Measurement of the iodine value of fats and oils is a representative experiment in food chemistry and lipid chemistry used to investigate the amount of unsaturated bonds contained in fats and oils.
The iodine value is expressed as the number of grams of iodine that add to 100 g of fat or oil and serves as an indicator for evaluating the degree of unsaturation of fats and oils.
Fats and oils containing larger amounts of unsaturated fatty acids have higher iodine values, and the iodine value is also related to susceptibility to oxidation and drying properties.
In a discussion of iodine value, it is not sufficient simply to write that “the iodine value was high” or “there were many unsaturated bonds.”
It is necessary to explain why iodine and other halogens add to double bonds, why fats and oils with a high degree of unsaturation are more susceptible to oxidation, what the differences are among drying oils, semi-drying oils, and non-drying oils, and why blank tests and back titration are necessary.
This article clearly explains, as examples of discussions that can be used in laboratory reports on iodine-value measurements of fats and oils, the meaning of iodine value, its relationship with the degree of unsaturation, susceptibility to oxidation, the concepts of the Wijs method and Hanus method, blank testing, sodium thiosulfate titration, starch indicator, causes of error, and points for improvement.
Note:
This article is a reference intended to assist with discussions of iodine-value measurement results for fats and oils obtained in food chemistry experiments, lipid chemistry experiments, organic chemistry experiments, and analytical chemistry experiments at universities and similar institutions.
For the actual sample amount, reaction reagent, reaction time, dark conditions, titrant, indicator, calculation formula, and safety precautions, always follow the instructions in your university’s laboratory manual and those given by your instructor or TA.
- What Is the Iodine Value of Fats and Oils?
- Main Items to Include in the Results
- Reference Experimental Values and Calculation Examples for Iodine-Value Measurement
- Reference Experimental Conditions
- Concept of Iodine-Value Measurement
- Titration Results for Different Types of Oil
- Example Calculation of the Difference From the Blank
- Example Calculation of Iodine Value
- Comparison of Iodine Value and Degree of Unsaturation
- Changes in Iodine Value During Storage
- Relationship With Peroxide Value
- Example Calculation of the Percentage Decrease in Iodine Value Due to Oxidation
- Example When the Measured Values Vary
- Example of How to Write the Results
- Points for Connecting the Results to the Discussion
- Example Discussion
- Summary
- Relationship Between Unsaturated Bonds and Iodine Addition
- Discussion of Fats and Oils With High Iodine Values
- Discussion of Fats and Oils With Low Iodine Values
- Degree of Unsaturation and Susceptibility to Oxidation
- Relationship With Drying Oils, Semi-Drying Oils, and Non-Drying Oils
- Difference Between Iodine Value and Saponification Value
- Relationship With Acid Value and Peroxide Value
- Concept of the Wijs Method and Hanus Method
- Importance of the Blank Test
- Concept of Sodium Thiosulfate Titration
- Starch Indicator and Endpoint Determination
- Effect of Reaction Time
- Effect of Light and Dark Conditions
- Effect of Sample Amount
- Causes of Error in Iodine-Value Measurement
- When the Results Can Be Considered Good
- Example Discussion When the Experiment Did Not Go Well
- How to Write Points for Improvement
- Difference Between a Superficial Discussion and a Good Discussion
- Examples of Expressions That Can Be Used in Reports
- Points to Check When Discussing the Iodine Value of Fats and Oils
- Summary
What Is the Iodine Value of Fats and Oils?
The iodine value is a value representing the number of grams of iodine that add to 100 g of fat or oil.
Unsaturated fatty acids in fats and oils contain carbon-carbon double bonds, and iodine and other halogens add to these double bonds.
Therefore, the higher the iodine value, the more unsaturated bonds are considered to be present in the fat or oil.
The iodine value is an indicator used to evaluate the degree of unsaturation of fats and oils.
It tends to be high in vegetable oils and fish oils containing large amounts of unsaturated fatty acids and low in fats and oils containing large amounts of saturated fatty acids.
It is an important value when considering the properties, oxidative stability, and drying characteristics of fats and oils.
Example Discussion:
The iodine value is the number of grams of iodine that add to 100 g of fat or oil and is an indicator of the amount of unsaturated bonds in fats and oils.
Because halogens add to the double bonds of unsaturated fatty acids, fats and oils with higher iodine values are considered to contain larger amounts of unsaturated bonds.
The iodine value determined in this experiment provides a clue for discussing the degree of unsaturation and susceptibility to oxidation of the sample fat or oil.
Main Items to Include in the Results
In the results of iodine-value measurement, organize the type of fat or oil sample, sample amount, type and amount of reaction reagent added, reaction time, reaction conditions in the dark, addition of potassium iodide, concentration of the sodium thiosulfate standard solution, blank titration volume, sample titration volume, iodine value, and other information.
Because the amount of iodine added to the fat or oil is determined from the difference from the blank test, the blank-test value is important.
