8.

0 CARBONYL COMPOUNDS
8.2 Physical and chemical properties of carbonyl compounds
OBJECTIVES
By the end of the subtopic you should be able to:
• Outline the mechanism of nucleophilic addition reaction of hydrogen cyanide with
aldehydes and ketones.
• Describe the reduction of aldehydes and ketones using NaBH4 suggest a suitable test
for a given carbonyl compound
1. PHYSICAL PROPERTIES
a. Physical state at room temperature
• Due to the C=O group on carbonyl compounds, the intermolecular forces between the
carbonyl compounds are dipole-dipole interactions.
• The dipole-dipole forces increases strength with increase in mass, so therefore the state of
carbonyl compounds differs from gas to liquid to solid with increase in mass.
• Methanal is a gas at room temperature, while ethanal is a volatile liquid.
• Other carbonyl compounds are liquid and solid at room temperature.

b. Boiling and melting points

• The melting and boiling point of a substance is determined with the type of intermolecular
forces between the molecules.
• In this case the intermolecular forces are dipole-dipole and therefore the melting and boiling
point increases with increase in mass.
• In general carbonyl compounds have higher boiling and melting point than hydrocarbons but
less than alcohols even if the mass of the molecules is the same.
• This is because hydrocarbons have weak Van der Waals forces and alcohols have strong
hydrogen bonds.
• Table 8.2.1: Comparison of boiling points of Butane, Propanal and Propanol
Compound Intermolecular Molecular mass Boiling
forces point/⁰C
Butane Van der Waals 58 0
Propanal Dipole-dipole 58 49
Propanol Hydrogen bonding 60 97
c. Solubility
i. In water
• For a substance to dissolve in water, it should be able to form interactions with water.
• Carbonyl compounds can form ionic interactions with water due to the permanent dipole
but the solubility is affected by the size of the carbonyl compound.
• One carbonyl compound can form ionic interaction with water on the oxygen molecule.
• So when the hydrophobic part of the carbonyl group becomes large, then the solubility
decreases.
• Smaller aldehydes and ketones such as methanal, ethanal and propanone are all soluble in
water.
ii. In organic solvents
• All aldehydes and ketones are soluble in organic solvents such as benzene, ether,
methanol and chloroform.
2. CHEMICAL PROPERTIES
• These are reactions which carbonyl compounds are involved.
• Since ketones and aldehydes have the same functional group, they are all involved in
similar chemical reactions.
a. Reduction of carbonyl compounds
• The reduction reaction is carried out in sodium borohydride, 𝑁𝑎𝐵𝐻4 dissolved in
methanol or Lithium aluminium hydride, 𝐿𝑖𝐴𝑙𝐻4 dissolved in dry ether.
• Alcohols are obtained from the reduction reaction as shown in the equation below

• Aldehydes yield primary alcohols.

• Ketones produce secondary alcohols.
b. Reaction with 2,4-dinitrophenylhydrazine
• All carbonyl compounds reacts with 2, 4-dinitrophenylhydrazine in a condensation
reaction.
• The following helps to remember the structure of 2,4-dinitrophenylhydrazine

• In the reaction of 2, 4-dinitrophenylhydrazine and a carbonyl compound, a water

molecule is removed and 2, 4-dinitrophenylhydrazone is produced.
• This reaction can be catalysed by a little acid.
• The 2, 4-dinitrophenylhydrazones produced are yellow or orange crystalline solids and there
are used to test for the presence of compounds.
• The melting points of the 2, 4-dinitrophenylhydrazones produced also enable to separate if
the carbonyl compound used was an aldehyde or ketone.
c. Addition reaction
• Addition reactions are made possible because of the polarity of the C=O bond.
• The carbonyl group has a carbon bonded to oxygen and due to the high electronegativity of
oxygen compared to carbon, the bond is polar.
• This means oxygen draws electrons towards itself and it obtains a partially negative charge
while carbon obtains a partially positive charge.

Fig 8.2.1: Polarity of carbonyl group

• The partially positive charge on carbon causes the carbonyl group to be reactive since
nucleophiles can attacked the slightly positive carbon atom.
• A nucleophile is a molecule (ammonia, NH3) or negatively charged ion (cyanide ion,
CN-), that has lone pairs of electrons.
• The nucleophile attacks the partially positive carbon atom and adds across the
carbon-oxygen double bond in aldehydes and ketones.
• This produce compounds known as hydroxynitriles, some texts refer them to as
cyanohydrins.
• The reaction is as follows:

Mechanism
• Consider: The addition of HCN to a carbonyl group to make hydroxynitriles.
 Warning: HCN is a very poisonous gas
and is not safe to carry out this reaction
in the laboratory.

• Therefore HCN is not stored but is made in-situ by mixing HCl and KCN.
• Although KCN is poisonous, it is safer to store since it is a solid.
• The nucleophile in this reaction is hydrogen cyanide, HCN and the following equation shows how
HCN is generated in-situ.
𝐾𝐶𝑁 𝑠 + 𝐻𝐶𝑙 𝑎𝑞 → 𝐻𝐶𝑁 𝑔 + 𝐾𝐶𝑙(𝑎𝑞)
• The mechanism consists of a series of numbered steps and the steps are as follows:
Step 1: Dissociation of HCN
𝐻𝐶𝑁 → 𝐻 + + 𝐶𝑁 −
• The 𝐶𝑁 − generated in this reaction is the one that attacks the partially positive charged carbon atom
in the carbonyl group.
Step 2: The nucleophilic attack of the slightly positive charged carbon atom
Step 3: The lone pairs on oxygen attacks the 𝐻 + ion from step 1

• The product of step 3 is a hydroxynitrile.

