METTLER TOLEDO Application M617-2012

Determination of Iodine Value According to Wijs (Edible Oils and Fats)

Selected Application Methods Method
7.2 IodineforValue
the determination of the iodine value in oil, margarine and fats according to Wijs.
(Iodine value according to Wijs, Mettler-Toledo Method M617-2012 from Application Brochure 24 [10])

Sample Oil, margarine, edible fat Preparation and Procedures

CAUTION:
- Use safety goggles, a lab coat and wear gloves.
Compound Unsaturated compounds If possible, work in a fume hood.
(double bonds) -C=C-
- Ensure accurate cleaning of electrode is
sufficient after each titration.
Chemicals - Wijs solution, 10 mL - Due to handling steps e.g. sample weighing and
(Iodine monochloride, ICl) pipetting, careful handling is required.
- Mercury acetate in acetic acid - For ecologic reasons, mercury acetate solution
10 mL of a 2.5% solution may be replaced by glacial acetic acid.
- Potassium iodide 20%, 20 mL
Preparations:
- Deionized water
- Standardization of Na2S2O3:
Weigh about 25 mg of potassium iodate,
Titrant Sodium thiosulphate,
c(Na2S2O3) = 0.1 mol/L dissolve it in 50 mL 0.1mol/L HCl add 1.0 g KI
and titrate with 0.1 mol/L Na2S2O3
- Back value:
• Add 10 mL iodine monochloride
Standard Potassium iodate, KIO3
M = 213.99 g/moL , z = 6 • Add 10 mL glacial acetic acid
20-30 mg • Stir for 300 s, add 20 mL of 20% KI
• Titrate with 0.1 mol/L Na2S2O3
- Sample preparation of olive oil:
Indication DMi140-SC
combined redox Pt ring sensor • Weigh about 0.17 g of olive oil
• Add 10 mL iodine monochloride and 10 mL
glacial acetic acid
Chemistry ICl3 + I2 → 3 ICl • Stir for 300 s, add 20 mL of 20% KI
• Titrate with 0.1 mol/L Na2S2O3
ICl + KI → I2 + KCl
2-
2 S2O3 + I2 → Remarks
- 2-
2I + S4O6
- Iodine Value (IV):
A measure of the degree of unsaturation of a fat
Calculation Iodine Value: g I2/100 g or fatty acid, defined as the number of grams of
R = (B[Back EQP]-Q)*C/m iodine capable of reacting with 100 g of the
C = M/(10*z) sample.
- It is usually determined indirectly by measuring
Back Value: mmoL the amount of an iodine containing reagent, e.g.
R=Q iodine monochloride, which remains after excess
C=1 has been added and reaction is complete.
Stored as B[Back EQP]
- The IV of saturated fatty acids is zero.
- Literature:
Waste - Organic waste (no mercury) o Swiss Food Manual, SLMB
disposal - Special waste (with mercury) (“Schweizerisches Lebensmittebuch”).
http://www.slmb.bag.admin.ch/slmb/index.html
o Referred for the iodine value of samples:
Author, Sohel Ansari, IMSG, May 2012 http://en.wikipedia.org/wiki/Iodine_value
Version Revised by: C. De Caro,
MSG AnaChem, June 2012

METTLER TOLEDO Page 1 of 5 Titration Application M617-2012

METTLER TOLEDO Dairy Solution Guide 39

Selected Application Methods Instruments - T70/T90 Titration Excellence
(With minor method modifications also a T50 Titration Excellence can be used).
- Additional dosing unit (ME-51109030)
- 2 DV1020 burettes 20 mL (MT-51107502)
®
Accessories - LabX pro titration software
- XP205 Balance

