DEFINITION
The iodine value is a measure of the unsaturation of fats and oils and is expressed in terms of the
number of centigrams of iodine absorbed per gram of sample (7o iodine absorbed).
SCOPE
Applicable to all normal fats and oils with iodine values in the range of l8-165 that do not contain
conjugated double bonds (see Notes, I ).

APPARATUS prepared 0. l N KI solution and one drop of a 50 ppm


l. Glass-stoppered iodine flasks-5OO mL. chlorine solution made by diluting I mL of a commer-
2. Glass-stoppered volumetric flasks- 1000 mL, for cial5Vo sodium hypochlorite (NaOCl) solution to 1000
preparing standard solutions. mL. The deep blue color produced must be discharged
3. Pipet-25 mL, for accurately dispensing 25.0 mL of by 0.05 mL of 0. I N sodium thiosulfate.
Wijs solution. 8. Potassium dichromate-reagent grade. The potassium
4. Volumetric dispenser-20 mL, l-mL adjustability, for dichromate is finely ground and dried to constant weight
l07o potassium iodide (KI) solution. at about I l0"C before using (see Notes, Car.rtlor).
5. Volumetric dispenser-2 mL, l-mL adjustability, for 9. Sodium thiosulfate (NarSrO. . 5H2O)-0.1 N, accu-
starch solution. rately standardized, prepared from reagent-grade
6. Volumetric dispenser-5O mL, l-mL adjustability, for NarSrO. . 5H2O (see Notes, 6).
distilled water. Standardization of sodium thiosulfate-Weigh
7. Repeater pipet-with filling flask, 20 mL, for cyclo- 0.16-0.22 g of finely ground and dried potassium
hexane. dichromate into a 500-mL flask or bottle by difference
8. Analytical balance-accurate to + 0.0001 g. from a weighing bottle. Dissolve in 25 mL of water, add
9. Magnetic stirrer. 5 mL of concentrated hydrochloric acid, 20 mL of
10. Filter paper-Whatman no. 4l H, or equivalent. potassium iodide solution and rotate to mix. Allow to
I l. Beakers-50 mL. stand for 5 min, and then add 100 mL of distilled water.
12. Hot air oven. Titrate with sodium thiosulfate solution, shaking contin-
13. Timer. uously until the yellow color has almost disappeared.
Add l-2 mL of starch indicator and continue the titra-
REAGENTS tion, adding the thiosulfate solution slowly until the blue
l. Wijs solution-see Notes, 2 and Caution. color just disappears. The strength of the sodium thio-
2. Potassium iodide (KI) solution-100 g/L (107o solu- sulfate solution is expressed in terms of its normality.
tion), prepared by dissolving 100 g of reagent grade KI
in 1000 mL of deionized water. Normality of Na,SrO, solution =
3. Cyclohexane-reagent grade (see Notes, 3 and 20.394 x mass of KrCrrOr, g
Cautitn).
4. Glacial acetic acid-reagent grade (see Notes, olume. mL of sodium thiosulfate
Caution).
5. Reagent for diluting sample-prepared by mixing PROCEDURE
cyclohexane and glacial acetic acid, l: l, v/v. The L Melt the sample, if it is not already liquid (the tempera-
absence of oxidizable matter in the reagent is verified ture during melting should not exceed the melting point
by shaking l0 mL of the reagent with I mL of saturated of the sample by more than 10'C), and filter through
aqueous potassium dichromate solution and 2 mL of
concentrated sulfuric acid; no green coloration should Table 1
appear. Sample weights.
6. Hydrochloric acid-reagent grade (see Notes, Caution). Iodine Value expected Mass, g, + 0.001
7. Soluble starch solution-recently prepared, tested for
<5 3.000
sensitivity (see Notes, 4). Make a paste with I g of
5-20 1.000
natural, soluble starch (see Notes, 5) and a small
amount of cold distilled water. Add, while stirring, to
2t-50 0.400

100 mL of boiling water.