Main Items to Include in the Results
- Type of fat or oil sample
- Mass of the fat or oil sample
- Type of reaction reagent
- Amount of reaction reagent added
- Reaction time
- Whether the reaction was carried out in the dark
- Amount of potassium iodide added
- Concentration of the sodium thiosulfate standard solution
- Blank titration volume
- Sample titration volume
- Difference from the blank test
- Timing of addition of the starch indicator
- Color change at the endpoint
- Iodine value
- Average value from multiple measurements
- Comparison with literature values and other fats and oils
- Causes of error and points for improvement
Example of How to Write the Results:
A halogenating reagent was added to the fat or oil sample and allowed to react for a fixed period, after which the unreacted iodine was titrated with a sodium thiosulfate standard solution following the addition of potassium iodide.
The amount of iodine added to the unsaturated bonds in the fat or oil was determined from the difference between the blank-test and sample-test titration volumes.
The obtained value was converted to the amount per 100 g of fat or oil and expressed as the iodine value.
Reference Experimental Values and Calculation Examples for Iodine-Value Measurement
Here, for iodine value, an indicator of the degree of unsaturation of fats and oils, titration volumes, differences from the blank, calculation of iodine value, differences among types of oils, and the relationship with susceptibility to oxidation are organized using reference experimental values.
The iodine value is a value expressing in grams the amount of iodine that adds to 100 g of fat or oil.
The more double bonds a fat or oil contains, the more iodine adds, resulting in a larger iodine value.
Therefore, iodine value can be used as an indicator for comparing the degree of unsaturation of fats and oils.
Reference Experimental Conditions
| Item | Details |
|---|---|
| Measurement target | Edible fats and oils |
| Measurement method | After iodine addition, the remaining iodine is titrated with sodium thiosulfate |
| Sample mass | 0.200 g |
| Titrant | 0.100 mol/L sodium thiosulfate standard solution |
| Blank titration volume | 25.60 mL |
| How to interpret the reaction | Iodine adds to double bonds |
| Evaluation items | Iodine value, degree of unsaturation, susceptibility of fats and oils to oxidation |
Concept of Iodine-Value Measurement
When a reagent containing iodine is added to fats and oils, iodine adds to the carbon-carbon double bonds in the fats and oils.
The iodine remaining after the reaction is titrated with sodium thiosulfate, and the amount of iodine that added to the fat or oil is determined from the difference from the blank.
| Operation | Meaning | How to Interpret the Result |
|---|---|---|
| Blank test | Titrate the iodine remaining without adding fat or oil | Provides an estimate of the total amount of iodine added |
| Sample measurement | Allow iodine to add to the fat or oil and titrate the remaining iodine | The smaller the titration volume, the more iodine the fat or oil consumed |
| Difference from blank | Corresponds to the amount of iodine added to the fat or oil | The larger the difference, the higher the degree of unsaturation |
Titration Results for Different Types of Oil
Reference examples are shown for iodine-value measurements of different types of fats and oils under the same conditions.
The blank titration volume is assumed to be 25.60 mL, and the sample mass is 0.200 g in all cases.
| Sample | Type of Fat or Oil | Sample Titration Volume | Difference From Blank | Iodine Value | Interpretation of Degree of Unsaturation |
|---|---|---|---|---|---|
| A | Coconut oil | 23.95 mL | 1.65 mL | 10.5 | Low degree of unsaturation |
| B | Olive oil | 12.95 mL | 12.65 mL | 80.3 | Moderate |
| C | Canola oil | 8.10 mL | 17.50 mL | 111.1 | High degree of unsaturation |
| D | Soybean oil | 5.65 mL | 19.95 mL | 126.7 | High degree of unsaturation |
| E | Fish oil | 0.80 mL | 24.80 mL | 157.5 | Very high degree of unsaturation |
Example Calculation of the Difference From the Blank
The amount of iodine that added to the fat or oil corresponds to the difference between the blank titration volume and the sample titration volume.
Difference from blank = Blank titration volume − Sample titration volume
For soybean oil, the blank titration volume is 25.60 mL and the sample titration volume is 5.65 mL.
Difference from blank = 25.60 − 5.65 = 19.95 mL
The larger this difference, the more iodine the fat or oil consumed, indicating that more double bonds are considered to be present.
Example Calculation of Iodine Value
The iodine value can be determined using the following equation.
Iodine value = (Blank titration volume − Sample titration volume) × Sodium thiosulfate concentration × 12.69 ÷ Sample mass
Here, the titration volume is expressed in mL, the concentration in mol/L, and the sample mass in g.
For soybean oil, the difference from the blank is 19.95 mL, the sodium thiosulfate concentration is 0.100 mol/L, and the sample mass is 0.200 g.
Iodine value = 19.95 × 0.100 × 12.69 ÷ 0.200
Iodine value = 126.7
Therefore, in this reference example, the iodine value of soybean oil is determined to be 126.7.
Comparison of Iodine Value and Degree of Unsaturation
Oils with higher iodine values are considered to contain more double bonds.
Therefore, iodine value can be used as a guide for comparing the degree of unsaturation of fats and oils.
| Type of Fat or Oil | Iodine Value | Main Characteristics | Approximate Susceptibility to Oxidation |
|---|---|---|---|
| Coconut oil | 10.5 | Contains a large proportion of saturated fatty acids | Relatively resistant to oxidation |
| Olive oil | 80.3 | Contains a large proportion of monounsaturated fatty acids | Moderate |
| Canola oil | 111.1 | Contains large amounts of unsaturated fatty acids | Somewhat susceptible to oxidation |
| Soybean oil | 126.7 | Contains polyunsaturated fatty acids | Susceptible to oxidation |
| Fish oil | 157.5 | Contains large amounts of highly unsaturated fatty acids | Very susceptible to oxidation |
In this reference example, coconut oil had the lowest iodine value and fish oil had the highest iodine value.
