Test for Aldehyde/Ketone

Course no. Chem 222/ 122

Course Name: Organic Chemistry Sessional

Department of Chemistry
Bangladesh University of Engineering & Technology (BUET)

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 Aldehyde/Ketone
Aldehydes and Ketones are compounds containing carbonyl group. Carbonyl group consisting of a
carbon atom bonded to oxygen atom by a double bond.

In Aldehydes the carbonyl carbon is attached to atleast one hydrogen atom and to a carbon
containing group (aliphatic or aromatic). Formaldehyde is an exception, in which carbonyl group is
attached to two hydrogen atoms.

But in ketones the carbonyl carbon is attached to two aliphatic or aromatic groups.

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Examples of Aldehyde/Ketone

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 Physical Properties

 The carbon-to-oxygen double bond is quite polar, more polar than a carbon-to-
oxygen single bond.
 The electronegative oxygen atom has a much greater attraction for the bonding
electron pairs than does the carbon atom.
 The carbon atom has a partial positive charge, and the oxygen atom has a partial
negative charge:

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 Physical Properties

 In aldehydes and ketones, charge separation leads to dipole-dipole interactions

 Dipole-dipole interactions significantly affect the boiling points
 Formaldehyde is a gas at room temperature. Acetaldehyde boils at 20°C; in an open
vessel, it boils away in a warm room
 Most other common aldehydes are liquids at room temperature
 Although the lower members of the homologous series have pungent odors, many
higher aldehydes have pleasant odors and are used in perfumes and artificial
flavorings

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 Physical Properties
The oxygen atom of the carbonyl group engages in hydrogen bonding with a water molecule.

The solubility of aldehydes is therefore about the same as that of alcohols and ethers.
Formaldehyde, acetaldehyde, and acetone are soluble in water. As the carbon chain
increases in length, solubility in water decreases. All aldehydes and ketones are soluble in
organic solvents and, in general, are less dense than water.

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 Physical Properties
Aldehydes are readily oxidized to carboxylic acids, whereas ketones resist oxidation. They are even
oxidized by oxygen (O2) in air to carboxylic acids.

The ease of oxidation helps chemists to identify aldehydes. A sufficiently mild oxidizing
agent can distinguish aldehydes not only from ketones but also from alcohols.
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 Identification Tests
Identification of aldehydes and ketones is based on two types of reactions, addition reaction
to the double bond and oxidation reaction. You will perform the following tests to identify
the presence of these functional groups:
1. Solubility test in water
2. Solubility in NaOH
3. Iodine in KI test
4. Acidified K2Cr2O7 (Jones reagent) test
5. 2,4-dinitrophenyl hydrazine (2,4-DNPH) test
6. Tollen’s reagent test
7. Fehling’s solution test
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 Solubility in Water
Procedure: To about 0.5 cm3 of the sample add one or two drops of distilled water, then add
a further 3 cm3 approximately. Note the solubility in cold water.

If the substance is soluble in water, you will see a clear solution with no separate layers. If it
is insoluble, you will see separate layers or a cloudy solution or solid residue. Record your
observations.

Aldehydes and ketones are soluble in water, but their solubility decreases with increase in
chain length.

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 Solubility in NaOH
Procedure: To about 0.5 cm3 of the test sample in a test tube add about 5 cm3 of NaOH
solution dropwise and boil gently.
 If a compound does not dissolve in water but does dissolve in NaOH(aq) then it must be
reacting with the NaOH
 The solubility of aldehydes and ketones in aqueous NaOH depends upon the overall
polarity of the aldehyde or ketone molecule rather than on a reaction with sodium
hydroxide to make it soluble
 The presence of NaOH in the water won’t make much of a difference to the solubility of
these types of materials if there is no chemical reaction that takes place between the
chemical and the sodium hydroxide
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 Iodine in KI (Iodoform) Test
Iodoform reaction: A chemical reaction in which a methyl ketone is oxidized to a
carboxylate by reaction with aqueous HO- and I2. The reaction also produces
triiodomethane/ iodoform (CHI3), a yellow solid which may precipitate from the reaction
mixture in acetone.

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 Iodine in KI (Iodoform) Test
Procedure:
 To about 0.5 cm3 of the test sample add about 2 cm3 of Iodine in Potassium
Iodide solution
 Add NaOH solution dropwise until the colour of the iodine is almost discharged
 Warm the mixture in a water bath for 2-3 minutes. Then cool the test sample and
observe for any color change.
Observation and inference: A yellow precipitate along with an “antiseptic” smell
indicates the presence of methyl ketone group in the test sample.
Note: a false positive result may occur if the test tube was cleaned with acetone
before use, and residual acetone remained in the tube.
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Iodine in KI (Iodoform) Test

The yellow precipitate confirms the presence of

the methyl ketone moiety in acetophenone.
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 Iodine in KI (Iodoform) Test
If the sample is not water soluble, a small organic layer separate from the solution may be
seen (it will likely be on top). This layer may become dark yellow or brown from dissolving
the iodine. Vigorously mix the tube to encourage a reaction, but if the darkened organic layer
remains and no precipitate forms, this is still a negative result.

c) Positive result, d) Negative

result when the sample is insoluble
in the reagent.

