Tests for Aldehydes and Ketones - Organic Compounds Testing

Content Overview

• Purpose
• Concept
• 2,4-Dinitrophenylhydrazine Examination
• Sodium Bisulphite (NaHSO ₃ )- Examination
• Schiff’s Test
• Fehling’s Examination
• Tollen’s Examination
• Chromic Acid Test
• Sodium Nitroprusside Examination
• Required Materials
• Equipment Setup
• Procedure for aldehydes and ketones test
• Findings
• Results and Analysis

Purpose:

The goal is to identify the existence of aldehydes or ketones functional group in a provided organic compound.

Concept:

Aldehydes and ketones of small molecular weights are volatile compounds. The identification of these compounds is based on two types of reactions, the addition reaction to the double bond and the oxidation reaction .

In aldehydes, the carbonyl group is connected to a hydrogen atom and an aliphatic or aromatic group. Formaldehyde is an exception where the carbonyl present in formaldehyde is attached to two hydrogen atoms. In ketones, the carbonyl group is attached to two aliphatic or aromatic groups.

Further Reading: Viva Questions for Aldehydes and Ketones Tests

The following tests are used to identify the presence of aldehydes and ketones.

1. 2,4-dinitrophenylhydrazine test
2. Sodium bisulphite examination

The difference between a ketone and an aldehyde lies in the carbonyl group. The carbonyl group present in aldehydes is easily oxidised to carboxylic acids , whereas the carbonyl group in ketones is not easily oxidised. This difference in reactivity forms the basis for distinguishing between aldehydes and ketones. They are generally differentiated by the following tests.

1. Schiff’s examination
2. Fehling’s test
3. Tollen’s examination
4. Chromic acid test
5. Sodium nitroprusside examination

(a) 2,4-Dinitrophenyl Hydrazine Examination:

Aldehydes and ketones react with 2,4-dinitrophenylhydrazine to produce an orange-yellow precipitate.

The chemical reaction is outlined below.

Note: The formation of orange-yellow crystals indicates the presence of a carbonyl group.

(b) Sodium Bisulphite (NaHSO ₃ )Examination:

Aldehydes and ketones combine with sodium bisulphite to form well-crystallized water-soluble products known as “aldehyde bisulphite” and “ketone bisulphite”.

The chemical reaction is outlined below.

Note: The formation of a crystalline precipitate confirms the presence of a carbonyl group.

Distinguishing Examinations between Aldehydes and Ketones:

(c) Schiff’s Examination:

Schiff’s reagent is prepared by passing sulphur dioxide into a solution of the dye fuchsin. The solution becomes colourless due to the formation of an additional product. Aldehydes abstract sulphurous acid from Schiff’s reagent and restore the pink colour. The colouration is due to the formation of a complex compound. Ketones, in general, do not respond to this reaction.

The reaction should not be subjected to heat. Some ketones give a light pink colour with Schiff’s reagent therefore light pink colour formation is not a positive test.

Note: Appearance of pink, red or magenta colour indicates the presence of aldehyde group.

(d) Fehling’s Examination:

Fehling’s solution is a complex compound of Cu ²⁺ . When the aldehyde compound is treated with Fehling’s solution Cu ²⁺ is reduced to Cu ⁺ and the aldehyde is reduced to acids. During the reaction, a red precipitate is formed.

Aromatic aldehydes do not respond to Fehling’s examination. An aqueous solution of the compound may be used instead of an alcoholic solution. Formic acid also gives this test.

Note: The appearance of red precipitate confirms the presence of an aldehydic group.

(e) Tollen’s Examination: (Silver Mirror Test)

This examination is also known as the silver mirror test. Tollens reagent consists of silver ammonia complex in ammonia solution. Aldehydes react with Tollens reagent giving a grey-black precipitate or a silver mirror. Always a freshly prepared Tollen’s reagent should be used. Aldehydes are oxidised to the corresponding acids, and silver in Tollens reagent is reduced from +1 oxidation state to its elemental form. Generally, ketones do not respond to this test.

RCHO + 2[Ag(NH ₃ ) ₂ ]OH → R-COONH ₄ + 3NH ₃ + H ₂ O + 2Ag↓(silver mirror)

Apart from aldehydes some other compounds also respond to Tollen’s test, but the presence of aldehydes is confirmed when the given substance shows a positive test for Tollen’s test, but if the given compound passes 2,4-dinitrophenylhydrazine test.

Note: The appearance of a shiny silver mirror confirms the presence of aldehydes.

(f) Chromic Acid Examination:

Aldehydes react with chromic acid and yields a green to blue precipitate. Ketones do not react with chromic acid. Some of the primary and secondary alcohols also give this test but they do not give the dinitrophenylhydrazine test.

The chemical reaction is given below.

