All Organic

Topic Reference Reading from Solomons, Organic Chemistry 6th edition
Acid-Base Theory (Unit 1) 90-93, 96-101

Acid-Base Theory (Unit 2) 102-118, 320, 433-434, 795-796, 903-905, 970-972
Isomerism (Unit 1) 59-61
Isomerism (Unit 2) 178-185, 188, 193-198, 200
Nomenclature 41-47, 65-75, 128-137, 284-286, 288-289, 415-417, 615-617,
705-706, 792-793, 797-800, 899-900
Reaction Mechanism (Unit 1) - Introduction to Mechanism 87-90, 94-96
Reaction Mechanism (Unit 2) - Nucleophilic substitution 224-233, 238-252, 256-259
Reaction Mechanism (Unit 3) - Nucleophilic substitution 260
Reaction Mechanism (Unit 4) - Nucleophilic substitution 913-914
Reaction Mechanism (Unit 5) - Nucleophilic substitution 438-443
Reaction Mechanism (Unit 6) - Nucleophilic substitution 923-924, 926-927, 966
Reaction Mechanism (Unit 7) - Elimination 260-262, 265-268, 300, 302-305
Reaction Mechanism (Unit 8) - Elimination 308, 312, 318-319, 443-444
Reaction Mechanism (Unit 9) - Nucleophilic addition 719
Reaction Mechanism (Unit 10) - Nucleophilic addition 470-472, 716-719, 729-734, 759-761
Reaction Mechanism (Unit 11) - Nucleophilic addition 708-711
Reaction Mechanism (Unit 12) - Nucleophilic addition 805-817, 820-824
Reaction Mechanism (Unit 13) - Nucleophilic addition 919-921
Reaction Mechanism (Unit 14) - Nucleophilic addition 711, 825-827, 918
Reaction Mechanism (Unit 15) - Electrophilic addition 327-333
Reaction Mechanism (Unit 16) - Electrophilic addition 336-339, 346-351, 422-425
Reaction Mechanism (Unit 17) - Electrophilic substitution 617-618, 655-658
Reaction Mechanism (Unit 18) - Electrophilic substitution 658-664, 930-931, 974
Reaction Mechanism (Unit 19) - Electrophilic substitution 930-931, 974
Reaction Mechanism (Unit 20) - Radical reactions 334-335, 366-379, 393-397
Amino acids 1146-1148
Oxidation and Reduction 165-166, 473-475, 690-691, 915-916
Uses of compounds with different functional groups
Structure determination (Unit 1)
Structure determination (Unit 2) 295-297
Structure determination (Unit 3) 359-360, 742
Structure determination (Unit 4) 541-547
Organic synthesis 169-171
Organic Laboratory Technique (Unit 1)
Summary of Organic Reactions (I. Alkanes) Page 1
I. Alkanes
A. Cracking
heat , catayst
very long alkane → long alkane + short alkene
B. Combustion
y y
CxHy + (x + 4 ) O2(g) → xCO2(g) + 2 H2O(l)
C. Chlorination
Chain initiation (chain initiating step)
hυ
Cl Cl Cl + Cl Cl· radical is generated.
Chain propagation (chain propagating step)

H H
Cl H C H Cl H + C H Cl· radical is consumed.
H H
H H
Cl Cl C H Cl + Cl C H Cl· radical is regenerated.
H H
Chain termination (chain terminating step)

Cl + Cl Cl Cl
H H
Energy
Cl C H Cl C H
H H + radical is destroyed.
H H H H
H C C H H C C H
H H H H
A mixture of products would be obtained.

Summary of Organic Reactions (II. Alkenes and alkynes) Page 2
II. Alkenes and alkynes

A. Addition reactions
1. Reaction with bromine in CCl4

Br Br
in dark
Br2 + R C C R
R C C R
R R
in R R
CCl4
1,2-dibromoalkane
Note : Test for C=C or C≡C bond
2. Reaction with bromine water

Br OH
Br2(aq) + R C C R in dark
R C C R
R R
R R
halohydrin
Note : Test for C=C or C≡C bond
3. Reaction with hydrogen bromide

H Br H
H C C C H major product
H H H
H
H 2-bromopropane
C C C H + H Br
H
H H Br H H
propene H C C C H minor product
H H H
1-bromopropane
Note : Follows Markownikov's orientation
4. Reaction with conc. sulphuric(VI) acid

OH
O S O
R C C R
conc. H2SO4(l) + H O
R R
R C C R
R R
alkyl hydrogensulphate(VI)
Note : A reversible reaction
OH
O S O H OH
H O + H2O(l) R C C R + H2SO4(aq)
R C C R R R
R R alcohol
alkyl hydrogensulphate(VI)
Note : Laboratory preparation of alcohol
5. Reaction with water

H3PO4
CH2 CH2 + H2O CH3 CH2 OH
300 ºC
ethane ethanol
Note : Industrial preparation of alcohol
6. Catalytic hydrogenation of oil

Note : hardening of oil
B. Ozonolysis of alkene
CH3 CH3 O O
(1) O3, CH2Cl2, -78 ºC
CH3CHCH CH2 CH3CH C H + H C H
(2) Zn / H2O
3-methylbut-1-ene 2-methylpropanal methanal
Note : Can be used to determine the structure of the alkene with characterization of the derivatives of carbonyl compounds
formed.
C. Oxidation cleavage of double bond

O O
CH3CH2 CH3 (1) KMnO4, OH-, hot
C C CH3CH2 C CH2CH3 + H3C C CH3
(2) H+
CH3CH2 CH3
3-ethyl-2-methylpent-2-ene pentan-3-one propanone
CH3 CH3 O
(1) KMnO4, OH-, hot
CH3CHCH CH2 CH3CH C OH + CO2 + H2O
(2) H+
3-methylbut-1-ene 2-methylpropanoic acid
Note : The outcomes are different from the ones from ozonolysis.
a) Reaction with cold acidic or alkaline permanganate solution

H H
H H
cold KMnO4(aq) H C C H
H C C H
H3O+ or OH- O O
ethane
H H
ethane-1,2-diol
D. Oxymercuration of alkyne
H
R C C H H
HgSO4(aq) keto-enol
R C C H H2SO4(aq) O R C C H
tautomerization
terminal H O H
alkyne Markovinkov methyl ketone
orientation
E. Polymerization of alkenes
Chain initiating step
O O O
heat
R C O O C R 2 R C O 2R + 2 CO2
Diacylperoxide alkyl radical
Chain propagating step

H H
H H
R C C R C C
H H H H
H H H H H H H H
etc.
R C C C C R C C C C long chain polymer
H H H H H H H H
Chain terminating step

H H H H H H H H
combination
R (CH2 CH2)n C C C C (CH2 CH2)n R R (CH2 CH2)n C C C C (CH2 CH2)n R
H H H H H H H H
H H H H H H H H
disproportionation
R (CH2 CH2)n C C C C (CH2 CH2)n R R (CH2 CH2)n C C H C C (CH2 CH2)n R
H H H H H H H
oxidation product reduction product
Summary of Organic Reactions (III. Aromatic hydrocarbons) Page 5
III. Aromatic hydrocarbons

A. Substitution reactions of benzene
1. Nitration
NO2
conc. HNO3(aq)
conc. H2SO4(l)
55°C
benzene
nitrobenzene
Note : No reaction if conc. H2SO4(l) is not added.
2. Halogenation
X
X2
FeX3 or AlX3
benzene halobenzene
3. Sulphonation
O
O S O H
conc. H2SO4
heat
benzene
benzenesulphonic acid
O
O S O H O-Na+ OH
NaOH(s) H3O+
350°C
benzenesulphonic acid sodium phenoxide phenol

/ sodium phenolate
Note : Industrial preparation of phenol
4. Alkylation
R
RX and AlX3
benzene alkylbenzene
B. Oxidation of alkylbenzene
O
R C OH
1) KMnO4, OH-, heat
2) H3O+
alkylbenzene benzenecarboxylic acid

Summary of Organic Reactions (IV. Halogeno-compounds) Page 6
IV. Halogeno-compounds
A. Nucleophilic substitution
1. Reaction with sodium hydroxide

NaOH(aq)
R X R OH
haloalkane alcohol
X OH
NaOH(aq)
heat
halobenzene phenol
Note : Prolonged heating is required for the alkaline hydrolysis of halobenzene.
2. Reaction with potassium cyanide

KCN(aq)
R X R CN
haloalkane nitrile
3. Reaction with ammonia

H N H + R X H N R
+ HX
H H
ammonia haloalkane 1° amine
H N R R N R
+ R X + HX
H H
1° amine haloalkane 2° amine
R N R R N R
+ R X + HX
H R
R
R N R + R X R N R X-
R R
3° amine haloalkane quaternary ammonium halide
Note : A mixture of products would be obtained.
4. Reaction with alkoxide

R X + R' O-Na+ R O R'
haloalkane sodium alkoxide ether
5. Reaction with carboxylate ion

O O
- +
R X + R' C O Na R' C O R
haloalkane sodium ester
carboxylate
Summary of Organic Reactions (IV. Halogeno-compounds) Page 7
B. Elimination reaction
1. Reaction with alcoholic sodium hydroxide to form alkene

X H
NaOH(alc.)
R C C R R C C R
R R R R
haloalkane alkene
2. Reaction with alcoholic sodium hydroxide to form alkyne

X X
boiling NaOH(alc.)
R C C R R C C R
H H
1,2-dihaloalkane alkyne
Summary of Organic Reactions (V. Hydroxy compounds) Page 8
V. Hydroxy compounds
A. Reactions of alcohols
1. Formation of halide
a) by halogenating agent
PCl5 / PCl3 / SOCl2
R OH R Cl
alcohol chloroalkane
b) by heating with halide salt in acidic medium

+ -
R OH Na X , conc. H2SO4(l) R X
alcohol heat haloalkane
2. Formation of alkoxide
2 C2H5OH(l) + 2 Na(s) → 2 C2H5O-Na+(alc.) + H2(g
C2H5OH(l) + NaOH(s) d C2H5O-Na+(alc.) + H2O(l)
3. Oxidation of alcohols
H
O O
R C O H [O] [O]
R C H R C O H
H
1° alcohol aldehyde carboxylic acid
R
[O] O
R C O H
R C R
H
2?alcohol ketone
R
R C O H [O] Resistant
to oxidation
R
3?alcohol
4. Dehydration of alcohols
H H
H C C H conc. H SO H H
2 4
H O heat H C C H
H ethene
ethanol
5. Esterification
O O
conc. H2SO4(l) H2O
R OH + R' C OH R' C O R +
heat
alcohol carboxylic ester
acid
6. Triiodomethane formation
H H
O I
R C C H NaOH(aq) + I2(aq)
R C + H C I
O H -
O I
H
carboxylate iodoform
alcohol with ion (yellow ppt.)
1-hydroxyethyl group
Note : 1. Test for the presence of 1-hydroxyethyl group.
2. Shorten the carbon chain by 1 C.
Details :
H H
H
R C C H oxidation
+ I2 + 2 OH- R C C H + 2 I- + 2 H2O
O H
O H
H
alcohol with methyl ketone
1-hydroxyethyl group
O H O I
NaOH(aq) + I2(aq)
R C C H R C + H C I
H O- I
methyl ketone carboxylate iodoform
ion (yellow ppt.)
7. Distinction between primary, secondary and tertiary alcohols
a) With potassium dichromate(VI)

H
O O
R C O H [O] [O]
R C H R C O H
H
R
[O] O
R C O H
R C R
H
2?alcohol ketone
R
to oxidation
R
3?alcohol
b) Lucas' test
H
R C OH conc. HCl(aq)
no reaction
ZnCl2(aq)
H
1° alcohol
H H
R C OH conc. HCl(aq) R C Cl slow reaction
ZnCl2(aq)
R R
2° alcohol
R R
R C OH conc. HCl(aq) R C Cl fast reaction
ZnCl2(aq)
R R
3° alcohol
Note : 3º alcohol will turn cloudy quickly, 2º alcohol will turn cloudy slowly but 1º alcohol will not turn cloudy at all.
B. Reactions of phenol
1. Reaction with sodium

OH O-Na+
Na + H2
sodium phenoxide
phenol
/ sodium phenolate
2. Reaction with sodium hydroxide

OH O-Na+
NaOH(aq) + H2O
sodium phenoxide
phenol
/ sodium phenolate
Note : Phenol is soluble in sodium hydroxide solution.
3. Esterification
O
OH O
C O R
R C Cl or
O O
R C O C R
phenol ester
4. Reaction with bromine

OH OH
Br Br
Br2(aq)
Br
2,4,6-tribromophenol
phenol
(a white ppt.)
Note : A test for phenol.
Summary of Organic Reactions (VI. Carbonyl compounds) Page 11
VI. Carbonyl compounds

A. Nucleophilic addition
1. Reaction with hydrogen cyanide

O H
O
+ HCN R C R
R C R
C N
2. Reaction with sodium hydrogensulphate(IV)

R R
+ -
O C + Na HSO3 H O C SO3-Na+
CH3/H CH3/H white precipitate
Note: 1. Sensitive to steric hinderance and reacts with aldehyde and methyl ketone only.
2. Can be used to purify aldehyde or methyl ketone.
B. Addition-elimination (condensation)
1. Reaction with hydroxylamine

R
O H N OH
+ C N OH + H2O
R C R H
R
hydroxylamine oxime (white ppt.)
Note : 1. A test for aldehyde or ketone.

2. Identify the carbonyl compound by characterization.
2. Reaction with 2,4-dinitrophenylhydrazine

R H H H
R
O C + H N N NO2 C N N NO2 + H O
2
R
R O2N O2N
2,4-dinitrophenylhydrazine 2,4-dinitrophenylhydrazone
(orange ppt.)
Note : 1. Test for aldehyde or ketone but no reaction with carboxylic acid and its derivatives
2. Identify the carbonyl compound by characterization.
3. Triiodomethane formation
O H O I
NaOH(aq) + I2(aq)
R C C H R C + H C I
H O- I
ion (yellow ppt.)
Note : 1. Test for methyl ketone.
2. Shortens the carbon chain by 1 C
Summary of Organic Reactions (VI. Carbonyl compounds) Page 12
C. Oxidation and reduction
1. Oxidation of aldehyde with potassium dichromate(VI)

O O
[O]
R C H R C OH
aldehyde carboxylic acid
Note : Orange acidified potassium dichromate will turn to green chromium(III) ion.
2. Oxidation of aldehyde with Tollens' reagent

O O
Tollen's reagent - +
R C H R C O NH4 + Ag(s)
[Ag(NH3)2]OH(aq) ammonium
aldehyde silver mirror
carboxylate
Note : Test for aldehyde
3. Oxidaton of aldehyde with Fehling's reagent

O Fehling's reagent O Cu2O
- +
R C H R C O brick red ppt.
aldehyde carboxylate ion
Note : Test for aldehyde
4. Resistance of ketones to oxidation

O
[O]
R C R no reaction
Note : Ketone is stable to general oxidation.
5. Reduction with sodium tetrahydridoborate / lithium tetrahydrioaluminate

O- O H
O H3O+
+ NaBH4(aq) R C R/H R C R/H
R C R/H
H H
aldehyde
alkoxide alcohol
or ketone
O- O H
O H3O+
+ LiAlH4(ether) R C R/H R C R/H
R C R/H
H H
aldehyde
alkoxide alcohol
or ketone
Note : LiAlH4 cannot be used in aqueous medium.
6. Haloform reaction
O H O I
NaOH(aq) + I2(aq)
R C C H R C + H C I
H O- I
ion (yellow ppt.)
Note : 1. Test for methyl ketone.
2. Shorten the carbon chain by 1 C.
Summary of Organic Reactions (VII. Carboxylic acids and their derivatives) Page 13
VII. Carboxylic acids and their derivatives

A. Formation of carboxylic acid
1. Hydrolysis of nitrile
O
dil. H2SO4(aq) R C OH
R C N
reflux
nitrile carboxylic acid
Note : Complete hydrolysis of nitrile
2. Oxidation of alcohol
H
O O
R C O H [O] [O]
R C H R C O H
H
Note : Aldehyde intermediate can be separated from the reacting mixture by distillation.
3. Oxidation of aldehyde
O O
[O]
R C H R C OH
aldehyde carboxylic acid
4. Oxidation of alkylbenzene
O
R C OH
1) KMnO4, OH-, heat
2) H3O+
alkylbenzene benzenecarboxylic acid
B. Reactions of carboxylic acid
1. Formation of salt
O O
NaOH(aq)
R C OH R C O-Na+
carboxylic acid sodium carboxylate
2. Formation of acyl chloride

O O
PCl5 / PCl3 / SOCl2
R C OH R C Cl
alcohol chloroalkane
3. Formation of anhydride
O O
H C OH H
C
140°C O + H2O
C
H C OH H
O O
butenedioic
cis-butenedioic acid
anhydride
Note : Intramolecular dehydration
O O O O
P2O5 (P4O10)
CH3 C OH + HO C CH3 CH3 C O C CH3
ethanoic acid ethanoic acid ethanoic anhydride
Note : Intermolecular dehydration
O O O O
- + + Cl
CH3 C O Na C CH3 CH3 C O C CH3 + NaCl
4. Formation of ester
O O
R X + R' C O-Na+ R' C O R
haloalkane sodium ester
carboxylate
O O
+ R OH
R C Cl R C O R
acyl
alcohol ester
chloride
O O O
+ R OH
R C O C R R C O R
acid
alcohol ester
anhydride
O H3O+ O
+ R OH
R C OH heat R C O R
carboxylic
alcohol ester
acid
5. Formation of amide
O
cold dil. H2SO4(aq)
R C N R C NH2
or hot conc. H2SO4(l)
nitrile amide
Note : Partial hydrolysis of nitrile.
6. Reduction with lithium tetrahydridoaluminate

H
O (1) LiAlH4(ether)
R C OH
R C OH (2) H3O+
H
carboxylic
1° alcohol
acid
C. Reactions of acyl chlorides and anhydrides
1. Reaction with water

O O
H2O(l) + HCl
R C Cl R C OH
acyl carboxylic
chloride acid
O O O O
H2O(l) +
R C O C R' R C OH R' C OH
acid carboxylic
anhydride acid
2. Reaction with alcohol

O O
ROH + HCl
R C Cl R C OR
acyl ester
chloride
O O O O
ROH +
R C O C R' R C OR R' C OH
acid
anhydride ester
3. Reaction with ammonia

O O
conc. NH3(aq)
R C Cl R C NH2
acyl
amide
chloride
O O O
conc. NH3(aq)
R C O C R' R C NH2
acid
amide
anhydride
4. Reaction with amine

O O R
RNH2
R C Cl R C NH
acyl
N-substituted amide
chloride
O O O R
RNH2
R C O C R' R C NH
acid
N-substituted amide
anhydride
D. Reactions of ester
1. Acid and base-catalysed hydrolyses

O O
H3O+
R C O R R C OH + R OH
heat
ester carboxylic alcohol
acid
O O
NaOH(aq)
R C O R R C O- + R OH
heat
ester carboxylate alcohol
ion
Note : Rate of hydrolysis : alkaline medium > acidic medium > neutral medium

O H
(1) LiAlH4(ether)
R C O R R C OH
(2) H3O+
H
ester 1° alcohol
E. Reactions of amide
1. Hydrolysis of amide
O O
H3O+ reflux
R C NH2 R C OH
amide carboxylic acid
O - O
OH reflux
R C NH2 R C O-
amide carboxylate ion
2. Dehydration of amide
O P2O5 or (CH3CO)2O
or SOCl2 R C N
R C NH2
3. Hofmann degradation of non-substituted amide

O Br2 / NaOH(aq) R N H
R C NH2
H
1?amine
amide with 1 C less
Note : Only applicable to non-substituted amide.

H
O 1) LiAlH4 / ether
R C N H
R C NH2 2) H3O+
H H
amide 1° amine
Note : Amide is the only acid derivative which will not be reduced to alcohol.
Summary of Organic Reactions (VIII. Nitrogen compounds) Page 17
VIII. Nitrogen compounds

A. Formation of amine
1. From nitrile
H H
(1) LiAlH4(ether)
R C N R C N
(2) H3O+
H H
nitrile 1° amine
Note : LiAlH4 could not be used in aqueous medium.
2. From amide
H
O 1) LiAlH4 / ether
R C N H
R C NH2 2) H3O+
H H
amide 1° amine
Note : Amide is the only acid derivative which will not be reduced to alcohol.
3. 1º, 2º, 3º amines and quaternary ammonium compounds by alkylation

H N H + R X H N R
+ HX
H H
H N R R N R
+ R X + HX
H H
R N R R N R
+ R X + HX
H R
R
R N R + R X R N R X-
R R
3° amine haloalkane quaternary ammonium halide
Note : A mixture of products would be obtained.
4. Phenylamine from nitrobenzene

NO2 NH2
1) Sn, conc. HCl(aq)

2) OH-(aq)
B. Base properties of amine
1. Salt formation
H
R N H
+ HCl R N H Cl-
H
H
Summary of Organic Reactions (VIII. Nitrogen compounds) Page 18
C. Reactions of amine
1. Reactions with ethanoyl chloride and benzoyl chloride

O
R N H O H
+ CH3 C Cl
H CH3 C N R
amine ethanoyl N-substituted ethanamide
chloride
R N H O O H
+ C Cl C N R
H
benzoyl
amine N-subsituted benzenecarboxamide
chloride
2. Reaction with nitric(III) acid

H
HNO2 0-5°C
R N R+ + N2
H carbocation nitrogen
aliphatic bubbles
primary
amine
+
NH2 N N
HNO2 0-5°C
aromatic
benzenediazonium
primary
ion
amine
Note : A test used to distinguish aliphatic primary amine from aromatic primary amine.
3. Coupling reaction of benzenediazonium ion with naphthalen-2-ol and phenol

HO
+
N N OH
N N
naphthalen-2-ol
benzenediazonium
ion red orange ppt.
+
N N
N N OH
OH
phenol
benzenediazonium
orange ppt.
ion
Note : Tests for benzenediazonium ion. Indirect tests for aromatic primary amine.
Summary of Organic Reactions (IX. Other reactions) Page 19
IX. Other reactions

Radical addtion of X2 to benzene
X H
H X
X2 uv X H
H X
X H
H X
Reactions of benzenediazonium ion

+
N N CN
CuCN
+
N N
H3PO2
Preparation of vinyl chloride

H H H H H H
Cl2
C C H C C H alcoholic C C
Electrophilic NaOH
H H addition Cl Cl Cl H
Anti-Markownikov's addition
H Cl H
H C C C H minor product
H H H
H
H 2-chloropropane
C C C H + H Cl + R O O R
H
H H alkyl peroxide Cl H H
propene H C C C H major product
H H H
1-chloropropane
Test for terminal alkyne

+
R–C≡CH Cu
( NH )
→ R–C≡C-Cu+(s) (red ppt.)
3 2
+
R–C≡CH Ag
( NH )
→ R–C≡C-Ag+(s) (white ppt.)
3 2
Test for phenol

[Fe(H2O)6]3+(aq) + 2C6H5O-(aq) → [Fe(H2O)4(C6H5O)2]+(aq) + 2H2O(l)
from neutral from phenol purple complex
iron(III) chloride
Nomenclature of Organic compounds
I. Nomenclature of organic compounds

A. Labelling of carbon
1. Methyl, primary, secondary and tertiary carbon
2. α carbon, β carbon and γ carbon
B. Skeletal formula / Stick formula
II. Nomenclature of hydrocarbon

A. Alkyl and aryl group
III. Other functional group

A. Halogeno-compounds
B. Alkanols and phenol
C. Aldehydes and ketones
D. Carboxylic acids
1. Carboxylic acid derivatives – esters, acid chlorides, anhydrides and amides
E. Nitriles
F. Amines
G. Amino-acids
H. Ethers
IV. Priority of functional groups

V. Examples
VI. Other common abbreviations
Acid-Base Theory
I. Definition of acid-base
A. Arrhenius definition
B. Bronsted-Lowry definition
C. Lewis definition
II. Strength of acid and base
A. Leveling effect
III. Factors determining the strength of a Bronsted-Lowry acid
A. Relative stability of the conjugate base comparing with the acid
1. Inductive effect
(1) Amine vs Amide
2. Resonance effect
a) Resonance effect on a benzene ring
(1) Phenol
(2) Aromatic amine
3. Intramolecular hydrogen bond
4. Solvation / hinderance to solvation
a) Steric hinderance to solvation
b) Effect of solvent
5. Strength of the bond between the proton and the conjugate base
6. Electronegativity of the atom
a) Effect of hybridization
Isomerism
I. Structural isomerism
A. Chain isomerism
B. Position isomerism
C. Functional group isomerism
D. Tautomerism / Tautomerization
II. Stereoisomerism
A. Diastereomerism / Geometrical isomerism
1. Physical properties of cis-/trans-geometrical isomers of 1,2-dichloroethene
2. Physical and chemical properties of cis-/trans-geometric isomers of butenedioic
acid
a) Physical properties
b) Chemical properties
B. Optical isomerism / Enantiomerism
1. Physical properties
2. Optical activity
a) Plane polarized light
b) Measurement of optical activity by polarimeter
c) Specific rotation
3. Chiral centre
4. Racemic mixture / Racemic modification / Racemic form / Racemate
Reaction Mechanism Page 1
Reaction Mechanism
I. Bond breaking
A. Bond breaking of a bond to carbon
II. Types of reactive species
A. Free radical (electron deficiency)
B. Electrophile (electron deficiency)
C. Nucleophile (electron rich)
III. Classification of reaction
A. Types of reaction
1. Substitution
2. Addition
3. Elimination
IV. Nucleophilic substitution

1. Nucleophile
2. Leaving group
B. SN2 reaction (1 step reaction)
C. SN1 reaction (2 steps reaction)
D. Competition between SN1 and SN2 reactions
E. Alkanol from haloalkane (RX → ROH)
1. Alkaline hydrolysis of haloalkane
2. Hydrolysis of haloalkane
F. Rate of hydrolysis of haloalkane, haloalkene and halobenzene
G. Other relevant reactions
1. Reactions of haloalkane
a) Nitrile from haloalkane (RX → RCN)
b) Alkylation of ammonia and amine (NH3 → RNH2)
c) Use of SN2 reaction in organic synthesis
2. Reactions of alkanol
a) Haloalkane from alkanol (ROH → RX)
(1) Use of chlorinating and brominating reagent
b) Luca's test to distinguish 1º, 2º and 3º alkanol
3. Reactions of amine
a) Action of nitric(III) acid on 1º amine
(1) 1º aliphatic amine
(2) 1º aromatic amine
b) Laboratory preparation of phenol from benzenamine
V. Elimination reaction
A. Elimination reaction
1. Stability of elimination product
2. E2 reaction (not required in A-Level)
B. Competition between substitution and elimination reaction
1. Effect of temperature
2. Effect of bulkiness of the substrate and base
3. Effect of bascity of the nucleophile
C. Conditions favouring substitution and elimination reaction
D. Other relevant reactions
1. Reaction of haloalkanes with alcoholic sodium hydroxide to alkene, diene and
alkyne
2. Preparation of vinyl chloride
3. Dehydration of alkanol
VI. Nucleophilic addition (Nucleophilic addition-elimination)
A. AdN reaction
1. Addition of HCN to carbonyl compound
2. Rate of nucleophilic addition
a) Electronic effect
(1) Inductive effect
(a) Effect of protonation
(2) Resonance effect
b) Steric effect
3. Other relevant reactions
a) Reactions of carbonyl group
(1) Reduction of carbonyl compound by LiAlH4 and NaBH4
(2) Addition of NaHSO3 to carbonyl compound
(3) Condensation reaction with hydroxylamine
(4) Condensation reaction with 2,4-dinitrophenylhydrazine
(5) Haloform reaction / Iodoform reaction
b) Reactions of carboxylic acid and its derivatives
(1) Carboxylic acid and its derivatives
(a) Difference between carbonyl compound and carboxylic acid
and its derivatives
(b) Reactivities of carboxylic acid and its derivatives
(2) Formation of different acid derivatives
(a) Use of chlorinating agent to prepare acyl chloride
(b) Formation of ester (Esterification with alkanol and phenol)
(c) Formation of acid anhydride
(i) Through intramolecular dehydration by heating
(ii) Through intermolecular dehydration by a very strong
dehydrating agent
(iii) From acyl chloride
(d) Formation of amide (Acylation and benzoylation of amine)
(3) Reaction of ester
(a) Hydrolysis of ester
(4) Reaction of amide
(a) Reduction of amide and other acid derivatives
(b) Hofmann degradation of amide
c) Reactions of nitrile
(1) Hydrolysis of nitrile and amide
(a) Dehydration of amide
(2) Reduction of nitrile
VII. Electrophilic addition
A. Addition of HBr to alkene
1. Markownikoff's rule.
2. Reactivity of alkene towards electrophilic addition
B. Other relevant reaction
1. Addition of Br2 to alkene
2. Addition of H2SO4 to alkene
a) Preparation of alkanol from alkene
3. Hydration of alkene
4. Ozonolysis of alkene
5. Preparation of ethane-1,2-diol
a) Oxidative Cleavage of double bond
b) Comparision of ozonolysis and oxidative cleavage
6. Oxymercuration of alkyne
VIII. Electrophilic substitution

A. Representation of arenium ion
1. Sulphonation of benzene
a) Preparation of phenol
2. Nitration of benzene
a) Reduction of nitrobenzene
3. Halogenation of benzene
4. Alkylation of benzene (Friedel-Crafts alkylation)
5. Diazocoupling of diazonium ion
a) Colour of a substance
6. Bromination of phenol
IX. Free radical Reaction
A. Formation of free radical
B. Free radical Substitution
1. Chain reaction e.g. chlorination of methane
a) Chain initiation (chain initiating step)
b) Chain propagation (chain propagating step)
c) Chain termination (chain terminating step)
2. Reaction between H2(g) and Cl2(g)
C. Free radical Addition
1. Chain reaction e.g. Polymerization of alkene
2. Anti-Markownikoff orientation
Amino acids
I. Amino acids
A. Zwitterion
B. Polypeptides
Oxidation and Reduction
I. Oxidation
A. Combustion of alkane
B. Oxidation of alkanol and aldehyde
C. Oxidation of aromatic side chain
II. Reduction
A. Reduction of nitrobenzene
B. Catalytic hydrogenation (Hydrogenation of alkene)

Uses of Different Compounds
I. Uses of halogeno-compounds
A. Use as solvent
B. Manufacture of polymer
2. Physical properties of PVC and Teflon
II. Uses of alcohols
A. Use as solvent
B. Alcoholic drink
C. Blending agent
D. Ethan-1,2-diol
III. Uses of carbonyl compounds
A. Preparation of urea-methanal
B. Use of propanone
IV. Uses of carboxylic acids and their derivatives
A. Food preservatives
B. Manufacture of nylon and terylene
C. Use of ester
V. Uses of amines and their derivatives
A. Azo compounds as dyes in dyeing industries
B. Amine derivatives as drugs
Determination of Structure
I. Determination of empirical formula and molecular formula
A. Different kinds of formula
B. Determination of empirical formula
C. Determination of molecular formula
II. Degree of unsaturation
A. Determination of degree of unsaturation
B. Meaning of degree of unsaturation
III. Sodium fusion test
IV. Test for different functional groups by wet chemistry
V. Introduction to IR and NMR spectroscopy
A. Use of infra-red (IR) spectrum in the identification of functional groups
1. More examples
Organic synthesis
I. Retrosynthetic analysis
II. Structural analysis
A. Chain length
1. Carbon chain
2. Nitrogen and Oxygen containing chain
B. Degree of unsaturation
C. Oxidation or Reduction
D. Position of functional group
III. Systematic approach to organic synthesis

IV. Examples
Organic Laboratory Technique
I. Purification of organic compound
A. Solvent extraction
B. Steam distillation
C. Chromatography
D. Recrystallization
E. Filtration and Suction filtration
II. Use of quickfit apparatus
A. Handling of quickfit apparatus
B. Different setup of quickfit apparatus
1. Reflux setup
2. Distillation setup
III. Testing for purity
A. Determination of melting point
B. Determination of boiling point

Nomenclature of Organic compounds
I. Nomenclature of organic compounds

B. Skeletal formula / Stick formula
II. Nomenclature of hydrocarbon

A. Alkyl and aryl group

C. Aldehydes and ketones
D. Carboxylic acids
E. Nitriles
F. Amines
G. Amino-acids
H. Ethers

V. Examples
Nomenclature of organic compounds Page 1
Topic Nomenclature of organic compounds Unit 1
Reference 13
Reading Organic Chemistry, Fillans, 3rd Edition pg. 50–65
Guidelines for systematic chemical nomenclature, HK Exam. Authority pg. 7–17
Chemical nomenclature, symbols and terminology for use in school science. pg. 58–65
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 380–381, 400–401, 414, 428, 432, 438, 439,
Reading 446, 453, 467, 484, 498, 516–517
Organic Chemistry, 6th Edition, Solomons, pg. 41-47, 65-75, 128-137, 284-286, 288-289, 415-417, 615-617,
705-706, 792-793, 797-800, 899-900
Syllabus Nomenclature of organic compounds

Classification of hydrocarbons
Priority of functional group in IUPAC naming
Notes I. Nomenclature of organic compounds
The basic idea of the IUPAC (International Union of Pure and Applied Chemistry) system of naming is that by
following some rules, a name can be assigned to a molecule. And from the assigned name, the original molecule
can be reconstructed unambiguously.
A given structure may have several different names but a name will only give 1 structure.
H H H H
For example, the structure is called H C C C C O H is called butan-1-ol or 1-butanol but no matter
H H H H
butan-1-ol or 1-butanol refer to the same structure.
IUPAC system of naming is a kind of substitutive nomenclature. In substitutive nomenclature, hydrogen atoms in
a named 'parent' hydrocarbons are considered to be substituted by other groups.
Actually, the IUPAC system of naming is not very strict. It is possible to have more than 1 name for a given
molecule. But no matter which name is assigned, only 1 structure can be rebuilt.
To facilitate discussion, carbon atoms on a carbon chain can be labelled by 2 different methods.
The first way is based on the no. of carbon atoms attached to the carbon to be concerned.
If no other carbon is attached to the carbon, the carbon atom is called a methyl carbon.
If 1 carbon atom is attached to the carbon, the carbon atom is called a primary carbon, 1º carbon
If 2 carbon atoms are attached to the carbon, the carbon atom is called a secondary carbon, 2º carbon
If 3 carbon atoms are attached to the carbon, the carbon atom is called a tertiary carbon, 3º carbon
H CH3 CH3 CH3

H C X H C X CH3 C X CH3 C X
H H H CH3
methyl carbon 1° carbon 2° carbon 3° carbon
e.g. CH3CH2OH is called a primary alkanol since the hydroxyl group is attached to a 1º carbon.
Another way is according to the position of the carbon relative to a substituent (functional group).
If the carbon is immediately next to the substituent, it is called a α carbon.
The carbon attached to the α carbon is called a β carbon.
The carbon attached to the β carbon is called a γ carbon.
O
C C C X
C C C C
γC βC αC carbonyl
γC βC αC
carbon
B. Skeletal formula / Stick formula / Bond line formula
In order to make the presentation simple, sometimes skeletal formula is used instead of the full structural formula
or condensed structural formula. In the skeletal formula, all atomic symbols of carbon and hydrogen are omitted.
Skeletal formula / Skeletal formula /

Full structural Condensed Full structural Condensed
Stick formula / Stick formula /
formula structural formula formula structural formula
Bond line formula Bond line formula
H3C CH3 H H
H H
H C C CH2 CH
H C C H CH3 CH3
H C C CH2 CH
H H CH3CH3 H
H
H
H H H H C H
C C
H C C C H CH3CH2CH3
H H H
C C
H C H
H
H H
H H H
HH C HH
CH3 H C C C H
CH3CHCH3
H C C C H
H C C C H
CH3CH(CH3)CH3
H H H
H H
H H
H H
H H H H
H C C H CH2 CH2 H C C C C H
CH3CH2CH(OH)CH3
H C C H CH2 CH2 H H O H
OH
H
H H
H CH3CHCH2 H O H H
O
H C C C H H C C O C C H CH3COOCH2CH3
H H H CH3CH CH2 H H H
O
H H
H C H
H C C C H
CH3C(CH2)CH3
H H
II. Nomenclature of Hydrocarbon
Some examples
H H H H
H C C C C O H is called butan-1-ol (or 1-butanol). (a primary alcohol)
H H H H
H
H3C C CH2 CH3 is called 2-methylbutane (or isopentane). iso- means 1 C is attached to the next-to-end C.
CH3
CH3
CH3 H3C C
CH3
H3C C CH2 CH3 is called 2,2-dimethylbutane (or tert-butylethane). is called the tert-butyl group.
CH3
CH3 CH2 CH2 CH CH2 CH2 CH3

CH is called 4-(1-methylethyl)heptane (or 4-isopropylheptane).
H3C CH3
CH3 NH2 is called methanamine (or methylamine).
O
C H benzenecarbaldehyde (or benzaldehyde)
O
C OH benzenecarboxylic acid (or benzoic acid)
The basis of IUPAC substitutive nomenclature is that every name consists of a root, one suffix and as many
prefixes as necessary.
prefix - root - suffix
Root represents the longest carbon chain containing the principal functional group as indicated by the suffix and
also it should contain the largest no. of substituent.
Suffix represents the functional group with the highest priority among all the functional groups present.
Prefix represents other functional group and arranged in alphabetical order.
Cl 3-amino is a prefix
CH3 CH CH2 CH2 OH 3-amino-2-chlorobutan-1-ol 2-chloro is a prefix
e.g. butan- is a root
NH2
-ol is a suffix
The numbers are called locants used to indicate the position of the functional group.
The numbers are arranged to give
(a) the lowest possible number to the group cited by a suffix (principal functional group), then
(b) the lowest possible individual numbers (not sum) to those cited as prefixes.
CH3 CH2 CH CH CH2 CH2 CH2 CH2 CH CH3

CH3 CH3 CH3
2,7,8-trimethyldecane (not 3,4,9-trimethyldecane)
N.B. hyphen (-) is used to separate number from letter.

comma (,) is used to separate number from number.
Name of the first 10 straight chain hydrocarbons
1. methane (meth-) 4. butane (but-) 7. heptane (hept-/hepta-) 10. decane (dec-/deca-)

2. ethane (eth-) 5. pentane (penta-) 8. octane (oct-/octa-)
3. propane (prop-) 6. hexane (hex-/hexa-) 9. nonane (nona-)
For the parent chain containing double bond or triple bond, suffixes -ene and -yne are used respectively.
C C ethene C C ethyne C C C propyne C C C C but-1-ene C C C C but-2-yne
C C C C C C C hepta-1,3-diene
If the chain contains both double bond and triple bond, the name will be ended with -yne.
C C C C C pent-3-en-1-yne C C C C C pent-1-en-3-yne
C C C C C C hex-3-ene-1,5-diyne
N.B. -e- is omitted if it is followed by a vowel e.g. y, a, o.
If both double bond and triple bond has the same lowest possible number, double bond will be given a higher
priority.
C C C C C pent-1-en-4-yne
C C C C C C hexa-1,3-dien-5-yne
Classification of hydrocarbons
Hydrocarbons
Aliphatic (Acyclic) Alicyclic (Cyclic) Aromatic
cyclohexane benzene
Alkane Alkene Alkyne (Arene)
CH3 CH3 CH2 CH2 CH CH
ethane ethene ethyne
Aliphatic (Acyclic) : Hydrocarbon with no ring structure. It can be further classified into straight chain and
branched hydrocarbon.
Alicyclic (Cyclic) : Hydrocarbon with ring structure.
Aromatic : A special kind of ring compound with extra stability due to delocalization of electrons.
Benzene and naphthalene are aromatic. Originally, 'aromatic' means having a sweet smell since
the firstly discovered aromatic compounds possess special smell.
A. Alkyl, vinyl, allyl and aryl group
When a hydrogen is removed from an alkane, the structure is called an alkyl group R–. It is cited by adding -yl.
H
H C methyl group
H
When a hydrogen is removed from an alkene, the structure is called a vinyl group. It is cited by adding -enyl.
H H H
H C C C prop-2-enyl group
H
When a hydrogen is removed from an alkyne, the structure is called an allyl group. It is cited by adding -ynyl.
H
H C C C prop-1-ynyl group
H
N.B. The carbons are counted from the point joining to the main chain.
When a hydrogen is removed from a benzene, the structure is called a phenyl group Ph– or .
phenyl group
However if a phenyl group is attached to a –CH2–, it is called the benzyl group.
CH2 benzyl group

Phenyl group and other substituted phenyl group (e.g. chlorophenyl group) are collectively called aryl group Ar–.
NH2 phenylamine (or more accurate benzenamine).