Fish oil contains large amounts of highly unsaturated fatty acids with many double bonds, which is considered to be why its iodine value was high.
Changes in Iodine Value During Storage
When fats and oils are oxidized, double bonds may react with oxygen and decrease.
Therefore, iodine value may decrease in oils in which oxidation has progressed.
| Sample | Storage Condition | Storage Period | Iodine Value | How to Interpret the Change |
|---|---|---|---|---|
| Soybean oil | Fresh oil | 0 days | 126.7 | Many double bonds remain |
| Soybean oil | Room-temperature dark storage | 14 days | 123.8 | Slight decrease |
| Soybean oil | Light exposure | 14 days | 118.5 | Decreases because of oxidation |
| Soybean oil | Stored at 40°C | 14 days | 114.2 | Oxidation progresses because of heat |
| Soybean oil | Opened and left standing | 14 days | 112.6 | Larger decrease because of contact with air |
The iodine value decreased more under harsher storage conditions.
This was considered to result from double bonds in the fats and oils being consumed in oxidation reactions, thereby decreasing the degree of unsaturation.
Relationship With Peroxide Value
Iodine value is an indicator of the degree of unsaturation, while peroxide value is an indicator of the amount of early oxidation products.
Comparing both makes it easier to separately consider whether a fat or oil has a structure that is susceptible to oxidation and whether oxidation has actually progressed.
| Fat or Oil | Iodine Value | Peroxide Value After 7 Days at 40°C | Interpretation |
|---|---|---|---|
| Olive oil | 80.3 | 2.10 meq/kg | Moderate degree of unsaturation and relatively little oxidation |
| Canola oil | 111.1 | 3.25 meq/kg | High degree of unsaturation and oxidation proceeds relatively readily |
| Soybean oil | 126.7 | 4.40 meq/kg | Contains many double bonds and peroxides readily increase |
| Fish oil | 157.5 | 8.65 meq/kg | Contains many highly unsaturated fatty acids and is susceptible to oxidation |
Oils with higher iodine values tended to show higher peroxide values after storage.
This is considered to result from oils containing more double bonds being more susceptible to oxidation reactions.
Example Calculation of the Percentage Decrease in Iodine Value Due to Oxidation
Comparing iodine values before and after storage makes it possible to evaluate how much the degree of unsaturation changed because of oxidation.
Percentage decrease in iodine value (%) = (Iodine value before storage − Iodine value after storage) ÷ Iodine value before storage × 100
When soybean oil was opened and left standing, the iodine value before storage was 126.7 and the iodine value after storage was 112.6.
Percentage decrease = (126.7 − 112.6) ÷ 126.7 × 100 = 11.1%
From this result, part of the double bonds was considered to have been oxidized by leaving the oil open, causing the iodine value to decrease by approximately 11.1%.
Example When the Measured Values Vary
In iodine-value measurement, the measured values may vary depending on reaction time, light protection, titration endpoint, and sample weighing.
The following shows an example in which the same soybean oil was measured three times.
| Measurement | Sample Titration Volume | Difference From Blank | Iodine Value |
|---|---|---|---|
| 1st | 5.65 mL | 19.95 mL | 126.7 |
| 2nd | 5.72 mL | 19.88 mL | 126.2 |
| 3rd | 5.58 mL | 20.02 mL | 127.0 |
| Average | 5.65 mL | 19.95 mL | 126.6 |
The three measured values ranged from 126.2 to 127.0 and agreed relatively well.
Reducing errors in endpoint determination and sample mass makes it easier to obtain reproducible values.
Example of How to Write the Results
When the iodine values of various fats and oils were measured, the values were 10.5 for coconut oil, 80.3 for olive oil, 111.1 for canola oil, 126.7 for soybean oil, and 157.5 for fish oil.
From these results, coconut oil was considered to have a low degree of unsaturation, while fish oil was considered to have a very high degree of unsaturation.
For soybean oil, the sample titration volume was 5.65 mL compared with a blank titration volume of 25.60 mL, giving a difference of 19.95 mL.
Using a 0.100 mol/L sodium thiosulfate standard solution and a sample mass of 0.200 g, the iodine value was calculated to be 126.7.
In addition, when soybean oil was stored for 14 days, the iodine value was 123.8 under room-temperature dark storage, 118.5 under light exposure, 114.2 after storage at 40°C, and 112.6 when opened and left standing.
The iodine value decreased more under harsher storage conditions, suggesting that double bonds in the fats and oils may have decreased because of oxidation.
Points for Connecting the Results to the Discussion
In a discussion of iodine value, it is useful to relate the magnitude of the value to the degree of unsaturation of the fat or oil and further explain susceptibility to oxidation and changes caused by storage conditions.
- Has the difference between the blank titration volume and sample titration volume been correctly determined?
- Can it be explained that oils with higher iodine values contain more double bonds?
- Can the reason iodine values differ among types of fats and oils be explained in relation to fatty-acid composition?