R-CHO + 2CrO ₃ + 3H ₂ SO ₄ → 3R-C(O)-OH + 3H ₂ O + Cr ₂ (SO ₄ ) ₃ (green colour)

Note: The appearance of green or blue colour precipitate confirms the presence of aldehydes.

(g) Sodium Nitroprusside Examination:

Ketone responds to this examination. Ketone reacts with alkali and forms an anion which further reacts with sodium nitroprusside and forms a coloured complex ion. Aldehydes do not respond to this test.

The chemical reaction is given below.

CH ₃ COCH ₃ + OH ^– → CH ₃ COCH ₂ ^– + H ₂ O

[Fe(CN) ₅ NO] ^2- + CH ₃ COCH ₂ ^– → [Fe(CN) ₅ NO.CH ₃ COCH ₂ ] ^3-

Note: The appearance of red colouration shows the presence of ketone.

Required Materials:

1. Schiff’s reagent
2. Silver nitrate solution
3. Fehling’s solutions A
4. Fehling’s solutions B
5. Dilute ammonium hydroxide solution
6. 2,4-Dinitrophenylhydrazine reagent
7. Chromic acid
8. Sulphuric acid
9. Sodium bisulphite
10. Test tubes
11. Test tube holder
12. Beaker

Equipment Setup:

Procedure for aldehydes and ketones test:

(a) 2,4-Dinitrophenyl Hydrazine Examination:

1. Dissolve the provided organic compound in ethanol.
2. To this solution, add an alcoholic solution of 2,4-dinitrophenyl hydrazine.
3. Shake the mixture well.
4. If there is a formation of yellow to orange precipitate then the given compound is an aldehyde or ketone.
5. An orange precipitate is obtained from carbonyl compounds in which the C=O groups are conjugated with C=C.

(b) Sodium Bisulphite Examination:

1. Take a saturated solution of sodium bisulphite in a clean test tube.
2. Add 1ml of the given organic compound to be tested.
3. Shake well and leave it for 15-20 minutes.
4. If there is a formation of white precipitate, then the presence of the carbonyl group is confirmed.

(c) Schiff’s Examination:

1. Take the given organic compound to be tested in a clean test tube.
2. Add 2-3 drops of Schiff’s reagent.
3. If there is instant pink or red colour formation then the presence of aldehyde is confirmed.

(d) Fehling’s Examination:

1. Fehling’s solution is prepared by mixing equal amounts of Fehling’s A and Fehling’s B solution.
2. Take the given organic compound in a clean test tube.
3. Add Fehling’s solution to it and heat the solution gently.
4. If a brick-red precipitate appears, then the presence of aldehyde is confirmed.

(e) Tollen’s Examination: (Silver Mirror Test)

1. Take 1ml of silver nitrate solution in a clean test tube.
2. Add dilute sodium hydroxide solution to it, and a brown precipitate forms.
3. Add dilute ammonia solution dropwise till the brown precipitate of silver oxide dissolves.
4. To this freshly prepared Tollen’s reagent, add the given organic compound to be tested.
5. Place the test tube in a warm water bath for about 5 to 10 minutes.
6. If there is the appearance of a silver mirror on the sides of the test tube confirms the presence of an aldehyde.

(f) Chromic Acid Examination:

1. Take the given organic compound in a clean test tube.
2. Add 1ml of chromic acid reagent to the given organic compound.
3. The appearance of a green or blue colour precipitate indicates the presence of aldehydes.

(g) Sodium Nitroprusside Examination:

1. Dissolve sodium nitroprusside in distilled water in a clean test tube.
2. Add 1ml of the given organic compound to be tested.
3. Shake well and add sodium hydroxide solution dropwise.
4. If there is the appearance of red colour then the presence of ketone is confirmed.

Findings:

2,4-Dinitrophenyl Hydrazine Examination	The formation of orange-yellow crystals indicates the presence of the carbonyl group
Sodium Bisulphite Examination	The formation of crystalline precipitate confirms the carbonyl group.
Schiff’s Examination	The appearance of pink, red or magenta colour indicates the presence of the aldehyde group.
Fehling’s Examination	The appearance of red precipitate confirms the presence of an aldehydic group.
Tollen’s Examination (Silver Mirror Test)	The appearance of a shiny silver mirror confirms the presence of aldehydes.
Chromic Acid Examination	The appearance of green or blue colour precipitate confirms the presence of aldehydes.
Sodium Nitroprusside Examination	The appearance of red colouration shows the presence of ketone.

Results and Analysis:

The provided organic compound has ___________ (aldehyde/ketone) functional group.

Safety Precautions:

1. The reagents should be freshly prepared to perform the test.
2. Do not directly heat the reaction mixture on the flame.
3. After performing the Tollen’s examination, wash the test tube with nitric acid to destroy the silver mirror, because it’s an explosive substance.