The presence of halogen (–X) is always cited by the prefixes (fluoro-), (chloro-), (bromo-) and (iodo-).
Cl Br Br
H C H chloromethane H C C H 1,2-dibromoethane
H H H
The presence of hydroxyl group (–OH) is cited by suffix (-ol) or prefix (hydroxy-)
H H OH OH H O
H C C OH ethanol H C C H ethane-1,2-diol HO C C OH hydroxyethanoic acid
H H H H H
N.B. (-e-) of the root is omitted if it is followed by an vowel e.g. -o- or -y-.
When a hydrogen on the benzene is substituted by a hydroxyl group, the compound is called phenol.
OH phenol O2N OH 4-nitrophenol
C. Aldehydes (Alkanals) and ketones (alkanones)

O O
Aldehyde (Alkanal) contains a terminal carbonyl group C . It has the general formula R C H .
It is cited by suffix (-al) or prefix (oxo-).
O O O
CH3 C H ethanal H C C OH oxoethanoic acid
O O
Ketone contains a non-terminal carbonyl group C . It has the general formula R C R
It is cited by suffix (-one) or prefix (oxo-) if the C is counted in the root or prefix (carbonyl-) if the C is not
counted in the root.
O O O
CH3 C CH2 CH2 CH3 pentan-2-one CH3 C CH2 C OH 3-oxobutanoic acid
D. Carboxylic acids (Alkanoic acid)

O
Carboxylic acid contains a carboxyl group C OH . It is cited by suffix (-oic acid) or (-carboxylic acid) or by
prefix (carboxy-).
O O O
CH3 C OH ethanoic acid HO C CH2 C OH propanedioic acid.
O
C OH benzenecarboxylic acid (common name : benzoic acid)
O H H
HO C C N+ H Cl- (carboxymethyl)ammonium chloride
H H
N.B. 1. locant is not necessary for dioic acid since the carboxyl groups must occupy the ends of the C chain.
2. When suffix (-carboxylic acid) or prefix (carboxy-) is used, the C in the carboxyl group is not
counted as a part of the parent chain.
Esters, acid chlorides, anhydrides and amides are all derivatives of carboxylic acid.
The derivative is formed by replacing –OH hydroxyl group with other functional groups.
–OH replaced by General formula Example

Carboxylic acid O O
R C OH CH3 C OH ethanoic acid
Ester –OR O O
R C O R' CH3 C O CH2CH2CH3 propyl ethanoate
Acid chloride –Cl O O

(acyl chloride) R C Cl CH3 C Cl ethanoyl chloride
Anhydride –OOCR O O O O
(formed by R C O C R' CH3 C O C CH3 ethanoic anhydride
dehydration of
alkanoic acid) O O
CH3 C O C CH2CH2CH3
butanoic ethanoic anhydride

Amide –NH2 O O
R C NH2 CH3 C NH2 ethanamide
O O
R C is called the acyl group. e.g. CH3 C ethanoyl group.
E. Nitriles
Nitrile contains cyano group –C≡N. It is cited by suffix (-nitrile) or (-carbonitrile) for cyclic nitrile or by prefix
(cyano-)
CH3 C N ethanenitrile C N benzenecarbonitrile
H O
C N cyclohexanecarbonitrile N C C C OH cyanoethanoic acid
H
N.B. When suffix (-carbonitrile) or prefix (cyano-) is used, the C in the cyano group is not counted as a part of
the parent chain.
F. Amines
Amine contains amino group –NH2. Amine is alkyl or aryl derivative of ammonia, with the hydrogen replaced by
alkyl group or aryl group. It is cited by suffix (-amine) or prefix (amino-).
CH3 CH CH2 NH2

CH3
CH3 NH2 methanamine (methylamine) 2-methylpropan-1-amine
CH3 N CH2CH3
H
N-methylethanamine (ethylmethylamine)
CH3 N CH2CH3
CH2CH2CH3
N-ethyl-N-methylpropan-1-amine (ethylmethylpropylamine)
NH2 benzenamine (phenylamine).
N
N-phenylbenzenamine (diphenylamine).
H
H2N CH2 CH2 OH 2-aminoethanol
N.B. The locant N- is used to indicate the alkyl or aryl group is attached to the N, not the parent C chain.
G. Amino-acids
Amino-acid contains both amino group –NH2 and carboxyl group –COOH.
O
H2N CH2 CH2 C OH 3-aminopropanoic acid
H. Ethers
Ether contains –O–R group. It is cited by prefix (R-oxy-) e.g. methoxy-.
CH3 O CH2 CH3 methoxyethane (ethyl methyl ether)
CH3CH2 O CH2CH3 ethoxyethane (diethyl ether)
H3C O CH2CH2 O CH3 1,2-dimethoxyethane
N.B. In some circumstances, -oxy- is used alone to indicate the presence of oxygen.
If a compound has more than 1 functional group. The functional group with the highest priority would be named
as the suffix and all others would be named as prefixes.
e.g.
O
C CH3 HO
O O O
O HO C C O CH2 CH3 N C O CH2CH3
C OH
2-ethanoyloxybenzenecarboxylic ethoxycarbonylmethanoic acid 4-ethoxy-2-hydroxybenzenecarbonitrile

acid
V. Examples
Steps in writing CH3

C CH2 CH CH3 CH3
CH3
C
CH3
CHCH2CH2CHCH2CHO
CH3 OH
IUPAC name OH
1. Identify the principal functional group hydroxyl group (–OH) alkanal group (–CHO)
2. Identify the parent chain containing the C C C C C O
principal functional group OH OH C C C C C C C C H
3. Number the parent chain so that the pentane-2,4-diol oct-6-enal

principal functional group is on the
lowest numbered carbon.
4. Label other substituents as prefixes. 2-methyl 3-methyl, 7-methyl
5. Group the prefixes, arrange them in 2-methylpentane-2,4-diol 3,7-dimethyloct-6-enal
alphabetic order and join with the root.
C2H5C(CH3)=CHCH2CH2CO2H
Steps in writing O
OH
C C C
IUPAC name
C C C C C C C OH
C
1. Identify the principal functional group carboxyl group (–COOH) hydroxyl group (–OH)
2. Identify the parent chain containing the O OH
principal functional group C C C C C C C OH C C C
3. Number the parent chain so that the hept-4-enoic acid propan-1-ol

4. Label other substituents as prefixes. 5-methyl 1-phenyl
5. Group the prefixes, arrange them in 5-methylhept-4-enoic acid 1-phenylpropan-1-ol
Steps in writing C
C
C C C C
C
C C C O C C
IUPAC name C C
1. Identify the principal functional group double bond (C=C) Nil

2. Identify the parent chain containing the C C C C C C C C
principal functional group
3. Number the parent chain so that the but-1-ene butane
4. Label other substituents as prefix. 3-methyl, 3-methyl 1-ethoxy, 3-methyl, 3-methyl
5. Group the prefixes, arrange them in 3,3-dimethylbut-1-ene 1-ethoxy-3,3-dimethylbutane
Abbreviation Functional group Structure Example
R– Alkyl group
H H
Me– Methyl group H C H C H Me–H
H H
H H H H
Et– Ethyl group H C C H C C H Et–H
H H H H
Ph– Phenyl group H Ph–H
Ar– Alkyl group H Ar–H
X– Halogeno group Cl–, Br–, I–
Glossary nomenclature IUPAC parent chain prefix root suffix locant

functional group aliphatic (acyclic) alicyclic (cyclic) alkane alkene alkyne
alkyl group vinyl group allyl group aryl group phenyl group alkanol phenol
hydroxyl group aldehyde (alkanal) ketone (alkanone) carbonyl group
carboxylic acid (alkanoic acid) carboxyl group ester acid chloride (acyl chloride) anhydride
amide acyl group nitrile amine amino group ether
Past Paper 94 2C 8 c i ii iii

Question 96 2C 9 c i ii
97 2B 5 d i ii iii
98 2B 7 c i ii
94 2C 8 c i ii iii
8c Give a systematic name to each of the following compounds.
i CH3 CH3 1
CH3CH CH CH2CH CH2
4,5-dimethylhex-1-ene 1 mark
ii O 1
CH3CH2CH2 O C CH2CH2CH3
propyl butanoate 1 mark

iii O 1
CH3CH2 C CHCH2CH3
OH
4-hydroxyhexan-3-one 1 mark
C Badly-answered. Many candidates did not know the general rules for systematic naming.
96 2C 9 c i ii
9c Give a systematic name to each of the following compounds :
(Deduct ½ marks for each minor mistake. Max. Deduction = 2 marks)
i CH3 OH 1
CH3 CH CH2 CH CH3
4-methylpentan-2-ol / 4-methyl-2-pentanol 1 mark
ii CH3 1
CH3
CH3
O
2,5,5-trimethylcyclohex-2-enone 1 mark
C Disappointing answers for (i). Some candidates did not know the basic rules of nomenclature. Very few gave the
correct name for (ii).
97 2B 5 d i ii iii
5d Give a systematic name to each of the following compounds: 3
i CH3 CH3
N
ii O
CH3CH2 C CH(CH3)CH2CH3
iii H CH3
C
C
HO2C H
98 2B 7 c i ii
7c Give a systematic name to each of the following compounds : 2
i CH3
CH2CH3
ii CH3CH=CHCH2CHO
Acid-Base Theory
B. Bronsted-Lowry definition
C. Lewis definition
A. Leveling effect
III. Factors determining the strength of a Bronsted-Lowry acid
1. Inductive effect
(1) Amine vs Amide
2. Resonance effect
a) Resonance effect on a benzene ring
(1) Phenol
(2) Aromatic amine
a) Steric hinderance to solvation
b) Effect of solvent
5. Strength of the bond between the proton and the conjugate base
Acid-base Theory Unit 1 Page 1
Topic Acid-base Theory Unit 1
Reference 14.1
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 41–43, 138–140, 185–186, 252–254
Organic Chemistry, Solomons, 5th Edition pg. 86–109, 830–834, 942–943
Organic Chemistry, Fillans, 3rd Edition pg. 218–220, 301–313
Organic Chemistry, Morrison Boyd, 6th Edition pg. 33–35, 729–736, 849–852, 903–905
Organic Chemistry, 6th Edition, Solomons, pg. 90-93, 96-101
Syllabus Acid-base Theory

Expression of Ka and pKa
Relative strength of acids and bases
ef
Notes A. Acid-base Theory
wis d initio
Le Lowry d n
d e
At the early stage of development of acid-base theory, acid was only te nius defi f
described as a sour substance. And base is only a substance which neutralizes
in tion
e
A rr h s
B rφ n
it io
ni
the sour taste of an acid.
Common
n
Nevertheless, scientists find that acids and bases bear some other properties. Sense
According to these properties, they developed a series of definitions to
describe acid and base. They are called Arrhenius definition, Brønsted Lowry
definition and Lewis definition. The coverage of the latter definition is
boarder than the former one.
In 1884, Swedish chemist Svante Arrhenius proposed that
Acid – a hydrogen-containing compound that, when dissolved in water, produces hydroxonium ions, H3O+(aq).
Base – a substance that, when dissolved in water, produces hydroxide ions, OH-.
Examples of Arrhenius acid

e.g. H2SO4(l) + H2O(l) → H3O+(aq) + HSO4-(aq)
HSO4-(aq) + H2O(l) → H3O+(aq) + SO42-(aq)
Examples of Arrhenius base

e.g. NaOH(s) + aq → Na+(aq) + OH-(aq)
KOH(s) + aq → K+(aq) + OH-(aq)
This is the definition learned in certificate level.

B. Brønsted-Lowry definition
Arrhenius theory is criticized that

1. Acid is restricted to hydrogen-containing species and base is restricted to hydroxide-containing species.
2. The theory is only applicable to aqueous medium where a lot of acid-base reaction takes place in the absence
of water.
In 1923, Danish chemist Johannes Brønsted and British chemist Thomas Lowry proposed, a boarder definition, that
Acid – a proton donor
Base – a proton acceptor
e.g. HCl(aq) + CuO(s) → Cu2+Cl-2(aq) + H2O(l)

proton proton
donor acceptor
e.g. NH3(aq) + H2O(l) d NH4+(aq) + OH-(l)

proton proton proton proton
acceptor donor donor acceptor
(base) (acid) (conjugate (conjugate
acid of NH3(aq)) base of H2O(l))
e.g. HCl(aq) + H2O(l) d H3O+(aq) + Cl-(aq)

donor acceptor donor acceptor
(acid) (base) (conjugate (conjugate
acid of H2O(l)) base of HCl(aq))
e.g. H2O(l) + H2O(l) d H3O+(aq) + OH-(aq)

acceptor donor donor acceptor
(base) (acid) (conjugate (conjugate
acid of H2O(l)) base of H2O(l))
When a Brønsted-Lowry acid, a proton donor, donates a proton, it becomes a potential proton acceptor and is
called the conjugate base of the acid. Stronger a proton donor, weaker will be the conjugate base.
Conversely, when a Brønsted-Lowry base, a proton acceptor, accepts a proton, it becomes a potential proton donor
and is called the conjugate acid of the base. Stronger a proton acceptor, weaker will be the conjugate acid.
All Arrhenius acids and bases can be classified into Brønsted-Lowry acid and base accordingly.
C. Lewis definition
The American chemist Gilbert N. Lewis (1923) proposed an even broader definition for acid and base. He
proposed that
Acid – an electron acceptor

Base – an electron donor
This definition offers many advantages, including

i. The acids are not limited to compounds containing hydrogen.
ii. It works with solvents other than water.
iii. It does not require formation of a salt or of acid-conjugate pairs.
Since all chemical species are potential electron acceptor or electron donor, virtually, all chemical species are
either Lewis acid or Lewis base.
e.g. H3N:(g) + BF3(g) → H3N→BF3(s)

electron electron
donor acceptor
(Lewis base) (Lewis acid)
Most of the chemical reaction is caused by redistribution of electrons which leads to rearrangement of atoms and
formation of a new substance. Therefore, all kind of reactions may be considered as Lewis acid-base reaction.
Concept of Lewis acid-base is very useful in describing reaction mechanisms.
In measuring the strength of acid, Brønsted-Lowry definition is usually used.
Strength of an acid can be measured by an equilibrium constant called acidity constant or acid dissociation
constant, Ka.
For an acid, HA in water
[H3O+(aq)][A-(aq)]
HA(aq) + H2O(l) d H3O+(aq) + A-(aq) Equilibrium constant, Keq = [HA ][H O ]
(aq) 2 (l)
Acidity constant, Ka is defined as
[H3O+(aq)][A-(aq)]
Ka = [HA(aq)] = Keq[H2O(l)] where [H2O(l)] is a constant since water is the solvent in large excess.
For a stronger acid, more HA(aq) molecules will dissociate into H3O+(aq) ion and A-(aq) ion and give a larger value for
K a.
Similar to concentration of H+(aq) ion, Ka can also be expressed in a negative log scale.
pH = - log [H+] A low pH means a high concentration of H+(aq) ion.
pKa = - log Ka A low pKa means a larger value for Ka and a stronger acid.
Relative strength of selected acids and their conjugate bases
Stronger an acid, weaker will be its conjugate

base.
Stronger a base, weaker will be its conjugate
acid.
N.B.
Redox reaction can be considered as a
competition for electron.
oxidizing agent + e- d reducing agent
In redox reaction, only strong oxidizing agent

reacts with reducing agent.
Similarly, acid base reaction can be considered

as a compeition for proton.
cojugate base + H+ d conjugate acid
In acid base reaction, only strong acid react

with strong base.
The strength of an acid or a base is also an indicator of their stability. A strong acid or base is less stable than
a weak acid or base. A strong acid tends to react with a strong base to form a weak conjugate base and weak
conjugate acid.
A. Leveling effect
An acid stronger than hydroxonium ion H3O+(aq), does not show difference in acidity in water. The water will
convert all those acid molecules into H3O+(aq) ions.
HCl(aq) + H2O(aq) → H3O+(aq) + Cl-(aq)

strong strong weak weak
acid base acid base
HBr(aq) + H2O(aq) → H3O+(aq) + Br-(aq)

strong strong weak weak
acid base acid base
A base stronger than hydroxide ion, e.g. NH2- amide ion, also does not exist in aqueous medium. Water will
convert all those base molecules into OH-(aq) ions.
NH2- + H2O(l) → NH3(aq) + OH-(aq)
This is known as leveling effect of solvent.
Glossary Arrhenius acid-base Brønsted-Lowry acid-base Lewis acid-base
Past Paper
Question
Topic Acid-base Theory Unit 2
Reference 14.0 14.2–14.4

Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 41–43, 138–140, 185–186, 252–254
Organic Chemistry, Fillans, 3rd Edition pg. 218–220, 301–313
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 471, 499–501, 519–520
Reading Organic Chemistry, 6th Edition, Solomons, pg. 102-118, 320, 433-434, 795-796, 903-905, 970-972
Syllabus Factors determining the strength of an acid
Notes III. Factors determining the strength of a Bronsted-Lowry acid

1. Inductive effect
2. Resonance effect
5. Size of the conjugate base
The strength of an acid is mainly determined by the relative stability of the conjugate base comparing with the
acid.
The equilibrium constant is related to the standard free energy change (∆Go) equation
Ka
∆Go = -2.303 RT log Keq = -RT ln Keq = -RT ln [H O ] where ∆Go = ∆Ho - T∆So
2 (l)
∆Go is an indicator of the relative stability of the product comparing with the reactant. A very negative value
means the product is more stable than the reactant. For a reaction with small change in entropy, i.e. reaction
without change in physical state, the ∆Go is roughly the same as ∆Ho.
Since Ka = Keq [H2O(l)], a very negative value of ∆Go means a very strong acid. The acidity of the acid increase as
the relatively stability of the conjugate base increase comparing with the acid molecule.
I. Inductive effect
H O H O
H C C O H + H2O H C C O- + H3O+
H H
Upon ionization in water, an ethanoic acid molecule forms a carboxylate ion and a hydroxonium ion. An electron-
withdrawing (-I) groups stabilize the negative charge of the carboxylate anion by dispersing the negative charge.
This increases the acidity of the acid.
Inductive effects of halogen atoms on acid strength

Acid Structure pKa (H2O) at 25ºC
Ethanoic CH3CO2H 4.76 Relatively weak acid
Iodoethanoic ICH2CO2H 3.12
Chloroethanoic ClCH2CO2H 2.85
Trichloroethanoic Cl3CCO2H 0.7
Trifluoroethanoic F3CCO2H 0.23 Relatively strong acid
Butanoic CH3CH2CH2CO2H 4.81
2-Chlorobutanoic CH3CH2CHClCO2H 2.81 Relatively strong acid
3-Chlorobutanoic CH3CHClCH2CO2H 4.05
4-Chlorobutanoic ClCH2CH2CH2CO2H 4.52 Relatively weak acid
Note : pKa is a log scale, increase by 1 in pKa means 10 folds decrease in acid strength.
As inductive effect is transmitted through σ- Inductive effects of various Groups

bond, it decreases quickly with increasing
distance from the negative centre. It is only a
short range effect.
Electron-donating :
positive inductive effect (+I)
Electron-withdrawing :
negative inductive effect (-I)
2. Resonance effect
ethanoic acid phenol ethanol

Acid CH3COOH Ph-OH CH3CH2OH
pKa 4.76 9.9 16
Experimentally, ethanoic acid is 1.7 × 1011 times more acidic than ethanol. This cannot be explained satisfactorily
by the presence of extra oxygen atom. Comparing choroethanoic acid and ethanoic acid, the presence of the
chlorine atom only contribute a 81 times difference in acidity.
The exceptionally high acidity of ethanoic acid can be explained by the resonance stabilized ethanoate ion formed
from ethanoic acid.
Comparing the structure of ethanoic acid and ethanoate ion, The ethanoate ion has identical resonance structures.
In contrast, the two resonance structures of the carboxylic acid molecules are not identical. One of the resonance
structure even involves charge separation and makes it less stable.
Species with identical resonance structure implies a more evenly distributed electron cloud which is relatively more
stable. This makes ethanoate exceptionally stable and ethanoic acid exceptionally acidic.
Free energy
O
CH3 C O
OH CH3 C
O-
H+
f O-
+
O CH3 C
CH3 C O
OH
pKa = 4.76
As the product is stabilized more than the reactant, the

Ka of the acid will increase. ∆G'
Inductive effect and Resonance effect are collectively ∆G' is more negative (less positive) than ∆G
called Electronic effect.
Reaction coordinate
A carboxylic acid yields a resonance-stabilized anion; it is a stronger acid than an alcohol.

(The plots are aligned with each other for easy comparison.)
(1) Amine vs Amide
For a similar reason, amine is more basic than amide.

H
H
+ H+ CH3 CH2 > N H
CH3 CH2 N H +
H
Alkyl group is an electron-donating group, it will stabilize the conjugate acid formed and make the amine more
basic.
O H
O H
+ H + CH3 C < N H
CH3 C N H +
H
Just the opposite, acyl group is an electron-withdrawing group, it will destabilize the conjugate base formed and
make the amide less basic.
a) Resonance effect through a benzene ring
(1) Phenol
H H H
Resonance effects of various groups
O O+ O+
- - H+
O -
O O O
-
-
Since the phenoxide ion is more stabilized by resonance than the
phenol molecule, phenol is much more acidic than other
alcohols.
e.g. pKa of phenol = 9.9
pKa of CH3CH2OH = 16
(This is a wrong explanation used in HK A-level, for more up-
to-date explanation, please read Solomon pg.942–943)
Though phenol is acidic, phenoxide ion does not have identical

resonance structures. Phenol is less acidic than carboxylic acid.
Thus, phenol reacts with strong alkali, e.g. NaOH, but not with
weak alkali, e.g. Na2CO3 or NaHCO3.
This can be used as a test to distinguish phenol and ethanoic

acid.
Vorlander's rule of resonance effect on benzene ring

1) Saturated groups (containing only single bonds between all atoms) are electron donating (+R).
O
e.g. F , Cl , O C
R (has a lone pair on the atom)
2) Unsaturated groups (containing multiple bonds between any atoms) are electron withdrawing (-R).
O
O N
e.g. C N , C , O (has a multiple bond between the first and the second atom)
The acidity of phenol increases as the benzene ring is substituted by nitro group, –NO2.
pKa of 4-nitrophenol = 7.15
pKa of 2,4,6-trinitrophenol = 0.42
Since the nitro group is very far from the hydroxyl group, the inductive effect is very negligible. Comparing with
inductive effect, reasonance effect has a much longer range.
-
O O O
-
N+ N+ N+
O O- O O- -O O-
By resonance, the negative charge on the 4-nitrophenoxide ion is more dispersed. This gives extra stability to the
4-nitrophenoxide ion and make nitro substituted phenol more acidic.
(2) Aromatic Amine
The basicity of amine can also be explained in the same way.
H H N H
H N H
N CH2CH2CH2CH3
H
H
pKb 3.2 4.8 9.4
basicity decreases
The high basicity of butan-1-amine can be explained by the presence of the electron-donating alkyl group. This
stabilizes the conjugate acid CH3CH2CH2CH2NH3.
Consider the equilibrium
H
H N H
H N H
+ H+
H
H N H
is an electron withdrawing group by inductive effective -I. It destabilizes the conjugate acid
H
H N H H N H H N H
and make the least basic one. Furthermore, is also stabilized by resonance but is not.
Therefore, the equilibrium position will be lying on the left hand side.
H N H H N H H N H
Existence of intramolecular hydrogen-bond may have positive or negative effect on the acidity of an acid.
Example 1 – butenedioic acid
H CO2H
C
H
C
CO2H
(Z)-butenedioic acid / cis-butenedioic acid (maleic acid) pKa1 = 1.83 pKa2 = 6.07
H CO2H
C
HO2C
C
H
(E)-butenedioic acid / trans-butenedioic acid (fumaric acid) pKa1 = 3.03 pKa2 = 4.44
For a dibasic acid, there are 2 pKa values. The first dissociation of maleic acid is more complete but the second
dissociation is just the reverse.
Comparatively, only the acid molecule that undergoes 1st dissociation may undergo 2nd dissociation. Therefore,
the value of pKa2 is not as important as pKa1 in determining the acidity of an acid. i.e. maleic acid is more acidic
that fumaric acid.
This can be explained by a H-bond stabilized conjugate base of maleic acid.
O O O
C Oδ
-
H C O H H H C O-
C C C
H + H+ + 2H+
C C C
H C O H H C Oδ- H C O-
O O O
H-bond stabilized
The first conjugate base is stabilized by formation of intramolecular H-bond which causes a stronger 1st
dissociation and weaker 2nd dissociation.
O O O
H C O H H C O H C O
C C C
+ H+ + 2H+
C C C
H O C H H O C H O C H
O O O
Not H-bond stabilized
2H+ + A2- 2H+ + A2-
H+ + HA-
H+ + HA-
H2A H2A
Dissociation of maleic acid Dissociation of fumaric acid

Example 2 – hydroxybenzenecarboxylic acid
H
O O
C H
O O
C OH
HO
2-hydroxybenzenecarboxylic acid 4-hydroxybenzenecarboxylic acid
2-hydroxybenzenecarboxylic acid is about 40 times more acidic than that of 4-hydroxybenzenecarboxylic acid
since the conjugate base is once again stabilized by intramolecular H-bond.
H δ- δ-
O O
-O O
O O C H C
C H
O O-
O
a) Effect of solvent
Acid shows higher acidity in polar solvent. e.g. Hydrogen chloride is a strong acid in water but not acidic in
methylbenzene. Ions can be stabilized in polar solvent but not in non-polar solvent.
b) Steric hinderance to solvation
Bulky acid ⇒ hindered negative centre ⇒ less solvation stabilization ⇒ unstable conjugate base ⇒ lower acidity
The theory regarding the strength of acid is also applicable to the strength of base. The strength of a base is also
depending on the relative stability of the conjugate acid comparing with the parent base.
Amines exhibit a similar steric hinderance to solvation.
In gas phase where there is no solvation, the order of base strength is (CH3)3N > (CH3)2NH > CH3NH2 [3º > 2º >
1º] which is governed by the positive inductive effect (+I) of methyl group only.
But in water, the order of base strength of methylamines is (CH3)2NH > CH3NH2 > (CH3)3N [2º > 1º > 3º]. The
result is a combination of inductive effect and steric hinderance to solvation. The bulky conjugate acid formed,
aminium ion, is less stabilized by solvation.
5. Size of the conjugate base - (Strength of bond between the proton and the conjugate base)
On moving down a group (from F–H to I–H), the bond length increases and bond strength decreases tremendously
(from 568 kJmol-1 to 298 kJmol-1).
Acidity H–F< H–Cl < H–Br < H–I

pKa 3.2 -7 -9 -10
bond dissociation energy / kJmol-1 568 432 366 298
Ionic size of the conjugate base (X-) increa
 →
sin g
As the size of the conjugate base gets larger, the charge density on the X- gets lower and becomes more stable. As a
result HI is most acidic one.
Indeed, acidity is depending on relative stability instead of bond strength. However, an acid molecule possessing a
weak bond is usually unstable, it tends to lose the proton to the base (water) to form a more stable system.
H–I(aq) + H2O(aq) d I-(aq) + H3O+(aq)

less stable combination more stable combination
The overall change can be considered as the breaking of a weak H–I bond and formation of a strong H–O bond, as
a result the overall stability of the system is enhanced.
N.B. Solely strength of bond would not be accepted as a valid explanation to the difference in acidity.
Besides the dispersion of the negative charge on the conjugate base, an increase in attraction between the electrons
and the nucleus also enhances the stability of the conjugate base.
High electronegativity makes an atom attract the negative charge more strongly and form a more stable anion.
Therefore, F- ion is more stable than OH- ion as F is more electronegativity than O.
On moving across a period (from C–H to F–H), the bond strength only increases moderately from 425 kJmol-1 to
568 kJmol-1. The effect of difference in size is outweighed by the big difference in electronegativity.
Acidity H3C–H < H2N–H < HO–H < F–H

pKa 50 38 15.74 3.2
bond dissociation energy / kJmol-1 425 431 498 568
Electronegativity of the atom 2.5 3.0 3.5 4.0
(Pauling scale)
hybridization s character pKa
Ethyne H C C H sp 50% 25
Ethene
H H sp2 33.3% 44
C C
H H
H H
Ethane sp3 25% 50
H C C H
H H
The stronger the s character a carbon atom possesses, the closer will be the bonding electron to the nucleus. This is
because s orbital is closer to the nuclei than the p orbital. The carbon atom possessing more s character behaves
like a more electronegative atom and leads to a more stable carbanion.
H H H H
Stability H C C > C C > H C C
H H H
Consequently, the acidity of hydrocarbon decreases with following order : alkyne > alkene > alkane.
Glossary Arrhenius acid-base Brønsted-Lowry acid-base Lewis acid-base acidity constant

leveling effect free energy change inductive effect resonance effect electronic effect
Vorlander's rule intramolecular hydrogen bond steric hinderance
Past Paper 91 2C 9 a ii
Question 92 1A 3 c 92 2C 9 b
93 1A 3 f i ii
94 1B 4 a
95 1A 3 b
96 1A 2 e ii iii 96 1A 3 b
99 2A 4 c i
91 2C 9 a ii
9a Outline chemical tests which would allow you to distinguish between the compounds in the following pairs.
Describe what you would observe in each case.
ii COOH OH 2
Add solution of sodium hydrogencarbonate to the compounds. PhCOOH will react to give CO2 bubble
(effervescence observed). PhOH give no observable change.
COOH COO-Na+
+ NaHCO3 + CO2
92 1A 3 c
3c In aqueous media, why does ammonia act as a base whereas hydrogen fluoride acts as an acid? 2
Higher electronegativity of F than N on HF makes HF acidic because the proton experiences less electron sharing
and is easier to release. 1 mark
The prominent lone pair on N in NH3, comparing with the withheld electrons pair on F in HF, donates the lone
pair more readily and favours basic properties. 1 mark
C This question required reasons, rather than statements in the form of equations. Various explanations might have
been provided; such as a discussion of the different shielding and ease of release or acceptance of protons when
there is a change in the electronegativity of the atom to which they are bonded.
92 2C 9 b
9b Arrange the following hydroxy-compounds in order of increasing acidity. Explain your order. 5
OH OH OH
NO2
OH
OH OH
< <
NO2
1 mark
Acidity depends on the equilibrium HA d H+ + A- 1 mark
Phenoxide ion is stabilized by resonance, ½ mark
O- O O O
- -
-
i.e. ½ mark
∴phenol is more acidic than cyclohexanol.
The nitro group in the nitrophenol is electron withdrawing which attracts electron and is capable of resonance,
thus further stabilizes the phenoxide ion. 1½ mark
O- O
N N -
-
O O- O O
½ mark
C Many candidates did not use the equilibrium between the acid and its conjugate base to interpret the acid strength.
Candidates described –NO2 group incorrectly in this answer as a deactivating group rather than an electron-
withdrawing group. A few candidates regarded the nitro-group as electron-donating.
93 1A 3 f i ii
3f Consider the following compounds:
O
H C CH3
and
OH OH
Y Z
i Account for the fact that both Y and Z are acidic.