- Can it be explained that oils with higher iodine values tend to be more susceptible to oxidation?
- Can the reason the iodine value decreased after storage be explained in relation to oxidation of double bonds?
- Can the degree of unsaturation and oxidative deterioration be discussed separately by comparison with peroxide value?
- Can reaction time, light protection, titration endpoint, and errors in sample mass be discussed as factors affecting the measured values?
Example Discussion
In this experiment, iodine values were measured for several types of fats and oils and their degrees of unsaturation were compared.
The iodine value of coconut oil was low at 10.5, while that of fish oil was high at 157.5.
Because iodine value indicates the amount of iodine that adds to 100 g of fat or oil, a higher value indicates that more double bonds are present.
Therefore, fish oil was judged to have the highest degree of unsaturation among the fats and oils measured in this experiment.
The iodine value of soybean oil was 126.7, which was higher than the value of 80.3 for olive oil.
This was considered to result from soybean oil containing relatively large amounts of polyunsaturated fatty acids, whereas olive oil mainly contains monounsaturated fatty acids.
Because fats and oils with more double bonds add more iodine, the higher iodine value can be explained.
In soybean oil stored under different conditions, the iodine value decreased greatly when the oil was opened and left standing or stored at 40°C.
This was considered to result from the double bonds in the fats and oils being oxidized under the influence of oxygen in the air and heat, reducing the number of double bonds capable of adding iodine.
In particular, the oil left open was more readily exposed to oxygen and was therefore considered to have undergone oxidation more readily.
In addition, oils with higher iodine values tended to show higher peroxide values after storage.
This is because oils with higher degrees of unsaturation are more susceptible to oxidation reactions and more readily generate peroxides.
However, iodine value is an indicator of the degree of unsaturation, whereas peroxide value is an indicator of early oxidation products, so the two must be distinguished when evaluating deterioration of fats and oils.
Possible measurement errors include insufficient reaction time for iodine addition, decomposition of iodine caused by light, deviations in titration endpoint determination, and errors in weighing the sample mass.
Particularly in reactions involving iodine, light protection and control of reaction time are important, and if the conditions are inconsistent, the iodine value may be underestimated.
Summary
Iodine value is an indicator representing the amount of double bonds contained in fats and oils.
The amount of iodine added to the fat or oil is determined from the difference between the blank titration volume and the sample titration volume and calculated as a value per 100 g of fat or oil.
In this reference example, iodine values were large in oils with high degrees of unsaturation, such as fish oil, soybean oil, and canola oil, and small in coconut oil.
In a report, it is useful to discuss iodine value, degree of unsaturation, decreases during storage, susceptibility to oxidation, and the relationship with peroxide value in relation to one another.
Relationship Between Unsaturated Bonds and Iodine Addition
Unsaturated fatty acids in fats and oils contain carbon-carbon double bonds.
These double bonds undergo addition reactions with halogens such as iodine and bromine.
Iodine-value measurement uses the amount of halogen that adds to these double bonds to evaluate the amount of unsaturated bonds.
The more double bonds a fat or oil contains, the more iodine can add.
Therefore, fats and oils with high iodine values are considered to contain larger amounts of unsaturated fatty acids, while fats and oils with low iodine values are considered to contain higher proportions of saturated fatty acids.
However, because fats and oils are mixtures containing multiple fatty acids, iodine value represents an average degree of unsaturation.
R-CH=CH-R’ + I2 → R-CHI-CHI-R’
Example Discussion:
Halogens such as iodine add to the carbon-carbon double bonds of unsaturated fatty acids.
Therefore, the more double bonds present in fats and oils, the greater the amount of iodine that adds and the higher the iodine value becomes.
Fats and oils that showed high iodine values in this experiment are considered to contain large amounts of unsaturated fatty acids.
Discussion of Fats and Oils With High Iodine Values
Fats and oils with high iodine values contain large amounts of unsaturated bonds.
In fats and oils containing large amounts of unsaturated fatty acids such as linoleic acid, linolenic acid, and oleic acid, many halogen molecules add to the double bonds, resulting in high iodine values.
Some vegetable oils and fish oils may have relatively high iodine values.
Fats and oils with high iodine values tend to be more susceptible to oxidation.
Double bonds readily react with oxygen, and oxidation may produce peroxides, aldehydes, and other compounds.
Therefore, although fats and oils with high iodine values have nutritional characteristics, attention must be paid to oxidative deterioration during storage.
Example Discussion:
Because the measured fat or oil had a high iodine value, it was considered to contain a large amount of unsaturated fatty acids.
Unsaturated fatty acids contain carbon-carbon double bonds to which halogens such as iodine add, causing the iodine value to become high.
In addition, fats and oils containing many unsaturated bonds react readily with oxygen and may be more susceptible to oxidative deterioration during storage.
Discussion of Fats and Oils With Low Iodine Values
Fats and oils with low iodine values are considered to contain fewer unsaturated bonds and relatively larger amounts of saturated fatty acids.
Saturated fatty acids do not contain carbon-carbon double bonds and therefore hardly undergo iodine-addition reactions.
As a result, the amount of halogen consumed is small and the iodine value is also low.
Fats and oils with low iodine values are generally less susceptible to oxidation and tend to have higher storage stability.
