6.

1
Aldehyde and Ketone Both aldehyde and ketone are carbonyl
compound (organic with C=O in it). Both has the same molecular
formula as CnH2nO
6.1.1 Nomenclature of aldehyde

functioning group of aldehyde are
and end with al

butanal

3-methylpentanal

4-chloro-3methylbutanal

benzaldehyde

m- chlorobenzaldehyde

2-phenylethanal

6.1.2 Ketone : functioning group of ketone are

one

and end with

propanone

butanone

Pentan-2-one

hexan-3-one

2,4-dimethyl
pentan-3-one

cyclohexanone

Molecule

Butane (C4H10)

Propanal
(C2H5COH)

Propanone;
CH3COCH3

Propan-1-ol
C3H7OH

Ethanoic acid
CH3COOH

RMM

58

58

58

60

60

Boiling point
(oC)

48

56

97

118

Explanation : Butane is a non-polar molecule, where molecules were

held by temporary dipole-induced dipole. Propanal and propanone are
polar molecule, which has a permanent dipole-permanent dipole
attraction forces. However, the dipole moment of ketone is greater
than aldehyde, so ketone usually have higher b.p than aldehyde.
Propan-1-ol has high boiling point due to strong hydrogen bond
between them, however, ethanoic acid has greater hydrogen bond than
propan-1-ol, since they form dimer between them

+ -

+ -

Solubility : Lower aliphatic aldehydes such as methanal &

ethanal are soluble in water because they are able to form
hydrogen bond with water (as shown in diagram). Higher
member of aliphatic carbonyl compounds are insoluble as there
are presence of hydrophobic alkyl group

+ -

+ -

Isomerism of aldehyde and ketones : Given the molecular formula of

organic compound are C5H10O, out line all possible isomers of the
organic compound

6.2
Chemical preparation of aldehyde and ketone
6.2.1 Aldehyde
1. Oxidation of primary alcohol

Controlled oxidation of alcohol by using acidified potassium
dichromate (VI)

Prevention : Having excess alcohol over oxidant & distilled off
aldehyde.
+ H2O
propan-1-ol
propanal
2. Using catalytic oxidation (Cu at 400oC) on a 10 alcohol

propan-1-ol
propanal
This process is also known as dehydrogenation as hydrogen is
produced.

6.2.2 Ketone
1. Oxidation of secondary alcohol

Oxidation of alcohol by using acidified potassium dichromate (VI)

Unlike oxidation on 1o alcohol, it does not need prevention as ketone
formed will not further oxidise to other substances.
+ H2O
Propan-2-ol
propanone
2. Using catalytic oxidation (Cu at 400oC) on a 20 alcohol

propan-2-ol
propanone
This process is also known as dehydrogenation as hydrogen is
produced.

6.3
Chemical reaction of aldehyde and ketone
6.3.1 Reduction of aldehyde and ketone.

Reagent : LiAlH4 (lithium aluminium hydride) in dry ether

propanal
propan-1-ol
From reaction above, we can tell that 10 alcohol is formed back using
reduction. Hence, we can summarised the reaction as

Propan-1-ol

propanal

6.3.2 Oxidation of aldehyde

Aldehyde can be further oxidised to form carboxylic acid.

Reagent : KMnO4 / H+ (acidified potassium manganate (VII)

Propanal
propanoic acid
However, no further reaction for oxidation of ketone.

6.3.3 Addition reaction of aldehyde and ketone

Reagent : HCN (hydrogen cyanide) + little KCN

The nitrile compound formed is then further hydrolysed under acidic

condition, to form 2-hydroxybutanoic acid according to the equation

The nitrile compound formed can also be reduced to form amine, where

The mechanism can be describe as below.

Reagent : R-MgBr (Grignard reagent)

When aldehyde react with Grignard reagent (Chap 4.4.2), a secondary

alcohol is formed

KETONE

Reagent : HCN (hydrogen cyanide) + little KCN

The nitrile compound formed is then further hydrolysed under acidic

condition, to form butanoic acid according to the equation

Reduction

Reagent : R-MgBr (Grignard reagent)

When ketone react with Grignard reagent (Chap 4.4.2), a tertiary alcohol is
formed.

6.3.4 Condensation reaction of aldehyde / ketone

For aldehyde :

Reagent : (NO2)2C6H4NHNH2 (2,4-dinitrophenylhydrazine)

An orange precipitate surfaced when 2,4-dinitrophenylhydrazine is

added to aldehyde or ketone
For ketone

Reagent : (NO2)2C6H4NHNH2 (2,4-dinitrophenylhydrazine)

Similar to aldehyde, an orange precipitate will surface after the

reaction

Test

Aldehyde
Reagent : (I2 + NaOH) Iodine in
sodium hydroxide Only work for
ethanal as it has methyl-carbonyl
group

Triiodof Observation : a yellow crystal of

triiodomethane is observed
orm
Equation :
CH3CH=O + 3 I2 + NaOH 
CHI3 + HCOONa+ + 3 HI

Ketone
Reagent : (I2 + NaOH) Iodine in
sodium hydroxide Only work for
those which has methyl-carbonyl
group
Observation : a yellow crystal of
triiodomethane is observed
Equation : CH3COCH3 + 3 I2 + NaOH
 CHI3 + CH3COONa+ + 3 HIHI