Acidity depends on the equilibrium HB(aq) d H+(aq) + B-(aq) ½ mark
Both compounds have phenol functional group which can be involved in above equilibrium ½ mark
In cases of phenols, equilibrium lies to the right due to resonance stabilization of the phenoxide ion ½ mark
Explanation of resonance stabilization :
O O O -
O
- -
-
R R R R
½ mark
ii Which compound, Y or Z, is the stronger acid? Explain. 2
Y is the stronger acid. ½ mark
O
This is because the electron withdrawing C group further stabilizes the phenoxide ion. 1 mark
-
- O O
O O
H H
½ mark
C Most candidates explained the acidity of phenols in terms of the weakening of the O–H bond by resonance,
instead of a more formal consideration in terms of the stability of the phenoxide ion. Some could not write
resonance structures correctly. Few candidates explained acidity in terms of equilibrium.
94 1B 4 a
4a Describe a chemical test to show that ethanoic acid is a stronger acid than phenol. (Tests involving the use of a 2
pH meter or indicator paper are NOT accepted.)
Addition of Na2CO3(aq) or NaHCO3(aq) to CH3COOH(aq) gives CO2(g) / effervescence. 1 mark
Addition of Na2CO3(aq) or NaHCO3(aq) to phenol does not give CO2(g) /effervescent 1 mark
Or
Only CH3COOH(aq) reacts with Mg
Insoluble base oxide e.g. CuO(s) is soluble only in CH3COOH(aq)
C Some candidates did not read the question with enough care. Instead of giving a chemical test, they employed
physical methods (e.g. conductivity measurement) and therefore were not credited with marks. Others erroneously
stated that the stronger acid would require a larger volume of base for neutralization.
95 1A 3 b
3b Arrange the following carboxylic acids in the order of increasing acidity. Explain your arrangement. 3
ClCH2CO2H, ClCH2CH2CO2H and FCH2CO2H
ClCH2CH2CO2H < ClCH2CO2H < FCH2CO2H 1 mark
Inductive effect by electron withdrawing group stabilizes the carboxylate anions more than the carboxylic acids.
½ mark
F is more electronegative than Cl and closest to the carboxylate / carboxyl group ∴ FCH2CO2H is most acidic
½ mark
the Cl substituted carboxylic acids, inductive stabilization operates most effectively with decreasing distance. ∴
the order of increasing acidity follows the decreasing distance. 1 mark
C It was surprising to see that many candidates answered that the stronger the acid, the weaker the O–H bond.
Candidates should know that bond strength does not have a direct bearing on acidity and only the relative stability
of the acid and the conjugate base dictate the acidity.
96 1A 2 e ii iii
2e Which is the stronger acid in each of the following pairs of substances ? Briefly explain your choice.
ii HClO3 (aq) , HClO4(aq) 2
HClO4 ½ mark
the conjugate base ClO4- ½ mark
possesses a large no. of oxo croup (O atoms) ½ mark
is stabilized to a greater extent by resonance / mesomeric effect. ½ mark
Or,
In HClO4, the Cl has a higher oxidation state and ½ mark
a larger number of oxo groups (O atoms). ½ mark
which can induce a higher positive charge density on H.♣ ½ mark
iii HMnO4 (aq) , H2CrO4(aq) 2
HMnO4 ½ mark
The conjugate base MnO4- ½ mark
possesses a large no. of oxo group than HCrO4- ½ mark
is stabilized to a greater extent by resonance / mesomeric effect. ½ mark
Or,
Mn has a higher O.S. than Cr, ½ mark
MnO4- is singly charged while CrO42- is doubly charged, ½ mark
thus the conjugate base MnO4- is more stable. ½ mark
Or,
Mn has a higher oxidation state ½ mark
and a larger number of oxo groups, ½ mark
which can induce a higher positive charge density on H.♣ ½ mark
(For answers marked with ♣, maximum 1 mark)
C It was mentioned in the 1995 Subject Report that bond strength does not have a direct bearing on the acidity of a
compound, and that the relative stability of an acid and its conjugate base dictates the acidity. However, many
candidates still wrote that with the increase in polarization, the O−H bond in the oxoacid weakens and hence its
acid strength increases.
Most candidates correctly chose the stronger acid but gave an incorrect explanation. Many did not know that
resonance stabilization in oxoacids is related to the number of oxogroups attached. Some candidates drew wrong
structures for the oxoacids with H bonded to the central atom. As a result, they wrongly explained the acid
strength in terms of the polarization of the Cl–H or Mn–H bond.
96 1A 3 b
3b Arrange the following compounds in the order of increasing basic strength. Explain your arrangement. 3
NH2
NH2
, and NH3
NH2
NH2
< NH3 <
Basicity : 1 mark
The basicity of an amino compound depends on the position of the following equilibrium
RNH2 + H2O d RNH3+ + OH- ½ mark
The primary amine is a stronger base than NH3
Q Electron donating property / inductive effect of alkyl group stabilizes the RNH3+ to a greater extent. ∴ 1º
amine is more basic / the e- pair is more available. ½ mark
For the aromatic amine, overlapping of the orbital containing the lone pair in N with the e-electron cloud of the
benzene ring makes the lone pair less available. ½ mark
Thus, the equilibrium lies on the LHS. ½ mark
NH2
∴ is the weakest base
C Most candidates explained the relative strengths of the bases in terms of the availability of the lone pair of
electrons on the N atom. Only a few candidates completed their answers with a discussion of the equilibrium
position.
Some wrongly chose
NH2
as the strongest base, saying that the cation

+
NH3
is stabilized by resonance which leads to a dispersion of the positive charge.
99 2A 4 c i
4c i Arrange, with explanation, the compounds below in the order of increasing acidity.
HCO2H, CH3CO2H and CF3CO2H
Isomerism
A. Chain isomerism
II. Stereoisomerism
2. Physical and chemical properties of cis-/trans-geometric isomers of butenedioic
acid
B. Optical isomerism / Enantiomerism
2. Optical activity
c) Specific rotation
3. Chiral centre
Isomerism Unit 1 Page 1
Topic Isomerism Unit 1
Reference 15.0–15.1 15.2.1

Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 26–33
Organic Chemistry, Solomons, 5th Edition pg. 164–174, 179–186, 201–203, 175, 302, 836
Organic Chemistry, Fillans, 3rd Edition pg. 35–49
Organic Chemistry, Morrison Boyd, 6th Edition pg. 125–138, 144–146, 158–160
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 390–391
Organic Chemistry, 6th Edition, Solomons, pg. 59-61
Syllabus Isomerism
Structural isomerism
Stereoisomerism
Geometrical isomer (Diastereomer)
Notes Isomerism
Isomers are different compounds sharing Isomerism

(same molecular formula)
the same molecular formula.
Structural isomers are also called

constitutional isomers. The atoms of the Structural / Constitutional Stereoisomerism
isomers are connected in a different order. Isomerism (same structural formula /
(different structural formula / connectivity) connectivity)
They are said to have a different
connectivity.
Stereoisomers differs only in arrangement Chain Position Functional Tautomerism

of their atoms in space but have the same Isomerism Isomerism Group
Isomerism
connectivity.
Diastereomerism / Enantiomerism /
Geometrical Isomerism / Optical Isomerism
cis-trans Isomerism (Each isomer is not the
(Each isomer is the mirror image of
mirror images of its own)
its own)
A. Chain isomerism
They have different carbon chains or skeletons.
(Branched and unbranched chain)
e.g. C4H10
CH3 CH CH3
CH3 CH2 CH2 CH3 CH3
butane 2-methylpropane
They are molecules which have a substituent in different positions on the same carbon skeleton.
(Alkanol)
e.g. C3H8O
CH3 CH2 CH2 OH CH3 CH CH3
propan-1-ol OH
propan-2-ol
(Disubstituted benzene)
e.g. C8H10
CH3 CH3
CH3 CH3 CH3 CH3
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene

They are isomers in different homologous series and have different functional groups
(Ether and alcohol)
e.g. C2H6O
CH3 O CH3 CH3 CH2 OH
methoxymethane (dimethyl ether) ethanol
(Acid and Ester)

e.g. C4H8O2
O O
CH3 CH2 CH2 C O H CH3 CH2 C O CH3
butanoic acid methyl propanoate
Tautomerism is a kind of dynamic isomerism. It is a rapid and reversible interconversion of isomers associated
with the actual movement of electrons as well as of one or more hydrogen atoms.
Tautomerism must not be confused with resonance. Each tautomer is capable of independent existence and
potential isolation. Tautomers represent real compounds, whereas individual resonance structure does not.
(Keto-enol tautomerism)
e.g. C3H6O
O OH Interconvertible keto and enol forms are known as
tautomers, and their interconversion is called
CH3 C CH3 CH2 C CH3
tautomerizaton.
keto form enol form
> 99 % 1.5 × 10-4 % Usually the enol form contributes only a very small
propanone propen-2-ol percentage in the equilibrium.
II. Stereoisomerism
By definition, a diastereomer is a stereomer which is superposable with its own mirror image.
However, a pair of diastereomers are not mirror images of each other.
cis-trans isomerism is a kind of diastereomerism, where its existence is due to hindered / restricted rotation of
double bond. But-2-ene and hexa-2,4-diene are two of the examples.
They have similar but not identical chemical properties and very different physical properties.
(but-2-ene CH3CH=CHCH3)
CH3 CH3 CH3 H
C C C C
H H H CH3
cis-but-2-ene / (Z)-but-2-ene trans-but-2-ene / (E)-but-2-ene
For cis-isomer, the two identical groups (usually hydrogen atoms) are on the same side. (Latin: 'cis' = on this side)
For trans-isomer, the two identical groups are on the opposite sides. (Latin: 'trans' = across)
For trisubstituted or tetrasubstituted alkene, the terms cis and trans are either ambiguous or do not apply at all since
there is no two identical groups.
For this kind of structure, the configuration can be denoted by (E-Z) system which is based on the atomic number
(bulkness).
(Z) German: 'zusammen' = together

(E) German: 'entgegen' = across
Consider
Based on the atomic number,
Br Cl Br has a higher priority than H
C C Cl has a higher priority than F
H F
Since Br and Cl are on the same side (together), the
(Z)-2-bromo-1-chloro-1-fluoroethene structure is called (Z)-1-chloro-1-fluoro-2-bromoethene.
For further details, please read Solomons pg. 302 and 175
Cl Cl Cl H
C C melting point - 80 ºC C C melting point -50 ºC
H H boiling point 60 ºC H Cl boiling point 48 ºC
cis-1,2-dichloroethene dipole moment 1.90 D trans-1,2-dichloroethene dipole moment 0D
The boiling point of the cis-isomer is higher than that of the trans-isomer because the intermolecular forces among
the former one are stronger, i.e. it is polar. However, the melting point of the later one is higher because the trans-
isomer is more symmetrical in shape and can be packed more regularly in the solid crystal.
Because the melting point of a substance is affected by the packing of the molecule on top of the intermolecular
forces, boiling point is a better indicator of the strength of the intermolecular forces.
2. Physical and chemical properties of cis-/trans-geometrical isomers of butenedioic acid
Butenedioic acid is another example exhibiting geometrical isomerism.
H CO2H H CO2H
C C
C C
H CO2H (maleic acid) HO2C H (fumaric acid)
cis-butenedioic acid / (Z)-butenedioic acid trans-butenedioic acid / (E)-butenedioic acid
Maleic acid Fumaric acid

Dipole moment non-zero zero
Solubility Higher Lower
Melting point 131 ºC 287 ºC
Although the dipole moment of fumaric acid is zero, it is capable to form intermolecular hydrogen bond.
Therefore, the melting point is higher.
Dipole moment
Maleic acid has a stronger dipole moment than fumaric acid.
Maleic acid has 2 dipole The 2 dipole moments of

H CO2H moments pointing to the H CO2H fumaric acid opposing
C same side and gives a non- C each other and give a zero
C zero resultant. Therefore, C net dipole moment
H CO2H it is more soluble in polar HO2C H
solvent. i.e. water.
Melting point
Maleic acid has a lower melting point than fumaric acid.
Although maleic acid has a stronger dipole moment, the formation of intramolecular hydrogen bond reduces the
formation of intermolecular hydrogen bond. This reduces the extent of the hydrogen bond formed between
adjacent molecules in the crystal and causes a lower melting point than that of fumaric acid.
Acidic properties
Both acids show acidic properties in water but have different acidity.
H CO2H H CO2H
C C
C C
H CO2H maleic acid HO2C H fumaric acid
pKa1 = 1.83 pKa2 = 6.07 pKa1 = 3.03 pKa2 = 4.44
The difference is due to the formation of intramolecular H-bond stabilized conjugate base of maleic acid.
Dehydration
When maleic acid is heated to 140ºC, water is
evolved and anhydride forms.
By contrast, no reaction takes place when

fumaric acid is heated to 140ºC. At 290ºC, there
is sufficient energy to overcome the barrier of
rotation about the C=C double bond and the cis
configuration required for anhydride formation
is attained.
Interconversion between maleic acid and fumaric acid
Maleic acid can also be converted to fumaric acid by boiling with hydrochloric acid catalyst. Since fumaric acid is
more stable than maleic acid, the equilibrium lies much towards the fumaric acid side. This is because in fumaric
acid, the two bulky carboxyl groups are further apart and experience less steric repulsion.
Glossary structural / constitutional isomer stereoisomerism tautomerism / tautomerization

geometrical isomerism diastereomerism
Past Paper 92 1A 1 a i
Question 94 2C 7 a
96 2C 8 b i
97 1A 4 a i ii 97 1A 4 b i
98 1A 4 b i 98 2B 5 a ii
92 1A 1 a i
1a There are several isomers of benzenedicarboxylic acid.
i Draw the structures of all possible isomers of benzenedicarboxylic acid. 1½
CO2H
CO2H
CO2H
CO2H
CO2H
CO2H
½ mark each
94 2C 7 a
7a What do you understand by the terms “structural isomerism” and “stereoisomerism”? 3
Structural isomerism – occurrence of more than one structure for a given molecular formula 1 mark
Stereoisomerism – occurrence of more than one configuration (different arrangements of groups in space) for a
give structural formula. 1 mark
Examples to illustrate the two types of isomers. 1 mark
C Badly-answered. Not many candidates gave precise definitions for 'structural isomerism' and 'stereoisomerism'.
Instead, they just used examples (correctly or incorrectly drawn) to illustrate the various kinds of isomers. The
following terms were often used incorrectly : molecular formula, structural formula, empirical formula.
96 2C 8 b i
8b The following compounds can exist in isomeric forms :
In each case, state the type of isomerism and draw suitable representations for the isomers.
i butenedioic acid, and 2
Geometrical isomerism / cis-trans isomerism 1 mark
(Deduct ½ mark for spelling mistake)
COOH COOH
HOOC COOH
½ + ½ mark
C Many candidates did not assign trans- and cis-isomers. Some wrongly gave positional isomers as the answer.
97 1A 4 a i ii
4a The formula HO2CCH=CHCO2H can represent two compounds. 2
i Draw a structure for each compound, clearly showing the difference between them.
ii One of the compounds reacts with P2O5(s) to give compound A . Give the structure of A.
97 1A 4 b i
4b i Draw all possible isomeric structures of dimethylbenzene. 3
98 1A 4 b i
4b Alcohol E has the structure CH3CH(OH)C2H5.
i Draw the structures of three structural isomers of E, all of which are alcohols. 1½
98 2B 5 a ii
5a Consider the following compound F. 5
CH3 CH CH C CH
a b c d
F
ii Draw all possible three-dimensional structures for F, indicating the expected bond angles around the carbon atoms
a, b, c, and d in one of the structures.
Topic Isomerism Unit 2
Reference 15.2.2
Organic Chemistry, Solomons, 5th Edition pg. 164–174, 179–186, 201–203, 175, 302, 836
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 392–393, 420, 512
Organic Chemistry, 6th Edition, Solomons, pg. 178-185, 188, 193-198, 200
Syllabus Optical isomerism / Enantiomerism

Optical activities
Chiral centre
Racemic mixture
Notes B. Optical isomerism / Enantiomerism
Optical isomers are also known as enantiomers. Individual enantiomer is not the mirror images of its own.
From another point of view, enantiomers exist in pairs. They are non-superposable mirror images of each other. In
order to describe this properties, the molecules are said to be chiral. In Greek, 'chiral' means: 'cheir' = hand, since
the two hands are non-superposable mirror images of each other..
e.g. butan-2-ol
CH2CH3 CH2CH3 CH2CH3

C H H C ≡ C OH
H3C OH HO CH3 H3C H
(+)-2-butanol (-)-2-butanol
Plane symmetry in diastereomer (cis-but-2-ene)

Structurally, all chiral molecules do not have a plane of
symmetry.
H3C CH3
Unlike enantiomer, diastereomer has at least one plane C C 2nd plane of symmetry
of symmetry. And because of this difference, only H H
enantiomer shows optical activity.
1st plane of symmetry

The 2 enantiomers may be denoted by several different methods
i) (+) or (-) based on the optical activity of the enantiomers.
ii) (R-S) system based on the absolute configuration which is similar to the (E–Z) system for geometrical isomers.
For further details, please read Solomons, pg. 174–179
iii) By relative configuration comparing with a standard compound called Glyceraldehyde.

For further details, please read Solomons, pg. 199–201
Methods ii) and iii) will not be discussed in the Hong Kong A-level syllabus.
They have almost exactly the same chemical and physical properties except optical activity.
The mixing of 2 enantiomers causes melting point depression proving that the 2 isomers are indeed different.
(R)-butan-2-ol or (-)-butan-2-ol (S)-butan-2-ol or (+)-butan-2-ol

or (R)-(-)-butan-2-ol or (S)-(+)-butan-2-ol
Boiling point (1 atm) 99.5 ºC 99.5 ºC

Density (gcm-3 at 20 ºC) 0.808 0.808
Refractive index (20 ºC) 1.397 1.397
2. Optical activity
Optical activity is the properties possessed by certain substances of rotating the plane of polarization of polarized
light.
Light is an electromagnetic phenomenon.
A beam of light consists of two mutually perpendicular

oscillating fields: an oscillating electric field and an
oscillating magnetic field.
An ordinary light beam consists of oscillations of the electric field occurring in all possible planes perpendicular to
the direction of propagation.
By contrast, a plane-polarized light has an electric field oscillating only in one plane. It can be produced by
passing an ordinary light beam through a polarizer.
Because of the asymmetrical distribution of electron cloud in an enantiomer, an enantiomer is capable to interact
with the electric field and alter the direction of oscillation of the plane-polarized light.
If a substance rotates the plane-polarized light to the right hand side, it is said to be dextrorotatory. (Latin: 'dexter'
= right). And the enantiomer is denoted by (+)- prefix. e.g. (+)-butan-2-ol
Similarly, if the plane-polarized light is rotated to the left, the substance is said to be levorotatory, denoted by (-)-
prefix. (Latin: 'laevus' = left). e.g. (-)-butan-2-ol
c) Specific rotation (Details not required)
Since the degree of rotation is depending on a lot of factors including

i) length of the polarimeter tube
ii) concentration of the sample
iii) wave length of the light source
iv) temperature
v) nature of solvent
α
For the purpose of comparison, a specific rotation [α] is defined as [α] = .
c×l
where [α] is the specific rotation
α is the observed rotation
c is the concentration of the solution in gcm-3 of solution or density in gcm-3 for pure liquid
l is the length of the tube is dm
25
e.g. [α] D = +3.12º means the specific rotation is 3.12º in a clockwise direction at 25ºC using D line of a sodium
lamp. (λ = 599.6 nm). In reporting a specific rotation, the solvent used should be quoted.
N.B. The direction of the optical rotation has no direct relationship with absolute configuration of the molecule.
It can only be determined by the experiment. e.g. a molecule with (R) configuration may be dextrorotatory
or levorotatory.
3. Chiral centre
The C-2 of butan-2-ol has four different groups attaching to it tetrahedrally. The C-2
H
is called the chiral centre or chiral carbon. CH3 C* CH2CH3
By interchanging any two groups attached to the chiral centre, one enantiomer can be OH
converted to another.
A molecule contains one chiral centre only must be a chiral molecule.
If a mixture contains equal amount (50%-50%) of (+)-isomer and (-)-isomer, the mixture will show no optical
activity. Owing to the opposing effect of the two enantiomers, optically activity of one cancels that of another one.
Such kind of mixture is called racemic mixture and denoted by (±)- prefix. e.g. (±)-butan-2-ol
Glossary optical isomerism / enantiomerism chiral plane of symmetry optical activity

plane polarized light polarizer polarimeter dextrorotatory levorotatory specific rotation
chiral carbon racemic mixture
Past Paper 90 2C 8 a iv v
Question 93 2C 9 c
96 2C 8 b ii
98 1A 4 a ii 98 1B 8 a i
99 2B 6 c i ii iii
90 2C 8 a iv v
8a It is suggested that the structure of a compound having the molecular formula C12H11ClO4 is either A or B.
COOH COOH
CH3 CH3
Cl CH C CH C
CH3 CH2Cl
COOH COOH
A B
iv Assuming the compound has the structure A, give the structural formula of the hydrogenation product from 2
reaction with one mole of hydrogen. Would you expect the product to show optical activity? Explain your
answer.
COOH
CH3
Cl CH2 CH
CH3
COOH
1 mark
not optically active, because there is no chiral center. 1 mark
C Most candidates gave correct answers to this part.
v Repeat part (iv) assuming the compound has the structure B. 3
COOH COOH
CH3 CH3
CH2 C H CH2 C CH2Cl
CH2Cl H
COOH COOH
, 1 mark
not optically active, because it is a racemic mixture. 2 marks
C Over 90 % of the candidates were not aware that the hydrogenation product was a racemic mixture and hence
optically inactive.
93 2C 9 c
9c 2-Bromobutane can exist in isomeric forms. Draw a suitable representation for each of these isomers. 2
CH3 CH3
Et Et Br Et Et Br
Br C CH CH3 C Br H H
3
H H
or 1 mark each
C Candidates should pay more attention in providing a proper 3-dimensional structural formula.
96 2C 8 b ii
8b The following compounds can exist in isomeric forms :
In each case, state the type of isomerism and draw suitable representations for the isomers.
ii 2-aminopropanoic acid. 2
enantiomerism / optical isomerism 1 mark
(Deduct ½ mark for spelling mistake)
CO2H CO2H
H NH2 H2N H
CH3 CH3
½ + ½ mark
(Accept any appropriate representation of enantiomerism)
C Some candidates showed weakness in three-dimensional representations. Enantiomerism instead of optical
isomerism should have been given. Some wrongly gave stereoisomerism as the answer. Two incorrect
representations given by candidates are shown below.
NH2 NH2
H C CO2H C
H CO2H
CH3 CH3
98 1A 4 a ii
4a Alcohol E has the structure CH3CH(OH)C2H5.
ii What type of isomerism can be exhibited by E ?
98 1B 8 a i
8a Show how you would
i determine whether a sample of C2H5CH(OH)CH3 is in the (+) form or (±) form.
99 2B 6 c i ii iii
6c State the relationship between each pair of structures shown below:
i CH2CH3 CH2CH3
and
Cl Cl
Cl Cl
ii CH3 H CH3CH2 CH3

C C and C C
H CH2CH3 H H
iii Br H
C CH and C CH
3 3
CH2 CH H CH2 CH Br
Reaction Mechanism
I. Bond breaking
A. Free radical (electron deficiency)
B. Electrophile (electron deficiency)
C. Nucleophile (electron rich)
1. Substitution
2. Addition
3. Elimination
IV. Nucleophilic substitution

1. Nucleophile
2. Leaving group
F. Rate of hydrolysis of haloalkane, haloalkene and halobenzene
G. Other relevant reactions
2. Reactions of alkanol
a) Haloalkane from alkanol (ROH → RX)
3. Reactions of amine
V. Elimination reaction
3. Effect of bascity of the nucleophile
D. Other relevant reactions
1. Reaction of haloalkanes with alcoholic sodium hydroxide to alkene, diene and
alkyne
VI. Nucleophilic addition (Nucleophilic addition-elimination)
A. AdN reaction
1. Addition of HCN to carbonyl compound
b) Steric effect
3. Other relevant reactions
b) Reactions of carboxylic acid and its derivatives
(a) Difference between carbonyl compound and carboxylic acid
and its derivatives
(2) Formation of different acid derivatives
(b) Formation of ester (Esterification with alkanol and phenol)
(c) Formation of acid anhydride
(ii) Through intermolecular dehydration by a very strong
dehydrating agent
(d) Formation of amide (Acylation and benzoylation of amine)
(4) Reaction of amide
c) Reactions of nitrile
(1) Hydrolysis of nitrile and amide
b) Comparision of ozonolysis and oxidative cleavage
6. Oxymercuration of alkyne
VIII. Electrophilic substitution

a) Reduction of nitrobenzene
5. Diazocoupling of diazonium ion
IX. Free radical Reaction
1. Chain reaction e.g. Polymerization of alkene
2. Anti-Markownikoff orientation
Reaction Mechanism Unit 1 Page 1
Topic Reaction Mechanism Unit 1
Reference 16
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 40–41, 44–46
Organic Chemistry, Solomons, 5th Edition pg. 209–211
Organic Chemistry, Morrison Boyd, 6th Edition pg. 165–167
Reading Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 403–406, 440–441
Assignment Organic Chemistry, 6th Edition, Solomons, pg. 87-90, 94-96
Syllabus Introduction to reaction mechanism

Types of bond breaking
Types of reactive species
Types of reactions
Notes Reaction Mechanism
A chemical reaction is a sequence of bond-breaking and bond-forming steps involving bonding and nonbonding
electrons. A detailed description of a chemical reaction outlining each separate stage is called the Mechanism.
Chemical reaction can be interpreted as redistribution of e- and rearrangement of atoms which leads to formation of
new substance.
I. Bond breaking
All kinds of reactions are initiated by a bond breaking process. There are 2 kinds of bond breaking process :
Homolytic fission (Homolysis) – the electrons forming the bond broken are shared equally between the
fragments formed. This leads to formation of 2 radicals.
Heterolytic fission (Heterolysis) – the electrons forming the bond broken are shared unequally between the
fragments formed. This leads to formation of 1 cation and 1 anion.
Mode of bond breaking Electronegativity
Homolytic fission A≈B

A B A + B (Symmetrical fission)
Heterolytic fission A>B

A B A- + B+ (Unsymmetrical fission)
Heterolytic fission A<B

A B A+ + B- (Unsymmetrical fission)
movement of an electron pair

movement of a single electron
Homolysis Heterolysis
Carbon radical and carbocation are electron deficient species. Both of them do not have fulfilled octet.
Carbanion is an electron rich species. It has surplus electrons available for bonding.
With reference to different modes of bond breaking, 3 different reactive species may form.
A. Free radical (e.g. A· or B·) – An electron deficient species with unpaired electron. e.g. Cl·
B. Electrophile (e.g. A+ or B+) – An electron deficient species which tends to react with negative centre. e.g.
H+, Cl+, Br+, NO2+. All electrophile are also Lewis acids.
C. Nucleophile (e.g. A or B ) – An electron rich species which tends to react with positive centre. e.g. -OH, Cl-
- -
, CN-, H-. Some nucleophile contains a lone pair instead of a negative charge.
e.g. H2O, ROH, NH3, RNH2. All nucleophile are also Lewis bases.
Then, the reactive species reacts with the substrate and a new bond is formed.
According to the reactive species involved, most of the organic reactions can be classified into
1. Nucleophilic reaction
2. Electrophilic reaction
3. Radical reaction
And according to the outcome of the product, the reactions can be classified into
1. Substitution
2. Addition
3. Elimination S : Substrate R : Reagent

'
1. Substitution
Nucleophilic substitution – e.g. Hydrolysis of haloalkane to form alkanol (RX + H2O → ROH + HX)
Electrophilic substitution – e.g. Nitration of benzene (C6H6 + NO2+ → C6H5NO2 + H+)
Radical substitution – e.g. chlorination of methane (CH4 + Cl2 → CH3Cl + HCl → CH2Cl2 + HCl → etc.)
2. Addition
Nucleophilic addition – e.g. Addition of hydrogen cyanide to carbonyl compound (Formation of cyanohydrin)
Electrophilic addition – e.g. Addition of HBr to alkene (CH2=CH2 + HBr→ CH3–CH2Br)
Radical addition – e.g Polymerization of ethene (CH2=CH2 → –[CH2–CH2]n–)
3. Elimination
e.g. Dehydration of ethanol to ethene (CH3CH2OH → CH2=CH2 + H2O)

Mechanisms required in HK 97 A-Level syllabus

Nucleophilic Electrophilic Radical
Substitution 97 A-Level Details not required 97 A-Level
Addition 97 A-Level 97 A-Level 97 A-Level
Elimination Details not required Not present Not present
Although Elimination reaction is not known as Nucleophilic Elimination, like the Substitution and Addition, it
takes place in the presence of a strong base e.g. CH3CH2O-Na+ which is a nucleophile.
Glossary mechanism homolytic fission heterolytic fission carbocation / carbenium ion / carbonium ion
carbanion free radical electrophile nucleophile substitution addition elimination
Past Paper
Question
Reference 17.0.1–17.0.2
Organic Chemistry, Solomons, 5th Edition pg. 212–236, 240–243
Organic Chemistry, Morrison Boyd, 6th Edition pg. 172–203, 208–210
Organic Chemistry, 6th Edition, Solomons, pg. 224-233, 238-252, 256-259
Syllabus Nucleophilic substitution

SN2 reaction
SN1 reaction
Stability of carbocation
Competition between SN2 and SN1 reaction
Notes IV. Nucleophilic substitution
Nu + C L C Nu + L
δ+ δ-
Nu: – Nucleophile L: – Leaving group
When an electronegative atom (L) is attached to an C atom, the C–L bond would be polarized. The C atom
possesses a partial positive charge and is vulnerable to the attack of a nucleophile.
1. Nucleophile
Nucleophile is an electron rich species which donates its

electrons to the positive centre. The ability of a species Relation of nucleophilicity to basicity for atoms in
to be a nucleophile is called nucleophilicity. the same row (similar size) of the periodic table
Nucleophilicity of a nucleophile depends on 2 factors:
1. Availability of electrons (Lewis basicity)

2. Polarizability of electrons
1. Availability of electrons (Lewis basicity)
Nucleophilicity is parallel to Lewis basicity. i.e. the

ability to donate electron. e.g. OH- is a stronger
nucleophile than H2O.
N atom is more nucleophilic than O atom because N is
less electronegative and has less attraction on the lone
pair electrons and makes them more available. e.g. NH3
is a stronger nucleophile than H2O. Relation of nucleophilicity to basicity commonly
observed for atoms in same family (different size) at
2. Polarizability of electrons the periodic table
However, nucleophilicity is something more than just

basicity. Besides the availability of electrons, it is also
depending on the ability to form bond. This involves
distortion and redistribution of electron cloud. i.e.
polarizability of the species.
In general, polarizability is mainly depending on the

size and electronegativity of the atom.
For the atoms with similar size (atoms in the same period), thus similar polarizability, the nucleophilicity is parallel
to the basicity.
e.g. NH3 is a stronger nucleophile than H2O.
For atoms with very different size, the nucleophilicity is depending on both polarizability and basicity.
e.g. Though I- is a weaker base than Cl- ion, it is much bigger than Cl- ion and with much higher polarizability.
Experimentally, it is found that I- ion is a stronger nucleophile than Cl- ion.
N.B. The actual nucleophicity of a nucleophile has to be determined through measuring the rate of a
nucleophilic reaction.
2. Leaving group
It is observed that weaker a base, better will be the Relation of Leaving group ability to the bascity
leaving ability.
Basicity is also a measure of stability of a base. A weak

base is more stable than a strong base as the negative
charge on the molecule is less concentrated.
The formation of a more stable leaving group (a weak

base) involves a lower activation energy, so this is more
favorable.
(Refer to Rate of reaction Unit 4)
SN2 stands for Bimolecular nucleophilic substitution since 2 molecules are involved in the formation of the
transition state.
For an SN2 reaction, the rate of reaction depends on The energy profile for the reaction can be depicted as
both the concentration of nucleophile and the substrate. follows.
e.g. Rate ∝ [OH-][CH3CH2CH2CH2Br]
Rate = k[OH-][CH3CH2CH2CH2Br]
Inversion of configuration
The nucleophile approaches the substrate molecule from

the opposite side of the leaving group to minimize steric
repulsion.
The nucleophile forms a trigonal bipyramidal transition

state (pentavalent) with the substrate. The departure of
the leaving group results in an inversion of
configuration.
Effect of the structure of the substrate
The ease of approaching of the nucleophile affects the rate dramatically. A less sterically hindered C atom will be
more vulnerable to the attack of the nucleophile and involve a lower activation energy.
Simple haloalkanes show the following general order of reactivity in SN2 reactions:
methyl > primary > secondary > (tertiary) almost no reaction

(Refer to Rate of reaction Unit 4)
SN1 stands for Unimolecular nucleophilic substitution since only 1 molecule is involved in the formation of the
transition state in the rate determining step.
CH3 CH3
CH3 C Cl + OH-(aq) CH3 C OH + Cl-(aq)
CH3 CH3
Rate = k[(CH3)3CCl]
Step 1 (slow)
CH3 CH3
CH3 C Cl CH3 C + + Cl-
CH3 CH3
Step 2 (fast)
CH3 CH3
CH3 C+ -OH CH3 C OH
CH3 CH3
As formation of the transition state

for step 1 involves a higher
activation energy Ea’, the step 1
would be slower and known as the
rate determining step.
Carbocation intermediate
CH3
CH3 C+
CH3 is called a carbocation ion. It is an intermediate of SN1 reaction. Because it is at the bottom of a potential
well, unlike the highly unstable transition state, it is possible to isolate the intermediate from the reaction mixture
by cooling.
Since the rate determining step involves only the substrate, therefore the rate of SN1 reaction is independent of the
nature and concentration of the nucleophile.
The rate of reaction is governed by the stability of the carbocation intermediate since a more stable carbocation
involves a lower activation energy of formation.
A carbocation is an electron deficient species, it would be more stable if it is attached to electron releasing groups,
either by inductive or resonance effect.
As a result, simple haloalkane shows the following general order of reactivity in SN1 reactions:
tertiary > secondary > primary > methyl
The trend is just the reverse of that of SN2 reaction.
A carbocation attached to an unsaturated functional group is even more stable than 3º carbocation because it is
stabilized by resonance.
H H H H H H +
C H C H
H C C C H H C C C H
+ + H H
+
Racemization
The carbocation intermediate is trigonal planar and is achiral. The nucleophile approaches the carbocation from
either side of the plan with equal probability. Consequently, a racemic mixture of product will be formed.
Thus, SN1 reaction is not very useful in stereospecific synthesis.