Example 8.3.1: Addition of HCN to propanal make 2-hydroxy butane nitrile
• Generation of HCN in-situ.
𝐾𝐶𝑁 𝑠 + 𝐻𝐶𝑙 𝑎𝑞 → 𝐻𝐶𝑁 𝑔 + 𝐾𝐶𝑙(𝑎𝑞)
Step 1: Dissociation of HCN
𝐻𝐶𝑁 → 𝐻+ + 𝐶𝑁 −
Step 2: The nucleophilic attack of the slightly positive charged carbon atom

Step 3: The lone pairs on oxygen attacks the 𝐻 + from step 1

• The product formed is 2-hydroxy butane nitrile.

• This reaction is an example of a nucleophilic addition reaction.
• The reaction is faster in a slightly alkaline condition.
• The alkaline solution reacts with HCN to produce 𝐶𝑁 − and and 𝐻2 𝑂.
𝐻𝐶𝑁 + 𝑂𝐻− → 𝐻2 𝑂 + 𝐶𝑁 −
• The reaction makes 𝐶𝑁 − more available for nucleophilic attack.
• Benzaldehyde does not react in the same way, a different reaction occurs.
d. Reactions to identify carbonyl groups
• Carbonyl compounds can be identified by using 2,4dinitrophenylhydrazine and a
positive test produces 2, 4 dinitrophenylhydrazones which are yellow or orange
crystalline solids.
• There is need to experimentally differentiate between ketones and aldehydes from
the carbonyl compounds.
• Some chemical reactions are able to identify specific groups in carbonyl compounds
and these reactions are important in organic analysis.
i. Triiodomethane reaction
• The triiodomethane reaction occurs between iodine and specific carbonyl
compounds in the presence of aqueous sodium hydroxide.
• The reaction occurs at room temperature, but it may be necessary to warm up the
reaction mixture.
• The ketones or aldehydes that undergo this reaction should have following group:
• From the structure above, the only aldehyde that can give positive test is ethanal and
all methyl ketones can give positive test.
• Below is an example of a triiodomethane reaction:

• A positive result is the appearance of a very pale yellow precipitate of

triiodomethane (previously known as iodoform), CHI3.
ii. Oxidation reactions
• Aldehydes can be identified from ketones due to their ability to be oxidised.
• Aldehydes can be further oxidised to carboxylic acids while ketones are resistant to
oxidation.
• Reagents that can be used to distinguish aldehydes from ketones are:
a. Potassium dichromate(VI) solution, K2Cr2O7
b. Tollen’s reagent
c. Fehling solution

a. Using acidified potassium dichromate (VI) solution, K2Cr2O7

• A small amount of potassium dichromate (VI) solution is acidified with dilute sulphuric
acid and a few drops of the aldehyde or ketone are added. If nothing happens in the cold,
the mixture is warmed gently for a couple of minutes in a water bath.
• Ketones gives a negative result, this means there will be no colour change.
• Aldehydes cause the colour to change from orange to green.
• The orange dichromate (VI) ions will be reduced to green chromium(III) ions by the
aldehyde. In turn the aldehyde is oxidised to the corresponding carboxylic acid.
b. Using Tollen’s reagent, [Ag(NH3)2]+
• Tollen's reagent contains the diaminesilver(I) ion, [Ag(NH3)2]+, which is a mild
oxidising agent:
[Ag(NH3)2]+(aq) + e → Ag(s) + 2NH3(aq)
• It can be reduced by aldehydes, oxidising them to carboxylic acids:
R-CHO + H2O → RCOOH + 2H+(aq) + 2e-
• The overall equation for the reaction is:
R-CHO + 2[Ag(NH3)2]+ + H2O →RCOOH + 2Ag + 4NH3 + 2H+
• Thus aldehydes give a grey precipitate or "silver mirror" if boiled with
diaminesilver(I). This is a standard test for an aldehyde, since ketones cannot be
oxidised in this way.
c. Using Fehling’s solution
• Fehling’s solution is an alkaline solution containing Cu2+ ions. It is a mild oxidising agent:
2Cu2+ + 2e- + 2OH-→ Cu2O + H2O
• It is also reduced by aldehydes, and the overall equation for the reaction is:
R-CHO + 2OH- + 2Cu2+→ R-COOH + Cu2O + 2H+
• The blue Cu2+ is reduced to the brick-red precipitate Cu2O on gentle warming. This is
another standard test for an aldehyde.
• Ketones cannot be oxidised using this reagent.

•
 ASSESSMENT EXERCISE 8.2 PROPERTIES OF
CARBONYL COMPOUNDS
1. Name and draw the structures of the organic products obtained by the following
reactions. If there is no reaction, state “no reaction”.
a. propanal with acidified potassium dichromate
b. propanal with NaBH4
c. propanone with acidified potassium dichromate
d. propanone with NaBH4
e. butanal with Fehling’s solution
f. methylpropanal with Tollen’s reagent
g. butanone with Fehling’s solution [7]
2. Suggest starting materials for the production of the following hydroxynitriles:
a. 2-methyl, 2-hydroxybutanenitrile
b. 3-methyl, 2-hydroxybutanenitrile [2]
3. Write equations and give the mechanism for the reaction of butanone with HCN [5]