Results
Iodine value of olive oil
Results
No. Comment / ID Start time Sample size and results
1/6 Olive Oil 5/12/2012 4:58:38 PM 0.1692 g
R1 = 80.92482 g I2/100g Iodine Value
2/6 Olive Oil 5/12/2012 5:10:57 PM 0.1821 g
R1 = 80.97188 g I2/100g Iodine Value
3/6 Olive Oil 5/12/2012 5:22:22 PM 0.1670 g
R1 = 80.89459 g I2/100g Iodine Value
4/6 Olive Oil 5/12/2012 5:33:45 PM 0.1726 g
R1 = 80.83300 g I2/100g Iodine Value
5/6 Olive Oil 5/12/2012 5:45:38 PM 0.1646 g
R1 = 80.68458 g I2/100g Iodine Value
6/6 Olive Oil 5/12/2012 5:56:48 PM 0.1739 g
R1 = 81.11042 g I2/100g Iodine Value
Statistics
Number of results R1 n = 6
Mean value x = 80.90322 g I2/100 g Iodine Value
Standard deviation s = 0.14207 g I2/100 g Iodine Value
Rel.standard deviation srel = 0.176 %

Back Value
Statistics
Number of results R1 n = 3
Mean value x = 2.027 mmoL
Standard deviation s = 0.002 mmoL
Rel.standard deviation srel = 0.075 %

Sample Sample Mass n Mean value Std. deviation srel Reference

[g] [g I2/100g] [g I2/100g] [%] [g I2/100g]
-----------------------------------------------------------------------------------------------
Olive Oil 0.1646 - 0.1821 6 80.90322 0.14207 0.176 80 - 88
Coconut Oil 2.5941 - 2.6974 6 7.64682 0.01443 0.189 7 - 10
Palm Oil 0.2616 - 0.2844 6 56.50217 0.15748 0.279 44 - 58
Sunflower Oil 0.1018 - 0.1168 6 130.94139 0.23822 0.182 125 - 144
Peanut Oil 0.1429 - 0.1663 6 93.94350 0.27464 0.292 84 - 105
Margarine 0.2417 - 0.2821 6 42.37728 0.12651 0.299

Titration curve

Back value determination Sample titration

METTLER TOLEDO Page 2 of 5 Titration Application M617-2012

METTLER TOLEDO Dairy Solution Guide 40

Selected Application Methods Table of measured values
Volume Increment Signal Change 1st deriv. Time Temperature
mL mL mV mV mV/mL s °C
0.000 NaN 274.8 NaN NaN 0 25.0
0.571 0.571 276.7 1.9 NaN 4 25.0
0.857 0.286 277.9 1.2 NaN 8 25.0
1.000 0.143 278.4 0.5 NaN 11 25.0
1.358 0.358 279.5 1.1 NaN 46 25.0
1.858 0.500 281.0 1.5 2.96 49 25.0
2.358 0.500 282.4 1.4 2.37 53 25.0
2.858 0.500 283.4 1.0 1.91 57 25.0
3.358 0.500 284.8 1.4 1.40 61 25.0
3.858 0.500 284.8 0.0 1.15 67 25.0
4.358 0.500 285.1 0.3 0.83 71 25.0
4.858 0.500 285.8 0.7 0.54 75 25.0
5.358 0.500 285.8 0.0 0.08 79 25.0
5.858 0.500 286.3 0.5 -0.44 82 25.0
6.358 0.500 285.2 -1.1 -1.12 86 25.0
6.858 0.500 284.4 -0.8 -2.10 90 25.0
7.358 0.500 282.7 -1.7 -3.59 94 25.0
7.858 0.500 280.6 -2.1 -6.63 98 25.0
8.358 0.500 277.3 -3.3 -12.63 102 25.0
8.858 0.500 270.5 -6.8 -27.49 106 25.0
9.129 0.271 264.1 -6.4 -47.95 110 25.0
9.249 0.120 258.4 -5.7 -78.41 114 25.0
9.301 0.052 255.3 -3.1 -174.23 117 25.0
9.372 0.071 249.0 -6.3 -333.62 121 25.0
9.408 0.036 244.0 -5.0 -377.93 124 25.0
9.438 0.030 237.5 -6.5 -454.06 128 25.0
9.468 0.030 223.8 -13.7 -627.49 132 25.0
EQP 9.484919 NaN 189.8 NaN -637.15 NaN 25.0
9.498 0.030 163.5 -60.3 -497.28 152 25.0
9.528 0.030 149.1 -14.4 -431.50 164 25.0
9.572 0.044 139.2 -9.9 -384.94 178 25.0
9.619 0.047 134.6 -4.6 -270.22 184 25.0
9.736 0.117 127.2 -7.4 NaN 194 25.0
9.861 0.125 122.6 -4.6 NaN 201 25.0
10.088 0.227 117.2 -5.4 NaN 208 25.0
10.422 0.334 112.1 -5.1 NaN 216 25.0
10.922 0.500 107.2 -4.9 NaN 224 25.0

