EXPERIMENT 5

CARBONYL COMPOUNDS - REACTIONS OF ALDEHYDES AND KETONES

OBJECTIVE:

To investigate the reaction of aldehydes and ketones with certain reagents.

PRE LAB ASSIGNMENT:

1. Give a common structure for aldehydes and ketones.

2. What is the difference in the structure of aldehydes compared to ketones?

- The difference in the structure of aldehydes compared to ketones are the position of
the carbonyl group.

3. Draw the structures for methanal, butanal and butanone.

Methanal Butanal Butanone

4. Give an example for each of the following:
(i) Nucleophile
- Methyl magnesium bromide

(ii) Electrophile
- Methyl carbocation
INTRODUCTION:

Aldehydes and ketones are simple compounds which contain a carbonyl group - a carbon-
oxygen double bond. They are simple in the sense that they don't have other reactive groups
like -OH or -Cl attached directly to the carbon atom in the carbonyl group - as you might
find, for example, in carboxylic acids containing -COOH.

In aldehydes, the carbonyl group has a hydrogen atom attached to it together with either a
second hydrogen atom or, more commonly, a hydrocarbon group which might be an alkyl
group or one containing a benzene ring.

In ketones, the carbonyl group has two hydrocarbon groups attached. Again, these can be
either alkyl groups or ones containing benzene rings.

The slightly positive carbon atom in the carbonyl group can be attacked by nucleophiles. A
nucleophile is a negatively charged ion (for example, a cyanide ion, CN-), or a slightly
negatively charged part of a molecule (for example, the lone pair on a nitrogen atom in
ammonia, NH3).

During the reaction, the carbon-oxygen double bond gets broken. The net effect of all this is
that the carbonyl group undergoes addition reactions, often followed by the loss of a water
molecule. This gives a reaction known as addition-elimination or condensation. 
CHEMICALS:

Methanol (methyl alcohol)

Butanal (acetaldehyde)
Butanone (acetone)

REAGENTS:

Tollen’s reagent (silver nitrate in ammonia or ammonium hydroxide solution). Students

NEED to prepare this reagent in order it to be fresh prior of usage:

a. M AgNO3 (silver nitrate) solution

b. 4 M NH4OH (ammonium hydroxide) solution
c. 1 M NaOH (sodium hydroxide) solution

1.0 M Potassium permanganate solution (KMnO4)

Fehling’s solution = (Fehling A and Fehling B solution)
2,4-dinitrophenylhydrazine (2,4-DNPH)

Iodoform test:

a. Iodine solution
b. 1 M NaOH

APPARATUS:

6 test tubes
A test tubes rack
Water bath
Evaporating dish
Stopper
Wooden splints
Litmus paper or pH paper
PROCEDURES:

A. Oxidation
I) Tollen’s test

Preparation of Tollen’s reagent:

1 drop of dilute NaOH is added to 1 ml of diute AgNo3 solution. The grey soild of Ag2O
solid formed is dissolved by adding dilute NH4OH solution until a clear solution is
obtained. The solution is divided into two test tubes:

1. 5 drops of butanal is added in one of the test tube containing Tollen’s reagent. The
mixture is heated in a water bath about 10 minutes or more.
2. 5 drops of butanone is added in the other test tube containing Tollen’s reagent. The
mixture is heated in a water bath about 10 minutes or more. The result is compared.

II) Fehling’s test

1. 1 ml of Fehling A solution and 1 ml of Fehling B solution is added in a test tube. Then

5 drops of butanal is added in the test tube. The mixture is heated in a water bath. The
colour change and the precipitate formed (solid at the bottom of the test tube) is
observed and recorded.
2. The test is repeated with about 5 drops of butanone.

III) Reaction with oxidizing agent (acidified KMnO4)

1. 3 ml of dilute H2SO4 is added into 1 ml of KmnO4. Then 1 ml of butanal is added into

the mixture. The mixture is shook well and the colour change at the room temperature
and after heating is observed
2. The experiment is repeated by replacing butanal with butanone.

