Petroleum Iodine value in Bio Diesel Fuel (BDF)

Redox titration by
Automatic Potentiometric Titrator
JIS K 0070
Standard ASTM D1959
ISO 3961

1.Abstract
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 or Bio Diesel
Fuel.
The test method to determine iodine value of Bio Diesel Fuel (BDF) is standardized as in
ASTM D1959-97 Standard Test Method for Iodine Value of Drying Oils and Fatty Acids,
ISO 3961:1996 Animal and vegetable fats and oils – Determination of iodine value, and
JIS K 0070-1992 Test Method for Acid value, Saponification number, Ester number,
Iodine number, Hydroxyl value of Chemical products and Unsaponifiable matter.
The test sample is made out of bio diesel fuel dissolved in cyclohexane, added in excess
with Wijs reagent (0.1mol/L iodine monochloride acetic acid solution), left in a dark room
for 30 minutes reaction, then added with potassium iodide, potentiometric titrated with
0.1mol/L sodium thiosulfate solution for the excessive iodine monochloride to the
endpoint, which is the highest inflexion point.
The iodine value of BDF is calculated from titration volume of sodium thiosulfate
solution.
H H H H
CH3(CH 2)7C = C(CH 2)7COOH + I 2 CH3(CH 2)7C - C(CH 2)7COOH
I2 + 2Na 2S2O3 2NaI + Na 2S4O6 I I

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 D1959-97 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） Wijs reagent (0.1mol/L iodine monochloride acetic acid solution) is added to 50∼60%
in excess.
2) Wijs reagent is liable to change, and blank titration is required accordingly.
3) When Wijs reagent and sample react, iodine tends to evaporate. Therefore, use a
200mL conical flask with joint stopper.

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4. Post-measurement care
No special note

5. Test equipment
Main unit: Automatic potentiometric titration system (preamplifier: STD)

Electrode: Combination platinum electrode C-778 (junction liquid: 3.33M-potassium

chloride solution)

6. Reagent
Titrant: 0.1mol/L sodium thiosulfate (f = 1.003)
Additive: Cyclohexane
Wijs reagent (iodine trichloride 7.9g and iodine 8.9g each dissolved in
acetic acid, then, mixed together to make it total 1L)
100g/L potassium iodide solution

7. Test procedure
―Measurement―
1) Take 0.3g sample in a 200mL conical flask with stopper.
2) Add approximately 10mL cyclohexane, and dissolve.
3) Add Wijs reagent, and stir.
4) Plug the flask with stopper, and leave it for 30 minutes in a dark room at room
temperature.
5) Then, add 20mL of 100g/L potassium iodine solution and 100mL pure water.
6) Titrate with 0.1mol/L sodium thiosulfate solution, and obtain iodine value.
* Obtain blank level beforehand by performing blank test likewise.

8. Calculation formula
Iodine value (g/100g) = (BL1 − EP1) × TF × C1/s
BL1: blank level (47.5850mL)
EP1: Titration volume (mL)
TF: Factor of titrant (1.003)
C1: Concentration conversion coefficient (1.269)
(iodine (mg) equivalent to 0.1mol/L Na2S2O3⋅5H2O 1mL)
S: Sample amount (g)

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9. Example of measurement
-Ambient conditions-
Room temperature: 25°C Humidity: 61% Weather: Fair

The below parameters and titration curve are printed out when titrated by AT-610 unit.
-Titration parameters- -Titration results-
Model : AT-610
Serial No. : AT-00001
Method No./Name : [Calculation parameter]
01/lodine value
Titr.mode : Auto Titr Calc. type : Sample
Titr.form : EP Stop CO1 : On
Unit : g/100g
Formula :
[Titration parameter] (BL1-EP1)*TF*CI/S
EP position : EP1
Burette No. : 1 Decimal : 2
Max volume : 60.00 mL Fraction : Half adjust
Channel,Unit Evaluuation : Off
Ctrl. : Ch1,mV
Ref. : Off Active constant
pH polarity : Standard C1 : 1.269 *** R e s u l t ***
Direction : Auto Method No./Name :
Wait time : 0 s 01/lodine value
Dose mode : None [Reagent parameter]
Burette No./Reagent name Sample No. : 01-01
01/0.1mol/L Na2S2O3
[Control parameter] Date : 2007/07/30 11:50
[Reagent info]
Number of EP : 1 No. : 1 Titr.Reagent Name :
End sense : Auto Reagent name : 01/0.1mol/L-Na2S2O3
Gain : 1 01/0.1mol/L Na2S2O3
Data samplong : Std. TF : 1.003 Titr.time : 00:04:11
Ctl.speed mode : Std.
Other control : Std. [Blank list] Size : 0.3317 g
Stir. speef : 4 Blank1 : 47.58500
End point-1
Volume : 18.2186mL
Potential : 246.5 mV

Conc-1 : 112.69g/100g
Meaning of parameters on printout:
≪Titration parameter≫
Burette No.: the burette used for titration / Max Volume: of titration
Channel,Unit: Detector number and the unit of detected potential
pH polarity: direction of pH potential / Direction: of titration / Wait Time: before titration starts
Dose mode: the way of fixed dose
≪Control parameter≫
Number of EP: total EPs / End sense: direction / Gain: sensitivity of detection signal
Data sampling: conditions / Ctl.speed mode: Control speed mode
Other control: / Stir Speed: of stirrer
≪Calculation parameter≫
Calc.Type: calculation type / CO1: concentration formula 1 / Unit: of calculated results
BL1: blank level / EP1: first endpoint / TF: factor / C1(mg/mL): concentration conversion coefficient
/ K1: unit conversion coefficient S: sample size / EP position: for calculation /
Decimal number of digits after decimal point
Fraction: rounding fraction / Evaluuation of calculated results

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-Measurement data-
Sample Titrated Iodine value
n Statistics
(g) ( mL ) ( g/100g )
1 0.3317 18.2186 112.69
2 0.3117 20.0750 112.34 Mean 112.44 g/100g
3 0.3160 19.5926 112.75 SD 0.5722 g/100g
4 0.3239 19.2113 111.50 RSD 0.5089 %
5 0.2902 21.8341 112.95
＊ The data were obtained from 5 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 or Bio Diesel
Fuel.
Measurement of sample this time showed a good repeatability with 0.5% relative
standard deviation by the automatic potentiometric titrator.
The iodine in bio diesel can be measured precisely and conveniently by any of the
following titration systems.

【AT-610】 【AT-510】 【AT-500N-1】

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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
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performed at a time.

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