SN2 and SN1 reactions represent 2 extremes of the

nucleophilic substitution. Actually, the two reactions
compete with each other.
It is observed that 2º carbon has the slowest rate of

reaction. This is attributed to the crossing of two
opposing curves shown at the right, the mechanism is
changing from SN2 to SN1.
Although structure is the major factor that governs the

mechanism of substitution reaction, leaving group,
nucleophile and solvent also contribute.
Characteristics of SN2 and SN1 reaction

S N2 S N1
Mechanism One-step Two-step
−
R–L + Nu:  → R–Nu + L: R–L r → R+ Nu:
.d .s.
→ R–Nu
Kinetic Second order First order
Reagent nucleophilicity Rate-controlling Unimportant to rate
Structure of saturated Steric hindrance unfavorable Resonance stabilization favorable
carbon atom methyl > 1º > 2º >> 3º 3º >> 2º > 1º
Stereochemistry Inversion Racemization
H H
HO- H C X H C OH + X-
H H
O H
H
H H H
r.d.s. + + -
H O H C X H C O H + X- H C OH + H3O + X
SN2 deprotonation
H H H H H
Alkanol can be prepared from haloalkane by alkaline hydrolysis or hydrolysis in water. However, the
nucleophilicity of H2O is lower than that of OH-, the rate of hydrolysis is slower in neutral medium.
Glossary nucleophile leaving group nucleophilicity inversion of configuration steric hinderance

carbocation / carbenium ion / carbonium ion racemization
Past Paper 92 2C 8 c
Question 95 1A 3 a
96 1A 3 a
98 2B 5 c ii iii
92 2C 8 c
8c Outline a reaction mechanism for the hydrolysis of 1-bromopropane with dilute aqueous potassium hydroxide and 4
sketch a labelled energy profile diagram for the reaction.
CH3CH2 H
CH3CH2CH2 Br
HO C Br CH3CH2CH2OH + Br-
δ− δ−
-OH H
Transition state
2½ marks
label of axis ½ mark

energy profile 1 mark
C Some candidates gave SN1, Or E2 reaction mechanisms instead of the required SN2 mechanism.
Candidates confused "transition state" and "intermediate".
Charge distribution at the transition state was incorrectly marked, e.g.
OH
CH3CH2 C H
H
(no -ve charge)
Br
95 1A 3 a
3a Arrange the following carbocations in the order of increasing stability. Explain your arrangement. 3
+ +
CH2 CH2
+
, and
+ +
CH2 CH2
+
Stability < <
1 mark
+
CH2
+
A 2º carbocation is more stable than a 1º carbocation. ½ mark
The positive inductive / electron donating effect of CH2 group stabilize the cation to a greater extent than a H
atom. (no mark for +I) ½ mark
+
CH2
is the most stable Q the cation is stabilized by the delocalization of e- from the benzene ring /
resonance / mesomeric effect. 1 mark
H H
+
H C H C H
H C+
H or H + H
H H
C Many candidates did not know that cyclohexylmethyl cation, the least stable one, is a primary carbocation, while
cyclohexyl cation is a secondary carbocation and more stable. Most did well in explaining the stability of the
benzyl cation in terms of resonance, but some wrongly stated that its instability is due to the electron withdrawing
effect of the ring, a fact which has only minor influence on its instability.
96 1A 3 a
3a Arrange the following carbocations in the order of increasing stability. Explain your arrangement. 3
+ +
CH3 CH3 CH2
, and
+
Stability: 1 mark
+ +
CH2 CH3 CH3
< <
+
+ CH3
is the most stable.
Q It is stabilized by resonance / mesomeric effect / delocalization of e-, ½ mark

positive charge on carbocation is dispersed. ½ mark
+ CH3 CH3
etc.
+
(1 mark)
(Must show at least 2 resonance structures; deduct ½ mark for wrong structure)
+
CH3 CH2
is a secondary carbocation while is a primary carbocation ½ mark
+
Inductive effect / e- donating property of alkyl group stabilizes the secondary carbocation to a greater extent
½ mark
C The resonance structures for the carbocation
+
CH3
were poorly-drawn, with the positive charge and/or the double bonds arbitrarily placed. Some candidates
attributed the stability of a carbocation to the distance of the positive charge from the benzene ring. As a result,
they wrongly explained the stability of the above carbocation in terms of the fact that the positive charge is closest
to the benzene ring.
98 2B 5 c ii iii
5c Give the structures of the major organic product, H, in (ii) below.
Outline a mechanism for the formation of the major product in each of the two reactions.
ii NaOH
CH3CH2CH2I H
iii CH3 CH3

H2O
CH3CH2 C Br CH3CH2 C OH
CH3 CH3
(major product)
Reference 17.0.3
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 459
Organic Chemistry, 6th Edition, Solomons, pg. 260
Syllabus Nucleophilic substitution of haloalkane
Notes F. Rate of hydrolysis of haloalkane, haloalkene and halobenzene
Reagent : a nucleophile – H2O

H H H
r.d.s. +
H O H C X H C O H + X- H C OH + H+ + X-
SN 2 deprotonation
H H H H H
The rate of hydrolysis can be monitored by addition of acidified AgNO3(aq) into the reaction mixture. The X-
ion formed will be precipitated by the Ag+(aq) ion to form AgX(s) ppt. The solution must be kept acidic or
neutral if Ag+(aq) is present because in alkaline medium Ag+(aq) ion will be precipitated as Ag2O(s).
It is found that haloalkane hydrolyses faster than haloalkene and haloarene do. And iodoalkane hydrolyses
faster than bromoalkane and chloroalkane do.
The difference between haloalkane, haloalkene and haloarene can be explained by the strength of the C–X
bond involved. In an haloalkane, the C–X bond is just a simple single bond while in haloalkene and
haloarene, the C–X has certain double bond character and makes it stronger.
H H H H +
+ Cl Cl
H C C Cl H C C Cl
- -
H H H H
H Cl
H Cl
H H
double bond character
double bond character
The difference between chloroalkane, bromoalkane and iodoalkane, once again, can also be explained by the
bond strength. Since I atom has the largest size among I, Br and Cl atom, the bonding electron experience
most shielding effect from the nuclear charge and the C–I bond would be the weakest among the C–I, C–Br
and C–Cl bond.
Or this can be explained by the difference in leaving goup ability, I- is a better leaving group than Br- and Cl-.
Glossary alkylation elimination stereospecific

Past Paper 90 2C 8 a iii

Question 91 2C 9 a i
93 2C 8 a iii
95 2C 7 a i
96 2C 7 c ii
97 1B 8 c ii
90 2C 8 a iii
COOH COOH
CH3 CH3
Cl CH C CH C
CH3 CH2Cl
COOH COOH
A B
iii How would you distinguish A from B in the laboratory? 3

hydrolysis, followed by aq. AgNO3, B give white ppt. of AgCl. 3 marks
91 2C 9 a i
i CH3 CH2Cl 2
Cl
Warm the compound with aqueous KOH, cool, acidify with nitric acid, add AgNO3.
White precipitate of AgCl formed for ArCH2Cl; clear solution for CH3ArCl.
CH2Cl CH2OH
+ OH- + Cl-
; Ag+ + Cl- → AgCl↓

C Some candidates did not realize if alkaline hydrolysis was used, the system should be acidified before addition of
AgNO3.
93 2C 8 a iii
8a Give a chemical test to distinguish one compound from the other in each of the following pairs. Your answer
should include the reagents required, the observation expected, and the chemical equation(s) for each test.
iii CH2Cl Cl 3
and
Reagent: Aqueous silver nitrate solution 1 mark

Observation: Formation of white ppt. 1 mark
Equation:
CH2Cl CH2OH
+ H2O + HCl
Ag+ + Cl- → AgCl (white ppt.) 1 mark

95 2C 7 a i
7a Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Your answer
should include the reagents used, the observation expected and the chemical equation(s) for each test.
i Cl Cl 3
and
Treat compound with hot water (with or without ethanol) and then with a solution of silver nitrate(V). 1 mark
(*If NaOH is used in the hydrolysis, neutralisation must precede addition of silver nitrate.)
Cl OH
+ H2O + Cl- + H+
½ mark
Ag+(aq) + Cl-(aq) → AgCl(s) ↓ ½ mark
(White) precipitate is immediately formed. ½ mark
Cl
No ppt. with . ½ mark
C Many candidates failed to give the equations for the reactions.

Common mistakes included : using AgNO3(s) instead of AgNO3(aq); alkaline hydrolysis without subsequent
acidification; HCl for acidification instead of HNO3; alkaline AgNO3 solution; the wrong colour for AgCl(s).
96 2C 7 c ii
7c Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Your answer
should include the reagents used and the observation expected.
ii CH2Cl CH2I 2
and
Treat compound with AgNO3(aq)

CH2Cl
will give a white ppt./ ppt. at a slower rate ½ mark
CH2I
will give a yellow ppt./ppt. at a faster rate ½ mark
C Common mistakes included: AgNO3(s) instead of AgNO3(aq); alkaline hydrolysis without subsequent acidification;
HCl for acidification instead of HNO3; alkaline AgNO3 solution; Cl2 or Br2 to displace benzyl iodide to give
iodine; wrong colour for AgCl(s) and AgI(s). Most did not know the difference in the rate of hydrolysis of the two
compounds.
97 1B 8 c ii
8c For each of the following groups of compounds, suggest a chemical test which would enable each compound to be
distinguished from the other(s). In your answer also give the changes that you would expect to observe for each
compound.
ii C6H5CH2I and C6H5CH2Cl 2
Reference 17.1
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 460–461, 518
Syllabus Nucleophilic substitution of haloalkane
Notes G. Other relevant reactions
By using Na+CN-(aq), CN-(aq) functions as an nucleophile and haloalkane can be converted to a nitrile.
H H
N C- H C X H C CN + X-
H H
This reaction is an useful method to increase the length of the carbon chain by one. Thereafter, the cyano
group formed can be converted to amine, amide or carboxylic acid easily.
Since cyanide ion CN- is highly toxic, this experiment should never be attempted in A-Level.
H H H X- H
+
H N H H C X H C N H + H C N H + H X
H H H H H H
H H H X- H
+
H N H H C X H C N H + H C N H + H X
R H H R H R
1° amine 2° amine
H H R X- H
+
R N H H C X H C N H + H C N R + H X
R H H R H R
2° amine 3° amine
H H R
+
R N R H C X H C N R + X-
R H H R
3° amine 4° quaternary ammonium halide
In the preparation of 1º amine from ammonia and haloalkane, excess NH3 is necessary to neutralize the HX
formed and to minimize further alkylation of the 1º amine.
If excess RX is used instead of excess NH3, quaternary ammonium halide will be produced.
This method cannot be used to prepare 2º or 3º amine. If neither NH3 nor RX is in excess, a mix of 1º amine,
2º amine, 3º amine and quaternary ammonium halide will be obtained.
A strong base NH2- is less desirable than NH3 in this reaction because
1. In hydrolysis of haloalkane, no matter OH-(aq) or H2O(l) is used as the reagent, the same product, alcohol,
will be produced.
In the alkylation of ammonia, if NH2- is used instead of NH3 in the presence of water, NH2- will react with
water to produce OH- since NH2- ia a stronger base than OH-. Eventually, the OH- produced will react
with the haloalkane to produce alcohol instead. (Refer to Leveling effect in Acid base theory)
2. NH2- is a very strong base which may lead to elimination reaction instead of substitution reaction. (Refer
to the Mechanism of elimination reaction)
Since SN2 reactions always occur with complete inversion of configuration, SN2 reaction is very useful in
stereospecific synthesis.
Glossary alkylation elimination stereospecific
Past Paper 94 2C 8 b ii
Question 95 2C 8 a i 95 2C 9 b v
97 2B 6 a ii
94 2C 8 b ii
8b A cyanoalkane is usually prepared by reacting the corresponding bromoalkane with aqueous potassium cyanide.
ii Is it possible to use hydrogen cyanide instead of aqueous potassium cyanide to carry out this preparation? 2
Explain.
No, HCN is a weak acid, it ionizes only slightly in water. In HCN(aq), [CN-(aq)] is low, hence rate of SN2 reaction
with R–Br is slow. 2 marks
C Many candidates did not realize that HCN is a weaker nucleophile than CN-.
95 2C 8 a i
8a In an experiment, 46.3 g of 1-chlorobutane reacts with 30.0 g of sodium cyanide to give 35.2 g of pentanenitrile.
i Calculate the percentage yield of pentanenitrile. 3
Formula mass C4H9Cl = 92.562
Formula mass NaCN = 49.01
Formula mass C4H9CN = 83.122 ½ mark
46.3
No. of mole of C4H9Cl = 92.562 = 0.500 ½ mark
30.0
No. of mole of NaCN = 49.01 = 0.612 ½ mark
Since NaCN is in excess, C4H9Cl is the limiting reagent
35.2
No. of mole of C4H9CN = 83.132 = 0.423 ½ mark
no. of mole of C4H9CN 0.423
% yield = no. of mole of C H Cl × 100 % = 0.500 × 100 % = 84.6 % 1 mark
4 9
C Some candidates did not calculate the relative molecular masses methodically. Generally, they did not show a
good grasp of the concept of limiting reagent and percentage yield.
95 2C 9 b v
9b Identify K, L, M, N, P, R and S in the following reactions:
v 1
excess CH3I
N P
+
N
P: H3C CH3 1 mark
C the word 'excess' was overlooked and hence the following structure was given for P
N
CH3
97 2B 6 a ii
6a Each of the following conversions can be completed in not more than three steps. Use equations to show how you 9
would carry out each conversion in the laboratory and for each step, give the reagent(s), conditions, and structure
of the product.
ii
NH2 NHCH2
Reference 17.2
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 470, 472–473
Syllabus Nucleophilic substitution of alkanol
Notes 2. Reactions of alkanol
a) Haloalkane form alkanol (ROH → RX)
We have seen how alkanol can be prepared from haloalkane by hydrolysis. By changing the reaction
condition, alkanol can also be converted back to haloalkane.
H H
slow
X- H C OH H C X + HO-
H H
-
However, OH ion is a poor leaving group since it is a strong base. The rate of direct substitution by a halide
ion is rather slow.
By protonation (by adding acid), OH- can be converted to H2O which is a much better leaving group. Thus,
the rate of reaction can be accelerated considerably.
H H H
protonation + r.d.s.
H C O H +
H X
- H C O H H C X + H2O
H H H H
In case of chloroalkane, HCl is not reactive enough to react with alkanol. This is because Cl- is a much weaker
nucleophile than Br- and I-.
In the preparation of chloroalkane, ZnCl2 is added to catalyze the reaction. ZnCl2 is a Lewis acid which
increases the reactivity of the alkanol by enhancing the leaving ability of the OH- group.
R R R R
- r.d.s. Cl-
R C O H ZnCl2 R C O + ZnCl2 R C+ R C Cl
R R H R R
N.B. In alkaline or neutral medium, haloalkane will be hydrolysed to alkanol.

In acidic medium, alkanol can be converted back to haloalkane.
However, Cl- is a very weak base, thus a much better leaving group than OH- ion. Chloroalkane is usually less
stable than alkanol. The yield of the conversion of alkanol to chloroalkane using halide ion is rather low. It is
more convenient to use chlorinating agents to convert the –OH group to –Cl group directly.
Chlorinating agent :
SOCl2 (thionyl chloride), PCl5 (phosphorus pentachloride) or PCl3 (phosphorous trichloride)
CH3CH2–OH   3 → CH3CH2–Cl

2 5 SOCl , PCl , PCl
Brominating agent
Similarly, PBr3 is a commonly used brominating agent.
CH3CH2–OH  → CH3CH2–Br

PBr 3
This can also be done by heating the alcohol with a mixture of red phosphorus (less flammable than white
phosphorus) and bromine where P and Br2 reacts to produce PBr3..
In the presence of ZnCl2 catalyst, a Lewis acid, alkanol can be converted to chloroalkane by conc. HCl(aq).
Alkanol has a reactivity towards this reaction with the following order : tertiary > secondary > primary.
R R R R
- r.d.s. Cl-
R C O H ZnCl2 R C O + ZnCl2 R C+ R C Cl
R R H R R
Since the chloroalkane formed is immiscible with water and alkanol, it will form an emulsion with water and
alkanol. Depending on the rate of reaction, 3º alkanol will turn cloudy immediately, 2º alkanol will turn
cloudy gradually while 1º alkanol will not turn cloudy at all. Because 3º alkanol is the most reactive one, it is
believed that this is a SN1 reaction.
Glossary Lewis acid chlorinating / brominating agent Luca's test

Past Paper 96 2C 7 b i ii iii 96 2C 8 c i

Question 99 1B 8 b i ii 99 2B 7 a i ii
96 2C 7 b i ii iii
7b In an experiment 25 g of (CH3)3COH react with 36 g of HCl to give 28 g of (CH3)3CCl.
i Find the limiting reactant of the reaction showing clearly your calculation. 1½
Formula mass of (CH3)3COH = 74.12
Formula mass of HCl = 36.458
Formula mass of (CH3)3CCl = 92.562
25
No. of moles of (CH3)3COH = 74.12 = 0.337 ½ mark
36
No. of moles of HCl = 36.458 = 0.987 ½ mark
HCl is in excess. ∴ (CH3)3COH is the limiting reactant. ½ mark
C Well answered. Some candidates had no idea of a limiting reactant. Candidates calculated the relative molecular
masses carelessly. Some used 35.0 or 36.0 for the relative atomic mass of chlorine without referring to the
Periodic Table given in the examination paper.
ii Calculate the percentage yield of (CH3)3CCl. 1½
28
No. of moles (CH3)3CCl = 92.562 = 0.302 ½ mark
0.302
% yield = 0.337 × 100 = 89.6% (90%) 1 mark
C Many did not know how to calculate the percentage yield and they used the mass ratio instead of the mole ratio in
the calculation. The mechanism of reaction was poorly presented.
iii Name the type of the reaction and outline the mechanism of the reaction. (Movement of electron pairs should be 3
indicated by curly arrows.)
Unimolecular nucleophilic substitution / SN1 ½ mark
Mechanism 2½ marks
H +
+
OH H Cl O Cl
H
Cl-
C Many candidates did not distinguish between SN1 and SN2 reactions. Many candidates did not know where the
arrow should begin and where it should end.
Many started the mechanism with protonation of the alcohol by free H+ instead of by HCl. The first step is shown
below:
(CH3)3COH H Cl
Candidates should appreciate that H+ does not exist freely in solutions and it is always attached to a conjugate base
which can be a solvent molecule.
96 2C 8 c i
8c Identify K, L, M, N and P in the following reactions :
(Deduct ½ mark for each minor mistake; max. Deduction for the whole question = 2 marks)
i 1
PCl5
K (CH3)2CHCH2CH2Cl
K: OH or (CH3)2CHCH2CH2OH 1 mark
C Common mistakes made by candidates are listed below: (CH3)2CHCH2CH3 for K;
99 1B 8 b i ii
8b In an experiment to prepare 1-bromobutane, a mixture of butan-1-ol, potassium bromide and concentrated
sulphuric(VI) acid was heated under reflux for 30 minutes.
i Draw a labelled diagram of the set-up used.
ii Suggest how to isolate 1-bromobutane from the reaction mixture.
99 2B 7 a i ii
7a Lucas reagent, a mixture of ZnCl2 and concentrated HCl, can be used to distinguish the following alcohols from
one another :
(CH3)2CHCH2OH, CH3CH2CH(OH)CH3 and (CH3)3COH
i State the expected observation when these alcohols are separately treated with Lucas reagent.
ii Suggest why these alcohols behave differently towards Lucas reagent.
(Hint: the zinc ion binds strongly with the oxygen atom of an alcohol, weakening the C–O bond and creating a
better leaving group.)
Reference 17.3
Organic Chemistry, 6th Edition, Solomons, pg. 923-924, 926-927, 966
Syllabus Nucleophilic substitution of amine
Notes 3. Reactions of amine
NH2- is a very strong base, thus it is a very poor leaving group. Normally, 1º amine R–NH2 does not undergo
nucleophilic substitution reaction. However, upon the action of nitric(III) acid, amino group –NH2 group will be
converted to diazonium group –N+≡N. Diazonium group is a very good leaving group and leaves the substrate in
form of very stable N2.
Reagent : nitric(III) acid / nitrous acid (HNO2) or (H–O–N=O) or (HONO)

H
+
R N + HNO2 R N N + 2 H2O R+ + N2
H nitrogen
carbocation
aliphatic alkyldiazonium bubbles
primary ion
amine
Since HNO2(aq) is unstable, it is usually freshly prepared by dissolving NaNO2(s) in HCl(aq). Nevertheless, the
HNO2(aq) prepared must be kept below 5ºC otherwise it will decompose into NO2(g) readily.
NaNO2(s) + HCl(aq) → NaCl(aq) + HNO2(aq)
The diazonium salts (diazonium chloride if HCl(aq) is used in the preparation of HNO2(aq)) intermediate formed
is also highly unstable. Even at a temperature below 5ºC, the diazonium salt will still decompose gradually
with evolution of nitrogen bubbles.
This observation can be used to identify 1º aliphatic amine.
The fate of the carbocation R+ depends on whether it will undergo elimination or substitution reaction. A lot
of products may be obtained. e.g. alkene, haloalkane, alcohol and ether.
e.g. R+ + Cl- → R–Cl

R+ + H2O → ROH + H+
R+ + ROH → ROR + H+
If a 1º aromatic amine is treated with NaNO2(s) in HCl(aq) below 5ºC, no bubble will evolve. Comparing
with alkyldiazonium ion, benzenediazonium ion is more stable. This is because benzenediazonium ion is
stabilized by resonance and the C–N bond possess certain double bond character.
N N- N-
H H
+N N+ N+
H N N
+
H H
+
Benzenediazonium ion can also be converted to a lot of other products. Since N2 is an extremely good leaving
group, benzenediazonium ion is capable to form aryl cation by the departure of N2.
Nu Note : arenium ion will be studied in

+ the chapter of electrophilic
NH2 N N +
H H substitution.
NaNO2 H E
+ N2
HCl, 0-5 °C H H
H H
H
+
benzenamine diazonium ion H H
aryl cation
H
(not arenium ion)
arenium ion
E : a positive electrophile
attaching to the benzene ring
By using different nucleophile, different products can be obtained through a SN1 reaction.
The formation of aryl cation provide a very useful way to prepare phenol in laboratory. Upon heating, the
solution of benzenediazonium ion will be converted to phenol.
H
H
O H
+ + O H OH
NH2 N N +
H H
NaNO2
HCl, 0-5 °C + N2
H H
H
benzenamine diazonium ion
aryl cation
(not arenium ion)
In this reaction, water plays the roles of solvent and nucleophile. The water in the acid mixture behaves as an
nucleophile and reacts with the aryl cation intermediate to form a phenol.
Glossary nitric(III) acid / nitrous acid alkyldiazonium ion benzenediazonium aryl cation
Past Paper 92 1A 1 d
Question 94 1A 3 a iii iv
95 1A 3 d i iii
92 1A 1 d
1d Give the reagents and reaction conditions required to convert phenylamine into benzene. 2
, HCl, 0° C
NaNO
 2
→ Stand in H 3 PO 2 
→
NaNO2 ½ mark
HCl ½ mark or HONO 1 mark
0ºC ½ mark
H3PO2 ½ mark or EtOH ½ mark
C Few (10-15 %) knew of H3PO2 reagent.
94 1A 3 a iii iv
3a Consider the two compounds:
CH3CH2CHCH3 CH3CH2CH2NH2
OH and
C D
iii Write equation(s) to show the reaction(s) (if any) of nitric(III) acid with C and D separately. 2
C → no reaction
HNO2
½ mark
D → CH3CH2CH2OH + N2
HNO2
1½ mark
H CH3CH CH2
HNO2 +
D CH3CH2CH2 N N N2 + CH3CH2 C + CH3CH2CH2Cl etc.
or
unstable H CH3CH2CH2OH
If C is ignored, no mark for the first part.

If “only D reacts” award ½ mark for C.
If for D, “CH3CH2CH2N+≡N Cl-”, award ½ mark only
iv The reaction(s) in (iii) can be used to distinguish between C and D. What observation(s) would you look for in 1
this test?
In the case of D, colourless gas bubbles wil be seen or N2 gas evolved with D 1 mark
95 1A 3 d i iii
3d i Give the reactants and conditions for the preparation of benzenediazonium chloride in the laboratory. 1½
Reactant : NaNO2 / HCl or HNO2; aniline 1 mark
Condition : < 5 ºC or -10 to 5 ºC or ice bath ½ mark
iii If an aqueous solution of benzenediazonium chloride is heated, a solid, which is soluble in dilute NaOH, can be 2½
obtained.
Suggest a structure for the solid obtained and account for its solubility in dilute NaOH.
OH
(no mark for name) 1 mark

Phenol is weakly acidic ½ mark
The following equilibrium lies to the right in the presence of NaOH and the ionic phenoxide is more soluble
½ mark
OH O-
OH- + H2O +
½ mark
C Most candidates correctly produced the structure of phenol. But many candidates did not know that the solubility
of phenol in NaOH is due to the formation of a water soluble sodium phenoxide.
Reference 18.0
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 101–102, 108–109, 116, 159–160, 175–176
Organic Chemistry, Solomons, 5th Edition pg. 244–251, 317–319, 322–327, 332–333
Organic Chemistry, Fillans, 3rd Edition pg. 185–188, 206–210, 429–430
Organic Chemistry, Stanley H. Pine, 5th Edition pg. 466–477, 486–491
Organic Chemistry, 6th Edition, Solomons, pg. 260-262, 265-268, 300, 302-305
Syllabus Elimination Reaction

Competition between Substitution and Elimination reaction
Note V. Elimination reaction
In nucleophilic substitution, the nucleophile attacks the α carbon atom and leads to a substitution product.
Br H H
C2H5OH
CH3 C C H CH3 C O CH2CH3
55°C
H H CH3
97%
But besides this substitution product, another elimination product is also obtained
Br H H
C2H5OH
CH3 C C H CH3 C C H
55°C
H H H
3%
This experimental evidence shows that the reaction takes place through 2 competing pathways : substitution vs
elimination
Substitution
Br H
α β
CH3 C C H
H H H
H H +
CH3 C O CH2CH3 + Br- CH3 C O CH2CH3 + HBr
CH3 CH3
ether
CH3CH2 O H
In the substitution pathway, the ethanol molecule acts as a nucleophile. It displaces the Br atom from the
haloalkane molecule.
Elimination
Br H
CH3 C C H
H H H
H H
CH3 C C H+ Br- + CH3CH2 O H CH3 C C H + HBr + CH3CH2OH
+
H H
alkene
CH3CH2 O H
In elimination pathway, the ethanol molecule has another role. It acts as a base and subtracts the β H atom from
the haloalkane.
The role of the base is also supported by another evidence. By using a stronger base, the proportions of the two
products change dramatically.
Br H H H
C2H5OH
CH3 C C H CH3 C O CH2CH3 + CH3 C C H
C2H5O-Na+, 55°C
H H CH3 H
21% 79%
- +
Sodium ethoxide, C2H5O Na , is a very strong base which can be prepared by dissolved sodium metal in excess
ethanol. The ethanol also serves as a solvent.
2 C2H5OH(l) + 2 Na(s) → 2 C2H5O-Na+(alc.) + H2(g)
Alternatively, solid sodium hydroxide or potassium hydroxide dissolved in ethanol (alcoholic sodium hydroxide)
may also be used. This involves an equilibrium of formation of ethoxide ion, the strong base.
C2H5OH(l) + NaOH(s) d C2H5O-Na+(alc.) + H2O(l)
If there are two different kind of β hydrogen available for subtraction, the one which will lead to a more
substituted alkene will be preferred. This is because double bond (sp2 hybridized C) and triple bond (sp
hybridized C) are electron withdrawing by inductive effect, they will be stabilized by electron releasing alkyl
group.
H H Br H H H H H H H
γ β α β
H C C C C H H C C C C H + H C C C C H
H H H H H H H H H H
major product minor product
(di-substituted) (mono-substituted)
CH3CH2O-
Similar to the SN2 and SN1 mechanism, there are also E2 and E1 reactions, depending on the number of molecule
involved in the formation of the transition state.
E2 stands for bimolecular elimination reaction.
In E2 reaction, the rate of reaction depends on both the concentration of the substrate and the base. Comparing with
SN2 reaction, E2 involves more bond breaking and bond formation, thus a higher activation energy. i.e. SN2
reaction only involves 2 bond while E2 reaction involves 4 bonds.
Rate ∝ [substrate][base]
-
B: H B H
-
r.d.s. δ
-
C C C C + HB + L
C C
L Lδ -
transition state of
E2 reaction
E1 stands for unimolecular elimination reaction. In E1 reaction, the rate of reaction depends on the concentration
of the substrate only.
Rate ∝ [substrate]
-
H H B: H
r.d.s. δ+
C C C C C C + L- C C
-
+ HB + L
+
L L
δ−
transition state of intermediate
E1 reaction
E1 and SN1 reaction share the same intermediate – carbocation.
In SN1 reaction, the nucleophile is joined to the carbocation to yield a substitution product.
In E1 reaction, the nucleophile acts as a base rather. It removes the β-H and leads to an elimination product. E1
reaction is favoured by a strong and bulky base. e.g. (CH3)3CO-Na+. Also if the α C is sterically hindered by bulky
groups, e.g. 3º substrate, the E1 reaction will also be favoured over SN1 reaction.
Elimination reaction has a higher activation energy than Substitution reaction. This is because more bond breaking
and bond formation are involved in elimination than in substitution. As a result, an increase in temperature will
cause a larger increase in rate of elimination than in the rate of substitution.
45蚓
53% 47%
Br NaOH / CH3CH2OH
CH3 CH CH3 CH3 CH O CH2CH3
CH2 CH CH3 +
CH3
64% 36%
100蚓
Elimination reaction is favoured by a higher temperature.

If the α carbon is sterically hindered, e.g. in 3º haloalkane and use of bulky base (CH3)3CO-Na+, elimination will be
more favourable than the substitution reaction.
3. Effect of basicity of the nucleophile

In general, all nucleopiles are also bases. If the basicity of the nucleophile is very high (e.g. CH3CH2O-Na+),
elimination will compete with nucleophilic substitution.
There are only very few strong nucleophile but with low basicity, e.g. I-, CN- and CH3COO-Na+. They only
undergoes substitution reaction.
Substitution Reaction Elimination Reaction

Temperature Low High
(substitution has a lower activation (elimination has a higher activation
energy) energy)
Structure of the substrate Non-hindered α carbon Sterically hindered α carbon
(e.g. 1º haloalkane) (e.g. 3º haloalkane)
Bulkiness of the Low High
nucleophile
Basicity of nucleophile Low High
Glossary elimination steric hinderance alcoholic sodium hydroxide
Past Paper
Question
Reference 18.1–18.2
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 101–102, 108–109, 116, 159–160, 175–176
Organic Chemistry, Solomons, 5th Edition pg. 244–251, 317–319, 322–327, 332–333
Organic Chemistry, Fillans, 3rd Edition pg. 185–188, 206–210, 429–430
Organic Chemistry, Stanley H. Pine, 5th Edition pg. 466–477, 486–491
Organic Chemistry, 6th Edition, Solomons, pg. 308, 312, 318-319, 443-444
Syllabus Formation of alkene, diene and alkyne from haloalkane

Preparation of vinyl chloride from dichloroethane
Dehydration of alkanol
Note D. Other relevant reactions
1. Reaction of haloalkanes with alcoholic sodium hydroxide (sodium ethoxide) to alkene, diene and alkyne
-
C2H5O
H H H
β β
CH3 C C CH3 CH3 C C CH3
H Br H
more substituted alkene
(major product)
By heating with a strong base (e.g. C2H5O-Na+), a haloalkane can be dehydrohalogenated to an alkene.
-
H2N
H
CH3 C C CH3 CH3 C C CH3
Br
-
C2H5O alkene alkyne
H H (very unreactive)
CH3 C C CH3
Br Br X
-
H2N
H H H
H C C C CH3 H C C C CH3
H Br H
alkene allene
(very unreactive) (highly unstable)
For a 1,2-disubstituted haloalkane, use of C2H5O-Na+ will only give a very unreactive haloalkene.
C2H5O-Na+ is not strong enough to subtract the second hydrogen atom from the substrate. An even stronger
base Na+NH2- (or boiling C2H5O-Na+) is required to cause further elimination of the molecule.
Or, the 1,2-disubstituted haloalkane can be converted into alkyne by Na+NH2- (or boiling C2H5O-Na+) in one
step.
Further elimination of 1,2-disubstituted haloalkane

will only give alkyne but not allene (1,2-diene).
This is because allene is highly unstable where the
two π bonds are perpendicular to each other
without any overlapping.
Orbital representation of allene
Formation of alkyne versus formation of conjugated diene
Normally, a 1,2-disubstituted alkane will undergo elimination to form an alkyne in the presence of a very
strong base, e.g. Na+NH2- (or boiling C2H5O-Na+). But if the haloalkene does not possess β hydrogen, a
conjugated diene would be produced instead.
H CH3 H H H CH3 H H CH3

NaNH2 β NaNH2
H C C C C H H C C C C H X H C C C C H
β
H Br Br H H Br H formation H H
haloalkene of alkyne
impossible formation of unstable allene
(no further elimination) is not favourable
H CH3 H H CH3 H H CH3 H
NaNH2 NaNH2
H C C C C H H C C C C H H C C C C H
H Br Br H H Br H H H
formation of more stable
conjugated diene
Conjugated 1,3-diene is relatively stable comparing

with allene (1,2-diene). It has an extensive
delocalization of π electrons.
Orbital representation of conjugated 1,3-diene
The major use of vinyl chloride (chloroethene) is to prepare the plastic poly(vinyl chloride), PVC, by
polymerization. It can be prepared by chlorination of ethene followed by elimination in the laboratory.
-
CH3CH2O
H H Cl2 H H H H
alcoholic
C C Electrophilic H C C H NaOH C C
H H addition Cl H
Cl Cl
The mechanism of electrophilic addition of Cl2 to ethene will be discussed in the section of electrophilic
addition.
H H
H H H H
H H C C H H H H
H C C H H C C H +
+O H + H2O H H C C H + +O H
H O H +O H
H H
H H
H2O
Unlike other elimination reactions, dehydration of alkanol is done by heating with acid instead of base.
In a basic medium, the leaving group of the alkanol would be OH- which is a very strong base and poor leaving
group. This makes dehydration unfavorable.
In acidic medium, the hydroxyl group –OH is protonated and transformed into a better leaving group water, H2O.
Since there is no strong base present in the reaction medium, the reaction is mainly an E1 reaction. Therefore, the
reactivity of alkanol toward dehydration has the following order : 3º alkanol > 2º alkanol > 1º alkanol, parallel to
all other reactions with carbocation intermediate.
Use of dehydrating concentrated sulphuric acid also helps to remove the water and shift the equilibrium to the
product side. For the more reactive 3º alkanol and 2º alkanol, non-dehydrating and non-oxidizing concentrated
phosphoric acid may be used to prevent charring of the substrate.
Besides ethene (elimination product), ethoxyethane (substitution product) is also obtained. By varying the
temperature, the two products can be selected.
180 °C (E1)
CH2 CH2
conc. H2SO4(l)
CH3CH2 OH
CH3CH2 O CH2CH3
140 °C (SN1)
In the SN1 pathway, CH3CH2OH serves as the nucleophile and attacks the carbocation intermediate to form the
ether (ethoxyethane).
H H H H
H C C O+ C C H
H H H H H CH3CH2 O CH2CH3
H H H H
H C C O H +C C H
H H H H H H CH3CH2 O+ H
H C C O H H
H H
Glossary diene allene vinyl chloride electrophilic addition

Past Paper 91 2C 7 b i
Question 92 2C 9 a i
94 2C 9 b iii
98 1A 4 c ii
99 2B 5 b i ii
91 2C 7 b i
7b When compound P is treated with potassium hydroxide in ethanol, two products Q, C6H12, and R, C8H18O, are
obtained.
CH3
CH3 C CH2CH2Cl
CH3
P
i Give the structures and the systematic names for Q and R. 4

CH3 CH3 CH3
CH3 C CH2 CH2 Cl CH3 C CH CH2 CH3 C CH2 CH2 O CH2 CH3
+
CH3 CH3 CH3
P Q R
1 mark each
Q 3,3-dimethylbut-1-ene 1 mark
R 1-ethoxy-3,3-dimethylbutane 1 mark
C Most candidates could provide the correct structures for Q and R. However, they were generally weak in
nomenclature, especially for R.
92 2C 9 a i
9a Give the structural formula(e) of the major organic product(s) from each of the following reactions :
i Br 2
CH3CH2CHCHCH3 KOH (fused), 200°C
Br
CH3CH2C CCH3 or CH3 CH CH CH CH2