B. Reaction on carbonyl group

I) Condensation

1) 1 ml of methanol is added to 1 ml of butanal in a test tube. Then, 2 ml of 2,4-DNPH

reagent is added into the test tube. The mixture is shook well and observed. The
mixture is heated in a water bath for a few minutes. The mixture is cooled down and
the observation is recorded.
2) The experiment is repeated by replacing butanal with butanone.
C. Reactions on the methyl ketones
I) Iodoform test

1) 1 ml of butanal is added to 2 ml of iodine solution followed by aqueous solution of

NaOH drop by drop until the orange colour disappeared. The mixture is heated for a
few minutes. The mixture is cooled down and the observation is explained.
2) The experiment is repeated by replacing butanal with butanone.
 DISCUSSION:

Test Observation Equation Conclusion/

Butanal Butanone Reason
A. Oxidation Silver Dark RC(O)H + Tollen’s reagent
1. Tollen’s test mirror cloudy but 2Ag(NH3)2 + contains AgNO3
no silver + 3OH- → and NH3 in water;
mirror RC(O)O- + combine these two
appear 2Ag + 4NH3 + compounds to form
2H2O the complex ion
[Ag(NH3)2]+
II. Fehling’s test 2Cu2+ + 2e + Fehling’s solution
Blue Blue 2OH-  Cu2O is an alkaline
(before heating) + H2O solution containing
Cu2+ ions. It is a
mild oxidizing
agent.
First layer Second First layer Second R-CHO + The blue Cu2+ is
is oily layer is is dark blue layer is red 4OH- + 2Cu2+ reduced to the
(after heating) dark blue precipitate  R-COOH + brick-red
Third layer Cu2O + 2H2O precipitate Cu2O on
is red gentle warming.
precipitate
III. Reaction
with acidified First layer Second First layer Second
KMnO4 is layer is is layer is
colourless. dark purple colourless dark purple
(before heating)
Second Brown
(after heating) First layer layer is solution
is colourless with brown
colourless with brown precipitate
precipitate
B. Condensation
with 2,4-DNPH
Yellow Orange
(before heating)
Dark
(after heating) Goldish orange with
yellow orange
precipitate
C. Iodoform test
(reaction on
methyl ketones) Cloudy Cloudy

(before heating)

(after heating) Cloudy and Oily

oily
QUESTIONS:

1. Compound A, C4H8O gives orange precipitate with 2,4-DNPH and reacts with
Fehling’s reagent to form brick-red precipitate. A also reacts with acidified potassium
dichromate (VII) solution to form B, a carboxylic acid. From the observation above,
identify A and B. write the equations involved.
- 5 C4H8O + K2Cr2O7 + 2 H2SO4  5 C4H8O2 + Cr2SO4 + 2 H2O + K2SO4

A is sulphuric acid
B is butanoic acid

2. What is your observation if you differentiate 2-butanone and 2-methybutanal using

Tollen’s reagent and 2,4-DNPH? Write the equations involved.
- KMnO4 is also known as potassium permanganate. 2-butanone will turn into
aldehyde using the two solutions, while the other turns into ketone.
REFERENCES:

- http://www.answers.com/Q/What_is_the_observation_if_to_differentiate_2-
butanone_and_2-methylbutanal_using_Tollen's_reagent_and_KMnO4
- https://www.google.com/url?
sa=t&rct=j&q=&esrc=s&source=web&cd=4&cad=rja&uact=8&ved=0ahUKEwio
xYnhrPLKAhWDX5QKHQKrCQ8QFggwMAM&url=http%3A%2F%2Fwww.a-
levelchemistry.co.uk%2FAQA%2520A2%2520Chemistry%2FUnit
%25204%2F4.5%2520Compounds%2520Containing%2520the%2520Carbonyl
%2520Group
%2F4.5%2520notes.doc&usg=AFQjCNGElW2ela2OZUxxrrUv2L4MwfFkZQ&s
ig2=qGgfPwVNYTQvtkL_s7Tbig&bvm=bv.114195076,d.dGo
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