Petroleum Iodine value of Oil and Fat

Redox titration by
Automatic Potentiometric Titrator
JIS K 0070
Standard ASTM D 1959
ISO 3961

1.Abstract
Test method for measurement of iodine value of fats and oils stipulated in the below
quoted standards is generally practiced by Wijs Method using monobasic iodine,
however, Hanus Method is demonstrated here using iodine bromide.
Firstly, sample fat is dissolved in carbon tetrachloride, and Hanus reagent is added
and left in a dark room for reaction. Then, potassium iodide is added for titration with
0.1mol/L sodium thiosulfate.
The endpoint is the maximum inflexion point on titration curve.
The iodine value of fatty sample is calculated from titration volume of sodium
thiosulfate.

4I2 + Na2S2O3 ＋ 5H2O → 2NaI + ２H2SO4 ＋ ６HI

2.Reference
1) JIS K 0070-1992 Test Method for Acid value, Saponification number, Ester number,
Iodine number, Hydroxyl value of Chemical products and Unsaponifiable matter
2) ASTM D 1959-97 Standard Test Method for Iodine Value of Drying Oils and
Fatty Acids
3) ISO 3961:1996 Animal and vegetable fats and oils – Determination of iodine
value

3.Cautions in measurement
1) Reagent and additives must be handled in a well ventilated room or in a draft.
2) Blank test is required as necessary.
3) Use a 300mL conical flask with ground-in stopper to avoid sublimation of iodine
when the sample and Hanus solution react.

TIB-99424 Ver.01 1/4

4.Post-measurement care
Rinse the electrode with pure water, and keep it dipped in water to avoid drying up.

5.Test equipment
Main unit: Automatic potentiometric titration system (preamplifier: STD)
Electrode: Option Combination platinum electrode

6.Reagent
Reagent ： 0.1mol/L sodium thiosulfate （ｆ＝1.006）
Additives ： Pure water, Carbon tetrachloride, Hanus solution,
15% Potassium iodide

7.Measurement procedure
―Measurement―
1) Deliver 0.1g sample to a 300ｍL conical flask with ground-in stopper. Add
20.0mL carbon tetrachloride and seal. Dissolve in an ultrasonic washing
machine.
2) Add 25.0mL Hanus solution, and seal. Shake for one minute.
3) Keep it sealed and leave in a dark room (about 20°C) for 30 minutes.
4) Add 10.0mL of 15% potassium iodide and 100ｍL water, and seal. Shake for 30
seconds.
5) Titrate with 0.1mol/L sodium thiosulfate to obtain iodine value.
Likewise, perform blank test to obtain blank level.

8.Formula
Iodine value ( cｇ / g ) = ( BL1 － EP1 ) × TF × C1 ×K1 / SIZE
EP1 ： Titration volume ( mL )
BL1 ： Blank level ( 47.074mL )
TF ： Factor of titrant ( 1.006 )
C1 ： Concentration conversion coefficient ( 1.269 )
(Atomic mass of iodine: 126.9/100)
K1 ： Unit conversion coefficient ( 1 )
SIZE ： Sample size (ｇ)

TIB-99424 Ver.01 2/4

9.Example of measurement
－Ambient condition－
Room temperature：23 ℃ Humidity ： 23 ％ Weather ： Rainy

-Titration parameter- -Titration curve-

Model : AT-510
Method No. : 10
Titr.mode : Auto
Intermit
Titr.form : EP Stop

[Result parameter]
[Titration parameter]
<Calculation>
Form : EP Stop Calc. Type : Sample
APB No. : 1 Conc.1 : Set
Unit No. : 1 CO1=
Detector No. : 1 (BL1-EP1)*TF*C1*K1/SIZ
Unit : mV E
Max.Volume : 40.0mL
Wait Time : 0s Unit : cg/g
Direction : Auto EP No. : 1
Temp.Comp. : Off

[Control parameter] <Constant>

C1 : 1.269
End Point No. : 1 K1 : 1
End sense : Auto
End Point Area : Off <Titr. Constant>
Separation : Off Factor : 1.006
Over Titr.Vol. : 0mL Conc : 0.1
Gain : 1
Data samp.Pot. : 4.0mV <Blank>
Data samp.Vol. : 0.5mL Blank1 : 47.074
Stability : 0.5mV/s
Delay Time : 1s
Limit Time : 30s

(The above printout data are obtained from titration by AT-510 unit)
≪Titration parameter≫
Form: of titration / APB No. the burette used in titration / Unit No.: APB Unit File number
Detector No.: the detector used in titration/ Unit of potential / Max Volume: of titration
Wait Time: before titration starts/ Direction.: of titration
≪Control parameter≫
End Point No.: number of EPs / End sense: of EP detection / End Point Area: EP detection area
Separation: of potential / Over Titr.Vol. over-titrated volume / Gain: sensitivity of detection signal
Data samp.Pot.: potential change of sampling signal / Data samp.Vol. : titration volume of sampling signal
Stability: of EP potential / Delay Time: before stability check / Limit Time: of stability check
≪Calculation parameter≫
Calc.Type: of formula / Conc.1 formula 1 / Unit: of results
EP No. of calculation / Temp.Comp.: temperature compensation / C1(mg/mL): concentration conversion coefficient
K1: unit conversion coefficient / Factor: factor of titration liquid / Blank1: blank level 1

TIB-99424 Ver.01 3/4

－Measurement results－
Sample Titration Iodine value
n Iodine value
（g） (mL) (cg/g)
1 0.3096 23.5860 96.851 Mean 97.205 cg/g
2 0.3122 23.1431 97.855 SD 0.5634 cg/g
3 0.3100 23.5413 96.910 RSD 0.5796 %
＊The above test results are obtained by 3 tests of the same sample.
＊ Red underline shows the data from page 3/4.

10.Summary
The iodine value is expressed in grams of iodine for the amount of halogens linked with
100g test sample, and is used as degree of unsaturated bond of fats and oils.
Iodine value is used to compare the number of C=C contained in natural complex
mixture.
Measurement results this time shows favorable repeatability with 0.6% relative
standard deviation. Precise and reliable measurement is assured by the automated
potentiometry.
The iodine value of fats and oils can be perfectly measured by any of the following
titration systems manufactured by Kyoto Electronics (KEM).

【AT-610】 【AT-510】 【AT-500N-1】

Awarded Product of Supreme • Compact and cost performance • Low cost and high performance
Technology from Kyoto City model • Easy view with back light LCD
• Easy key entry by touch panel of • PC card expands data memory for • GLP/GMP conformed model
large color LCD （8-inch wide） convenience and versatility.
• Simultaneous titration in parallel
• Both potentiometric and Karl
Fischer moisture titration
(coulometric・volumetric） can be
performed at a time.

TIB-99424 Ver.01 4/4