Comments

• According to the “Schweizerisches Lebensmittelbuch” and most international standards, an

incubation of one hour is recommended after the Wijs solution is added to the sample.
• If the expected iodine value is higher than 150g /100g sample, an incubation of two hours even is
required.
• It is necessary to avoid any rest sticking onto the electrode or the propeller stirrer. In this way,
accuracy and reproducibility will be improved.
• The sample mass must be appropriate to the expected iodine value. A high degree of saturation (i.e.
less C=C double bonds) means a large sample size. For example, the mass of sunflower oil, which is
highly unsaturated, is very small and must be weighed with a precise balance.
• 10 mL of cyclohexane are added to the sample to completely dissolve fat, margarine or butter before
the titration is started. As a consequence of the additional volume, the stirrer speed in the first
function STIR may have to be increased to guarantee thorough mixing. The preceding back value
determination has to be done accordingly.
• Certain oils and fats dissolve completely, which allows an automated analysis procedure with a
Rondo/Rondolino sample changer. Other samples leave sticky residues, which are preferably
removed with a tissue. In these cases an automated procedure is not recommended.

METTLER TOLEDO Page 3 of 5 Titration Application M617-2012

METTLER TOLEDO Dairy Solution Guide 41

Selected Application Methods Method – Sample Determination and Back Value
Mode Equilibrium controlled
Sample Determination dE 1.0 mV
dt 3 s
t (min) 2 s
001 Title t (max) 60 s
Type General titration Evaluation and recognition
Compatible with T70 / T90 Procedure Standard
ID m617ATx Threshold 200 mV/mL
Title Iodine Value Tendency Negative
Author admin Ranges 0
Date/Time 2/19/2012 11:46:28 AM Add. EQP criteria Steepest jump
Modified at 6/1/2012 11:32:22 AM Steepest jumps 1
Modified by Administrator Termination
Protect No At Vmax 30.0 mL
SOP None At potential No
At slope No
002 Sample After number of
Number of IDs 1 recognized EQPs Yes
ID 1 Olive oil Number of EQPs 1
Entry type Weight Combined termination
Lower limit 0.0 g criteria No
Upper limit 5.0 g Accompanying stating
Density 1.0 g/mL Accompanying stating No
Correction factor 1.0 Condition
Temperature 25.0°C Condition No
Entry Arbitrary
011 Calculation R1
003 Titration stand (Manual stand) Result Iodine Value
Type Manual stand Result unit g I2/100 g
Titration stand Manual stand 1 Formula R1=(B[Back Value]-Q)*C/m
Constant C=M/(10*z)
004 Stir M M[Iodine]
Speed 30% z z[Iodine]
Duration 10 s Decimal places 5
Condition No Result limits No
Record statistics Yes
005 Dispense (normal)[1] Extra statistical func. No
Titrant Iodinemonochloride Send to buffer No
Concentration 0.1 mol/L Condition ___
Volume 10.0
Dosing rate 60.0 mL/min 012 Record
Condition No Summary No
Results Per sample
006 Instruction Raw results Per sample
Instruction Add 10 mL CH3COOH Table of meas. values No
Mode Confirmation Sample data No
Print Yes Resource data No
LabX Command No E - V Per sample
Condition No dE/dV - V Per sample
log dE/dV - V No
007 Stir d2E/dV2 - V No
Speed 40% BETA - V No
Duration 300 s E - t No
Condition No V - t No
dV/dt - t No
008 Instruction T - t No
Instruction Add 20 mL KI E - V & dE/dV - V No
Mode Confirmation V - t & dV/dt - t No
LabX Command No Method No
Condition No Series data No
Condition No
009 Stir
Speed 30% 013 End of sample
Duration 30 s
Condition No