2 marks
94 2C 9 b iii
9b Ethene and chloroethene can undergo polymerization to give polyethene (PE) and polyvinyl chloride (PVC)
respectively. PVC is more rigid and durable than PE, but incineration of PVC causes a more serious pollution
problem.
iii Show how ethene can be converted to chloroethene. 2
Cl2 - HCl
CH2 CH2 CH2Cl CH2Cl CH2 CHCl
NaOH / EtOH
720 - 920 K
CH2Cl CH2Cl CH2 CHCl
Or 2 marks
C Some candidates wrongly gave the structure of chloroethene as CH3CH2Cl.
98 1A 4 c ii
Alcohol E has the structure CH3CH(OH)C2H5.
4c On treatment with dilute H2SO4(aq), E gives mainly two isomeric compounds, F and G, both of which have the
formula C4H8. On treatment with bromine, both F and G give a product H with formula C4H8Br2.
ii What is the isomeric relationship between F and G ? 1
99 2B 5 b i ii
5b The following reaction produces a mixture of K and L.
NaOH(aq)
N CH3 heat C12H17NO + C12H15N
Br K L
i Give the structures of K and L. Name the types of reactions leading to their formation.
ii Outline a mechanism for the formation of K.
Reference 19.0
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 220–221, 228–231, 234–237, 239–244,
251, 254–258, 259–263, 265–267
Organic Chemistry, Solomons, 5th Edition pg. 680–682, 691–693, 701–707, 724–726, 790–793, 845–846
Organic Chemistry, Fillans, 3rd Edition pg. 225–226, 229–238, 240–243, 247–248, 251–259, 262, 275
Organic Chemistry, Morrison Boyd, 6th Edition pg. 669–671, 677–680, 683–684, 697–698, 724, 737–740,
755–778, 797–799, 802–807,830–831
Organic Chemistry, Stanley H. Pine, 5th Edition pg. 236–237, 254–255, 505
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 482, 484–485
Organic Chemistry, 6th Edition, Solomons, pg. 719
Syllabus Nucleophilic addition
Notes VI. Nucleophilic addition (Nucleophilic addition-elimination)

O
Besides substitution reaction with haloalkane, a nucleophile can also react with carbonyl group C and
cyano group C N through addition pathway. This type of reaction is called nucleophilic addition
reaction, AdN.
In carbonyl group, O is more electronegative than C, therefore the C=O bond is polarized by inductive effect
through the σ bond. The C=O bond is further polarized by mesomeric / resonance effect through the π bond.
The carbonyl group can be represented as

- δ-
O O O
or
C C C
+ δ+
Similar to the carbonyl group, in a cyano group, the C≡N bond is polarized by inductive effect and mesomeric
effect / resonance effect. A nitrile group can be represented as
+ - or δ+ δ-
C N C N C N
A. AdN reaction
As a result, the C atom will carry a little positive charge and this makes the atom more vulnerable to the attack
of a nucleophile.
Nucleophilic addition Nucleophilic substitution

δ-
O
O-
C
δ+ C
Nu+ Nu + C L C Nu + L
δ+ δ-
Nu
δ+ δ-
C N
C N-
Nu+
Nu
Comparing with nucleophilic substitution, O and N are joined to C by a multiple bond in carbonyl and cyano
group. Shifting of a bond pair will not cause departure of them.
1. Addition of HCN to carbonyl compound (Cyanohydrin formation)
-
δ H C N O H
O
C CN
-
- CN
- C + N C-
+ O
δ consumed regenerated C N
C
N C
-
C N cyanohydrin
Since HCN molecule is not a very good nucleophile, the rate of direct addition of HCN will be rather slow.
Alternatively, a mixture of cyanide salt and aqueous acid may be used e.g. NaCN(aq) and H2SO4(aq). The acid is
added into the reaction mixture drop by drop to prevent formation of excess HCN(g) which is highly toxic and
volatile. The experiment should be performed in the fume cupboard because of the high toxicity of the
HCN(g).
O H
O H2SO 4
+ NaCN H C H
H C H
C N
-
As CN ion is regenerated in the reaction, it acts as a catalyst speeding up the reaction.
This reaction has vital importance in organic synthesis. The product contains 1 more C atom than the
substrate. It provides a useful way to increase the length of a carbon chain. The cyano group (–C≡N) can then
be converted to other functional groups, e.g. carboxyl group, amide group, amino group, easily.
The cyanohydrin formation is found to be first order with respect to the carbonyl compound and first order
with respect to the cyanide.
O
Rate = k [ C ][CN-]
It can be shown that the proton is not involved in the rate determining step of the reaction.
Besides the concentration of the reactants, the susceptibility (reactivity) of the carbonyl carbon to the attack of
nucleophile also has key effect on the reaction rate.
The susceptibility depends on 2 factors

1. Electronic effect – inductive effect and resonance effect
2. Steric effect
Attachment of different substituent affects the positiveness of the carbonyl carbon and easiness of the bond
formation between the carbonyl carbon and the nucleophile.
When an electron donating group is attached to the carbonyl carbon, the carbon is made less positive and will
be less susceptible to the attack of the nucleophile. Therefore, propanone is less reactive than methanal.
δ- δ-
O O
C C
H δ+ H H3C δ+ CH3
methanal propanone
For most of the nucleophilic addition reactions, the reaction is catalyzed by acid. In acidic medium, the
oxygen atom of carbonyl group is protonated. This makes the carbonyl carbon more positive and more
reactive towards nucleophilic addition. Moreover, if the nucleophile is negatively charged, the product will be
a neutral one instead negatively charged.
H H
O O+ O
H+
C C C
+
4-methoxybenzenaldehyde is found to be less reactive than benzenaldehyde. This is because methoxy group is
an electron donating group which donates the electron to the carbonyl group. This makes the carbonyl carbon
less positive and less susceptible to nucleophilic addition.
O O O-
C +
CH3 O C CH3 O C
H H H
benzenecarbaldehyde
4-methoxybenzenecarbaldehyde (less reactive)
(more reactive)
(b) Steric effect
The first step of the reaction is the close approach of nucleophile to the carbonyl carbon. If the carbon is
sterically hindered by bulky groups surrounded, the reaction rate will be slowed down.
Comparing the rate of nucleophilic addition of propanone with that of methanal :

O O
Methanal Propanone
C C
⇒ less hindered carbonyl H H ⇒ more hindered carbonyl H3C CH3
carbon carbon
⇒ faster reaction rate ⇒ slower reaction rate
Nu Nu
Besides the electronic effect, the steric effect also favours the reaction of an alkanal over that of a ketone.
Glossary nucleophilic addition (AdN) carbonyl group nitrile group vulnerable cyanohydrin
susceptibility electronic effect inductive effect resonance effect steric effect
protonation
Past Paper 92 2C 9 c i ii
Question 93 2C 8 b ii
96 1A 3 f ii
98 1A 5 b
99 1A 5 b ii
92 2C 9 c i ii
9c Hydrogen cyanide reacts with butanone to give an addition product.
i Write a mechanism for the reaction. 2
O- OH +
O H+ OH OH
O H+
or
CN CN
CN
-CN -CN
2 marks
ii The addition product formed can exist in isomeric forms. State the type of isomerism, and draw suitable 2
representations of the isomers.
enantiomerism, (optical isomerism or stereoisomerism) 1 mark
OH OH
NC CH2CH3 NC CH3
CH3 CH2CH3
1 mark
C Candidates were still weak in providing a proper 3-D structural formula, e.g.
CN
C
CH3 OH
C2H5
(no heavy and dotted lines)
93 2C 8 b ii
8b Outline a mechanism for each of the following reactions, using curly arrows to show electron pair displacement.
In each case state what type of reaction takes place, and give the expected product.
ii butanone with hydrogen cyanide. 2½
Mechanism: AdN Nucleophilic addition ½ mark
Me
Me Me
C O H+ C O H NC C O H
+
Et NC- Et
Et
2 marks
C Wrong direction of curly arrows; ambiguity in indicating the starting and finishing location of the curly arrows.
Wrong spelling for the terms, "nucleophile".
Mixing up the meaning of terms, e.g. nucleophile and electrophile, addition and condensation.
96 1A 3 f i ii
3f i Give the structures of compounds D and E in the following organic synthesis : 2
O
+
C HCN H3O
H D heat E
OH OH
D: CN E: COOH
1 + 1 marks
(Deduct ½ mark for each minor mistake in the structures.)
ii Outline a reaction mechanism for the formation of D. (Movement of electron pairs should be indicated by curly 2
arrows.)
½ ½
+ H OH
O H CN ½ O
H H CN
-
CN
½ 4 × ½ marks
Or
½
½
O O- H+ OH
½
H H CN
CN
-
CN
½ 4 × ½ marks
C The reaction mechanism was poorly presented. Many candidates wrongly used curly arrows to represent the
direction of attack of reactants instead of the movement of electron pairs, e.g.
- +
O H
C H
CN
98 1A 5 b
5 Consider the five reactions of butanone (C4H8O) J shown in the reaction scheme below:
5b State the type of reaction involved in the formation of L and outline the mechanism of the reaction. 3
99 1A 5 b ii
5b Consider the following reactions :
CHO
HCN (1) LiAlH4
D + E
(2) H3O
ii Name the type of reaction involved in the formation of D and outline the mechanism of the reaction.
Reference 19.1
251, 254–258, 259–263, 265–267
755–778, 797–799, 802–807,830–831
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 485–487, 489 505
Organic Chemistry, 6th Edition, Solomons, pg. 470-472, 716-719, 729-734, 759-761
Syllabus Nucleophilic addition of carbonyl compound

Reduction of carbonyl compound
Addition of NaHSO3, NH2OH and 2,4-DNPH to carbonyl compound
Iodoform reaction
Notes 3. Other relevant reactions
LiAlH4 is called lithium tetrahydridoaluminate or lithium aluminium hydride.
LiAlH4 is a very powerful reducing agent. It provides hydride ion, H-, for
the reaction to take place. Since H- ion is a stronger base than OH- ion, a
H
solvent other than water must be used, otherwise H- ion will react with + -
Li H Al H
water and give H2. Ether (ethoxyethane or called diethyl either) is the most
common solvent for this reaction. H
N.B. Since the reaction is very vigorous and potentially explosive, it is not advisable to conduct such an
experiment in the laboratory of a secondary school.
H- is also a very powerful nucleophile. It reacts with and reduces carbonyl compound readily.
O OH
O-
C H C + H2O
C
carbonyl H O H H
H- H +
from compound from alkanol
alkoxide
LiAlH4 ion aqueous
acid
An aqueous acid serves as a work up to remove all the unreacted LiAlH4 and converts the alkoxide ion to an
alkanol.
NaBH4 sodium tetrahydridoborate or sodium borohydride is similar to LiAlH4. NaBH4 is a weaker reducing
agent which does not reacts with water. Therefore, it has the advantage that it can be used with aqueous
solvent.
O OH
-
C O H C + H2O
H C
carbonyl H O H H
+ - H +
Na H B H compound
alkoxide from alkanol
H ion aqueous
acid
N.B. Since hydride ion H- is a nucleophile, it does not react with electron rich C=C or C≡C.
Furthermore H- is a polar reagent while C=C and C≡C are non-polar substrates.
-
O O O H
O C C C
- -
O S O S O H O S O
HO O O
hydrogensulphite
addition product
CH3 CH3
O C + Na+HSO3- H O C SO3-Na+
CH3 CH3 white precipitate
In this reaction, sodium hydrogensulphite acts as a nucleophilic reagent. By the reason of the bulkiness of
hydrogensulphite ion, addition of NaHSO3 is very sensitive to steric hinderance. A non-hindered aldehyde
have about 90% yield and a slight more bulky methyl ketone have only 10 – 60 % yield. Other higher ketones
do not form any addition product at all.
aldehyde methyl ketone 2,2,4,4-tetramethylpropan-3-one
O H CH3 O CH3
O
R C C H CH3 C C C CH3
R C H
H CH3 CH3
increase in steric hinderance about the carbonyl carbon
Since the addition product is an ionic crystalline compound, this reaction can be used to distinguish aldehyde
and methyl ketone from other higher ketones. The latter do not give any precipitate at all.
Furthermore, this reaction is reversible. The equilibrium position can be shifted to left by addition of either an
acid or a base to remove the hydrogensulphite ion.
Addition of acid HSO3- + H+ → SO2 + H2O

Addition of base HSO3- + OH- → SO32- + H2O
Therefore, this reaction can be used to separate an aldehyde or a methyl ketone from a mixture.
The aldehyde or methyl ketone is first precipitated by sodium hydrogensulphite and filtered. It is regenerated
upon addition of an acid or a base.
N.B. Although methanal and ethanal forms addition product with sodium hydrogensulphate(IV), the
crystalline compounds formed are very soluble in water, therefore no ppt. will be obtained.
Hydroxylamine is a derivative of ammonia. Other amines are alkyl derivatives of ammonia but hydroxylamine
is a hydroxyl derivative of ammonia, with a hydrogen replaced by a hydroxyl group.
H N H H N OH H N R
H H H
ammonia hydroxylamine 1° amine
Hydroxylamine is another nucleophile. It also reacts with a carbonyl compound through nucleophilic addition
pathway. The difference is that the reaction intermediate formed has an acidic hydrogen atom attaching to the
nitrogen atom. This makes the intermediate undergo elimination (dehydration) readily with the neighbouring
hydroxyl group. The elimination product is called oxime.
The reaction is known as a nucleophilic condensation (or addition-elimination) reaction because it consists of
2 steps, nucleophilic addition followed by elimination.
Condensation reaction = Addition reaction + Elimination reaction
elimination
H H - H2O
H N OH C O HO N + C O- HO N C O H HO N C
H H
carbonyl oxime
hydroxylamine compound intermediate
addition reaction
Condensation reaction
H H
H H H N N NO2
H N N H
O2N
hydrazine 2,4-dinitrophenylhydrazine
2,4-dinitrophenylhydrazine, or in short DNPH / DNP, is a derivative of a nitrogen containing compound,

hydrazine. Pure DNPH is insoluble in water because it is not very polar. A little conc. H2SO4(l) is used to
dissolve the orange DNPH solid and then diluted to prepare the DNPH solution.
Reaction of 2,4-dinitrophenylhydrazine with carbonyl compound is similar to that of hydroxylamine. The

condensation product formed is called hydrazone.
addition reaction
H H H H H
H N N NO2 -O C N N NO2 HO C N N NO2
+
O C O2N H O N H
2 O2N
carbonyl 2,4-dinitrophenylhydrazine
compound - H2O
elimination
reaction
H
C N N NO2
O2N
2,4-dinitrophenylhydrazone
Use of derivative of hydroxylamine and 2,4-dinitrophenylhydrazine for characterization
Both oxime and hydrazone formed in the condensation reactions are high melting solid. By converting an
unknown carbonyl compound into the corresponding oxime and hydrazone, the carbonyl compound can be
identified. This is done by measuring the melting points of the oxime and hydrazone and comparing them with
the literature values.
Aldehyde or Ketone m.p. of oxime m.p. of 2,4-dinitrophenylhydrazone

Ethanal 46.5 ºC 168.5 ºC
Propanone 61 ºC 128 ºC
Benzenecarbaldehyde 35 ºC 237 ºC
2-methylbenzenecarbaldehyde 49 ºC 195 ºC
Formation of enolate ion
Both aldehyde and ketone show tautomerization. The keto form of the molecule coexists with the enol form of
the molecule. Keto-enol tautomerization is an dynamic equilibrium involving the movement of a hydrogen
atom.
H O δ-
O OH
- H+ δ- + H+
C C
α
+ H+ αC C - H+ αC C
H H
keto form enolate ion enol form
An intermediate, enolate ion, is formed during the transition between the keto form and the enol form. Enolate
ion can be considered as conjugate base of the keto or enol form.
O O- δ-
O
- δ-
C C C C or C C
H H H
Since the enolate ion is stabilized by resonance, the acidity of the α-hydrogen is much higher than other
hydrogen atoms attached to the carbon chain.
O H H
C Cα C
β
H H
α-hydrogen β-hydrogen
pKa ≈ 20 pKa ≈ 50
It is observed that α-hydrogen is almost 1030 times more acidic than β-hydrogen. In the presence of a base e.g.
NaOH, a carbonyl compound loses its α-hydrogen readily and forms an enolate ion.
-O H
O - H
O H H C Cα C + H2O
β
C Cα C H H
β
H H
Enolate ion possesses an electron rich carbon atom and behaves as a nucleophile.
Haloform reaction
Haloform has a general formula CHX3. Choroform CHCl3 and bromoform CHBr3 are liquid insoluble in
water. Iodoform CHI3 is a bright yellow precipitate. Formation of yellow precipitate of iodoform serves as a
O H OH H
C C H C C H
very useful test of methyl ketone and 1-hydroxyethyl group.
H H H
Haloform reaction consists of two steps :

1. Formation of trihalo ketone by nucleophilic substitution
2. Formation of haloform by nucleophilic addition-elimination
Formation of trihalo ketone from methyl ketone
The presence of a base, e.g. NaOH(aq), promotes formation of enolate ion. The enolate ion formed acts as a
nucleophile and displace the I- ion from the I2 molecule. Once the first α-hydrogen is substituted by an iodine
atom, the acidity of the remaining α-hydrogens will be increased due to the negative inductive effect of the
iodine atom. Consequently, the remaining two α-hydrogens will also be substituted by iodine atoms.
enolate ion formation nuleophilic substitution further substitutions
-O H
I I
O H O O I O I
- OH-, I2 OH-, I2
R C C H R C C H R C C I
R C Cα H α α α
H H H I
methyl ketone enolate ion triiodo ketone
-I effect of halogen make

the H even more acidic
Formation of haloform from trihalo ketone
The triiodo ketone formed is much more reactive than the original methyl ketone because –CI3 group is a
better leaving group than the original –CH3 group, as -CI3 ion is a much weaker base than -CH3 ion does.
-
O I O I
O I O I
R C -
R C C I R C C I C I
α R C H C I
O I O I
H O- I O- I
H H
triiodo ketone carboxylate iodoform
ion
For 1-hydroxyethyl group, it is first oxidized to methyl ketone by the iodine in alkaline medium. Then, the
methyl ketone formed is converted to carboxylate through the same mechanism mentioned above.
H H
oxidation H
C C H
+ I2 + 2 OH- C C H + 2 I- + 2 H2O
O H
O H
H
1-hydroxyethyl group methyl ketone
Besides testing of methyl ketone and 1-hydroxylethyl group, iodoform reaction is also used in organic
synthesis to shorten the carbon chain by one carbon atom. It also converts methyl ketone or 1-
hydroxyethyl group to carboxylate ion or carboxylic acid upon acidification.
N.B. 1. Haloform reaction can be used to test for methyl ketone and 1-hydroxyethyl group
2. It can be used to cut the carbon chain short by 1 C.
3. It oxidizes methyl ketone and 1-hydroxyethyl group to carboxylate.
Some chemistry text books say that NaOI(aq) is used to bring about iodoform reaction. In fact, according to the
mechanism, the reaction is actually brought about by OH-(aq) ion and I2(aq) molecule. NaOI(aq) takes the
advantages that it is prepared from I2(aq) and NaOH(aq).
NaOH(aq) + I2(aq) d NaOI(aq) + NaI(aq) + H2O(l)
As a personal preference, I prefer I2(aq) / NaOH(aq) to NaOI(aq) as the reagent used.

Glossary lithium tetrahydridoaluminate / lithium aluminium hydride ether acid work up

sodium tetrahydridoborate / sodium borohydride sodium hydrogensulphite hydroxylamine
oxime nucleophilic addition-elimination condensation reaction 2,4-dinitrophenylhydrazine
hydrazone characterization keto-enol tautomerization enolate β-hydrogen haloform
reaction / iodoform reaction methyl ketone 1-hydroxyethyl group trihalo ketone
Past Paper 90 2C 9 a ii iii

Question 91 1A 1 b i 91 2C 9 a iii
92 2C 8 b 92 2C 9 a iii
93 2C 8 a i
94 2C 9 a i
95 2C 7 a ii 95 2C 9 b i
96 2C 8 c v
97 1A 5 a v 97 2B 5 a i iii 97 2B 5 a i ii iii 97 2B 7 a ii 97 2B 7 b i
98 1A 5 a 5 c d i ii
99 2B 5 a i
90 2C 9 a ii iii
9a Each of the following carbonyl compounds P, Q and R reacts with 2,4-dinitrophenylhydrazine in the presence of a
strong acid to give a phenylhydrazone derivative.
O O O CH3
CH3 C CH2CH2CH3 CF3 C CH2CH2CH3 CH3 C CH2 CH CH3
P Q R
ii Under the same conditions, P, Q and R form phenylhydrazones at different rates. Predict with an explanation 5
which will react the fastest, and which the slowest.
Rate Q > P > R (slowest)
Taking P as a reference.
Q is faster than P because F substituent is electronegative. 1 mark
⇒ carbonyl carbon more electrophilic 1 mark
⇒ more susceptible to nucleophilic attack by -NH2 1 mark
R is slower than P because the -CH(CH3)2 group is more bulky and hindered the approach of the -NH2 to the
carbonyl carbon. (electron donating feature of -CH(CH3)2 is not significant due to long distance) 2 marks
C Many candidates considered the electronic effect but not the steric effect.
iii Explain why 2,4-dinitrophenylhydrazones are useful derivatives of carbonyl compounds. 2
2,4-dinitrophenylhydrazones of carbonyl compounds are high melting solids useful for characterization
OR are bright colour ppt useful for identifying carbonyl group 2 marks
C Many candidates confused 2,4-DNPs with azo dyes, and wrongly stated that the former were important dyes in
industry.
91 1A 1 b i
1b i CH3 CH3 3
C CH2 C O
H H
E F
Explain why hydroxylamine reacts with F and not with E, and give the product expected from the reaction.
C O
In F, the double bond is strongly polarized, due to the electronegativity of oxygen. In E there is no such
polarization.
OR
C O
+ -
The oxygen has a tendency to acquire electrons leading to in which the carbon is electron deficient.
1 mark
Hydroxylamine with N having lone electron pair is electron rich and takes part in nucleophilic addition at C.
HONH2 C O
OR
(This properties of NH2OH must be shown in some way) 1 mark
Product is Me-CH=NOH (no mark for Me-CHOH-NHOH) 1 mark
There are many ways to answer this question:
For all the 3 marks, answer MUST explain WHY polarization difference is responsible for the difference in
reactivity - answer MUST include the fact that NH2OH reacts as nucleophile or by nucleophilic addition.
C A noticeable number of candidates did not know the structure of hydroxylamine.
91 2C 9 a iii
iii O O 2
CH3 C
CH3
O O
C CH3
CH3
Add iodine and NaOH, will give yellow ppt of iodoform. No ppt observed for .
O - +
COO Na
C
CH3 + NaOH + I2 + CHI3
2 marks
C Many candidates wrote the formula of iodoform incorrectly as CH3I.
92 2C 8 b
8b Describe how 2,4-dinitrophenylhydrazine may be used to identify an unknown ketone such as butanone. Give an 4
equation for the reaction involved.
Take the unknown ketone to reacts with 2,4-DNPH; Get the solid derivative; Purified by recrystallization;
Determine its m.p.; Compare with literature data. 2½ marks
CH3
NHNH2
NH N CCH2CH3
NO2
O NO2
+
CH3CH2 C CH3
NO2
NO2
1½ mark
C Candidates gave the wrong structure for 2,4-dinitrophenylhydrazine, e.g.
NH2
NO2
NO2
Many candidates did not know how to make use of the m.p. of hydrazone as a means to identify the ketone. They
just mentioned the use of 2,4-DNP as a test for carbonyl functional group.
92 2C 9 a iii
iii O 2
C I2/NaOH(aq)
CH3
COO-Na+
+ CHI3
2 marks
93 2C 8 a i
i CH3CH2COCH2CH3 and CH3CH2OCH2CH3 3
Reagent: 2,4-DNPH 1 mark
Observation: red/orange/brown/yellow precipitate 1 mark
Equation:
NHNH2
NO2 O2N
Et
C O+ Et
Et C NNH NO2
Et
NO2
1 mark
C Incorrect structure for 2,4-dinitrophenylhydrazone.
94 2C 9 a i
9a Give the structural formula(e) of the major organic product(s) (P to V) formed in each of the following reactions.
i O 1
NH2OH
CH3 C CH2CH3 P
OH
N
P: 1 mark
95 2C 7 a ii
ii O O 3
CH3CH2CCH2CH3 and CH3CH2CH2CCH3
Treat compound with I2/OH- ½ + ½ mark

O O
I2
CH3CH2CH2CCH3 CH3CH2CH2C O-K+ + CHI3
KOH / NaOH ½ + ½ mark
yellow precipitate observed. ½ mark
O
No ppt. with CH3CH2CCH2CH3 ½ mark
C Many candidates failed to give the equations for the reactions.

Some candidates erroneously gave the silver mirror test as the answer. One common mistake was the wrong
formula for iodoform (CH3I instead of CHI3). Some candidates gave the wrong colour for CHI3. 'No observable
change' instead of 'no reaction' should be given because pentan-2-one does undergo reaction (iodination) under the
conditions.
95 2C 9 b i
i O N 1
2
H2NHN NO2 O2N
K NHN NO2
O
K: / cyclobutanone 1 mark
C candidates appeared to be unfamiliar with the cyclic structure and gave an acyclic ketone;
96 2C 8 c v
v O 1
NaHSO3
CH3CH2 C CH3 P
CH3
- +
SO3 Na or CH3CH2 C SO3-Na+
P: OH 1 mark
OH
C wrong structures for P, such as

SO3H SO3H
CH3CH2 C CH3 CH3CH2 C CH3
ONa OH
97 1A 5 a v
5a Give a structure for each of the compounds D, E, F. G and H: 5
v I2 / NaOH(aq)
C4H8O triiodomethane + sodium salt of a carboxylic acid
H
97 2B 5 a i ii iii
5a In an experiment, 10.0 g of butanone reacts with 5.0 g of hydrogen cyanide to give 11.0 g of 2-hydroxy-2- 6
methylbutanenitrile.
i Find the limiting reactant of the reaction, showing clearly your calculation.
ii Calculate the percentage yield of 2-hydroxy-2-methylbutanenitrile.
iii Name the type of reaction and outline the mechanism involved. (Movement of electron pairs should be indicated
by curly arrows.)
97 2B 7 a ii
7a Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Each test 12
should include the reagent(s), the expected observation with each compound and the chemical equation(s).
ii OH OH
CH2CH3 CH CH3
and
97 2B 7 b i
7b Identify J, K, L, M and N in the following reactions. 5
i O
C J CH NOH
H
98 1A 5 a c d i ii
5 Consider the five reactions of butanone (C4H8O) J shown in the reaction scheme below:
5a Suggest a reagent by which K may be formed and give the structure for K. 1
5c Give structures for compounds M, N, P and R. 4
5d i S is a structural isomer of J. S also reacts with 2,4-C6H3(NO2)2NHNH2 to give a red precipitate. Draw the structure 1
of S.
ii How may J and S be identified by making use of their reactions with 2,4-C6H3(NO2)2NHNH2 ? 1
99 2B 5 a i
5a Identify D, E, F, G and J in the following reactions.
i D
O NNH
Reference 19.2.0
251, 254–258, 259–263, 265–267
755–778, 797–799, 802–807,830–831
Syllabus Carboxylic acid and its derivatives

Preparation of acid derivatives
Reaction of acid derivatives
Notes b) Reactions of carboxylic acid and its derivatives
(a) Difference between carbonyl compound and carboxylic acid and its derivatives
O
Carboxylic acid consists of a carbonyl group C and a hydroxyl group –OH. Because of the presence of
carbonyl group, in certain extent, it shares the same reaction pattern of ordinary carbonyl compound.
However, carboxylic acid does not resemble the properties of ketone entirely. There are 3 major differences.
1. Carboxylic acid has reaction with sodium, phosphorus trichloride PCl3 and phosphorus pentachloride PCl5
while ketone or aldehyde haven't.
Since carboxylic acid also possesses a hydroxyl group, it shows some typical properties of a hydroxy
compound.
e.g. 2 H–O–H(l) + 2 Na(s) → H2(g) + 2 NaOH(aq)

O O
2 CH3 C OH (l) + 2 Na(s) → H2(g) + 2 CH3 C O-Na+ (acid)
The ethanoic acid used in this reaction must be dry, in which there is no free hydrogen ion. Otherwise,
Na(s) will react with the hydrogen ion vigorously and may cause explosion.
e.g. 3 H–O–H(l) + PCl3(l) → 3 HCl(g) + H3PO3(l)

O O
3 CH3 C OH (l) + PCl3(l) → 3 CH3 C Cl (l) + H3PO3(l)
e.g. 4 H–O–H(l) + PCl5(s) → 5 HCl(g) + H3PO4(l)

O O
CH3 C OH (l) + PCl5(s) → CH3 C Cl (l) + POCl3(l) + HCl(g)
In these reactions, the hydroxyl group –OH is substituted by –Cl atom. Another useful reagent for the
same purpose is thionyl chloride SOCl2 which has an even higher yield than PCl3 or PCl5.
2. Carboxylic acid and its derivatives undergoes condensation (addition-elimination) reaction instead of
addition reaction only.
In carboxylic acid, a hydroxyl group is attached to carbonyl carbon. It can be converted to a group leaving
group by protonation. Therefore, any nucleophilic addition is usually followed by elimination and leads to
condensation reaction.
O -
nucleophilic O elimination O
R C L -
R C L R C Nu + L
- addition
Nu Nu
Condensation reaction = Addition reaction + Elimination
3. Carboxylic acid and its derivatives have no reaction with 2,4-dinitrophenylhydrazine.
–OH is a +R and -I group. Since resonance effect is usually stronger than inductive effect, –OH is an
electron donating group in this case. It makes the carbonyl carbon less positive and less reactive than
ketone and aldehyde.
-
O O δ−O
CH3 C O H CH3 C O H or CH3 C O H
+ δ+
Similarly, all derivatives of carboxylic acid are with the resonance stabilized carbonyl group. They do not
react with 2,4-dinitrophenylhydrazine.
Carboxylic acid and its derivative shows the following order of reactivity. The trend is determined by the
leaving ability of the substitutent attaching to the carbonyl group.
Acid chloride Acid Carboxylic Ester Amide

(acyl chloride) anhydride acid
O O O O O O
R C Cl R C O C R' R C OH R C O R' R C NH2
Most reactive Least reactive

Leaving group Cl- RCOO - -
OH RO -
NH2-
Basicity of the
leaving group Low ––––––––––––––––––––––––––––––––––––––––––––––––––→ High
Glossary
Past Paper 95 2C 7 a iv
Question 97 2B 7 a iii
95 2C 7 a iv
iv O O 3
CH3CH2CNHCH2CH3 and CH3CH2CCH2NHCH3
Treat compound with a solution of 2,4-dinitrophenylhydrazine in methanol (or ethanol) 1 mark

O 2N O2N
O NH NO2
H2NNH NO2
NHCH3 N
NHCH3
1 mark
Orange / red / brown / yellow precipitate is observed. ½ mark
O
No ppt. with CH3CH2CNHCH2CH3 . ½ mark
OR
O - O
OH (aq)
-
CH3CH2CNHCH2CH3 heat CH3CH2C O + C2H5NH2
1 mark
HCl + -
C2H5NH2 C2H5NH3Cl
white fume 1½ mark
Comparison ½ mark
iv Many candidates failed to give the equations for the reactions.
Very badly answered. Few candidates could identify the keto group probably because they were not familiar with
compounds with more than one functional group. Some did not know that secondary amines do not react with
HNO2 to give N2. Most could not recall the chemistry of amides that are susceptible to hydrolysis.
97 2B 7 a iii
iii O O
C2H5 C O(CH2)2CH3 and C2H5 C CH2OC2H5
Reference 19.2.1
251, 254–258, 259–263, 265–267
755–778, 797–799, 802–807,830–831
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 462–463, 472, 505–508, 510–511, 520
Syllabus Preparation of acid derivatives

Reaction of acid derivatives
Notes (2) Formation of different acid derivatives
O -
nucleophilic O elimination O
R C L -
R C L R C Nu + L –L = –Cl, –COOR, –OH, –OR, –NH2
addition
-
Nu Nu Nu: = RCOO-Na+, Na+OH-, ROH, NH3
In general, a more reactive acid derivative can be converted to a less reactive acid derivative by using a
suitable nucleophilic reagent. The reaction is a simple nucleophilic addition-elimination reaction.
A less reactive derivative can also be converted to a more reactive derivative but the yield of conversion would
be rather low.
Exception : 1. Amide cannot be prepared from carboxylic acid and ammonia. This is because
carboxylic acid is an acid and ammonia is a base, they reacts to give a salt only. Amide
is usually prepared from acid chloride with ammonia.
2. Similarly, ester cannot be prepared from carboxylic acid and sodium alkoxide as they
will neutralize each other.
Acyl chloride is the most reactive acid derivative, it cannot be prepared from the other acid derivative. It is
prepared by converting the –OH group of carboxylic acid to –Cl group by chlorinating agent.
Chlorinating agent :
SOCl2 (thionyl chloride), PCl5 (phosphorus pentachloride) or PCl3 (phosphorous trichloride)
O SOCl2 or PCl5 or PCl3 O

R C OH R C Cl
(b) Formation of acid anhydride
Certain dioic acid can be dehydrated by heating through intramolecular dehydration to form cyclic acid
anhydride. This is only possible if the two hydroxyl groups of the two carboxyl groups are facing each other
spatially.
(ii) Through intermolecular dehydration by a very strong dehydrating agent
However, linear acid anhydride, e.g. ethanoic anhydride CH3COOCOCH3, cannot be prepared by heating
alone. Since the formation of the anhydride involves intermolecular dehydration, if the acid is heated strongly,
the thermal agitation will not allow the two acid molecules to get to each other for the dehydration. Therefore,
a very strong dehydrating agent e.g. phosphorus pentaoxide P2O5(s) (or P4O10(s)) should be used instead of
heating.
O O P2O5 O O
CH3 C OH + HO C CH3 CH3 C O C CH3
Similarly, it can also be prepared from reactive acyl chloride by mixing with a carboxylate salt.
O O O O
- + + Cl
CH3 C O Na C CH3 CH3 C O C CH3 + NaCl
(c) Formation of ester (Esterification with alkanol and phenol)
O
O-
carboxylic acid R' C O H O- H O
r.d.s. R' C O H
R' C O+ H R' C O R + H2O
R +O ester water
R O
H
R O H
charge separation
alcohol involved
Esterification is also a typical condensation reaction. An alcohol molecule is added to a carboxylic acid
molecule which elimination of water.
The nucleophilic oxygen atom is added to the carbonyl carbon. It can be seen that an intermediate with charge
separation in the structure is involved. This makes the reaction having a high activation energy, thus, a rather
slow rate.
Then, the proton possessed by the alcohol is shifted to the hydroxyl group to convert it to a better leaving
group, water H2O.
Contrastingly, esterification in the presence of any aqueous acid is found to be catalyzed.
Acid Catalyzed Esterification

H
H
O H
O +O r.d.s.
H+ R C OH O H
R C OH f R C OH
H f R C O H
O
+ H2O + H+
O R' +O H
f O
+ fR C OR'
R'
no charge R'
separation involved
In the acid catalyzed pathway, the carbonyl oxygen is first protonated. This activates the carbonyl group by
increasing the polarity of the C=O bond and makes the carbonyl carbon more positive and more vulnerable to
the attack of the nucleophile, alcohol. Furthermore, no reaction intermediate with charge separation is
involved in the acid catalyzed mechanism and a much lower activation energy would be involved.
Esterification of phenol
However, phenol is a weaker base than aliphatic alcohol because H H

of benzene ring is electron withdrawing.
O O
A substrate more reactive than carboxylic acid is required to give a reasonable yield. Phenol reacts with acyl
chloride and acid anhydride to form ester.
O
O
R C Cl -
OH O C R + Cl
O O
O O
R C O C R -
OH O C R+R C O
(d) Formatioin of amide (Acylation and benzoylation of amine)
O
Acylation means substitution by an acyl group C R . Two common reagents used in acylation are ethanoyl
O O O
chloride CH3 C Cl and ethanoic anhydride CH3 C O C CH3 . Both of them are reactive derivatives of carboxylic
acid, which reacts with nucleophile, e.g. NH3 or RNH2, readily. When ethanoyl chloride or ethanoic anhydride
O
are used, the reaction is also called ethanoylation since the acyl group involved is the ethanoyl group C CH3 .
O
-O
CH3 C Cl NH3 O
CH3 C Cl O H excess
CH3 C N H + Cl-
CH3 C NH2 + NH4+Cl-
H N H +
+ ethanamide
H N H H H
H
In ethanoylation of ammonia, excess ammonia is used to neutralize the HCl formed. In the reaction, one H on
O
ammonia molecule is substituted by an ethanoyl group C CH3 . Unlike esterification, catalysis by
protonation is impossible in here. The presence of aqueous acid will neutralize the nucleophile NH3 to non-
nucleophilic species NH4+ and stop the reaction. Furthermore, ethanoyl chloride or anhydride also reacts with
water directly.
O
Similar to acylation, benzoylation means substitution by an benzoyl group C . Benzoyl chloride is the
commonly used reagent. It is prepared by treating benzenecarboxylic acid (benzoic acid) with phosphorus
trichloride PCl3, phosphorus pentachloride PCl5 or thionyl chloride SOCl2.
O O
3 C OH + PCl3 3 C Cl + H3PO3
benzoyl chloride
The reactive benzoyl chloride reacts with the ammonia or amine through nucleophilic addition-elimination
similar to the ethanoylation discussed above.
O
-O
C Cl
NH3 O
C Cl O H excess
C N H + Cl- C NH2 + NH4+Cl-
H N H +
H N H + benzenecarboxamide
H H
or benzamide
H
Ester can be hydrolyzed in neutral, acidic or alkaline medium. Since OH- is a nucleophile stronger than H2O,
the rate of hydrolysis will be fastest in alkaline medium.
-
O O -
O
R' C O R + O - O
R' C O R R' C O R OH -
O R' C O H + H O R R' C O
H O O H
- H carboxylic alkanol carboxylate
OH H H acid ion
- -
OH is consumed OH is regenerated
OH- ion can be considered as a catalyst in the hydrolysis or it can be considered as a reagent which neutralizes
the carboxylic acid to carboxylate ion.
In acidic medium, hydrolysis is catalyzed by protonation of carbonyl group.

