KMnO₄ Test (Baeyer's Test): Oxidation Test for Unsaturation

The KMnO₄ Test, also known as Baeyer’s test, is a classical chemical test used in organic chemistry to identify certain functional groups in organic compounds.

It utilizes potassium permanganate (KMnO₄), a strong oxidizing agent, to detect unsaturation (carbon–carbon double bonds) and aldehydes.

A positive reaction is indicated by the disappearance of the purple color of KMnO₄ and the formation of a brown precipitate of manganese dioxide (MnO₂). This simple reaction serves as an effective qualitative test in laboratories and educational settings.

Test tubes representing KMnO₄Test and indicating positive test by formation of brown precipitates.

Principle of KMnO₄ Test

The KMnO₄ test is based on the oxidizing ability of potassium permanganate. In alkaline medium, KMnO₄ oxidizes organic compounds and is reduced from Mn⁷⁺ (purple) to Mn⁴⁺ (brown precipitate, MnO₂).

Alkenes: Double bonds are oxidized to vicinal diols.
Aldehydes: Oxidized to carboxylic acids.

The key observation is the fading of the purple color of KMnO₄ accompanied by the formation of a brown precipitate, indicating the oxidation of the organic substrate. Saturated compounds generally do not react, so the purple color remains unchanged.

Oxidation States of KMnO₄ and Corresponding Colors

Oxidation state of Mn	Chemical Species	Color in Solution	Solution
+7	Permanganate (MnO₄⁻)	Purple/ violet	Original KMnO₄ solution
+6	Manganate (MnO₄²⁻)	Green	Intermediate in alkaline medium
+5	MnO₄³⁻	Blue	Very unstable
+4	MnO₂	Brown/ Black precipitate	Oxidation product
+2	Mn²⁺	Colorless / Pale Pink	End product in acidic conditions

In the KMnO₄ test, the most common reduction observed is Mn⁷⁺ → Mn⁴⁺, which corresponds to the purple to brown color change.

Conical flasks representing the colours of KMnO4 reduction states with their structures.

Chemical Reactions and Functional Groups

1. Alkene Oxidation

Ethene reacts with KMnO₄ in alkaline solution:

Color change: Purple → Brown precipitate
Oxidation state change: Mn⁷⁺ → Mn⁴⁺

Redox reaction representing the colour and state change upon alkene reaction with alkaline KMnO4

Similarly if cinnamic acid reacts with KMnO₄, it’s (C-C) double bond part get oxidized forming Diol and KMnO₄ (purple) reduce to MnO₂ (Brown ppt) .

Redox reaction with KMnO4 test representing cinnamic acid ( Double bond ) oxidation to diol.

2. Aldehyde Oxidation

Benzaldehyde oxidation by KMnO₄:

Color change: Purple → Colorless or Brown
Oxidation state change: Mn⁷⁺ → Mn⁴⁺

Redox reaction of benzaldehyde with KMnO4, oxidized to carboxylic acid.

Behavior of KMnO₄ in Different Media

Medium	Reaction	Observation	Oxidation State Change	Example
Acidic	Strong oxidizing agent; reacts with most reducing agents, aldehydes, and some metals.	KMnO₄ (purple) → Mn²⁺ (colorless/pale pink)	Mn⁷⁺ → Mn²⁺	Oxidation of Fe²⁺ to Fe³⁺; aldehyde → acid
Basic / Alkaline	Reacts with alkenes, aldehydes, and some other oxidizable organic compounds. Forms diols from alkenes.	KMnO₄ (purple) → MnO₂ (brown precipitate)	Mn⁷⁺ → Mn⁴⁺	Ethene → ethane-1,2-diol; benzaldehyde → benzoic acid
Neutral / Nutrient Solution	Reacts slowly or selectively with oxidizable compounds; often used in biological or aqueous systems to test mild oxidation.	KMnO₄ (purple) may fade slowly; sometimes brown MnO₂ forms	Mn⁷⁺ → Mn⁴⁺ (slow)	Mild oxidation of glucose or alcohols in aqueous solution