However, resistance to oxidation is affected not only by degree of unsaturation but also by antioxidant components, degree of refining, storage temperature, light, and contact with oxygen.
Iodine value provides a clue for considering oxidative stability but cannot be used alone to make a complete judgment.
Example Discussion:
Fats and oils with low iodine values may contain fewer unsaturated bonds and higher proportions of saturated fatty acids.
Because saturated fatty acids do not contain double bonds, they hardly undergo iodine-addition reactions and therefore have low iodine values.
Such fats and oils contain fewer unsaturated bonds and are therefore considered to be relatively resistant to oxidation.
Degree of Unsaturation and Susceptibility to Oxidation
The susceptibility of fats and oils to oxidation is related to the number of unsaturated bonds.
The double bonds of unsaturated fatty acids are susceptible to oxidation, and oxidation proceeds particularly readily in polyunsaturated fatty acids containing multiple double bonds.
As oxidation progresses, peroxides, aldehydes, ketones, and other compounds are generated, leading to deterioration of odor and taste.
Fats and oils with high iodine values have high degrees of unsaturation and tend to be more susceptible to oxidation.
However, oxidation may be suppressed when antioxidants are present in the fat or oil or when the fat or oil is stored under light-blocking, low-temperature, and sealed conditions.
Susceptibility to oxidation should be discussed not only in relation to iodine value but also in relation to storage conditions.
Example Discussion:
Because unsaturated bonds readily react with oxygen, fats and oils with higher iodine values tend to be more susceptible to oxidation.
In particular, polyunsaturated fatty acids with multiple double bonds are readily oxidized and may generate peroxides and decomposition products during storage.
Therefore, storage conditions such as protection from light, low temperature, and sealing are important for fats and oils with high iodine values.
Relationship With Drying Oils, Semi-Drying Oils, and Non-Drying Oils
Fats and oils may be classified as drying oils, semi-drying oils, and non-drying oils according to how readily they dry in air.
Drying oils contain many unsaturated bonds and readily react with oxygen in the air to polymerize and harden.
In general, fats and oils with higher iodine values tend to show stronger drying properties.
Semi-drying oils contain a certain amount of unsaturated bonds but not as many as drying oils.
Non-drying oils have relatively low iodine values and do not readily harden in air.
However, the boundaries of these classifications are not strictly fixed and may vary depending on the composition of the fat or oil and measurement conditions.
Example Discussion:
Fats and oils with high iodine values contain many unsaturated bonds and readily undergo polymerization and hardening by reacting with oxygen in the air, so they tend to show the properties of drying oils.
On the other hand, fats and oils with low iodine values contain fewer unsaturated bonds and do not readily dry or harden in air, so they tend to show properties closer to non-drying oils.
In this way, iodine value provides a clue for discussing the drying properties of fats and oils.
Difference Between Iodine Value and Saponification Value
Iodine value is an indicator of the amount of unsaturated bonds in fats and oils.
In contrast, saponification value represents the amount of KOH required to saponify 1 g of fat or oil and is mainly related to fatty-acid chain length and the average molecular weight of the fat or oil.
In other words, iodine value and saponification value are both values describing properties of fats and oils, but they represent different things.
A fat or oil with a high iodine value is considered to have a high degree of unsaturation, but this does not necessarily mean that its fatty-acid chains are short.
Conversely, a fat or oil with a high saponification value may have a small average molecular weight, but this does not necessarily mean that it contains many unsaturated bonds.
In a report, the meanings of the two values must be distinguished and not confused.
Example Discussion:
Iodine value is an indicator of the amount of unsaturated bonds in fats and oils, whereas saponification value is an indicator used to consider average molecular weight and fatty-acid chain length from the amount of KOH required to saponify the fat or oil.
Therefore, a high iodine value indicates a high degree of unsaturation but does not directly indicate that the fatty-acid chains are short.
When discussing the properties of fats and oils, iodine value and saponification value must be treated separately.
Relationship With Acid Value and Peroxide Value
In fat and oil analysis, acid value and peroxide value are also commonly used in addition to iodine value.
Acid value indicates the amount of free fatty acids and serves as an indicator of hydrolytic deterioration of fats and oils.
Peroxide value is a value indicating the amount of peroxides produced during the early stages of oxidation of fats and oils.
Iodine value indicates the degree of unsaturation and does not directly represent deterioration itself.
However, fats and oils with high iodine values contain many unsaturated bonds and therefore tend to be more susceptible to oxidation.
Consequently, when considering oxidative deterioration, evaluating iodine value together with peroxide value makes the results easier to understand.
Iodine value can be regarded as an indicator of the structural background of susceptibility to oxidation, while peroxide value indicates the actual progress of oxidation.
Example Discussion:
Iodine value indicates the degree of unsaturation of fats and oils and has a different meaning from acid value and peroxide value.
Acid value indicates the amount of free fatty acids, while peroxide value indicates the amount of early oxidation products.
However, because fats and oils with high iodine values contain many unsaturated bonds and are susceptible to oxidation, evaluating them together with indicators such as peroxide value is useful when considering oxidative deterioration.
Concept of the Wijs Method and Hanus Method
Methods for measuring iodine value include the Wijs method and Hanus method.