Test

Aldehyde
Reagent : Fehling solution [solution of complex copper
(II) ion]
Positive Test : only works for aldehyde
Observation : blue solution turns to red precipitate of
Fehlings
Cu2O
solution
Equation :

red ppt.
Reagent : Tollen solution [solution of complex Ag(NH3)2]+]
Positive test : only work for aldehyde
Observation : colourless solution turn grey solid (silver
mirror)
Tollens
reagent Equation :

silver mirror

Ketone

No reaction
occur for
ketone

No reaction
occur for
ketone

propanone  2-bromopropane

propanal  2-hydroxybutanoic acid

propene  propanone

2-butenal  butanoic acid

Ethanal  Ethanamine

2. Outline a chemical test to distinguish between

a) propanal and propanone
Reagent : Fehling / Tollen reagent (for aldehyde) ; Iodine in NaOH (for ketone)
Observation : Red brick precipitate formed when added propanal while no changes for
propanone
Equation : CH3CH2CHO + 2 Cu2+ + 5 OH-  CH3CH2COO- + Cu2O + 3 H2O
b) ethanal and propanal
Reagent : Iodine in NaOH
Observation : Yellow precipitate formed when added to ethanal but no changes for
propanal
Equation : CH3CHO + 3 I2 + OH-  HCOO- + CHI3 + 3 HI

c) pentan-2-one and pentan-3-one

Reagent : Iodine in NaOH
Observation : Yellow precipitate formed when added to pentan-2-one but no changes
for pentan-3-one
Equation : CH3CH2CH2COCH3 + 3 I2 + OH- 
CH3CH2CH2COO- + CHI3 + 3 H2O + HI

6.5
6.5.1

Natural Compound with Carbonyl Group Carbohydrates

Monosaccharide

Simplest form of carbohydrates that cannot be hydrolysed to simple sugar

Examples : glucose and fructose

Glucose
Also known as aldose (functioning group
of COH)
Open ring
close ring

Fructose
Also known as ketose (functioning group
COCH3)
open ring
close ring

Adding glucose to Fehling solution will turn Adding fructose to Fehling will show no
changes to Fehling solution
the blue solution into a red precipitate
(positive test : aldehyde)

6.5.2 Disaccharide

Disaccharides are 2 monosaccharide joined together by glycosidic link.

The process of joining 2 monosaccharides are condensation process as water
molecule is given off as side product. Molecular formula of disaccharide is
C12H22O11.Example

3 most common disaccharides

=> sucrose (sugar cane)
=> maltose (barley)
=> lactose (milk)
Disaccharide can be break-up and formed back 2 monosaccharides by
hydrolysis of water

Most disaccharides are non-reducing sugar.

6.5.3 Polysaccharides

Polysaccharide ~ polymer containing long chains of
monosaccharide units. Example : starch and cellulose. They have
the empirical formula C6H10O5.

All saccharides are bond using glycosidic ring and they can be
hydrolysed by heating with diluted acid where
H + ; boil
(C6H10O5)n + n H2O
n C6H12O6.

Cellulose are mainly found in cell wall of plants. Cotton is almost
pure cellulose. It can be use to manufacture synthetic fiber
known as rayon.

A,B,C
C,E
C,D,E
C
C,D
E

Chiral carbon atom is formed since C1 can rotate freely in different position

Element

Carbon, C

Hydrogen, H

Oxygen, O

Mass

66.7

11.1

22.2

Mol = mass / mol

5.51 mol

11.1 mol

1.39 mol

Ratio

5.51 / 1.39 = 4

11.1 / 1.39 = 8

1.39 / 1.39 = 1

Orange precipitate is observed

Carbonyl compound
Butanone / CH3CH2COCH3

LiAlH4 in dry ether

Alcohol / hydroxyl group
CH3CH2CH(OH)CH3

Cl2 under UV

Cl2 under AlCl3

Iodine in NaOH
C gives yellow precipitate / crystal while F will not
C6H5COCH3 + I2 + OH-  C6H5COO- + CHI3 + HI

mass of CN needed = 0.03 x 60 = 1.8 g [1]

Mr = 154.5, amount = 1.8/154.5 = 0.012 mol [1]

H < D < G
 chlorine on the aryl ring is very inert /strong C-Cl bond / overlap between
unhybridise Cl with C in benzene ring1]
 chlorine on C=O is reactive because of highly + carbon atom bonded to
electronegative O and Cl/ due to inductive effect [1]

CH3CHO + HCN

KCN

CH3CH(OH)CN

Nucleophilic Additional reaction

CH3CH(OH)CN + 2 H2O + H+  CH3CH(OH)COOH + NH4+

hydrolysis

CH3CHO CH3CH(OH)COOH
44
90 or
4.40 g
9.00 g
% yield = 5.40 100 / 9.00
= 60%

E will give yellow precipitate when react with alkaline iodine solution
Product formed are CH3CH2CH2COO + CHI3

D reduced to form pentan-3-ol [1] while E is reduced to pentan-2-ol, which is optical

active / chiral carbon atom