H
+O H
R' C O R O
O H+
R' C O R
R' C O R H O
+
H O H
H
H
H
O O
O+ +H O R + H+ + H O R
R' C O+ R R' C O H
R' C O H
H O H
Therefore, the rate of hydrolysis of ester follows the following order :
alkaline medium > acidic medium > neutral medium.
Glossary Esterification acylation benzoylation
Past Paper 90 1B 4 c i ii
Question 92 1A 1 a iii 92 1B 5 a ii iv
93 2C 7 a iii
94 2C 9 a ii
95 2C 9 b ii
96 1A 3 d ii
97 1A 5 a iii
98 2B 7 a i
99 2B 6 a i
90 1B 4 c i ii
4c Amides are generally prepared by reacting equimolar amounts of an amine and an acid halide.
(Relative atomic masses : H, 1.0; C, 12.0; N, 14.0; O, 16.0; Cl, 35.5)
Calculate:
i the mass (in grams) of Y required to react with 4.0 g of benzoyl chloride (C6H5COCl), and 1½
Relative molecular mass of Y = 6 × 12.0 + 7 × 1.0 + 14.0 = 93.0
Relative molecular mass of C6H5COCl = 7 × 12.0 + 5 × 1.0 + 16.0 + 35.5 = 140.5 ½ mark
4.0 × 93.0
mass of Y = 140.5 = 2.65 g 1 mark
ii the percentage yield of the same reaction if 4.0 g of the amide product is obtained. 1½
Relative molecular mass of amide (C13H11NO) = 13 × 12.0 + 11 × 1.0 + 14.0 + 16.0 = 197.0
4.0 × 197 .0
100% yield = 140.5 = 5.6 g
4.0
percentage yield = 5.6 × 100% = 71% 1½ mark
C The calculation of percentage yield was very, very poorly answered. It is clear that such work is rarely done by
candidates. It is also obvious that this very simple concept is unknown to most candidates.
92 1A 1 a iii
iii On heating, one of the isomers gives a compound W, with formula C8H4O3. Give the structure of W. 1
O
C
O
C
O
1 mark
92 1B 5 a ii iv
5a Ethanolylation (acetylation) of phenylamine (C6H5NH2) may be carried out by refluxing for 1 hour with ethanoic
anhydride (acetic anhydride) giving a product which is insoluble in cold water.
(Ethanoic anhydride hydrolyses in water to give ethanoic acid. The b.p. of phenylamine and ethanoic anhydride
are 184°C and 140°C respectively; the m.p. and b.p. of the product are 114°C and 304°C respectively.)
ii Give the structure of the product from the ethanoylation reactions. 1
H O
N C CH3
1 mark
iv If 40g of phenylamine is to be ethanoylated, calculate the mass of ethanoic anhydride required. 2
(Relative atomic masses: H 1.0; C 12.0; N 14.0; O 16.0)
molecular mass of PhNH2 = 93
molecular mass of (CH3CO)2O = 102
Since PhNH 2 + (CH 3CO)2 O  → PhNHCOMe + CH 3CO 2 H
102 1
The mass of ethanoic anhydride required = 40 × × g = 43.9g 2 marks
93 1
C Calculation was very badly done, suggesting that few do experiments involving quantities.
93 2C 7 a iii
7a Give the structural formula(e) of the major organic product(s) formed in each of the following reactions.
iii NH2 2
CH3COCl
O
H N C CH3
1 mark
C This was generally well answered.
94 2C 9 a ii
ii NH2 1
CH3CH2COCl
Q
Q: O 1 mark
95 2C 9 b ii
ii O O 1
L
CH3CH2CH2COH CH3CH2CH2CCl
L : phosphorus(V) chloride / PCl5 or phosphorus(III) chloride / PCl3 or thionyl chloride / SOCl2 1 mark
C Common mistakes included : HCl for L;
96 1A 3 d ii
3d Give the structure of the major organic product(s) in each of the following reactions :
ii O O 1
heat
HO C CH2 CH2 C OH
O O
heat O
HO C CH2 CH2 C OH
O
1 mark
97 1A 5 a iii
iii SOCl2
CH3CH2CO2H F
98 2B 7 a i
7a Briefly explain why each of the following proposed reactions cannot lead to the target molecule. In each case, 12
using the same starting molecule, outline a feasible synthetic route to obtain the target molecule, with no more
than three steps. In each step, give the reagent(s) used, the conditions required and structure of the product.
i O O
CH3OH
C NHCH3 C OCH3
99 2B 6 a i
6a i Suggest a reagent for the following conversion :
O
Cl NH2 Cl NH CCH3
4-chlorophenylamine N-(4-chlorophenyl)ethanamide
Reference 19.2.2–19.2.3
251, 254–258, 259–263, 265–267
755–778, 797–799, 802–807,830–831
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 505, 519
Syllabus Reduction of acid and its derivatives

Hoffmann degradation of amide
Notes (3) Reaction of amide
Except amide, all other acid derivative are reduced by LiAlH4 to alcohol. The nucleophilic hydride ion, H-,
serves as a strong reducing agent in this reaction.
aldehyde
O - O OH
O O-
- H acid
R C L
R C L R C H + L R C H + H2O
R C H work up
H O H H
H- H H +
H-
where L = –Cl, –OOCR, –OH, –OR
The aldehyde intermediate cannot be isolated from the reaction mixture. It will be reduced directly to a
primary alcohol.
Exception : Reduction of amide
Amide will be reduced by LiAlH4 to amine instead of alkanol.
LiAlH4 can be considered to be comprised of three parts :

Li+ : a spectator ion
H- : a nucleophile, a very strong reducing agent
AlH3 : a Lewis acid, a catalyst activates the reactivity of a carbonyl group
The actual mechanism of the reaction is still not very clear, the following may be a possible one.
Simplified Proposed Mechanism

H H
H Al H -
H Al H
H- O+
O
-
R C N H R C N Li+
O
- H
H R C N Li+
acid-base reaction H H-
activation reduction
H H
-
H Al H H- H O H H H
+
O H R C N
- R C N -
R C N Li+ R C N H H
H H
H H imine H H
(further reduction) acid work up 1° amine
Depending on the original structure of the amide, it is reduced by LiAlH4 to 1º amine, 2º amine or 3º amine.
Amide is the only acid derivative which will not be reduced to 1º alcohol by LiAlH4.
H
O 1) LiAlH4 / ether
R C N H
R C NH2 2) H3O+
H H
amide 1° amine
O H
1) LiAlH4 / ether
R C N H R C N H
2) H3O+
R' H R'
N-substituted amide 2° amine
O H
1) LiAlH4 / ether
R C N R'' R C N R''
2) H3O+
R' H R'
N.N-disubstituted 3° amine
amide
This reaction is commonly used to prepare 2º and 3º amine where direct alkylation of 1º and 2º amine will
yield a mixture of 2º, 3º amine and quaternary ammonium ion.
Reduction selectivity of LiAlH4 and NaBH4
In term of reducing power, LiAlH4 is much

stronger than NaBH4. LiAlH4 can reduce all kinds
of carbonyl compound to alcohol. This includes
ketone, aldehyde and all kinds of acid derivatives
except amide. In contrast, NaBH4 is only strong
enough to reduce ketone and aldehyde to alcohol,
but not any acid derivative.
Reagent : a base – NaOH(aq) and an electrophile – Br2(l)
O
R C NH2 + Br2 + 4 NaOH R N H + 2 NaBr + Na2CO3 + 2 H2O
non-substituted H
amide 1° amine
Hofmann degradation is also known as Hofmann rearrangement. According to the mechanism, the 2 protons
on the amino group are first subtracted by the base. Therefore, only a non-substituted amide RCONH2 can
undergo Hofmann degradation.
Comparing with the reduction of amide by LiAlH4, Hofmann degradation provides a way to shorten the
carbon chain by 1 carbon atom.
H
O 1) LiAlH4 / ether
R C N H
R C NH2 2) H3O+
H H
amide 1° amine
O Br2 / NaOH(aq) R N H
R C NH2
H
1?amine
amide with 1 C less
Glossary reduction selectivity Hofmann degradation / Hofmann rearrangement

Past Paper 92 2C 8 a i ii
Question 93 2C 7 a iv
94 2C 9 a iii
95 2C 9 b vi vii
96 2C 8 a i ii 96 2C 9 a iii
97 1A 5 a i ii 97 2B 7 b iii
98 1B 8 b ii iii 98 2B 7 a iii
99 2B 5 a iv
92 2C 8 a i ii
8a Amines can be prepared from an amide or an alkyl halide.
i Illustrate this statement by the preparation of RCH2NHCH3. Both synthetic reaction sequences must start with 7
RCO2H. In each sequence, give the reagent(s) for each step and the structures of intermediate compounds.
(I) RCOOH PCl
→ RCOCl CH
5NH
→ RCONHCH3 LiAlH
→ RCH 2 NHCH3
3 2 4
3½ marks
LiAlH 4 PBr3 CH 3 NH 2
(II) RCOOH  → RCH 2 OH  
→ RCH 2 Br  
→ RCH 2 NHCH3 3½ marks
ii Explain which of your two methods is more suitable for preparing RCH2NHCH3. 2
CH 3 NH 2
(II) is less appropriate than (I) in preparation, since RCH2 Br  
→ also gives (RCH2)2NCH3. 2 marks
C The least well-answered part in IIC.
Common mistakes in conversions include :
1. Preparing an amide by direct reaction between an acid with NH3 or amine,
RCOOH + CH3NH2 RCONHCH3
RCOOH + NH3 RCONH2
2. Converting a secondary amide to a secondary amine employing Br2/OH- (Hofmann Degradation applicable to
primary (non-substituted) amide only)
-
Br2 / OH
RCONHCH3 RCH2NHCH3
3. Alkylating a primary amide with alkyl halide to obtain a secondary amide

CH3Br
RCONH2 RCONHCH3
93 2C 7 a iv
7a Give the structural formula(e) of the major organic product(s) formed in each of the following reactions.
iv O
LiAlH4
2
CH3 C CH2CH2COOCH3
OH
CH3 C CH2CH2CH2OH
H
reduction of ketone – 1 mark, reduction of ester – 1 mark
C Many candidates did not realize that esters could be reduced to alcohol by LiAIH4.
94 2C 9 a iii
iii LiAlH4 1
CH3CH CHCH2CH2COOH R
R: CH3CH CHCH2CH2CH2OH 1 mark

C Candidates were casual / careless in writing structural formula, particularly in putting the number of H atoms to
each C atom. Common mistakes included :
CH3CH2CH2CH2CH2CH2OH for R (saturating C=C)
95 2C 9 b vi vii
vi O 1
LiAlH4
C N(CH3)2 R
H CH3
C N
R: H CH3 1 mark
C wrong structure for R. such as

OH
CH3
N
CH3
vii CO2CH3 1
NaBH4
S
CO2CH3
S: OH 1 mark
C wrong structures for 5, such as

CH2OH COOCH3 COOCH3
OH OH O
Candidates did poorly in the cases of P. R and S. and were thus not familiar with the chemistry of exhaustive
methylation of amine, the hydride reduction of amide, and the mild reducing reagent sodium borohydride.
96 2C 8 a i ii
8a i An acyclic compound H of molecular formula C4H8O2 has a fruity smell. It does not produce a derivative 4½
with 2,4-dinitrophenylhydrazine nor with propanoyl chloride.
Deduce the functional group(s) of H. Draw FOUR possible structures for H.
H is not aldehyde / ketone ½ mark
because it does not form hydrazone derivative. ½ mark
or
R
N NH NO2
O2N
(½ mark)
H does not possess an –OH group / is not an alcohol ½ mark

because it does not form ester with propanoyl chloride. ½ mark
or
O
no R O C C2H5 formation (½ mark)
H has a fruity smell, The functional group(s) in F is most likely an ester. ½ mark
Any FOUR of the following structures (½ marks for each structure) 2 marks
H O H O O O O
O O
O O O O O
(Deduct ½ mark for each extra structure)

C Poorly answered. Many candidates did not appear to know the reaction of 2,4-dinitrophenylhydrazine and
propanoyl chloride and hence the formation of the respective 2,4-dinitrophenylhydrazone and ester was omitted.
Some did not know the reaction of ester with LiAIH4 or the structure of ethanoic anhydride.
ii On reduction with an excess of LiAlH4, H gives only one product, J. which reacts with ethanoic anhydride. 3½
Deduce, giving equations, the structure for H and also the structure for J.
O
O
O O
ROH R
O
1 mark
Among the four carbon esters only ethyl ethanoate gives one reduction product ½ mark
or, other esters give a mixture of alkanols on reduction (½ mark)
O
∴ structure of H is O
½ mark
and structure of J is OH ½ mark

Equation for the reduction of H
O
LiAlH4
CH3 C OC2H5 2 C2H5OH
½ mark
96 2C 9 a iii
9a Each of the following conversions can be completed in not more than three steps. Use equations to show how you
would carry out each of these conversions in the laboratory. For each conversion, give the reagent(s), conditions,
and structure of the intermediate(s).
(For answers with more than 3 steps, deduct 1 mark for each extra step.)
iii COCl NH2 3
O
(1)
NH3 Br2 / OH- (or OBr-) (½)
NH2
heat (½)
(1) 3 marks
C Many candidates wrongly thought that acid amide can be prepared directly from the reaction of carboxylic acid
with ammonia. Heating was omitted in the Hofmann degradation step.
97 1A 5 a i ii
5a Give a structure for each of the compounds D, E, F. G and H:
i (1) LiAlH4
CH3CH2CONH2 D
(2) H2O
ii Br2 / NaOH(aq)
CH3CH2CONH2 E
97 2B 7 b iii
7b Identify J, K, L, M and N in the following reactions.
iii O
CH3 L CH3
C CHC OCH3 C CHCH2OH + CH3OH
CH3 CH3
98 1B 8 b ii iii
8b 20.0 g of 4-nitrobenzoic acid (C7H5NO4) reacted with PCl5 to give a product which reacted
exothermically with NH3 to give T. After treatment with Br2(l) and NaOH(aq), T gave a solid. Crystallization of the
solid from ethanol gave 9.3 g of U (C6H6N2O2).
ii Give the structures of T and U.
iii Briefly give three reasons which could explain why the yield of U in the above preparation is not quantitative (i.e.
100%).
98 2B 7 a iii
7a Briefly explain why each of the following proposed reactions cannot lead to the target molecule. In each case,
iii O + O
LiAlH4, H3O
CH3CH2 C OH CH3CH2 C H
99 2B 5 a iv
iv CO2NH2
Br2 / NaOH
G
heat
CH3O
Reference 19.3
251, 254–258, 259–263, 265–267
755–778, 797–799, 802–807,830–831
Organic Chemistry, 6th Edition, Solomons, pg. 711, 825-827, 918
Syllabus Reaction of nitrile

Partial and complete hydrolysis of nitrile
Dehydration of amide
Reduction of nitrile
Notes c) Reactions of nitrile

O
Nitrile C N is quite similar to carbonyl group with the N replacing the O.
C
(1) Hydrolysis of nitrile
Nitrile can be hydrolysed to carboxylic acid or carboxylate by boiling with aqueous acid or alkali, with the
amide intermediate. By employing an suitable reaction condition, amide intermediate can be isolated from
further hydrolysis to carboxylic acid.
e.g. Heating with dilute sulphuric acid will yield carboxylic acid while heating with concentrated sulphuric
acid will only yield amide.
Or, amide can be obtained by hydrolysis using cold dilute acid instead of a hot one.
Partial hydrolysis of Nitrile to Amide

H isoamide amide
H
O H H
O H O H
H O
R C N H
R C N H O+ H R C N H
δ+ δ− -
R C N O H
tautomerization
Hydrolysis of Amide to Carboxylic acid

Temperatur Concentration Degree of
O - e of of sulphuric hydrolysis
O O hydrolysis acid
R C L -
R C L R C Nu + L Complete Low High
- Nu Partial High Low
Nu
Partial Low High
Hydrolysis of amide to carboxylic acid follows the regular pattern of the nucleophilic addition-elimination
reaction of acid derivatives.
O -
O H - -
R C NH2 O H O H
R C N H O O
R C N+ H R C N+ H NH3 NH4+
H O R C O H R C O-
H O + H O H H O H
H H
With the appropriate dehydrating agent, phosphorus pentoxide (P2O5, with molecular formula P4O10) or
boiling ethanoic anhydride (CH3CO)2O or thionyl chloride (SOCl2), amide can be converted back to nitrile.
O P2O5 or (CH3CO)2O
or SOCl2 R C N
R C NH2
Similar to the carbonyl group, nitrile group is susceptible to the reduction by hydride ion through nucleophilic
addition pathway. For carbonyl compound, the carbonyl group is reduced to alcohol. A nitrile is reduced to
amine by addition of hydride.
from LiAlH4
H- H H H H H H
H H3O+
R C N -Al H Li+ R C N -Al H Li+ R C N H
R C N Al H Li+
δ+ δ− H H H
H
nitrile primary amine
Glossary hydrolysis of nitrile dehydration of amide reduction of nitrile
Past Paper 96 1A 3 f i 96 2C 9 a i
Question 97 2B 6 a iii 97 2B 7 b iv
98 2B 6 d ii
99 1A 5 b i 99 2B 7 b i
96 1A 3 f i
3f i Give the structures of compounds D and E in the following organic synthesis : 2
O
+
C HCN H3O
H D heat E
OH OH
D: CN E: COOH
1 + 1 marks
(Deduct ½ mark for each minor mistake in the structures.)
96 2C 9 a i
i CH2Br CH2CH2NH2 3
(1) (? (1)
NaCN CN LiAlH4 or H2 / cat (Pd / Pt / Ni)
heat
(1) (? 3 marks
+
C Some candidates erroneously used HCN in the first and LiAlH4/H in the last step. Acid hydrolysis should be
followed by an alkaline work-up as the target molecule is an amine and not a salt.
97 2B 6 a iii
of the product.
iii O
CH3CH2 C
CH3CH2C N O
CH3CH2 C
O
97 2B 7 b iv
7b Identify J, K, L, M and N in the following reactions.
iv O
P2O5
CH3CH2CH2 C NH2 M
heat
98 2B 6 d ii
6d Identify K in the following reaction.
ii CONH CN
2
K
99 1A 5 b i
5b Consider the following reactions :
CHO
HCN (1) LiAlH4
D + E
(2) H3O
i Give the structures of D and E.
99 2B 7 b i
7b With no more than four steps, outline a synthetic route to accomplish each of the following transformations. In
each step, give the reagent(s) used, the conditions required and the structure of the product.
i O
CH3CHCH2CO2H
CH3CHCH2 C OCH2CH3
CO2H
OH
Reference 20.0
Organic Chemistry, Solomons, 5th Edition pg. 342–349, 351–356, 360, 366–370
Syllabus Electrophilic addition
Notes Electrophilic reaction is a kind of reaction initiated by electrophile. It includes electrophilic addition and
electrophilic substitution.
When an electrophile is attracted towards an negative, electron rich, centre, a bond may be formed between the
electrophile and the substrate.

+ -
δ
Because bromine is more electronegative than hydrogen, the H–Br bond is polarized, δ H Br .
Upon heterolytic bond fission, a H+ and a Br- will form. In this case, H+ ion
is the electron deficient species and is an electrophile. It is attracted
towards the electron rich double bond by the π electrons with the formation
of a carbocation intermediate.
H+ X-
H H X
r.d.s. +
C C C C C C
The reaction is completed by addition of the Br-, a nucleophile, to the carbocation.
For an unsymmetrical alkene, addition of hydrogen halide may have two possible orientation.
e.g.
H Cl H
H C C C H
H H H
H
H 1 2 2-chloropropane
C C C H + H Cl
H
H H Cl H H
propene H C C C H
H H H
1-chloropropane
If the H+ ion is attached to the C-1, the product will be 2-chloropropane. If the H+ ion is attached to the C-2, the
product will become 1-chloropropane.
It is found that in this reaction, 2-chloropropane is the major product and 1-chloropropane is the minor product.
This can be explained by the difference in activation energy involved in the two different pathway.
In 2-chloropropane formation, the rate

determining step is the attachment of the H+ ion
to the C-1 to form a 2º carbocation. While for
the 1-chloropropane, the H+ ion is attached to
the C-2 to form a 1º carbocation.
As 2º carbocation is more stable than the 1º

carbocation (refer to SN1 reaction), it involves a
lower activation energy of formation and forms
at a faster rate.
Formation of 2-chloropropane
H+ Cl-
H H H H Cl H
H r.d.s. +
C C C H H C C C H H C C C H
H
H H H H H H H H
2° carbocation 2-chloropropane
(more stable)
Formation of 1-chloropropane
Cl-
H+
H H H Cl H H
H r.d.s. +
H
H H H H H H H H
1° carbocation 1-chloropropane
(less stable)
This observation is generalized and is called Markownikoff's rule. Markownikoff’s rule states that “in the
addition of hydrogen halide to an alkene, the hydrogen atom adds to the carbon with more hydrogen
atoms.” or “if an unsymmetrical alkene combines with a hydrogen halide, the halide ion adds to the carbon atom
with the fewer hydrogen atoms.”
To be more general, the electrophile joins to the carbon will more hydrogen atoms to yield a more stable
carbocation.
Because the rate of electrophilic addition is depending on the stability of carbocation intermediate. Alkene has the
general order of reactivity towards electrophilic addition as follows.
H CF3 H H H H R R H H
C C C C C
< < < <
C C C C C
H H H H H R R R H
–F is an electron withdrawing group which makes the carbocation intermediate less stable.
–R is an electron donating group which make the carbocation intermediate more stable.
H H
C C is particularly reactive because the carbocation involved is stabilized by resonance.
H
H H + H
+
H C C H C C H C C +
H H H H H H
Glossary electrophilic addition Markownikoff’s rule
Past Paper 91 1A 1 a
93 2C 9 b
94 1A 3 b i ii
95 1A 3 c i ii
96 2C 9 b
98 2B 5 c i
91 1A 1 a
1a CH3 4
C CH2
H
E
Using E, give reagents and a mechanism to explain what is meant by each of the following :
A reaction obeying Markownikoff’s rule.
A polymerization reaction.
Markownikoff’s rule
The answer must involve “the addition of acid and explain and show the correct direction of addition”.
H Z
H Z + Z-
Me Me
Me Me Me
Acid; could be HI, HCl, H2SO4, H3O+, HX but not HNO3 ½ mark
Mechanism:
Correct use of arrows or H+ in the first step ½ mark
Intermediate Carbonium ion (draw or write) ½ mark
Correct product ½ mark
X
If wrong product Me e.g. but use of HX (max. ½ mark)
The mechanism is Electrophilic Addition
Polymerization reaction
Reagents: can be radical R·
or ion either cationic polymerization (e.g. above using an acid)
or anionic polymerization - using a base e.g. KNH2 ½ mark
Mechanism: Correct intermediate or arrows or indicate chain initiation, propagation and termination. 1 mark
Direction of addition is not important.
Product: must clearly show a polymer ½ mark
Radical e.g.
R
R
CH2 CH
R R
CH3
n
Cationic e.g.
Me Me Me Me CH2 CH
H+ CH2 CH2 etc.
H H Me CH CH2 CH CH3
n
Anionic e.g.
Me Me Me Me CH2 CH
NH2- CH2 CH2 etc.
NH2 CH2 CH CH2 CH CH3
H H n
C Whilst Markownikoff seemed to present few problems, the polymerisation was obviously more difficult -
problems with reagents, mechanism and product.
92 2C 9 a iv
iv H3C excess HBr/CCl
2
CHC CH 4
H3C
CH3 Br
Br
CH3 CH3
2 marks
93 2C 9 b
9b Outline the mechanism for the reaction between but-1-ene and HBr to give bromobutane. Explain why 2- 3
bromobutane is the major product, rather than 1-bromobutane.
H Br Br- Br-
CH3CH2CH CH2 CH3CH2CH CH3 CH3CH2CH2 CH2
or
CH3CH2CH CH3 CH3CH2CH2 CH2

Br Br
2-bromobutane 1-bromobutane
2-bromobutane is the major product because CH3CH2CH CH3 is more stable than CH3CH2CH2 CH2 .
2° carbocation 1° carbocation
(2 marks for mechanism, 1 mark for explanation)

C Many candidates simply stated the Markownikov's rule without offering any explanation.
94 1A 3 b i ii
3b i Give the major product from the reaction: 1
CH3CH=CH2 + HBr →
CH3CHCH3
Br 2-bromopropane or isopropyl bromide 1 mark
ii Outline the mechanism of this reaction. Another product is also formed. Give its structure and account for the 3
fact that it is only the minor product.
Mechanism:
Br- Br
CH3 CH CH2 H Br CH3 C CH3 CH3 C CH3

δ+ δ-
H H
1 mark
Minor product is CH3CH2CH2Br 1 mark
CH3 CH2 C H CH3 C CH3
It is a minor product because its intermediate H
is less stable than the secondary carbocation H
.
CH3 C CH3 CH3 CH2 C H
The secondary carbocation H
is more stable than the primary carbocation H
because the two
electron releasing methyl groups disperse the charge more and so stabilise the positive ion more effectively.
1 mark
Or
The carbocation formed exists as an equilibrium
CH3
H
C CH3
e CH3 CH2 C
H
H
more stable less stable

Mechanism – 1 mark
Minor product – 1 mark
Explanation – 1 mark
½ bonus mark – The electron release may be considered to be due to the inductive effect and the
hyperconjugative effect.
C In the mechanism of the reaction, the wrong direction of the curly arrows was a common mistake.
95 1A 3 c i ii
3c i Give the structure of the major product formed from the following reaction : 1
CH3
+ HBr
CH3
Br
1 mark
ii Outline a mechanism for the above reaction. (Movement of electron pairs should be indicated by curly arrows.) 2
CH3
H
or
CH3 CH3 CH3
H Br Br- Br
δ+ δ-
2 marks
C Generally well answered. Some did not use complete arrows to indicate the breaking of covalent bonds.
96 2C 9 b
9b Give the structure of the major product in the following reaction and outline the mechanism of the reaction. 3
(Movement of electron pairs should be indicated by curly arrows.)
CH2
+ HBr
Br
CH3
Major product :
1 mark
Mechanism :
- (?
Br
CH2 (? CH3 Br
CH3
H Br
(? (? 2 marks
C Candidates were poor in writing curly arrows. Many used H+ instead of HBr as the electrophile.
98 2B 5 c i
5c Give the structure of the major organic product, G, in (i) below. 7
Outline a mechanism for the formation of the major product in the reactions.
i H3C CH3 HBr
C C G
H3C H
Organic Chemistry, Solomons, 5th Edition pg. 342–349, 351–356, 360, 366–370
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 421–422, 424–425,
Syllabus Electrophilic addition
Notes B. Other relevant reaction
Bromine in CCl4
Normally, Br–Br molecule breaks symmetrically by homolytic fission. But under the influence of electron rich
double bond, Br–Br bond will be polarized when the molecule is approaching the double bond. The polarization
weakens the Br–Br bond and makes it break unsymmetrically.
Owing to the presence of lone pair, halogen atom is capable to form a single bond with the positive centre of the
carbocation formed.
δ−
Br
Br-
Br δ+
Br Br Br Br
+
C C C C C +C C C
carbocation bromonium
(does not form indeed) Br- ion
Bromonium ion intermediate is more stable than ordinary carbocation intermediate because the positive charge is
dispersed over the 3 membered ring. In ordinary carbocation, the positive charge is concentrated on one carbon
atom only.
Finally, the bromide ion Br- attacks the C atom from another side of the molecule and yield a 1,2-disubstituted
bromoalkane.
Overall reaction
Br Br
in dark
Br2 + R C C
R
R C C R
R R
R R
Bromine water
In the presence of water, halohydrin will be formed instead of 1,2-dihalide. This is because H2O is a better
nucleophile than Br-.
H H
Br H O Br O Br
C +C C C C C
bromonium
ion halohydrin
H O
H
H2O attacks the bromonium ion to form halohydrin.

Anyway, bromine water can also be used to test for double bond or triple bond.
N.B. Hydrin means a hydroxyl compound.
Alkene doesn't reacts with dil. H2SO4(aq) normally. However, it reacts with conc. H2SO4(l) to give an addition
product.
OH
O S O
O H O
+ - H O
C C H O S O H C C O S O H
C C
O O
sulphuric acid alkyl

molecule hydrogensulphate
This reversible reaction can be used to extract alkene from a mixture with alkane. By bubbling impure alkene
through conc. H2SO4(l), only alkene will dissolve in it. Conc. H2SO4(l) can be separated by separating funnel. By
heating the conc. H2SO4(l), alkene will evaporate and can be recovered.
Since H2SO4 is a strong acid, HSO4- would be a very weak base, therefore, HSO4- is a very good leaving group. By
adding water into alkyl hydrogensulphate, it can be converted to alkanol through nucleophilic substitution..
OH
O S O H H
H O nucleophilic H O H H O
C C substitution
C C C C
O H
alkyl H
hydrogensulphate alkanol
An alkene can also be converted to alkanol by direct hydration using the catalyst of aqueous sulphuric acid or
phosphoric acid. Hydration of alkene proceeds through an ionic mechanism and obeys the Markownikoff’s rule.
N.B. Water is a nucleophile which does not react with electron rich double bond directly.
e.g. Hydration of propene

+ O H
H O H
H
H O H H
H H
H H H H H +O H H O H
+
H + H O H
C C C H r.d.s. H C C C H H C C C H H C C C H
H H H H H
H H H H H H H H
regenerated
2º carbocation propan-2-ol
(more stable)
In the above mechanism, H3O+(aq) is consumed in the first step and regenerated in the last step. It only acts as a
catalyst.
Since propan-2-ol can be prepared by direct hydration of propene while propan-1-ol cannot be, propan-2-ol is
much cheaper than propan-1-ol. The cheap propan-2-ol is commonly used as the rubbing alcohol.
For those alkanols involving formation of less stable 1º carbocation, e.g. ethanol, a more vigorous reaction
condition is required.
H3PO4
CH2 CH2 + H2O CH3 CH2 OH
300 ºC
Comparing with H2SO4(l), H3PO4(l) is not an oxidizing agent with will not oxidize CH3CH2OH to CH3COOH.
The term ozonolysis means breaking down (-lysis) by ozone (ozon-).