5l-r00 0.200
Test for sensitiviry-Place 5 mL of starch solution
l0l-r50 0.130
in 100 mL of water and add 0.05 mL of freshly l5l-200 0.t00

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SAMPLNG AND ANALYSIS OF COMMERCIAL FATS AND OILS
Cd 1d-92 . lodine Value of Fats and Oils

two pieces of filter paper to remove any solid impurities 9. Prepare and conduct at least one blank determination
and the last traces of moisture. The filtration may be with each group of samples simultaneously and similar
performed in an air oven at 80-85'C, but should be in all respects to the sample.
completed within 5 min + 30 sec. The sample must be
absolutely dry. CATCULATIONS
Note-All glassware must be absolutely clean and (B-S)xNx 12.69
completely dry. l. Iodine value =
mass of sample, g
2. After filtration, allow the filtered sample to achieve a
temperature of 68-7 I + l'C before weighing the Where-
sample. B = volume of titrant. mL of blank
3. Once the sample has achieved a temperature of 68-71 + S = volume of titrant, mL of sample
1"C, immediately weigh the sample into a 500-mL N = normality of NarSrO solution
iodine flask, using the weights and weighing accuracy
noted in Table I (see Notes, 7). PRECISION
4. Add 15 mL of cyclohexane + glacial acetic acid 1. International Union of Pure and Applied Chemistry
(Reagents, 5) on top of the sample and swirl to ensure (IUPAC)/Intemational Organization for Standardization
that the sample is completely dissolved. (ISO) collaborative studies gave the statistical results
5. Dispense 25 mL of Wijs solution using the pipet shown in Table 2.
(Apparatus, 3) into the flask containing the sample,
stopper the flask and swirl to ensure an intimate NOTES
mixture. Immediately set the timer for 1.0 or 2.0 hr, Caution
depending on the iodine value of the sample: IV < 150, Wijs solution causes severe bums, and the vapors can cause
1.0 hr; IV > 150, 2.0 hr (see Notes, 8). lung and eye damage. Use of a fume hood is recommended.
6. Immediately store the flasks in the dark for the required Wijs solution without carbon tetrachloride is available com-
reaction time at a temperature of 25 + 5"C. mercially.
7. Remove the flasks from storage and add 20 mL of KI Cyclohexane is flammable and a dangerous fire risk. It
solution, followed by 100 mL of distilled water (see is moderately toxic by inhalation and skin contact. The
Notes, 9 and l0). TLV in air is 300 ppm.
8. Titrate with 0. I N NarSrO, solution, adding it gradu- Glacial acetic acid in the pure state is moderately toxic
ally and with constant and vigorous shaking (see Notes, by ingestion and inhalation. It is a strong irritant to skin and
I l). Continue the titration until the yellow color has tissue. The TLV in air is 10 ppm.
almost disappeared. Add l-2 mL of starch indicator Hydrochloric acid is a strong acid and will cause severe
solution and continue the titration until the blue color burns. Protective clothing should be worn when working
just disappears. with this acid. It is toxic by ingestion and inhalation and is a

Table 2
Statistical analysis of results obtained in IUPAC/ISO collaborative study (1 1 laboratories) of Wijs iodine value with carbon
tetrachloride and cyclohexane + glacial acetic acid (1:1) solventsa.

Sample Mean value r RSDT RSDR SD' SD*


(oil) CTC CHX CTC CHX CTC CHX CTC CHX CTC CHX CTC CHX CTC CHX

Sunflower 133.6 132.9 3.00 3.60 '7.20 4.80 1.07 t.29 2.5'7 t.1l t.43 I .71 3.44 2.28
Rened palm 53.1 53.0 0.65 0.82 t.43 r.90 0.23 0.29 0.s r 0.68 o.12 0.16 0.27 0.36
Crude fish 109. I 108.5 1.6-t 1.40 4.35 2.80 0.60 0.50 r.55 1.00 0.65 0.54 1.69 r.09
Tung r64.-5 163.1 3.11 2.39 5.27 4.32 1.24 0.8s 1.88 1.54 2.04 1.39 3.10 2.52
Tallow (beef) 11.2 46.9 1.37 1.33 2.75 2.10 0.49 0.48 0.98 0.7 5 0.23 0.22 0.46 0.35
Crude palm 52.5 52.6 1.36 2.ts 2.t2 2.89 0.49 0.77 0.76 r.03 0.26 0.40 0.40 0.54
Used fiying 37.7 31 .1 0.97 1.38 l.l8 2.48 0.35 0.49 0.42 0.89 0.13 0.19 0. l6 0.33
Palm kernel 18.2 18.3 o.t] 0. l4 0.5 t 0.64 0.06 0.05 0. r 8 0.23 0.0r 0.01 0.03 0.04
Olive 82.3 82.2 0.15 I .7 5 r.86 2.62 o.27 0.63 0.66 0.94 0.22 0.51 0.55 0.77