In these methods, a halogen is added to the unsaturated bonds in fats and oils, and the amount of unreacted halogen is determined by titration.
The amount of halogen consumed by the fat or oil is calculated from the difference from the blank test and expressed as the iodine value.
Although the reagents used differ depending on the experimental method, the basic concept is to determine the amount of halogen added to the unsaturated bonds.
If the reaction time, dark conditions, or amount of reagent is inappropriate, the addition reaction may be incomplete or side reactions may occur, resulting in errors in the iodine value.
Example Discussion:
In the Wijs method and Hanus method, a halogen is added to the unsaturated bonds in fats and oils, and the amount of unreacted halogen is determined by titration.
The amount of halogen consumed by the fat or oil is calculated from the difference from the blank test and expressed as the iodine value.
If the reaction time or dark conditions are inappropriate, the addition reaction may not proceed sufficiently and the iodine value may be underestimated.
Importance of the Blank Test
In iodine-value measurement, a blank test in which the same reagent procedures are performed without adding the fat or oil sample is necessary.
The blank test determines how much of the initially added halogen reagent is titrated.
In the sample test, halogen is consumed by addition to the unsaturated bonds in the fat or oil, so the amount of remaining halogen is smaller than in the blank test.
The difference between the blank-test and sample-test titration volumes corresponds to the amount of halogen that added to the fat or oil.
Without a blank test, the amount of halogen actually consumed by the fat or oil cannot be accurately determined.
The blank test also serves to correct for changes in reagent concentration and changes occurring during the procedure.
Example Discussion:
A blank test is necessary to determine the amount of halogen reagent under conditions where no fat or oil is added.
In the sample test, halogen adds to the unsaturated bonds in the fat or oil, so the amount of unreacted halogen titrated is smaller than in the blank test.
By using the difference between the blank and sample tests, the amount of halogen consumed by the fat or oil can be determined and the iodine value calculated.
Concept of Sodium Thiosulfate Titration
In iodine-value measurement, unreacted iodine may be titrated with a sodium thiosulfate standard solution.
Iodine, I2, is reduced to iodide ions, I-, by thiosulfate ions, S2O32-.
This reaction is used to determine the amount of iodine remaining.
Near the endpoint of the titration, adding starch indicator causes a blue-violet color to appear because of the iodine-starch reaction.
When sodium thiosulfate is added and the iodine disappears, the blue-violet color disappears, and this point is taken as the endpoint.
Deviations in endpoint determination directly affect the iodine value.
I2 + 2S2O32- → 2I- + S4O62-
Example Discussion:
Unreacted iodine can be quantified by titration with a sodium thiosulfate standard solution.
Because iodine is reduced to iodide ions by thiosulfate ions, the amount of remaining iodine can be determined from the amount of sodium thiosulfate consumed.
By comparing this remaining iodine amount with the blank test, the amount of iodine added to the unsaturated bonds in the fat or oil can be calculated.
Starch Indicator and Endpoint Determination
Starch indicator reacts with iodine to produce a blue-violet color.
In sodium thiosulfate titration, the starch indicator is added after the amount of iodine has become small, and the point at which the blue-violet color disappears is taken as the endpoint.
If starch is added from the beginning, iodine may be strongly retained and the endpoint may become difficult to determine.
If too much sodium thiosulfate is added beyond the endpoint, the amount of remaining iodine cannot be correctly determined.
Near the endpoint, the titrant is added one drop at a time, the solution is thoroughly mixed, and the point at which the blue-violet color completely disappears is confirmed.
Turbidity caused by fats, oils, or solvents may make disappearance of the color difficult to judge.
Example Discussion:
Starch indicator can be used to determine the endpoint of sodium thiosulfate titration because it forms a blue-violet complex with iodine.
At the endpoint, the iodine is consumed and the blue-violet color disappears.
If titration continues beyond the endpoint, the estimate of the remaining iodine amount becomes inaccurate and an error occurs in the iodine-value calculation, so careful titration is necessary near the endpoint.
Effect of Reaction Time
A certain reaction time is required for halogen addition to the unsaturated bonds in fats and oils.
If the reaction time is too short, addition to the unsaturated bonds may not proceed completely and the amount of iodine consumed by the fat or oil may be underestimated.
As a result, the iodine value is determined as too low.
On the other hand, if the reaction time is too long or the reaction is affected by light, side reactions or decomposition of the reagent may occur.
Therefore, it is important to follow the reaction time and dark conditions specified in the laboratory manual.
When comparing multiple samples, the reaction times must be kept consistent.
Example Discussion:
If the reaction time is short, halogen addition to the unsaturated bonds may not proceed sufficiently and the amount of iodine consumed by the fat or oil may be underestimated.
As a result, the iodine value is determined to be lower than the actual value.
Therefore, in iodine-value measurement, it is important to keep the reaction time consistent among samples and allow the reaction to proceed for the specified period in the dark.
Effect of Light and Dark Conditions
Iodine and halogenating reagents may decompose or undergo side reactions when exposed to light.
In addition, oxidation of unsaturated fatty acids may also be promoted by light.
Therefore, iodine-value measurement may specify that the reaction be carried out in the dark.
If dark conditions are not maintained, changes other than the amount of halogen that actually reacted with the fat or oil may affect the titration value.