Ozone reacts with an alkene vigorously to form a very unstable intermediate initial ozonide which rearranges
immediately to ozonide. Since the product is potentially explosive, it is carried out at a low temperature.
Upon treatment with zinc and water, the ozonide will be reduced to 2 carbonyl compounds, aldehyde or ketone,
depending on the original structure of the alkene.
Since there is a direct relationship between the structure of the carbonyl compound obtained and the structure of
the original alkene, ozonolysis is useful in locating the position of the double bond in an alkene.
CH3 CH3 O O
(1) O3, CH2Cl2, -78 ºC
CH3CHCH CH2 CH3CH C H + H C H
(2) Zn / H2O
3-methylbut-1-ene 2-methylpropanal methanal
N.B. CH2Cl2 is only the solvent.
In the presence of the reductive zinc metal, the aldehyde formed will not be oxidized to carboxylic acid.
If the alkene is a cyclic one, there will be only one product molecule instead of two.
O O
(1) O3, CH2Cl2, -78 ºC
H C CH2 CH2 CH2 CH2 C H
(2) Zn / H2O
cyclohexene hexane-1,6-dial
These characteristics of ozonolysis reaction makes it particularly useful in determining the structure of an organic
molecule.
N.B. The carbonyl compounds formed from ozonolysis can be identified by melting point determination of the
oxime and 2,4-dinitrophenylhydrazone derivatives.
A diol can be prepared by oxidation of a double bond using cold dilute basic / acidic potassium permanganate or
osmium tetroxide.
N.B. Basic potassium permanganate is more oxidative than acidic potassium permanganate and the reduction
product would be brown MnO2(s) instead of colourless Mn2+(aq).
By cold dilute basic / acid potassium permanganate By osmium tetroxide
Overall reaction
If an alkene is treated with hot basic potassium permanganate instead of a cold one, the product will not be a
diol. The hot basic potassium permanganate is strong enough to break the double bond by oxidation.
O O
CH3CH2 CH3 (1) KMnO4, OH-, hot
C C CH3CH2 C CH2CH3 + H3C C CH3
(2) H+
CH3CH2 CH3
3-ethyl-2-methypent-2-ene pentan-3-one propanone
The reaction is similar to ozonolysis of alkene. The difference is that any aldehyde formed will be oxidized to
carboxylic acid immediately.
O O
(1) KMnO4, OH-, hot
HO C CH2 CH2 CH2 CH2 C OH
(2) H+
cyclohexene hexane-1,6-dioic acid
And any terminal =CH2 group will be oxidized completely to carbon dioxide and water.
CH3 CH3 O
(1) KMnO4, OH-, hot
CH3CHCH CH2 CH3CH C OH + CO2 + H2O
(2) H+
3-methylbut-1-ene 2-methylpropanoic acid
The products obtained from the oxidation can also be used to deduce the structure of the alkene.
b) Comparison of ozonolysis and oxidative cleavage
Ozonolysis Oxidative cleavage

Reagent used 1) O3, CH2Cl2, -78ºC KMnO4, OH-, heat
2) Zn / H2O
=CR2 O O
(disubstituted terminal group) Ketone Ketone
R C R R C R
=CHR O Carboxylate ion / carboxylic acid
(monosubstituted terminal group) Aldehyde
H C R O O
-
R C O R C OH
=CH2 O
(non-substituted terminal group) Methanal CO2
H C H
6. Oxymercuration of alkyne (Preparation of ketone from alkyne)
Reagent : water, catalyst – Hg2+ ion (HgSO4) and strong acid (H2SO4)
H
R C C H H
HgSO4(aq) keto-enol
R C C H H2SO4(aq) O tautomerization R C C H
H O H
Markovinkov
keto form
orientation
In the presence of acid and mercuric ion (Hg2+) catalyst, water can be added to a triple bond to form an enol. Enol
is then rearranged to form a ketone. The addition of the water to the alkyne follows the Markownikoff’s rule.
Glossary bromonium ion hydrin alkyl hydrogensulphate phosphoric acid ozonolysis ozonide
diol osmium tetroxide oxidative cleavage oxymercuration mercuric ion
Past Paper 90 2C 8 a ii
Question 91 2C 7 a ii
94 1A 3 a ii
96 2C 9 a ii iv
97 1A 5 a iv 97 2B 6 a i 97 2B 7 a i 97 2B 7 b ii
98 1A 4 c i iii 98 2B 6 d iv 98 2B 7 a iv
90 2C 8 a ii
COOH COOH
CH3 CH3
Cl CH C CH C
CH3 CH2Cl
COOH COOH
A B
ii How would you show the presence of a carbon-carbon double bond in the side chain? 2
Decolourization of bromine water / permanganate solution. 2 marks
C Some candidates proposed very clumsy ways to detect the presence of a carbon-carbon double bond e.g.
ozonolysis.
91 2C 7 a ii
7a State with explanations, what you would observe in each of the following experiments, and write equations for the
reactions.
ii Propene is bubbled into aqueous alkaline potassium manganate(VII). 2½
The purple colour of KMnO4 turns green due to manganate(VI) ion MnO42-. As the ions are further reduced, the
green turns to a brown suspension of MnO2. 1½ mark
MnO4- CH3 CH CH2
CH3CH CH2 + MnO2
OH OH
1 mark
C Very few candidates recognized that MnO4- is reduced to MnO2 in alkaline medium; hence they gave wrong
observations.
94 1A 3 a ii
OH and
C D
ii Dehydration of C gives 3 products, E, F, and G all with the formula C4H8. On treatment with ozone followed 4
hydrolysis, E gives methanal among other products, but F and G do not give methanal. Give structures for E, F
and G and an equation for the ozonolysis reaction involving E.
CH3 CH3 CH3 H
C C C C
F and G : H H cis-but-2-ene and H CH3 trans-but-2-ene 1 mark each
E: CH3 CH2 CH CH2 but-1-ene 1 mark

O O
O3, -78°C
CH3 CH2 CH CH2 H C H + CH3CH2C H
Zn / H2O
1 mark
C Some candidates produced very poor drawings of the cis- and trans- isomers of but-2-ene.
96 2C 9 a ii iv
ii Br 3
O O
C(CH3)3 H C (CH3)3 C C(CH3)3
- + (?
(CH3)3CO K (1) O3
or alc. KOH, heat (2) (CH3)2S or Zn or Et3N or Ph3P
(1) (?
(1) 3 marks
C Some candidates omitted heating in the first step and wrongly used KMnO4 in the last step. Some used O3 and Zn
together as one step instead of as two steps.
iv OH 3
OH
OH
conc. H2SO4 or H3PO4

- -
or P2O5 or Al2O3 (? MnO4 / OH (?
heat cold (?
(?
(1) 3 marks
C Heating was omitted in the dehydration step. NaOH or NaOEt was wrongly used as the dehydrating agent. Most
candidates did not give the correct conditions (cold and weakly alkaline) for the dihydroxylation of the alkene.
97 1A 5 a iv
iv (1) O3
C8H16 butanal only
G (2) Zn / CH3CO2H
97 2B 6 a i
6a Each of the following conversions can be completed in not more than three steps. Use equations to show how you 9
of the product.
i (CH ) CCH CH (CH ) CC CH
3 3 2 3 3
97 2B 7 a i
i
and
97 2B 7 b ii
ii OH
K
CH2
CH2Br
98 1A 4 c i iii
4c On treatment with dilute H2SO4(aq), E gives mainly two isomeric compounds, F and G, both of which have the
formula C4H8. On treatment with bromine, both F and G give a product H with formula C4H8Br2.
i Draw structures for F, G and H. 3
iii Outline the mechanism for the formation of H from either F or G. 1
98 2B 6 d iv
6d Identify M in the following reaction. 4
iv CH 3 (1) O3
M
(2) Zn, H2O
98 2B 7 a iv
iv Br
NaOH
CH3CH2CH CH3 H3CC CCH3
Reference 21.0
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 133–135, 183, 205, 208, 274, 276
Organic Chemistry, Solomons, 5th Edition pg. 636–644, 652, 842–843, 939–940, 946
Organic Chemistry, Fillans, 3rd Edition pg. 157–160, 205
Organic Chemistry, Morrison Boyd, 6th Edition pg. 517–518, 525–527, 529, 832, 898
Organic Chemistry, Stanley H. Pine, 5th Edition pg. 639, 641–647
Syllabus Electrophilic substitution

Aromaticity
Arenium ion
Notes VIII. Electrophilic substitution
Benzene is another molecule containing multiple bond besides alkene and alkyne. With the presence of π
electrons, it is also an ideal substrate for the electrophilic attack by an electrophile.
E+ H H
H H
H H
However, benzene reacts with bromine less readily than alkene or alkyne does. And, even if there is reaction,
substitution product is the only product obtained.
Br
H H
+ HBr
H H
H H
H H substitution product
Br Br
H H X
Br H
H Br
H
H
H H
H
addition product
The difference is caused by the aromaticity of the benzene ring.
N.B. Aromaticity – the extra stability associated with the benzene ring through resonance. Or to be more
precise, any ring system with (4n + 2) number of π electron will have this kind of extra
stability, where n is a natural number. For benzene, n = 1.
When a Br–Br molecule is added to a benzene ring, the hybridization of 2 carbon atoms are change from sp2
hybridization to sp3 hybridization. The aromaticity of the benzene ring is lost. This involves a very high activation
energy and is unfavorable. On another hand, the bromobenzene formed from substitution is still aromatic where
the activation energy involved is relatively lower.
H H
Br H + H Br
sp2 H H
substitution
the aromaticity
H H is retained
H H sp3
H H Br H
H
addition H
+ H
Br
Br Br
H H
breaking down
of aromaticity
Although the substitution product is aromatic, inevitably, the aromaticity of a benzene ring is lost temporarily when
an electrophile is added to the ring. This makes substitution reaction of benzene occur only in the presence of a
catalyst or under a very rigorous condition.
E
H H H E H
E+ H
H H H + H H H + H
+
H H H H H H
Arenium ion
(temproray lost Aromaticity is retored
in aromaticity)
H H E H E H
H
r.d.s.
H H H + H H H + H+
H H H H H H
Arenium ion
The positive charge possessed by the electrophile is dispersed over the ring of arenium ion. And by losing a
hydrogen ion, the aromaticity is restored.
The reaction conditions and mode of reaction can be summarized as follows :
Reaction condition Mode of reaction

Normal circumstance no reaction
With Lewis acid catalyst electrophilic substitution
In the presence of uv or radical initiator radical addition
The arenium ion intermediate can be represented by the drawings of several resonance structures or a single
resonance hybrid.
H E H E H E H E
+
+
OR +
+
resonance
resonance structures
hybrid
Glossary electrophilic substitution electrophile aromaticity arenium ion
Past Paper
Question
Reference 21.1.1–21.1.4
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 441–444, 447–448
Organic Chemistry, 6th Edition, Solomons, pg. 658-664, 930-931, 974
Notes B. Other relevant reaction
Benzene reacts with fuming sulphuric acid (H2S2O7 = SO3 + H2SO4) readily at room temperature or with
concentrated sulphuric acid (H2SO4) slowly. If necessary, moderate heating may be employed (≈ 80ºC) to
accelerate the reaction.
Indeed, the electrophile is not SO42- ion since it is negatively charged. It is the sulphur trioxide molecules, SO3. It
is either present in the fuming sulphuric acid or from the self dissociation of concentrated sulphuric acid molecules.
H2SO4 + H2SO4 d H3O+ + HSO4- + SO3
SO3H
+ H2SO4 + H2O
Overall reaction
benzenesulphonic
acid
Since the reaction is reversible, benzenesulphonic acid can be desulphonated by heating to a temperature over
100ºC, or by diluting the sulphuric acid, or by passing steam through the sulphonic acid.
Sodium salt of sulphonic acid can be used to prepare phenol by fusion with solid sodium hydroxide.
SO3-Na+ O-Na+
+ 3 NaOH 350°C + Na2SO3 + H2O
sodium benzenesulphonate
O-Na+ OH
+ HCl + Na+Cl-
phenol
Concentrated nitric acid does not react with benzene at all. Ordinary concentrated nitric acid contains only H+ ion
and NO3- ion. NO3- ion is a nucleophile which does not react with benzene.
In the presence of concentrated sulphuric acid, concentrated nitric acid reacts with it to produce nitronium ion /
nitryl cation / (NO2+) which is an electrophile.
Since sulphuric acid is a stronger acid than nitric acid, it protonates the hydroxyl group of the nitric acid and
converts it into a better leaving group. Without sulphuric acid, the concentration of NO2+ ion in conc. nitric acid is
rather low.
2HNO3 e NO2+ + NO3- + H2O
Formation of nitronium ion (nitryl cation)
+ O O O + + O
H O N - S
O H O N -
O O O- + HSO 4
H H H
a better
leaving group
+ + O +
H O N O N O + H2O
O- nitronium
H
ion
Electrophilic substitution by nitronium ion

-
O O
N+
H H H
H
r.d.s.
+ H H H + H
O N O
H H H H
Arenium ion
O -
N+ O -
+ O
H O N H
H
H + H H H + H2SO4
-
HSO4
H H H H
Arenium ion
Since nitro group –NO2 is an electron withdrawing group, it decreases the electron density of the benzene ring.
Therefore, further nitration of nitrobenzene is more difficult and requires prolonged heating.
- - - - -
O + O O + O O + O
N N N
Formation of trinitrobenzene takes days of prolonged heating.

At room condition, halogen does not react with benzene at all.
X2
no reaction
The reaction is found to be catalyzed by Lewis acid, e.g. FeCl3, FeBr3 and AlCl3. The Lewis acid accepts an
electron pair from the halogen molecule. This polarizes the halogen molecule and promotes the formation of
positive halogen ion.
X X FeX3 X+ + FeX4-
Lewis acid electrophile
(an electron
acceptor)
Halogen X2 and iron can also be used instead because the halogen reacts with the iron readily to produce the Lewis
acid e.g. FeX3 catalyst.
2 Fe + 3 X2 → 2 FeX3
Example of bromination of benzene is illustrated as follows :

Similar to halogenation of benzene, benzene can also be alkylated in the presence of anhydrous AlCl3 and
haloalkane. This method is named after the inventors, Charles Friedel and James M. Crafts.
AlCl3 is a Lewis acid which catalyzes the reaction by promoting the formation of carbocation (an electrophile).
Cl Cl
-
R Cl Al Cl R+ + Cl Al Cl
Cl carbocation Cl
(an electrophile)
Then, the carbocation attacks the benzene ring through an electrophilic substitution pathway. Eventually, the
benzene ring is alkylated (replacing a hydrogen by an alkyl group) and AlCl3 is regenerated.
H H R H
H
r.d.s.
+ H H H + H
R
H H H H
Arenium ion
R H R H
H
Cl
- H + H H H + HCl + AlCl3
Cl Al Cl
Cl H H H H
Arenium ion Alkylbenzene
Summary of different electrophilic substitution reaction of benzene

Reaction Reagent Catalyst Condition Electrophile
Sulphonation conc H2SO4(l) / H2S2O7(l) Nil 80 ºC SO3
Nitration conc. HNO3(aq) conc. H2SO4(l) 55 ºC NO2+
Halogenation X2 FeCl3 / AlCl3 X+
Alkylation R–Cl FeCl3 / AlCl3 R+
Glossary sulphonation fuming sulphuric acid benzenesulphonic acid fusion nitration

nitronium ion / nitryl cation benzenamine / aniline halogenation Lewis acid
Friedel-Crafts alkylation
Past Paper 92 2B 6 Ab iii 92 2B 6 Bb iii

Question 96 2C 8 c iii
97 2B 7 b v
92 2B 6 Ab iii Bb iii
6Ab
What are the products of the reactions between
iii concentrated nitric(V) acid and concentrated sulphuric(VI) acid? 1
2HNO3 + H2SO4 d NO2+ + H3O+ + NO3- + HSO4- 1 mark
6Bb
What are the products of the reactions between
iii concentrated sulphuric(VI) acid and concentrated nitric(V) acid? 1
2HNO3 + H2SO4 d NO2+ + H3O+ + NO3- + HSO4- 1 mark
C The products of this reaction were not widely known.
96 2C 8 c iii
iii NO2 1
NO2
M
CH3
CH3
NO2
M : conc. HNO3, conc.H2SO4 (heat) 1 or 0 mark

C HNO3 / H2SO4 or HNO2 or HNO3 for M. Both nitric(V) and sulphuric(VI) acids used should be concentrated and
the abbreviation conc. should be used instead of c;
97 2B 7 b v
v
(1) conc. H2SO4
N
(2) NaOH(aq)
Reference 21.1.5–21.1.6
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 476–477, 521, 523–524
Organic Chemistry, 6th Edition, Solomons, pg. 930-931, 974
Notes 5) Diazocoupling of diazonium ion

+
NH2 N N
NaNO2
HCl, 0-5 蚓
benzenamine diazonium ion

(an aromatic
primary amine)
When benzenamine is treated with HNO2(aq) (or NaNO2(s) / HCl(aq)) at 0–5 ºC, diazonium ion is formed.
Beside the substrate of nucleophilic substitution, diazonium ion is also an electrophile which is capable to accept
electron form a benzene ring.
+
Nucleophilic substitution of N N Nu
diazonium ion (SN) - + N2
Nu
(The high leaving ability of
N2 makes diazonium ion a
good substrate of diazonium ion
nucleophilic substitution)
Electrophilic substitution of
+
diazonium ion (SE) N N H
(The positive charge and the OH N - N
OH + H2O
multiple bond on the azide N H N
group makes diazonium ion a OH
good electrophile) OH
+
diazonium ion naphthalen-2-ol
azo dye
(an orange red ppt.)
Phenol compound (e.g. naphthalen-2-ol) is particularly reactive to electrophilic substitution because the electron
density of the benzene ring is enhanced by the hydroxyl group.
H H H
O O+ O+
-
If napthalen-2-ol is used, the substitution product formed is an orange red ppt. The colour of the ppt. is so intense
that it can be used as a dye. Since the compound contains nitrogen, it is called azo dye.
Normally, most simple organic molecules are colourless because they absorbs ultra-violet and infra-red only. A
substance is coloured only if it absorbs light from the visible region.
The colour of azo dye is due to the presence of the extensive π system. This makes the difference between the
energy levels smaller. Therefore, the molecule will absorb visible light during electron transition.
For the same reason, some transition metal ions are coloured in the presence of water. (This will be discussed in the
section of transition metal : d-d transition).
H H
O O
N N
N N
Lewis structure of azo dye Orbital representation of azo dye
Through resonance, the lone pair on the oxygen is donated to the benzene ring. This makes the ortho (2,6) and
para (4) positions of the benzene more electron rich than the meta (3,5) position does. Therefore, ortho and para
positions of the benzene ring is more vulnerable to the attack of an electrophile. The hydroxyl group is said to be
ortho-para directing.
H H H H
O +O +O O
- -
Phenol reacts with aqueous bromine solution readily to form white precipitate of 2,4,6-tribromophenol. The
formation of the ppt. can be served as a test for phenol. Since the yield of the reaction is almost 100%, the reaction
can also be used in quantitative analysis (e.g. titration).
H H
O O
Br Br
+ 3 Br2 + 3 HBr
Br
2,4,6-tribromophenol
(a white precipitate)
Because phenol is found to be more reactive than ordinary benzene, hydroxyl group is also known as an activating
group in electrophilic substitution of benzene.
Glossary diazocoupling napthalen-2-ol dye azo dye ortho position para position
meta position ortho-para directing activating group
Past Paper 90 1B 4 b ii
Question 91 1B 5 b 91 2C 7 a iii
94 2C 9 a iv
95 1A 3 d ii
96 1B 4 b 96 2C 8 c ii
97 1B 8 a i ii
98 2B 7 a ii
90 1B 4 b ii
4 A mixture contains equal amounts of X, Y and Z.
CH3
OH NH2
Br
X Y Z
b.p. 182°C b.p. 184°C b.p. 184°C
4b Outline tests involving observable colour changes to show that:

ii Y is a primary aromatic amine, and 1
Add NaNO2 and dil. HCl to Y at 5ºC followed by 2-naphthol (β-naphthol). An orange ppt. denotes presence of a
primary aromatic amine. 1 mark
91 1B 5 b
5a CH3 CH3
NH2 NO2
X Y
The amine X, C7N9N, may be prepared from Y, C7H7NO2, by reaction with excess hot granulated tin and
concentrated hydrochloric acid.
5b Describe simple chemical tests which would enable a distinction to be made between X and phenylmethylamine 4
(C6H5CH2NH2). Your answer should include chemical equations, reaction conditions and a description of any
visible change.
For X
CH3 N N Ar
CH3
HONO/HCl OH OH
NH2 0°C N N Cl-

+
no observable change orange or red or yellow ppt.
Basic reaction with HONO/0ºC for both X and phenylmethylamine 1 mark

No observable change in the first step ½ mark
Formation of diazonium salt ½ mark
Use of 2-naphthol ½ mark
Formation of orange or red or yellow ppt. ½ mark
For phenylmethylamine
HONO/HCl
Ph NH2 Ph OH + N2
0°C
Formation of alkanol ½ mark

Nitrogen gas bubbles observed. ½ mark
No coloured ppt. with β-naphthol (2-naphthol).
C Many cases of use of aryl sulphonic acids suggest some very bad teaching – as the use of sulphonic acid to
distinguish amines is not in the syllabus.
91 2C 7 a iii
reactions.
iii Aqueous phenol is treated with aqueous bromine. 2
The reddish brown solution of bromine is decolourized. Tribomophenol appears as a white precipitate. 1 mark
OH
OH
Br Br
+ Br2
Br
1 mark
C Most candidates did not give full observations. They only mentioned decolorisation of bromine or formation of
white precipitate, but not both.
94 2C 9 a iv
iv NH2
NaNO / HCl OH
2
2
S T
< 5°C
+ N N
S: N N T: 1 mark each
OH
C Candidates were casual / careless in writing structural formula, particularly in putting the number of H atoms to
each C atom. Common mistakes included :
OH
N N for T (wrong position of coupling)
95 1A 3 d ii
3d ii Write the structure of the product formed in the diazocoupling of naphthalen-2-ol with benzenediazonium 1
chloride.
N N
OH
(the diazocoupling must at the correct position) 1 mark
C The structure of the diazo-coupled product was generally poorly drawn, with no indication of the correct
regiochemistry and the correct valence of nitrogen.
96 1B 4 b
4b Describe the experimental procedures of a chemical test that you would employ in order to demonstrate that a 4
liquid-sample is an aromatic primary amine. State the observation of your test.
Add NaNO2/HCl (or HNO2) in a test tube. 1 mark
Cool the mixture to 0 - 5ºC / ice temperature. 1 mark
Add napthalen-2-ol (β-naphthol) / phenol(aq). 1 mark
Observation : bright red ppt. (with naphthalen-2-ol) / bright orange ppt. (with phenol) 1 mark
(Award ½ mark for coloured precipitate)
C Fairly well answered. Most candidates correctly described the procedures involved in the chemical test. But the
name 'naphthalen-2-ol' was spelt wrongly in many cases.
Some candidates gave chemical tests which were non-specific, e.g., heating the intermediate diazonium salt to
give bubbles of nitrogen gas could be used to show that the given liquid sample was an aromatic primary amine.
96 2C 8 c ii
ii + - CH3 1
N N Cl
L N
N
HO
L : HO CH3
1 mark
97 1B 8 a i ii
8a i Give the reaction conditions and the necessary chemicals/reagents required for the formation of 3
benzenediazonium ion from phenylamine.
ii Benzenediazonium ion reacts with naphthalen-2-ol to give compound T. Give the structure of T.
98 2B 7 a ii
ii
OH
NH2 N N OH
heat
Reference 22–23
Organic Chemistry, Fillans, 3rd Edition pg. 127, 141–142
Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 407–409, 426–431, 445–446
Syllabus Free radical Substitution (chlorination of methane)

Free radical Addition (polymerization of alkene)
Notes IX. Free radical Reaction
Free radical is a species containing 1 or more unpaired electrons. Halogen atom and alkali metal atom are two
examples of them. Oxygen molecule may also be considered as a free radical. This is because it contains two
unpaired electron and is paramagnetic.
Examples of free radicals
As free radical does not have a fulfilled octet, it is an electron deficient species. If possible, it tends to react with
an electron rich species e.g. an double bond. Most of the free radicals are very reactive and cannot be isolated.
Free radical is formed in 3 ways :
1) Homolytic fission of a bond
A B A + B
hυ
Cl Cl Cl + Cl
or heating
chlorine
free radical
heat
R O O R R O + O R
The energy required to break the bond is furnished by exposing the molecule to light (photolysis, hυ) or by
heating of the molecule. A radical forms more readily if atom A and B have similar electronegativity and the
A–B bond is weak. Peroxide molecule containing weak O–O bond is usually used as a radical source.
2) By reaction of a molecule with another free radical
X
A B A + B X
a new
free radical
R O H Br R O H + Br
When a free radical gets in contact with another molecule, it may gain an electron from the molecule in order
to attain octet. The molecule which loses an electron to the free radical becomes another free radical.
Since the product is still a free radical, the reaction may continue.
3) By oxidation-reduction process
H
CH3 C + Br- + Na+
CH3 CH2 Br Na
H
Radical can be formed from a molecule by a single electron transfer.

Most free radicals reacts through a chain mechanism.
A chain mechanism consists of three steps :

1. chain initiation,
2. chain propagation,
3. chain termination.
Besides free radical reaction, nuclear fission of 235U in nuclear bomb is also a chain reaction.
Chlorination of methane is a typical example of a chain reaction.
hυ
Cl Cl Cl + Cl Cl· radical is generated.
In the presence of light or heat, Cl–Cl bond breaks symmetrically and yields 2 Cl· radical.
H H
H H
H H
H H
Depending on the amount of the reactants present, mono-substituted chloroalkane may undergo further
substitution.
Cl Cl
H H
Cl Cl
H H
Cl + Cl Cl Cl
H H
Energy
Cl C H Cl C H
H H + radical is destroyed.
H H H H
H C C H H C C H
H H H H
When two free radicals meet each other, they may join together to form a molecule. However, free radical is
very reactive, the molecule formed will also be very energetic. It breaks apart instantaneously and forms two
free radicals again.
The molecule formed will become stable only if the energy of the molecule is dissipated immediately. This
happens when the molecule collides with the wall of the container once it is formed and transfers the energy to
the wall.
Since the occurrence of the chain termination is rather rare, it is estimated that a single Cl· radical may lead to
chlorination of thousands of methane molecule.
Apparently, there is more than 1 way of chain propagation and chain termination, the presence of a mixture of
products is always a characteristic of radical reaction.
Reaction between H2(g) and Cl2(g) is also a free radical substitution reaction where the rate of reaction is very
sensitive to the presence of light.
Under controlled condition, H2(g) burns in Cl2(g) smoothly to produce HCl(g), from which HCl(aq) is prepared.
However, if a mixture of H2(g) and Cl2(g) is exposed to strong light, the result may be explosive.
Chain initiation
hυ
Cl–Cl  → Cl· + Cl·
Chain propagation
Cl· + H–H → H–Cl + H·

H· + Cl–Cl → H–Cl + Cl·
Chain termination
H· + H· → H–H + energy
Cl· + Cl· → Cl–Cl + energy
Besides the reaction with saturated compound, free radical reacts with unsaturated compound more readily because
radical is an electron deficient species.
1. Chain reaction e.g. polymerization of alkene
In polymerization of alkene, an organic peroxide is usually added into the alkene as a radical initiator.
Diacylperoxide is commonly used.
Chain initiating step
O O O
heat
Diacylperoxide alkyl radical
When diacylperoxide is heated, it dissociates into alkyl radical and carbon dioxide consequently.
Chain propagating step
H H
H H
R C C R C C
H H H H
H H H H H H H H
etc.
H H H H H H H H
The electron deficient alkyl radical reacts with double bond of the alkene repeatedly and results in a very long
chain polymer.
Chain terminating step
H H H H H H H H
combination
H H H H H H H H
H H H H H H H H
disproportionation
H H H H H H H
There are 2 possible terminating steps : combination and disproportionation
In combination, two radicals combine together to form a molecule. In disproportionation, a hydrogen atom is
transferred from a radical to another. Thus, the one lost the hydrogen is oxidized and the other radical is reduced.
2. Anti-Makownikoff orientation
H Cl H
H C C C H
H H H
H 2-chloropropane
H 1 2
C C C H + H Cl
H
H H Cl H H
propene H C C C H
H H H
1-chloropropane
In the electrophilic addition of HCl to propene, 2-chloropropane is found to be the major product because its
formation involves a lower activation energy. The mechanism is also known as ionic addition of alkene where a
hydrogen ion is added to the propene molecule first.
-
H
+ Cl
H H H H Cl H
H r.d.s. +
H
H H H H H H H H
2?carbocation 2-chloropropane
(more stable)
However, in the presence of an peroxide (a radical initiator), 1-choropropane will become the major product. It is
obvious that the two reactions have 2 different reaction pathways.
When an peroxide is added, the reaction proceeds through an radical mechanism. Similar to a carbocation, a
radical is also an electron deficient species. The influence of the substituent on the stability of a radical is similar
to that of a carbocation.
Relative H R R R H
Stability of C > R C > R C > H C > H C
Free radical
H R H H H
benzyl 3 methyl
radical radical radical
Chain initiation
heat
R O O R R O + O R
R O H Cl R O H + Cl
In the chain initiation step, the free radical formed from homolysis of the organic peroxide subtracts an hydrogen
atom from the H–Cl molecule. An Cl· radical is formed first.
Chain propagation
H Cl
Cl H Cl H Cl H H
H r.d.s.
C C C H H C C C H H C C C H + Cl
H
H H H H H H H H
2º radical
1-chloropropane
(more stable)
The Cl· radical is added to the propene molecule and a 2º radical is formed. This accounts for the fact that 1-
chloropropane is the major product of the reaction.
The main difference between the ionic mechanism and the radical mechanism is that in ionic mechanism a
H+ ion is added to propene first while in radical mechanism a Cl· radical is added to propene first.
The effect of the peroxide on the orientation of the addition is also known as “peroxide effect”.
Glossary free radical species paramagnetic homolytic fission photolysis free radical
free radical substitution chlorination of methane chain reaction chain initiation
chain propagation chain termination free radical addition polymerization of alkene
diacylperoxide radical initiator combination / coupling disproportionation
anti-Makownikoff’s rule peroxide effect
Past Paper 91 2C 7 a i
Question 94 2C 9 b ii
97 1A 4 c ii
98 2B 6 d iii
99 1A 5 a i ii iii
91 2C 7 a i
reactions.
i A mixture of pentane and bromine in tetrachloromethane is exposed to sunlight. 3½
The reddish brown bromine turns colourless. The reaction is a free-radical chain reaction. Depending on the
amount of bromine, a variety of substitution products is obtained. 2½ mark
CH3CH2CH2CH2CH3 + Br2 → CH3CH2CH2CH2CH2Br + CH3CH2CH2CH2CHBr2 etc. 1 mark
94 2C 9 b ii
9b Ethene and chloroethene can undergo polymerization to give polyethene (PE) and polyvinyl chloride (PVC)
respectively. PVC is more rigid and durable than PE, but incineration of PVC causes a more serious pollution
problem.
ii Use equations to show a mechanism of the polymerization of ethene. 3
The polymerisation of CH2=CH2 is a free-radical addition reaction. An organic peroxide is added as an initiator.
Initiation
heat 2R O
R O O R
O O O
heat
OR Diacylperoxide alkyl radical 1 mark

Propagation
H H
H H
R C C R C C
H H H H
H H H H H H H H
etc.
H H H H H H H H
1 mark
Termination
H H H H H H H H
combination
H H H H H H H H
H H H H H H H H
disproportionation
H H H H H H H
OR
1 mark
C
Mistake in using ' ' instead of ' ' to describe one-electron shift in free radical reaction.
97 1A 4 c ii
4c ii Outline a free radical mechanism for the conversion of ethene to poly(ethene). Your answer should include
appropriate arrows to show how the new bonds are made.
98 2B 6 d iii
6d Identify L in the following reaction.
iii
H2C CH L CH2 CH
Cl Cl n
99 1A 5 a i ii iii
5a Under certain conditions, methane reacts with chlorine to give chloromethane as the major product.
i State the conditions for the reaction.
ii Outline the mechanism and name the mechanistic steps of the reaction.
iii Is the reaction of methane with chlorine an appropriate method for the preparation of dichloromethane ? Explain.
Amino acids
I. Amino acids
A. Zwitterion
B. Polypeptides
Amino acids Page 1
Topic Amino acids
Reference 24
Organic Chemistry, Solomons, 5th Edition pg. 1096
Syllabus Amino acid

Zwitterion
Polypeptide
Notes I. Amino acids
Amino acid is a bifunctional compound containing amino group (–NH2) and carboxyl group (–COOH).
O NH2 O
H2N CH2 C O H CH3 CH C O H
α β α
aminoethanoic 2-aminopropanoic
acid acid
Both aminoethanoic acid and 2-aminopropanoic acid are also called α-amino acid because the amino group is
attached to the α carbon. All the naturally occurring amino acids are α-amino acids, the only difference between
them are the –R attached to the α carbon.
Amino acid
R = H Glycine
R O
CH3 Alanine
H2N Cα C O H
H CH3
Valine
α-amino acid CH CH3
CH2 OH Tyrosine
A. Zwitterion
Acid pKa Conjugate base

stronger acid CH3COOH 4.76 CH3COO- weaker conjugate base
weaker acid CH3NH3+ 10.6 CH3NH2 stronger conjugate base
Since CH3COOH is a stronger acid than CH3NH3+, thus CH3NH2 is a stronger base than CH3COO-, the carboxyl
group is capable to react with the amino group by intramolecular proton migration.
H R O +
H R O +
H R O
+ -H + - -H -
H N C C O H + H N C C O + H N C C O
+H +H
H H H H H
Cationic form Zwitterion Anionic form
(Predominant at low pH) (Dipolar ion) (Predominant at high pH)
At low pH, the concentration of H+(aq) is high, the cationic form of amino acid will be predominant.
At high pH, the concentration of H+(aq) is low, the anionic form of amino acid will be predominant.
At medium pH, beside cationic form and anionic form, amino acid may also exist in form of dipolar ion (also
known as zwitterion.
Because of the of the formation of zwitterion, amino acids has

1. high melting point
2. high solubility in water but low solubility in organic solvent
3. large dipole moment..
Amino acids Page 2
B. Polypeptides
Amine is capable to condense with carboxylic acid through nucleophilic pathway to give an amide.
(Refer to Mechanism of nucleophilic addition)
H O O H
R N H + R' C OH R' C N R + H2O
amine carboxylic acid
amide group
(or peptide linkage)
Amino acid is a bifunctional compound which is capable to undergo successive condensation (polymerization)
with elimination of water.
H successive condensation H2N CONH CONH CO2H

H2N C COOH
R R R R
polypeptide
amino acid
(a tripeptide consists of 3 monomers)
The polymer formed is also known as polypeptide (protein) since the amino acids (monomers) are linked together
by peptide linkage (amide group).
Moreover, polypeptide can also be hydrolyzed back to amino acid in the presence of enzyme or acid / alkali
catalyst. e.g. reflux with 6M HCl(aq) for 24 hours.
Glossary amino acid bifunctional a-amino acid zwitterion (dipolar ion) predominant
polypeptide polymerization amide group (peptide linkage)
Past Paper 91 1A 1 c
Question 93 1A 3 e i iii
94 1A 3 c ii
98 1C 10 98 2B 6 a ii iii
99 1A 6 a 99 2B 5 a v
91 1A 1 c
1c Give the structure of a dipeptide. 4
Give a reagent that could cleave your dipeptide into smaller units.
Draw the zwitter-ionic form of one such smaller unit
R O R' R O R'
NH2CHCNHCHCO2H NH3CHCNHCHCO2
or 2 marks
R, R’ can be H, Me, Et, Ph, etc. (must be specified, if no -½)
Note: must be from α-amino acids.
(If an amide from NON-α-amino acid, with –CO2H and –NH2 1 mark)
(If just an amide, e.g. RNHCOR -1½ mark)
dil. H2SO4 or enzyme by acid hydrolysis (any acid) 1 mark
(Alkali causes racemisation, therefore ½ mark only)
R
NH3CHCO2
Zwitter ion: 1 mark
C This was considered by many to be very short and easy for 4 marks. However it was not very well answered
especially since many misused R in such dipeptide structures as NH2RCO2H.
Amino acids Page 3
93 1A 3 e i iii
3e A dipeptide, W, yields only valine and glycine on hydrolysis.
CH3 CH CH CO2H
CH3 NH2 H2NCH2CO2H
valine glycine
i How many different structural isomers are possible for W? Draw one of these structures. 2
2 Structural isomers are possible for W. ½ mark
O C CH2 NH2
NH2 O H H N O
CH3CHCH C N CH2CO2H CH3CHCH C OH
CH3 3 CH
or 1½ mark
iii Draw the structure of the predominant form in which glycine exists in aqueous solution: with acidic conditions 2
and under basic conditions.
CH3 CH CH CO2H
under acidic conditions CH3 NH3
+
1 mark
CH3 CH CH CO2-
under basic conditions CH3 NH2
1 mark
94 1A 3 c ii
3c Hydrolysis of a protein gives rise to a number of amino acids.
ii Draw the structure of an amino acid in its zwitter-ionic form. 1
N+H3
CH3 CH CO2-
α 1 mark
No mark for non-ionic form
97 2B 5 b i ii
5b The following equation represents the acid hydrolysis of a dipeptide D to produce compounds E and F. one of
which is a chiral compound.
CH3 O +
H3O
H2N CH C NHCH2CO2H E + F
D
i Name all functional groups in D .
ii Give one structure for E and one for F. Draw a suitable representation for the chiral product.
98 2B 6 a ii iii
6a Consider the structures of the two synthetic polymers shown below.
CH2CH2 HN(CH2)6NHCO(CH2)4CO
n n
poly(ethene) nylon-6.6
ii Briefly explain why aqueous acids can more readily attack nylon-6,6 than poly(ethene) inducing degradation.
iii Apart from acidic conditions, state one other condition under which nylon-6,6 degrades more readily than
poly(ethene).
99 1A 6 a
6a Consider the amino acids, F and G.
H
+ -
H3N C CO 2
+ -
H3NCH2CO2
F G
Draw three-dimensional structures of all dipeptides formed from F and G.
99 2B 5 a v
Amino acids Page 4
v O
+
H3O
NH J
heat
(Hint: J is a polymer.)
Oxidation and Reduction
I. Oxidation
II. Reduction

Oxidation and Reduction Page 1
Topic Oxidation and Reduction
Reference 25
Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 95, 144–145, 178, 243–244
Organic Chemistry, Solomons, 5th Edition pg. 669, 454–456, 458, 714
Organic Chemistry, 6th Edition, Solomons, pg. 165-166, 473-475, 690-691, 915-916
Objectives Oxidation and reduction

Hydrogenation of double bond
Notes Oxidation and Reduction
I. Oxidation
y y
CxHy + ( x + 4 ) O2 → x CO2 + 2 H2O
y z y
CxHyOz + ( x + 4 - 2 ) O2 → x CO2 + 2 H2O
Reagent : any strong oxidizing agent – e.g. KMnO4 / H+(aq) or K2Cr2O7 / H+(aq)
Both 1º and 2º alkanol can be oxidized by strong oxidizing agent.
1º alkanol can be oxidized to aldehyde and then carboxylic acid easily.