010 Titration (EQP) [1]

Titrant
Titrant Na2S2O3
Concentration 0.1 mol/L
Sensor
Type mV
Sensor DM140-SC
Unit mV
Temperature acquisition
Temperature acquisition No
Stir
Speed 30%
Predispense
Mode Volume
Volume 1.0 mL
Wait time 30 s
Control
Control User
Titrant addition Dynamic
dE (set value) 5.0 mV
dV (min) 0.03 mL
dV (max) 0.5 mL

METTLER TOLEDO Page 4 of 5 Titration Application M617-2012

METTLER TOLEDO Dairy Solution Guide 42

Selected Application Methods Evaluation and recognition
Back Value Determination Procedure Standard
Threshold 200 mV/mL
001 Title Tendency Negative
Type General titration Ranges 0
Compatible with T70 / T90 Add. EQP criteria Steepest jump
ID m617BTx Steepest jumps 1
Title Back Value Termination
Author admin At Vmax 30.0 mL
Date/Time 6/1/2012 11:30:52 AM At potential No
Modified at 6/1/2012 11:56:35 AM At slope No
Modified by Administrator After number of
Protect No recognized EQPs Yes
SOP None Number of EQPs 1
Combined termination
002 Sample criteria No
Number of IDs 1 Accompanying stating
ID 1 Back value - Solvent Accompanying stating No
Entry type Fixed volume Condition
Volume 10.0 mL Condition No
Density 1.0 g/mL
Correction factor 1.0 011 Calculation R1
Temperature 25.0°C Result Consumption
Entry Arbitrary Result unit mmol
Formula R1=Q
003 Titration stand (Manual stand) Constant C=1
Type Manual stand M M[None]
Titration stand Manual stand 1 z z[None]
Decimal places 3
004 Stir Result limits No
Speed 30% Record statistics Yes
Duration 10 s Extra statistical func. No
Condition No Send to buffer No
Condition ___
005 Dispense (normal)[1]
Titrant Iodinemonochloride 012 Record
Concentration 0.1 mol/L Summary No
Volume 10.0 Results Per sample
Dosing rate 60.0 mL/min Raw results Per sample
Condition No Table of meas. values No
Sample data No
006 Instruction Resource data No
Instruction Add 10 mL CH3COOH E - V Per sample
Mode Confirmation dE/dV - V Per sample
Print Yes log dE/dV - V No
LabX Command No d2E/dV2 - V No
Condition No BETA - V No
E - t No
007 Stir V - t No
Speed 40% dV/dt - t No
Duration 300 s T - t No
Condition No E - V & dE/dV - V No
V - t & dV/dt - t No
008 Instruction Method No
Instruction Add 20 mL KI Series data No
Mode Confirmation Condition No
LabX Command No
Condition No 013 End of sample

009 Stir 014 Blank

Speed 30% Name Back Value
Duration 30 s Value B = Mean[R1]
Condition No Unit mmol
Limits No
010 Titration (EQP) [1] Condition No
Titrant
Titrant Na2S2O3 015 Calculation R2
Concentration 0.1 mol/L Result Mean Back Value
Sensor Result unit mmol
Type mV Formula R2=Mean[R1]
Sensor DM140-SC Constant C = 1
Unit mV M M[None]
Temperature acquisition z z[None]
Temperature acquisition No Decimal places 3
Stir Result limits No
Speed 30% Record statistics Yes
Predispense Extra statistical
Mode Volume functions No
Volume 10.0 mL Send to buffer No
Wait time 60 s Condition No
Control
Control User 016 Record
Titrant addition Dynamic Summary Yes
dE (set value) 5.0 mV Results Yes
dV (min) 0.03 mL Raw Results No
dV (max) 0.5 mL Resource data Yes
Mode Equilibrium controlled Calibration curve No
dE 1.0 mV Method No
dt 3 s Series data No
t (min) 2 s Condition No
t (max) 60 s

METTLER TOLEDO Page 5 of 5 Titration Application M617-2012

METTLER TOLEDO Dairy Solution Guide 43