If the amount of light exposure differs among samples during the reaction, the reliability of comparisons also decreases.
It is important to shield the reaction containers from light and react all samples under the same conditions.
Example Discussion:
Dark conditions are necessary in iodine-value measurement to prevent decomposition and side reactions of the halogenating reagent.
If light is present, the condition of the reagent may change and the titration value may be affected by factors other than the amount added to the unsaturated bonds in the fat or oil.
Therefore, the reaction must be carried out under light-shielded conditions and all samples must be kept under the same reaction conditions.
Effect of Sample Amount
Because iodine value is expressed as the amount of iodine added per 100 g of fat or oil, errors in weighing the sample affect the result.
If the sample mass is recorded as smaller than the actual value, the calculated iodine value becomes higher.
Conversely, if the sample mass is recorded as larger, the calculated iodine value becomes lower.
In addition, if too much fat or oil is used, the reaction reagent may become insufficient or the addition reaction may not proceed completely.
If too little is used, the difference in titration volume becomes small and the effect of reading errors becomes larger.
It is important to accurately weigh the sample amount specified in the laboratory manual.
Example Discussion:
Because iodine value is calculated as a value per 100 g of fat or oil, errors in sample mass directly affect the result.
If a smaller amount of fat or oil is collected but recorded as a larger amount, the iodine value is calculated as too low.
In addition, if too much sample is used, the halogenating reagent may become insufficient and the addition reaction may be incomplete, so the specified sample amount must be accurately weighed.
Causes of Error in Iodine-Value Measurement
Causes of error in iodine-value measurement include errors in weighing the sample, insufficient reaction time, inadequate dark conditions, decomposition of the halogenating reagent, insufficient amount of reaction reagent, errors in endpoint determination, concentration errors in the sodium thiosulfate standard solution, variation in blank-test values, and insufficient dissolution of the fat or oil.
Because the iodine value is determined from the difference from the blank test, even small deviations in titration values have an effect.
Causes that make the value lower include incomplete addition reactions, short reaction times, and insufficient dissolution of the sample.
Causes that make the value higher include side reactions, deviations in endpoint determination, and underestimation of the sample mass.
Organizing the causes of error into overestimation and underestimation makes the discussion easier.
Example Discussion:
Possible causes of error in iodine-value measurement include incomplete halogen addition caused by insufficient reaction time, inadequate dark conditions, errors in the standard-solution concentration, and deviations in endpoint determination.
If the addition reaction is incomplete, the amount of iodine consumed by the fat or oil is underestimated and the iodine value becomes low.
On the other hand, side reactions or underestimation of the sample mass may cause the iodine value to be overestimated.
When the Results Can Be Considered Good
Iodine-value measurements can be considered to have produced good results when the blank-test and sample-test titration values are stable, variation among multiple iodine-value measurements is small, and the results do not contradict the trends expected from the types of fats and oils.
For example, obtaining high iodine values for fats and oils containing large amounts of unsaturated fatty acids and low iodine values for fats and oils containing large amounts of saturated fatty acids can be considered a reasonable trend.
In addition, if the reaction time and dark conditions are followed and the endpoint color can be clearly determined, the reliability of the results increases.
When comparing with literature values, differences caused by variety, place of origin, degree of refining, and storage condition of the fats and oils must also be considered.
Example Discussion:
In this experiment, there was no large variation among the multiple titration values, and the determined iodine values agreed with the trends expected from the types of sample fats and oils.
Because high iodine values were obtained for fats and oils considered to contain large amounts of unsaturated fatty acids, the measurement results were considered to approximately reflect the amount of unsaturated bonds in the fats and oils.
In addition, because the reaction time and dark conditions were kept consistent, the comparison among samples was considered valid.
Example Discussion When the Experiment Did Not Go Well
When iodine-value measurement does not go well, possible causes are considered from results such as variation in titration values, iodine values far from literature values, an excessively small difference from the blank test, difficulty determining the endpoint color, or a nonuniform reaction solution.
Organizing the causes according to sample amount, reaction time, dark conditions, reagent concentration, endpoint determination, and blank testing makes the discussion easier.
Example Discussion:
In this experiment, the determined iodine value was lower than expected.
One possible cause is that the reaction time was too short and halogen addition to the unsaturated bonds did not proceed sufficiently.
In addition, if the fat or oil was not sufficiently dissolved in the reaction solvent, contact with the reagent may have been inadequate and the amount of iodine consumed may have been underestimated.
How to Write Points for Improvement
In a discussion of iodine-value measurement, writing not only the causes of error but also points for improvement makes the report easier to organize.
Points for improvement can be organized according to sample weighing, reaction operation, titration operation, standard solution, and calculation and analysis.