Explanation:

Acidic medium: KMnO₄ is a very strong oxidizer and is reduced completely to Mn²⁺, commonly used in titrations (permanganometry).
Alkaline medium: KMnO₄ oxidizes alkenes to diols or aldehydes to acids, forming MnO₂ as a brown precipitate; this is the basis of the Baeyer test.
Neutral / aqueous (nutrient solution): Oxidation occurs slowly and selectively, useful in mild reactions or biological/aqueous systems.

Materials and Reagents

Potassium permanganate solution (1–2% aqueous)
Sodium carbonate (alkaline medium)
Organic sample
Test tubes and droppers

Step-by-Step Procedure

For alkaline medium

Dissolve a small amount of the organic compound in water or aqueous ethanol.
Prepare an alkaline KMnO₄ solution using sodium carbonate.
Add KMnO₄ solution dropwise to the sample.
Shake gently and observe any color change.

Test tubes representing the procedure of KMnO4 test in alkaline medium resulting in brown ppt of MnO2.

For acidic medium

Dissolve a small amount of the organic compound in water or aqueous ethanol.
Prepare an acidic KMnO₄ solution using sulfuric acid.
Add KMnO₄ solution dropwise to the sample.
Shake gently and observe any color change.

Test tubes representing KMnO4 test in acidic medium resulting in colourless/pale pink Mn2+.

Observation and Interpretation

Purple → Brown/Colorless	Positive KMnO₄ test; unsaturation or aldehyde present.
Purple remains	Negative KMnO₄ test; no reaction.

Example of Positive results:

Alkenes: Rapid decolorization with brown MnO₂ formation.
Aldehydes: Gradual decolorization as aldehydes oxidize to carboxylic acids.

Comparison of Bromine Water Test and KMnO₄ Test

Feature	Bromine Water Test (Br₂/H₂O)	KMnO₄ Test (Baeyer Test)
Purpose	Detects unsaturation (C=C, C≡C) in organic compounds	Detects unsaturation (C=C) and oxidizable functional groups (aldehydes, alcohols)
Reaction Type	Electrophilic addition across double/triple bonds; substitution with activated aromatics (phenols, anilines)	Oxidation: Alkenes → diols; Aldehydes → carboxylic acids
Observation	Bromine color (brownish-red) disappears if double/triple bond present	Purple KMnO₄ decolorizes; brown MnO₂ precipitate forms
Reactivity with Aromatics	Activated aromatics undergo electrophilic substitution	Aromatics generally do not react under normal conditions
Medium Required	Usually neutral or slightly aqueous	Alkaline medium for unsaturation; acidic medium for strong oxidation
Example Reaction	Ethene + Br₂ → 1,2-dibromoethane Phenol + Br₂ → 2,4,6-tribromophenol	Ethene + KMnO₄ → ethane-1,2-diol Benzaldehyde + KMnO₄ → benzoic acid

Precautions

Use freshly prepared KMnO₄ solution.
Maintain alkaline conditions.
Avoid contamination with other oxidizable substances.
Handle KMnO₄ with care; it is a strong oxidizing agent.

Applications

Educational Laboratories: Detect unsaturation and aldehydes in organic samples.
Research & Industry: Preliminary functional group analysis.
Organic Synthesis: Confirm presence of C=C bonds.