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 Iodine in KI (Iodoform) Test
A positive result will be obtained for an aldehyde or ketone containing the following group:

"R" can be a hydrogen atom or a hydrocarbon group (for example, an alkyl group). If "R" is
hydrogen, then you have the aldehyde acetaldehyde or ethanal, CH3CHO.
 Acetaldehyde is the only aldehyde to give the iodoform reaction
 If "R"is a hydrocarbon group, then you have a ketone. Lots of ketones give this reaction,
but those that do all have a methyl group on one side of the carbon-oxygen double bond.
These are known as methyl ketones.
Note: Other substances that yield methyl ketones by oxidation also give a positive iodoform
test 15
 2,4-DNPH Test (Brady’s Test)
 2,4-dinitrophenyl hydrazine (a substituted hydrazine) can be used to qualitatively detect
the carbonyl group of an aldehyde or ketone
 Most aldehydes or ketones will react with the orange reagent to give a red, orange, or
yellow precipitate
 Esters, acids and amides are generally not reactive enough to give a positive result for
this test, because there is resonance-associated stability as a lone-pair of electrons
interacts with the p orbital of the carbonyl carbon resulting in increased delocalization in
the molecule.

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 2,4-DNPH Test
Procedure:
 Take few drops of the test sample in a test tube
 If the compound is solid then dissolve small amount of the sample in ethanol in a test
tube
 Add few drops of alcoholic solution of 2,4-DNPH to the sample
 Shake the mixture and observe for any color change/precipitate formation in the test
tube

Observation and inference: Formation of orange precipitate will indicate the presence of
carbonyl group in the test sample.
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2,4-DNPH Test

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Observation of 2,4-DNPH Test

b) Negative result, c) Positive result from a non-conjugated

carbonyl, d) Positive result from a conjugated carbonyl. 19
Differentiating Tests for Aldehyde/Ketone
The major difference between aldehydes and ketones is that an aldehyde is readily
oxidized to carboxylic acid whereas ketones cannot be oxidized easily. This difference
forms the basis of the tests for distinguishing aldehydes and ketones.

The following are the positive tests for aldehydes but not for ketones:
1. Tollen’s reagent test
2. Fehling’s solution test
3. Jones reagent test

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 Tollen’s Reagent Test

 This test is also called the silver mirror test

 Tollen’s reagent consists of silver ammonia complex in ammonia solution
(Ammoniacal silver nitrate)
 Aldehydes react with Tollen’s reagent to form elemental silver, accumulated onto the
inner surface of the reaction vessel, producing silver mirror on the inner surface of
the vessel.

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 Tollen’s Reagent Test
Procedure:
 Take few drops of the test sample in a test tube
 Add 4-5 drops of freshly prepared Tollen’s reagent to the test tube
 Warm the test tube in a water bath for about 5 to 10 minutes
 Observe for any change in the test tube

Observation and inference: Appearance of a silver mirror in the sides of the test tube
conforms the presence of an aldehyde.

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 Tollen’s Reagent Test
Aldehydes are oxidized to the corresponding acid and silver in Tollen’s reagent is reduced
from +1 oxidation state to its elemental form. Generally ketones do not respond to this test.

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 Observation

(left to right) 2-pentanone (negative), isobutyraldehyde,

benzaldehyde (positive).
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 Fehling’s Solution Test
 The reagents used in this test are Fehling’s solution A and Fehling’s solution B
 Fehling’s solution A is an aqueous solution of copper sulphate
 Fehling’s solution B is a clear solution of sodium potassium tartrate (Rochelle salt)
and strong alkali (usually NaOH)
 The final Fehling’s solution is obtained by mixing equal volumes of both Fehling’s
solution A and Fehling’s solution B that has a deep blue colour
 In Fehling’s solution, copper (II) ions form a complex with tartrate ions in alkali.
When aldehyde compound is treated with Fehling’s solution Cu2+ is reduced to Cu+
and the aldehyde is reduced to acid. During the reaction, a red precipitate is formed.

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 Fehling’s Solution Test
Procedure:
 Mix 1 cm3 of Fehling’s solution (I) with an equal volume of Fehling’s solution (II) in a
test tube
 Add 4-5 drops of the test sample to the test tube
 Warm the mixture gently in a water bath and observe for any change

Observation and Inference:

 Appearance of a brick-red precipitate indicates the presence of aldehyde group in the
test sample
 Benzaldehyde may or may not give this test. Aromatic aldehydes do not respond to
Fehling’s test. 26
Fehling’s Solution Test

Negative Positive

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Fehling’s Solution Test

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 Jones Reagent Test
 A solution of K2Cr2O7 or CrO3 in H2SO4 is termed as Jones reagent. It is named after its
discoverer, Sir Ewart Jones
 This test distinguishes aldehydes from ketones
 It is a potent oxidizing agent which rapidly oxidizes aldehydes to carboxylic acids
 Aldehydes react with the yellow-orange Jones reagent containing a Cr (VI) atom. Over
the course of the organic oxidation, the Cr is reduced to Cr (III)
 The orange-yellow Jones reagent will immediately turn green in the presence of
aldehyde
 Ketones do not react with Jones reagent.

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 Jones Reagent Test
Procedure:
 To 5 drops of the test sample add 10 drops of dill H2SO4 and 5 drops of K2Cr2O7
 Warm the mixture and note the colour and odour of the product

Observation and inference: Formation of blue-

green or dark solution indicates the presence of
aldehyde in the test sample.

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 Jones Reagent Test
The orange Cr6+ reagent converts to blue green Cr3+ species, which often precipitates in
acetone

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