Determination of peroxide value of oils and fats

I. Introduction
Peroxide value (PV), usually expressed as milliequivalent of peroxide oxygen per kg
sample, is a useful indicator of the extent of oxidation of fats and oils. It measures the
amount of total peroxides in the samples. In this procedure, sample is dissolved in acetic
acid and chloroform solvent with the addition of potassium iodide solution. Iodide is
oxidized to iodine by peroxides present in the sample. The liberated iodine is titrated with
sodium thiosulfate standard solution in the presence of starch indicator. The general
reaction scheme is as follows:

2 Na2S2O3 + I2 → 2NaI + Na2S4O6

Fresh oils usually have PV well below 10 meq/kg. A general rule is that PV should not be
above 10–20 meq/kg fat to avoid rancidity flavor. It would be important to note that PV
may also be expressed (in SI units) as millimoles (mmol) of active oxygen per kilogram of
oil. In this case, the value expressed in millimoles of active oxygen per kilogram is half
that expressed in milliequivalents of active oxygen per kilogram.

II. Materials
- 250 mL glass-stoppered conical flask.
- Chloroform.
- Glacial acetic acid.
- Saturated solution of KI.
- Distilled water.
- 0.01 N Na2S2O3.
- 1% starch indicator solution.

III. Procedure
Note: Conduct analysis in diffuse daylight or artificial light shielded from direct light source.
- Weigh 3-5 g of sample into a 250 mL glass-stoppered conical flask.
- Add 10 mL of chloroform.
- Swirl to dissolve.
 - Add 20 mL glacial acetic acid.
- Mix well.
- Add 1 mL of a saturated solution of KI.
- Mix well.
- Incubate at room temperature for 10 minutes with occasional shaking.
- Add 25 mL of distilled water.
- Titrate slowly with 0.01 N Na2S2O3 with vigorous shaking until yellow is almost
gone.
- Add 5 drops of 1% starch indicator solution.
- Continue titration (shaking vigorously to release all I2 from chloroform layer)
until blue just disappears.
- Conduct blank determination by using 5 mL of water.

IV. Calculation
PV is calculated by the following formula:
(𝐚 − 𝐛) × 𝟏𝟎
𝐏=
𝐦
a: Volume in mL of 0.01 N Na2S2O3 used for the test sample
b: Volume in mL of 0.01 N Na2S2O3 used for the blank
m: Weight in g of the sample