Multiple Choice Questions

MCQ 1

1. What is the oxidation state of manganese in potassium permanganate?

A. +2

B. +4

C. +6

D. +7

MCQ 2

2. What forms on a positive Tollens Test?

A. Mn²⁺

B. MnO₂

C. MnO₄²⁻

D. MnO₄³⁻

MCQ 3

3. A positive KMnO₄ test with an organic compound indicates:

A. Saturated hydrocarbon

B. Unsaturation or aldehyde

C. No reaction

D. Aromatic ring

MCQ 4

4. KMnO₄ is reduced from Mn⁷⁺ to:

A. Mn²⁺

B. Mn³⁺

C. MnO₂

D. MnO₄²⁻

MCQ 5

5. KMnO₄ test is performed in:

A. Acidic medium

B. Neutral only

C. Alkaline medium

D. Any medium

MCQ 6

6. A compound that does not decolorize KMnO₄ is:

A. Ethene

B. Benzaldehyde

C. Hexane

D. 1‑butene

Viva questions

What is the KMnO₄ (Baeyer) test used for?
Why does the purple color of KMnO₄ disappear in a positive test?
What product indicates a positive KMnO₄ test?
How does KMnO₄ oxidize alkenes?
What reagent is used to make KMnO₄ alkaline?
How do you differentiate between saturated and unsaturated hydrocarbons using KMnO₄?
What happens to aldehydes when treated with KMnO₄?
Why must the KMnO₄ solution be fresh?
What observation confirms a negative KMnO₄ test?
Why is the test carried out in alkaline rather than acidic medium?

FAQ’s

Primary alcohols can be oxidized to aldehydes and further to carboxylic acids, while secondary alcohols form ketones. Tertiary alcohols generally do not react under mild KMnO₄ conditions, so no decolorization occurs.

Alkaline medium stabilizes the formation of diols from alkenes and prevents rapid decomposition of KMnO₄, ensuring a visible and controlled color change.

Alkenes react with KMnO₄ to form a cyclic manganate ester intermediate, which hydrolyzes to form a vicinal diol while reducing Mn⁷⁺ to Mn⁴⁺ (MnO₂).

Aldehydes are oxidized by KMnO₄ to carboxylic acids, resulting in decolorization of the purple solution and formation of MnO₂ precipitate, whereas most ketones do not react under similar conditions.

The brown precipitate (MnO₂) confirms the reduction of Mn⁷⁺ to Mn⁴⁺, providing direct evidence of oxidation of the organic substrate.

Yes, electron-rich aromatic compounds such as stilbene derivatives undergo oxidation at the double bonds, forming diols or carboxyl derivatives, indicated by purple to brown color change.

Higher KMnO₄ concentrations can cause over-oxidation and may mask subtle differences between reactive functional groups, while too dilute solutions may not show a visible color change, reducing sensitivity.

Saturated hydrocarbons lack reactive π-electrons, so the strong oxidizing agent KMnO₄ does not react under mild conditions, keeping the solution purple.

By titrating a known volume of KMnO₄ against the compound and measuring the amount consumed for complete decolorization, one can calculate the number of double bonds per molecule.

Conclusion

The KMnO₄ Test is an effective and rapid qualitative method for detecting carbon–carbon unsaturation in alkenes and alkynes. The test operates through oxidative decolourisation of purple potassium permanganate to brown manganese dioxide, providing a clear visual indication of unsaturation. It remains a fundamental tool in organic chemistry for preliminary analysis and identification of unsaturated compounds.

References

Vogel, A. I. Vogel’s Textbook of Practical Organic Chemistry, 5th Edition, Longman, 1989, pp. 345–348.
Furniss, B. S., Hannaford, A. J., Smith, P. W. G., & Tatchell, A. R. Vogel’s Textbook of Practical Organic Chemistry, 5th Edition, Prentice Hall, 1989, pp. 343–347.
Mendham, J., Denney, R. C., Barnes, J. D., & Thomas, M. J. K. Vogel’s Textbook of Quantitative Chemical Analysis, 6th Edition, Pearson, 2000, pp. 456–458.
Ahluwalia, V. K., & Aggarwal, R. Comprehensive Practical Organic Chemistry, Universities Press, 2000, pp. 231–233.

The Oxidation Trick of KMnO₄ Test: Seeing Unsaturation Happen

Principle of KMnO₄ Test

Oxidation States of KMnO₄ and Corresponding Colors