Improvements to Sample and Reaction Operations
- Accurately weigh the fat or oil sample
- Completely dissolve the fat or oil in the reaction solvent
- Add the reaction reagent accurately
- Follow the specified reaction time
- Maintain dark conditions during the reaction
- Keep the reaction conditions consistent for all samples
- Use the specified sample amount so that the reagent does not become insufficient
Improvements to Titration Operations
- Confirm the concentration of the sodium thiosulfate standard solution
- Perform the blank test under the same conditions
- Remove air bubbles from the burette
- Read the scale at eye level
- Add the starch indicator at the appropriate time
- Add the titrant one drop at a time near the endpoint
- Carefully confirm disappearance of the blue-violet color
Improvements to Calculation and Analysis
- Correctly use the difference between the blank-test and sample-test titration volumes
- Accurately reflect the sample mass
- Confirm the units of the iodine value
- Correctly convert the value to an amount per 100 g
- Perform multiple measurements and calculate the average value
- Compare with literature values and other fats and oils
- Distinguish the meanings of iodine value, saponification value, acid value, and peroxide value
Example of How to Write Points for Improvement:
To improve the accuracy of iodine-value measurement, the fat or oil sample must be accurately weighed and sufficiently dissolved in the reaction solvent before the halogenating reagent is added.
In addition, it is important to follow the specified reaction time and dark conditions and allow the addition reaction to the unsaturated bonds to proceed sufficiently.
During titration, the blank test must be performed under the same conditions, and near the endpoint sodium thiosulfate should be added one drop at a time while carefully confirming disappearance of the blue-violet color.
Difference Between a Superficial Discussion and a Good Discussion
In a discussion of iodine-value measurement of fats and oils, simply writing that “the iodine value was high” or “the degree of unsaturation was high” results in a superficial discussion.
A good discussion relates the addition reaction to unsaturated bonds, susceptibility to oxidation, drying properties, blank testing, endpoint determination, and causes of error.
| Superficial Discussion | Good Discussion |
|---|---|
| The iodine value was high. | Because the iodine value was high, the fat or oil was considered to contain a large amount of unsaturated fatty acids with carbon-carbon double bonds. This is because the more unsaturated bonds are present, the more halogen can add. |
| It is easily oxidized. | Unsaturated bonds readily react with oxygen, and particularly in polyunsaturated fatty acids, oxidation readily produces peroxides and decomposition products. Therefore, fats and oils with high iodine values tend to be susceptible to oxidative deterioration. |
| A blank test was performed. | The blank test is an operation in which the amount of unreacted halogen is determined without adding fat or oil, and the amount of halogen added to the unsaturated bonds in the fat or oil can be calculated from the difference from the sample test. |
| The value deviated. | The deviation in the measured value may have resulted from insufficient reaction time, inadequate dark conditions, insufficient dissolution of the fat or oil, errors in the standard-solution concentration, deviations in endpoint determination, or variation in the blank test. |
Examples of Expressions That Can Be Used in Reports
The following expressions can be used when writing the results and discussion of iodine-value measurements of fats and oils.
Adjust the necessary parts according to your own experimental results.
- The iodine value is the number of grams of iodine that add to 100 g of fat or oil.
- The iodine value is an indicator of the amount of unsaturated bonds in fats and oils.
- Halogens add to the double bonds of unsaturated fatty acids.
- Fats and oils with higher iodine values are considered to contain larger amounts of unsaturated fatty acids.
- Fats and oils with lower iodine values may contain higher proportions of saturated fatty acids.
- Fats and oils containing many unsaturated bonds are susceptible to oxidation and tend to deteriorate during storage.
- Fats and oils with high iodine values tend to show the properties of drying oils.
- Iodine value indicates the degree of unsaturation and has a different meaning from saponification value and acid value.
- The amount of iodine added to the fat or oil is determined from the difference between the blank-test and sample-test titration volumes.
- Insufficient reaction time and inadequate dark conditions are causes of error in iodine-value measurement.
Points to Check When Discussing the Iodine Value of Fats and Oils
Checking the following points before writing the report makes the discussion easier to write.
- Is the definition of iodine value explained?
- Is iodine addition to unsaturated bonds explained?
- Is the relationship between iodine value and degree of unsaturation described?
- Are the characteristics of fats and oils with high and low iodine values explained?
- Is the relationship with susceptibility to oxidation considered?
- Is the relationship with drying oils, semi-drying oils, and non-drying oils considered?
- Are the differences from saponification value, acid value, and peroxide value distinguished?
- Is the meaning of the blank test explained?
- Is the sodium thiosulfate titration reaction understood?
- Are the starch indicator and endpoint determination explained?
- Are the effects of reaction time and dark conditions considered?
- Do the points for improvement correspond to the causes of error?
Summary
The iodine value of fats and oils is the number of grams of iodine that add to 100 g of fat or oil and is an indicator of the amount of unsaturated bonds contained in fats and oils.
Because iodine and other halogens add to the carbon-carbon double bonds of unsaturated fatty acids, fats and oils containing more double bonds have higher iodine values.
Conversely, fats and oils containing large amounts of saturated fatty acids have lower iodine values.
Fats and oils with high iodine values have high degrees of unsaturation and tend to be susceptible to oxidation.
Unsaturated bonds readily react with oxygen, and during storage they may produce peroxides and decomposition products, leading to deterioration of odor and taste.
Iodine value also provides a clue for considering the properties of drying oils, semi-drying oils, and non-drying oils.
In a report, rather than simply writing that “the iodine value was high or low,” organize and discuss the addition reaction to unsaturated bonds, susceptibility to oxidation, drying properties, blank testing, sodium thiosulfate titration, starch indicator, reaction time, dark conditions, causes of error, and points for improvement.
Iodine value is an important analytical value for understanding the relationship between the structure and properties of fats and oils.