HSBOII' 102.6 102.3 L40 2.20 4.80 5.10 0.50 0.'79 t .71 1.82 0.51 0.80 1.76 r .86
HSBO2I' t1.l 71.8 1.10 l.-50 3.70 2.10 0.61 0.54 I .32 0.7 5 0.45 0.40 0.99 0.56
HFOi' 73.0 12.8 1.70 1.60 2.50 2.30 0. I o.5l 0.89 0.82 0.11 0.42 0.6s 0.60
"See References, 3. RSD., relative standard deviation, repeatability; RSD*, relative standard deviation, reproducibility; SD., standard
deviation, repeatability; SD*, standard deviation, reproducibility; CTC, carbon tetrachloride; CHX, cyclohexane + glacial acetic acid
( l:l); HSBO, hydrogenated soybean oil; HFO, hydrogenated hsh oil.

'Additional study involving l7 laboratories.


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SAMPLING AND ANALYSIS OF COMMERCIAL FATS AND OILS
Cd 1d-92 . lodine Value of Fats and Oils

strong irritant to eyes and skin. The use ofa properly operat- starches: Soluble Starch for Iodometry, Fisher 55l6-
ing fume hood is recommended. When diluting the acid, 100; Soluble Potato Starch, Sigma 5-2630; Soluble
always add the acid to the water, never the reverse. Potato Starch for Iodometry, J.T. Baker 4006-04.
Potassium dichromate is toxic by ingestion and inhala- 6. The sodium thiosulfate solution may be purchased from
tion. There is sufficient evidence in humans for the carcino- a chemical supplier. However, it still must be accurately
genicity of chromium [+6], in particular, lung cancer. It is a standardized in the laboratory.
strong oxidizing agent and a dangerous fire risk when in 7. The weight of the sample must be such that there will
contact with organic chemicals. be an excess of Wijs solution of 50-60Vo of the amount
added, i.e., 100-1507o ofthe amount absorbed.
NUMBERED NOTES 8. The indicated reaction times are those specified in the
l. When the iodine value is determined on materials IUPAC Iodine Value Method 2.205 (References, 1) and
having conjugated systems, the result is not a measure were the reaction times used in the IUPAC/ISO valida-
of total unsaturation, but rather is an empirical value tion study of the cyclohexane + acetic acid method.
indicative of the amount of unsaturation present. Previous AOCS versions of iodine value methods speci-
Reproducible results are obtained that afford a compari- fied a reaction time of 0.5 hr, regardless of the iodine
son of total unsaturation. When the iodine value is value, but noted that "a longer reaction time may be
required on fatty acids, see Method Tg la-64. necessary for oils with high iodine value." The longer
2. Because the preparation of the Wijs solution is time- reaction times appear to be particularly critical when
consuming and involves the use of both hazardous and cyclohexane is used as a replacement for carbon tetra-
toxic chemicals, this solution may be purchased from a chloride (References, 2).
chemical supplier. Solutions are available which 9. If the reaction is not terminated within 3 min after the
contain no carbon tetrachloride, and such solutions reaction time, the sample must be discarded.
should be used. A11 Wijs solutions are sensitive to 10. The sample must be titrated within 30 min of reaction
temperature, moisture and light. Store in a cool and termination, after which the analysis is invalid.
dark place, and never allow to come to a temperature ll. Mechanical stirring is recommended for agitation
above 25-30"C. The laboratory preparation of Wijs during the addition of thiosulfate.
solution is noted in AOCS Official Method Cd 1-25.
3. Fresh cyclohexane should be used. Erratic results may RETERENCES
be obtained if old cyclohexane is used. See Reagents, 5 1. Standard Methods for the Analysis of Oils, Fats and
for a test for the presence of oxidizable substances. Derivatives, International Union of Pure and Applied
4. l7o sfarch solution may be purchased from a chemical Chemistry, 7th edn., Blackwell Scientific Publications,
supplier. 1987, IUPAC Method 2.205.
5. "Potato Starch for Iodometry" is recommended, 2. AOCS collaborative study results using cyclohexane
because this starch produces a deep blue color in the afone appear in J. Am. Oil Chem. Soc. 65:745 (1988).
presence of the iodonium ion. "Soluble Starch" is not 3. IUPAC collaborative study results using cyclohexane +
recommended because a consistent deep blue color may glacial acetic acid (l:l) appear in Pure Appl. Chem.
not be developed when some soluble starches interact 62:2339 (1990) and were repofed tn INFORM 1:484
with the iodonium ion. The following are suitable (reeO).

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