2º alkanol will only be oxidized to ketone.
Since 1º and 2º alkanol turns K2Cr2O7/H+(aq) green, K2Cr2O7 / H+(aq) cannot tell which is 1º alkanol and which is
2º alkanol. 1º and 2º alkanol can only be distinguished by Luca's test.
3º alkanol can easily distinguished from 1º and 2º alcohol since it has no reaction with common oxidizing
agent.
H
O O
R C O H [O] [O]
R C H R C O H
H
R
[O] O
R C O H
R C R
H
2?alcohol ketone
R
to oxidation
R
3?alcohol
In the oxidation of the primary alkanol, aldehyde can

be prevented from further oxidation by distilling it
off the reaction mixture once it is formed. This is
because aldehyde has a lower boiling point than both
alkanol and carboxylic acid.
Reagent : a very strong oxidizing agent – hot KMnO4 / OH-(aq) or hot H2CrO3 (chromic acid)
N.B. chromic acid is the same as K2Cr2O7(aq) in acidic medium.
benzylic hydrogen
benzylic H O
carbon
H C H C OH
1) KMnO4/OH- (aq), heat
+ 3 [O] + H2O
2) H+(aq)
benzenecarboxylic acid
(benzoic acid)
Benzenecarboxylic acid can be prepared by oxidation of aromatic side chain using a very strong oxidizing
agent. The oxidation involves the abstraction of benzylic hydrogen by the oxidizing agent. i.e. all alkyl
groups containing benzylic hydrogen can be oxidized to carboxyl group.
benzylic hydrogen
H O R no benzylic hydrogen
R C R C OH R C R
1) KMnO4/OH- (aq), heat 1) KMnO4/OH- (aq), heat resistant to
2) H+(aq) 2) H+(aq) oxidation
Oxidation of aromatic side chain is not limited to

alkyl group. Alkenyl, alkynyl and acyl groups are
also oxidized by hot alkaline potassium
permanganate in the same way.
II. Reduction
In organic synthesis, nitrobenzene can be converted to benzenamine / aniline by reduction. Fe in dil. HCl(aq) or Sn
in conc. HCl(aq) can be employed for this purpose. The ammonium salt –NH3+ obtained, is then neutralized by OH-
(aq).
NO2 NH2
(1) Sn / conc. HCl
(2) OH-
benzenamine
nitrobenzene
/ aniline
In Sn / conc. HCl, Sn is oxidized to Sn2+ by H+(aq) first. Since Sn2+ is a very strong reducing agent which is oxidized
to Sn4+ readily, it can reduce the nitro group to amino group. High concentration of Cl- ions form complex [SnCl4]2-
2+ 2+
(aq) with Sn . This makes Sn a little bit more stable and suitable to be used as a reagent in the laboratory.
H2C=CH2(g) + H2(g) → CH3–CH3(g) (Ni catalyst, 400ºC)
As hydrogen is adsorbed to the catalyst surface, the formation of hydrogen–metal bonds provides sufficient energy
to dissociate H–H bonds. Hydrogen atoms are thereby made available on the catalyst surface for the reaction with
the π bond. As hydrogen atoms are removed, the catalyst surface is regenerated and becomes available to adsorb
more hydrogen molecules.
The ethene molecule may also be adsorbed on the metal surface. This weakens the π bond in the molecule as well.
Glossary chromic acid benzylic hydrogen alkenyl group alkynyl group

Past Paper 91 1B 5 a ii
91 2C 9 a iv
93 1A 3 a iii
95 2C 9 b iii
97 1A 5 b 97 1A 6 a i 97 2B 7 a iv
98 2B 6 d i
99 2B 5 a ii iii
91 1B 5 a ii
5a CH3 CH3
NH2 NO2
X Y
ii If 6 g of X is obtained from 10 g of Y, what is the percentage yield of the reaction? 2
(Relative atomic masses : H, 1.0; C, 12.0; N, 14.0; O, 16.0)
relative molecular mass of X, C7H9N = 107
relative molecular mass of Y, C7H7NO2 = 137
107
Theoretical yield = × 10 g for 100% yield
137
107
Percentage yield = 6 ÷ ( × 10) × 100% = 76.8% (76.7 - 76.9%) (-½ mark for wrong no of sig. fig.) 2 marks
137
91 2C 9 a iv
iv OH H 2
CH3CH2CH2 C CH3 CH3CH2CH2 C CH2OH
CH3 CH3
Warm the compound with acidic Na2Cr2O7. The primary alcohol will turn the solution from orange Cr(VI) to
green Cr(III). No change in colour for the tertiary alcohol.
Primary alcohol easily oxidized, not tertiary alcohol.
H H
[O]
CH3CH2CH2 C CH2OH CH3CH2CH2 C COOH
Na2Cr2O7
CH3 CH3
C Many candidates incorrectly suggested the use of iodoform test to distinguish between the tertiary and the primary
alcohols.
Some candidates applying the Lucas test provided the inaccurate observation that tertiary alcohol gave white
precipitate, instead of turbidity, on reaction with Lucas reagent.
93 1A 3 a iii
3a Consider the following compound, X:
iii Upon catalytic hydrogenation, one mole of X reacts with two moles of H2. 2
Draw the structure of the product and give its systematic name.
CH3CH2CH2CH2CO2H 1 mark
Pentanoic acid or n-pentanoic acid 1 mark
95 2C 9 b iii
iii M 1
CH2 CHCO2CH3 CH3CH2CO2CH3
M : Pd or Ni or Pt / H2 (½ mark for H2 / cat. only) 1 mark

C Common mistakes included : LiAlH4 or H2 without catalyst for M;
97 1A 5 b
5b Consider the following reactions:
conc. H2SO4 HBr
J K
heat
CH3CH2COCl
CH3CH2CH2OH L NHNH2
NO 2
Na2Cr2O7 NO 2
+ M N
H3O (a red precipitate)
Give structures for J, K, L, M and N.
97 1A 6 a i
6a i Vegetable oils (e.g. peanut oil) can undergo the following chemical reactions to give useful solid products P and
Q.
excess H2 / Pt
P
Vegetable oil
NaOH(aq)
heat Q
Give one use each for P and Q . Suggest a possible structure for P .
97 2B 7 a iv
7a Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Each test
iv O O
C2H5 C C2H5 and CH3(CH2)3 C H
98 2B 6 d i
6d Identify J in the following reaction.
i NH2
(1) Sn / conc. HCl
J (2) NaOH
H3C
99 2B 5 a ii iii
ii CH2CH3 CO2H
E
O2N O2N
iii CH2CH2OH
+
Na2Cr2O7 / H3O
heat F
HO
CH3
Uses of Different Compounds
I. Uses of halogeno-compounds
A. Use as solvent
A. Use as solvent
B. Alcoholic drink
C. Blending agent
D. Ethan-1,2-diol
B. Use of propanone
C. Use of ester
A. Azo compounds as dyes in dyeing industries
Uses of compounds with different functional groups Page 1
Topic Uses of compounds with different functional groups
Reference 26
Reading
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 452, 466–467, 525–526, 575
Reading
Syllabus Uses of halogeno-compounds

Uses of alcohols
Uses of carbonyl compounds
Uses of carboxylic acid and their derivatives
Uses of amine and their derivatives
Notes I. Uses of halogeno-compounds
A. Use as solvent
Chlorinated hydrocarbons are good solvents for oils and greases, so they are widely used in dry-cleaning
industry. Trichloroethene, CCl2=CHCl and tetrachloroethene, CCl2=CCl2 are two examples of dry-
cleaning fluids. They are relatively non-flammable, easily removed because of their volatility and have
little or no structural effect on fabrics. These properties make them an ideal choice for use as dry-cleaning
fluids.
Some halogeno-compounds are important raw materials in the plastic industry. Poly(chloroethene)
[Polyvinyl chloride, PVC] is produced by addition polymerization of chloroethene in the presence of a
catalyst.
n CHCl=CH2 → –[CHCl–CH2]n–
Poly(tetrafluoroethene) [PTFE, "Teflon"] is produced by addition polymerization of tetrafluoroethene

under pressure in the presence of a catalyst.
n CF2=CF2 → –[CF2–CF2]n–
Vinyl chloride can be prepared by chlorination of ethene followed by elimination in the laboratory.
-
CH3CH2O
H H Cl2 H H H H
alcoholic
C C Electrophilic H C C H NaOH C C
H H addition Cl H
Cl Cl
Industrially, vinyl chloride is prepared by heating 1,2-dichloroethane at 500 ºC.
H H H H
Heat, 500蚓
H C C H C C
Cl Cl Cl H

PVC is one of the largest consumers of
plasticizers. Pure PVC is rigid, easily cracked
and broken, and cannot be readily processed.
The rigidity is due to the intermolecular force
which occurs between the slightly negative
chlorine atoms on one polymer chain and the
slightly positive hydrogen atoms on an
adjacent polymer chain.
By the addition of suitable plasticizers,
interaction between the polymer chains can be
reduced and a flexible form of PVC can be
produced. Modified PVC is suitable for
raincoats, garden hose, and seat covers for
automobiles, etc.
Comparing with PVC, molecule of Telfon is

non-polar. And owing to the high
F F F F F
electronegativity and low polarizability of F, C C C C C
the polarizability of Telfon molecule is also
very low. This makes the intermolecular forces F F F F F
acting amount the molecules very weak and
makes Telfon to make the non-sticky surface
coating.
A. Use as solvent
Many hydroxy compounds are good solvents, for example, methanol and ethanol are commonly used as
solvents in laboratory and in industry. Industrial methylated spirit contains 95% ethanol/water mixture and
5% methanol.
B. Alcoholic drink
Ethanol is an essential component in alcoholic beverages. The ethanol in alcoholic drinks is produced by
the fermentation of sugar or starch.
C. Blending agent
Ethanol can also be used as a motor fuel blending agent. As ethanol contains oxygen atom in its molecular
structure, adding it to petrol helps the fuel to burn more efficiently. As a consequence, emission of carbon
monoxide is reduced.
D. Ethan-1,2-diol
Ethane-1,2-diol is miscible with water in all proportions and has a high boiling point (hence not easily
vaporized). These properties make it an ideal choice for use as an anti-freeze. Ethane-1,2-diol is also a raw
material in the manufacture of a polyester known as Terylene (or Dacron). The polyester is produced by
condensation polymerization of ethane-1,2-diol and benzene-1,4-dicarboxylic acid.
O O
n HOCH2CH2OH + n HO2C CO2H O CH2CH2 O C C + (2n -1) H2O
n
Carbonyl compounds play an important role in the manufacture of plastics. Urea-methanal is produced by
condensation polymerization between urea and methanal under heat and pressure.
O O H O H H
n H2N C NH2 + n H C H N C N C + (n - 1) H2O
H n
In the presence of excess methanal, further heating causes cross-linkage to form between the polymer
chains and hence a rigid structure is produced.
B. Use of propanone
Propanone is the raw material in the production of methyl 2-methylpropenoate which is the monomer of
poly(methyl 2-methylpropenoate) [Perspex].
Propanone is also an important solvent used in industry and laboratory as it can dissolve a variety of
organic compounds.
Benzoic acid and sodium benzoate are commonly used as food preservatives in non-alcoholic beverages,
fruit juices, margarine, ketchup, salads, jams and pickled products.
Nylon 6.6, –[CO(CH2)4CONH(CH2)6NH]n– , is an example of polyamides. It is the synthetic fibre for

making ropes, threads, cords, lady's stockings, underwear and dresses.
Industrially, nylon 6.6 is prepared by heating hexane-1,6-diamine and hexanedioic acid under heat and
pressure. In laboratory preparation, hexanedioyl dichloride is used instead of hexanedioic acid to increase
the yield. However, it is also more expensive.
O O
Terylene, O CH2CH2 O C C
n
is an example of polyesters. It is the synthetic fibre for making wash-
and-wear garments.
C. Use of ester
Liquid esters are good solvents and are used in all-purpose adhesives, nail varnish removers and as
thinners for paints. Volatile esters have characteristic sweet fruity smells and are therefore generally used
as artificial flavourings in food and drinks.
A. Azo compounds as dye in dyeing industries
Primary aromatic amine is used as a starting material for the manufacture of azo dyes. It reacts with
nitric(III) acid to form diazonium salt which can undergo coupling reaction to form azo-compound.
HNO2 + Ar' H
Ar NH2 Ar N2 Ar N N Ar'
0-5蚓
azo compound
As azo-compounds are highly coloured, they are widely used in dyeing industry. Some examples of
organic dyes are shown below. A recognition of the azo group, –N=N–, is all that is required.
N.B. : Students are NOT expected to reproduce the structures of these dyes.
Direct brown 138 (brown dye for fabrics) Methyl orange (orange dye for fabrics)
NH2 NH2
NH2 CH3
H2N N N N N +-
N N Na O3S N N N
CH3
- +
SO3 Na NH2
Sunset yellow FCF Ponceau (red dye for food product)

(orange-yellow dye for food product)
HO
+-
Na O3S N N
+-
Na O3S N N
+-
Na O3S
- +
SO3 Na
- +
SO3 Na
Students should be made aware of the use of amine derivatives as drugs. A recognition of the amino group
or derived functional group of amine is all that is required. Some examples of these amine drugs are
shown below.
N.B. : Students are NOT expected to reproduce the structures of individual drugs.
Chlorpheniramine – CH2CH2N(CH3)2
an antihistamine that helps to relief allergic
N CH
disorders due to cold (runny nose, watery eyes), chlorpheniramine
hay fever, itchy skin, insect bites and stings, etc. It
is present in some over-the-counter drugs such as Cl
Coltalin, Coricidin, Dristan, and Piriton.
Chlorpromazine – CH2CH2CH2N(CH3)2
a tranquillizer that sedates without inducing sleep.
N
It is used to relieve anxiety, excitement, chlorpromazine
restlessness or even mental disorders.
S
Acetaminophen –
(also known as paracetamol, or p-acetaminophenol)
an analgesic that relieves pains such as headaches. O
It is believed to be less corrosive to the stomach
HO NH C CH3 acetaminophen
and is an alternative to aspirin.
Acetaminophen is present as the active ingredient
in some over-the-counter pain-killers such as
Panadol, Saridon, Tylenol and Fortolin.
Glossary PVC Telfon plasticizer polarizability blending agent anti-freeze

Terylene / Darcron urea-methanal perspex
Past Paper 90 1A 1 c ii
Question 91 1A 1 e
92 1A 1 a ii
95 2C 9 b iv
99 2B 5 c i ii iii
90 1A 1 c ii
1c HOOC CH2CH2CH2CH2 COOH
E
ii Show how E, by reaction with suitable reagents, may be converted into an important commercial product. 2
any diamine
NH2 CO2NH3R
H2N (CH2)4 ∆ NH(CH2)6NH2CO(CH2)4CO
E n
∆ CO2NH3R Polyamide
1 mark for process, 1 mark for product 2 marks
OR via an acid chloride
COCl NH2
SOCl2 (CH2)4 H2N NH(CH2)6NH2CO(CH2)4CO
E n
COCl ∆ Polyamide
∆ ∆
Other nylons are possible e.g. Nylon 6,6. Important is salt salt 
 → amide or acid chloride 
 → amide .
91 1A 1 e
1e Give all reagents and show how 1,4-dimethylbenzene may be converted into useful polyester. 3
COCl O
CH3 CO2H COCH2CH2O
SOCl2 HOCH2CH2OH
oxidation
Reagents:
KMnO4 COCl
CH3 CO2H C
HOCH2CH2OH
O
H+ or pressure/heat n
3 marks
½ mark for KMnO4
½ mark for dicarboxylic acid
½ mark for the correct diol
½ mark for the reaction conditions
1 mark for the correct product
C Many candidates failed to give a polyester, giving amides instead, or the correct ester (many guessed quite odd
alcohols : HOCH2(CH2)4CH2OH for example.)
92 1A 1 a ii
ii One of these isomer is used to make terylene. Outline the reaction involved. 2½
( )
CO2H CO2
OH O
CH2 various methods
+
CH2
OH
CO2H CO n
(I) (II) Terylene
COCl
(II)
methods (i) SOCl2 → COCl →
(ii) Heat (I) and (II) under pressure
(iii) H+ or acid or H2SO4 or conc H2SO4
(I) ½ mark
(II) 1 mark
Methods ½ mark
Terylene formula ½ mark
C Few gave details of reagents for condensation reaction.
95 2C 9 b iv
iv O O 1
N
HOCH2CH2OH C C OCH2CH2O
n
O O O O
N: Cl C C Cl or HO C C OH 1 mark
C Common mistakes included : benzoyl chloride for N;
97 1A 4 b ii
4b ii Upon oxidation, one of the isomers of dimethylbenzene produces a compound with the formula C8H6O4. This
compound on condensation with ethane-1,2-diol gives a useful textile material B . Give the structure of B.
99 2B 5 c i ii iii
5c Dacron is the most common of the group of polymers known as polyesters. A segment of the polymer chain is
shown below.
O O O O
C C OCH2CH2O C C OCH2CH2O
i Suggest two types of material which can be made from polyesters.

ii Draw the structures of the two monomers used in manufacturing Dacron. Name the type of polymerization
involved.
iii How can Dacron be degraded in the environment ?
Determination of Structure
I. Determination of empirical formula and molecular formula
A. Determination of degree of unsaturation
B. Meaning of degree of unsaturation
III. Sodium fusion test
V. Introduction to IR and NMR spectroscopy
1. More examples
Structure Determination Unit 1 Page 1
Topic Structure Determination Unit 1
Reading Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 281–382
Syllabus Determination of empirical formula and molecular formula

Degree of unsaturation
Notes I. Determination of empirical formula and molecular formula
Formulas are frequently used in chemistry to represent a particle. Like equation, there are many different kind
of formulas depending on the usage.
Empirical formula - showing the simplest whole number ratio of atoms present (applicable to all kind of
compound).
e.g. sodium chloride (ionic compound) water (molecular compound) ethane (molecular compound)
NaCl H2O CH3
Ionic formula - showing the simplest whole number ratio of ions present (only applicable to ionic
compound)
e.g. sodium chloride (ionic compound)

Na+Cl-
Molecular formula - showing the actual number of different atoms in a molecule
e.g. water (molecular compound) ethane (molecular compound)

H2O C2H6
Structural formula - showing the connection of the atoms in a molecule
e.g. water (molecular compound) ethane (molecular compound)

H H
H C C H
O
H H H H
The word empirical means "based on observation or experiment, not the theory". By determining the relatively
amount of each kind of element in a compound experimentally, the empirical formula can be determined.
Example :
A compound X containing only carbon, hydrogen and oxygen burned completely in air to form carbon dioxide
and water as the only products. 2.43 g of X gave 3.96 g of carbon dioxide and 1.35 g of water. Find the
empirical formula of X.
(Given : Atomic mass of H = 1.0, C = 12.0 and O = 16.0)
Answer :
12.0
Since all the C is converted to carbon dioxide, the amount of C present = 3.96 g × 12.0 + 16.0 × 2 = 1.08 g
1.0 × 2
Similarly, all the H is converted to water, the amount of H present = 1.35 g × 1.0 × 2 + 16.0 = 0.15 g
The remaining mass must from O, therefore the amount of O present = 2.43 g - 1.08 g - 0.15 g = 1.20 g
Because empirical formula shows the relative number of atoms present, the mass has to be converted to the
number of atoms (no. of mole of atoms) first.
C H O
Mass 1.08 g 0.15 g 1.20 g
No. of mole of atoms 1.08 g 0.15 g 1.20 g
12.0 gmol-1 = 0.090 mol 1.0 gmol-1 = 0.15 mol 16 gmol-1 = 0.075 mol
The relative no of 0.090 mol 0.15 mol 0.075 mol
mole present 0.075 mol = 1.2 0.075 mol = 2 0.075 mol = 1
The simplest whole no. 1.2 × 5 = 6 2 × 5 = 10 1×5=5
ratio
The empirical formula of compound X is C6H10O5.
From the empirical formula and the molecular mass, molecular formula can also be determined.
Example:
Empirical formula of ethane is CH3 and the molecular mass is 30.0. Find the molecular formula.
Answer :
Empirical formula shows the simples whole no. ratio of atoms present but molecular formula shows the actual
no. of atoms present. The different between them is only a whole number (an natural no.) factor.
Formula mass of empirical formula × natural no. = Formula mass of molecular formula
(12.0 + 1.0 × 3.0) × n = 30.0

15.0 × n = 30.0
30.0
n = 15.0 = 2
Molecular formula of ethane = (CH3)2 = C2H6.
Example :
Continue from the example given above. If the molecular mass of compound X (with the empirical formula
C6H10O5) is 485, what will be its molecular formula ?
Answer :
Formula mass of empirical formula × natural no. = Formula mass of molecular formula
(12.0 × 6 + 1.0 × 10 + 16.0 × 5 ) × n = 485

162.0 × n = 485
485
n = 162.0 = 2.99
n≈3
Molecular formula of X is (C6H10O5)3 = C18H30O15

Open chain alkane has the general formula CnH2n+2. It has the maximum no. of hydrogen (2n+2) that can be
joined to the C skeleton, it is said to be saturated (with H).
For a compound with the general formula CnH2n-2, it has 4 H less than the maximum number. 2 moles of
hydrogen (H2) is required to convert 1 mole of CnH2n-2 to a saturated compound. Therefore, the degree of
unsaturation of CnH2n-2 is said to be 2.
A. Determination of degree of unsaturation (or double bond equivalent)
Halogen – Both hydrogen (H) and halogen (X) atom form only 1 covalent bond, they can be treated as the
same in the determination of degree of unsaturation.
e.g. Both C4H10 and C4H9Br are saturated compounds with degree of unsaturation zero.
H H H H H H H H
H C C C C H H C C C C Br
H H H H H H H H
Oxygen – O atom forms 2 covalent bond, it uses up a bond to the C and a bond to the H in a saturated
compound. It has no effect on the degree of unsaturation.
e.g. Both C2H6 and C2H6O are saturated.
H H H H
H C C H H C C O H
H H H H
e.g. Both C3H6 and C3H6O2 have 1 degree of unsaturation.
H H H H H O
H C C C H H C C C O H
H H H
Nitrogen – N atom forms 3 covalent bond, it uses up a bond to the C and 2 bonds to the H in a saturated
compound. The presence of each N makes the molecule require one more H atom to become
saturated. (Each N increases the degree of unsaturation by ½.)
e.g. Both CH4 and CH5N are saturated.
H H H
H C H H C N H
H H
Degree of unsaturation can be interpreted as the difference between the no. of H required and the no. of H
available.
(no. of C × 2 +2) - (no. of H + no. of X) + no. of N

Degree of unsaturation =
2
B. Meaning of degree of unsaturation (or double bond equivalent)
Degree of unsaturation cannot tell the actual structure of the molecule, but it provides some information about
it.
One degree of unsaturation may represent the presence of : 1. 1 double bond, or

2. a ring structure.
e.g. C4H8
H H
H H H H H C C H
H C C C C H H C C H
H H H H
e.g. C4H8O
H H
O
H H O H H C C H
H C C C C H H C C H
H H H H H
Two degree of unsaturation may represent the present of : 1. 2 double bonds, or

2. 1 double bond and a ring structure, or
3. 2 ring structures
4. 1 triple bond.
e.g. C6H10
H H H
H H H
C H H C
H C C C
H H H H H H H C C H H H H H
H C C C
H C C C C C C H
H H C C H H C C C C C C H
H
H H H H H H H H H H
Glossary empirical formula ionic formula molecular formula structural formula

degree of unsaturation
Past Paper 92 2C 7 a
Question 94 2C 7 b i ii
95 2C 9 a i ii
96 2C 8 a i
98 2A 1 b
99 2B 7 c i ii
92 2C 7 a
7 A carboxylic acid P, with a relative molecular mass less than 100, contains C, 55.8%; H, 7.0%; and O, 37.2% by
mass . An attempt to convert P to its methyl ester Q by prolonged refluxing of P with methanol in the presence of
aqueous H2SO4 gave the desired ester Q but with much of the starting material P unchanged.
(Relative atomic masses : H 1.0; C 12.0; O 16.0)
7a Determine the molecular formula of P. 2
P : C4H6O2 2 marks
94 2C 7 b i ii
7b Give, with explanation, THREE possible structures for each of the compounds (G,H and J) below.
For (i) - (iii), 1 mark for the first correct structure, ½ mark for the second and ½ mark for the third structure.
i G is a sweet smelling liquid which contains 54.4% carbon, 9.2% hydrogen, and 36.4% oxygen and has a relative 5
molecular mass between 80 and 100.
Mole ratio C : H : O
54.4 9.2 36.4
12.01 1.008 16.00
= 4.530 9.127 2.275
= 2 4 1 1 mark
Empirical formula of G is C2H4O
Since relative molecular mass of G is between 80 and 100, ∴ molecular formula of G is C4H8O2. 1 mark
G is a sweet smelling liquid, ∴ it is an ester 1 mark
Possible structure of G :
O O CH3 O O
H C OCH2CH2CH3 H C OCH CH3 C OCH2CH3 CH3CH2 C OCH3 (any 3) 2 marks
CH3
C Generally well-answered. Some candidates missed out the hint in the question for an 'ester'.
ii H, C5H9Cl, is an acyclic chloroalkene which is optically active. 3
H possesses a chiral carbon and a C=C bond 1 mark
Possible structure of H
H H H
Cl Cl
* *
H * Cl * Cl (any 3) 2 marks
C A number of candidates did not realize the implication of optical activity on chemical structures. Many candidates
considered a pair of enantiomers as two different structures.
95 2C 9 a i ii
9a An acyclic hydrocarbon G, with relative molecular mass of between 60 and 80, contains 85.6% carbon and 14.4%
hydrogen by mass.
i Determine the molecular formula of G. 2
85.6
Mole % of C = 12.01 = 7.13
14.4
Mole % of H = 1.008 = 14.29
C : H = 7.13 : 14.29 = 1 : 2
∴ Empirical formula of G is CH2 1 mark
Since m.w. is between 60 and 80
The molecular formula of G must be C5H10 1 mark
ii Give all possible structures for the molecular formula determined in (i). 4
½ mark each for the 1st to 4th structure

1 mark each for the 5th and 6th structure
C Some candidates did not appear to understand the term 'acyclic'. Very few could give all six structures. Many did
not realize that pent-2-ene can exist in cis- and trans-forms.
96 2C 8 a i
8a i An acyclic compound H of molecular formula C4H8O2 has a fruity smell. It does not produce a derivative 4½
with 2,4-dinitrophenylhydrazine nor with propanoyl chloride.
Deduce the functional group(s) of H. Draw FOUR possible structures for H.
H is not aldehyde / ketone ½ mark
because it does not form hydrazone derivative. ½ mark
or
R
N NH NO2
O2N
(½ mark)
H does not possess an –OH group / is not an alcohol ½ mark

because it does not form ester with propanoyl chloride. ½ mark
or
O
no R O C C2H5 formation (½ mark)
H has a fruity smell, The functional group(s) in F is most likely an ester. ½ mark
Any FOUR of the following structures (½ marks for each structure) 2 marks
H O H O O O O
O O
O O O O O
(Deduct ½ mark for each extra structure)

C Poorly answered. Many candidates did not appear to know the reaction of 2,4-dinitrophenylhydrazine and
propanoyl chloride and hence the formation of the respective 2,4-dinitrophenylhydrazone and ester was omitted.
Some did not know the reaction of ester with LiAIH4 or the structure of ethanoic anhydride.
98 2A 1 b
1b A gaseous compound D contains carbon and hydrogen only, and has density of 1.15 gdm-3 at 95.3 kPa pressure
and 298 K. Assuming that D behaves ideally, calculate its molar mass and deduce its molecular formula.
(1 kPa = 1 × 103 Nm-2)
99 2B 7 c i ii
7c Compound M is a hydrocarbon isolated from oranges and lemons.
i M contains 88.2% by mass of carbon and has a relative molecular mass of 136.2. Deduce the molecular formula of
M.
ii Based on the reactions given below, deduce the structure of M.
Pt
M + 2H2 CH3 CH(CH3)2
O O
(1) O3
M CH3 C(CH2)2CHCH2C H + HCHO
(2) Zn dust
C
O CH3
Reference 27.3 27.4.1–27.4.4

Reading Principles of Organic Chemistry, Peter R.S. Murray, 2nd Edition pg. 61
Organic Reactions at Advanced Level, D.G. Davies and T.V.G. Kelly, pg 5–6
Work Out Chemistry A-Level, David Burgess, pg 160–162
Assignment Chemistry in Context, 5th Edition, Thomas Nelson and Sons Ltd., pg. 472, 487–489
Reading Organic Chemistry, 6th Edition, Solomons, pg. 295-297
Syllabus Sodium fusion test

Test for phenol
Notes III. Sodium fusion test (Ignition test)
Lassaigne sodium fusion test is a qualitative analysis used to test for any Nitrogen, Sulphur and Halogen in an
organic compound.
The organic compound is first decomposed by heating with sodium metal strongly in a ignition tube. The
decomposed substance is dissolved in water and filtered. The filtrate is then examined for the presence of Nitrogen,
Sulphur and Halogen.
Nitrogen – If nitrogen is present, cyanide ions are formed during the fusion. Iron(II) ions is added to form the
complex hexacyanoferrate(II) ions.
Fe2+(aq) + 6CN-(aq) → Fe(CN)64-(aq)
A drop of FeCl3(aq) is added to react with hexacyanoferrate(II) ions to give a precipitate of Prussian
blue.
Fe(CN)64-(aq) + Fe3+(aq) → Fe[Fe(CN)6]- (blue ppt.)
Sulphur – If sulphur is present, sulphide ions are formed during the fusion. In the presence of S2-(aq), a few drops
of freshly prepared solution of sodium nitroprusside will turn the solution purple.
Halogen – If halogen is present, halide ions are formed during the fusion. The filtrate has to be boiled with dil.
nitric acid in fume cupboard to remove any CN- present because CN- will also form ppt. with
acidified AgNO3(aq).
The presence of any halide ions will form ppt. with acidified AgNO3(aq).
Cl- – white ppt. of AgCl which turns purple grey under light.
Br- – yellow ppt. of AgBr which turns yellowish grey under light.
I- – yellow ppt. which is stable under light.
Criteria of a good test

1. Simple – If possible, a single step reaction is better than a multiple steps reaction.
2. Obvious change – The reaction must be accompanied with an obvious change e.g. colour change, evolution of
bubble, formation of ppt..
For example, formation of an immiscible layer is usually not a very obvious observation. A
reaction taking place doesn’t mean it can be served as a test.
3. Mild reaction condition – Under vigorous condition, there may be other side reactions.
For R–C≡C–H, because the H on the terminal alkyne is exceptionally acidic, it can be displaced by Cu+ or Ag+ to
form an ionic ppt.
Two common reagents are used are diamminecopper(I) chloride [Cu(NH3)2]+Cl- and diamminesilver(I) nitrate
[Ag(NH3)2]+NO3-.
+
R–C≡CH Cu
( NH )
→ R–C≡C-Cu+(s) (red ppt.)
3 2
+
R–C≡CH Ag
( NH )
→ R–C≡C-Ag+(s) (white ppt.)
3 2
Test for phenol
Phenol turns 'neutral' aqueous iron(III) chloride from yellow-orange to purple in colour.
The phenoxide ion (or called phenolate ion) C6H5O- acts as a ligand with a lone electron-pair on the oxygen atom
forming a dative bond with the iron(III) cation.
[Fe(H2O)6]3+(aq) + 2C6H5O-(aq) → [Fe(H2O)4(C6H5O)2]+(aq) + 2H2O(l)
It is important that the test be carried out in neutral or near-neutral conditions. If the conditions are alkaline, there
will be plenty of C6H5O- ions but the iron(III) ions will precipitate as iron(III) hydroxide.
In acidic medium, the concentration of C6H5O- ions is very minimal. The molecular phenol molecule C6H5OH is a
very weak ligand which does not complex with iron(III) ions.
Test for 1º, 2º and 3º alcohol
Both 1º and 2º alkanol can be oxidized by strong oxidizing agent.
1º alkanol can be oxidized to aldehyde and than carboxylic acid easily.

2º alkanol will only be oxidized to ketone.
Since 1º and 2º alkanol turns K2Cr2O7/H+(aq) green, K2Cr2O7 / H+(aq) cannot tell which is 1º alkanol and which is
2º alkanol. 1º and 2º alkanol can only be distinguished by Luca's test.
3º alkanol can easily distinguished from 1º and 2º alcohol since it has no reaction with common oxidizing
agent.
H
O O
R C O H [O] [O]
R C H R C O H
H
R
[O] O
R C O H
R C R
H
2?alcohol ketone
R
to oxidation
R
3?alcohol
D. Test for aldehyde
Aldehyde is easily oxidized to carboxylic acid by any oxidizing agent. This characteristic can be used to test
for the presence of the aldehyde. e.g. aldehyde turns acidified K2Cr2O7(aq) from orange to green.
1) KMnO4 / H+ or OH- (cold)

2) K2Cr2O7 / H+
O O
3) HNO3
R C H R C OH
4) Pt catalyst / O2
aldehyde 5) Cu catalyst / O2 carboxylic acid
6) Ag2O
1. Silver Mirror Test / Tollen’s Test
Tollen’s reagent, diamminesilver(I) hydroxide [Ag(NH3)2]OH is prepared by dissolving silver(I) oxide in

excess NH3. It oxidizes aldehyde slowly to carboxylate. The silver(I) ion is reduced to silver metal and
deposited on the surface of test tube to form a silvery surface.
R–CHO(aq) + 2 [Ag(NH3)2]OH(aq) → RCOO-NH4+(aq) + 2 Ag(s) + H2O(l) + 3 NH3(aq)

silver mirror
The test tube used must be very clean otherwise the silver will not deposit on the test tube surface to form a
silver mirror. Instead, it will deposit in the middle of the solution to form gray ppt.
Potential hazard of using Tollen’s reagent
The Tollen’s reagent is potentially explosive if allowed to evaporate to dryness.
2. Fehling’s Test
Fehling’s reagent consists of

Solution A : CuSO4(aq)
Solution B : Sodium potassium tartrate in excess NaOH(aq). O
C O-
Fehling’s solution is freshly prepared by addition of Solution B to Solution A until the
blue ppt. just redissolves to give a deep blue solution due to the formation of a Cu(II) H C OH
complex ion. The tartrate ion serves as the complexing agent in here. HO C H
The presence of complexing agent keeps the Cu2+(aq) soluble even in alkaline medium. C O-
O
R–CHO(aq) + Cu2+(aq) + NaOH(aq) + H2O(l) → RCOO-Na+(aq) + Cu2O(s) + 4H+(aq) tartrate ion
blue brick red ppt.
Upon reduction, the Cu(II) ion is reduced to Cu(I) with the formation of brick red ppt. of
Cu2O.
3. Benedict’s Test
Benedict’s solution is an aqueous solution of Na2CO3, CuSO4 and sodium citrate. Its
action is similar to that of Fehling’s solution. But in Benedict’s solution, the complexing C COO-
agent is the citrate ion instead of the tartrate ion. HO C COO-
C COO-
R–CHO + Cu2+ NaOH + H2O → RCOO-Na+ + Cu2O + 4H+
blue brick red ppt. citrate ion
N.B. Cu+(aq) ion is unstable in aqueous medium. It disproprotionates spontaneously to

Cu2+(aq) and Cu(s).
2Cu+(aq) d Cu(s) + Cu2+(aq)
Therefore, the reacting medium is keep alkaline to prepcipitate any Cu+ formed
to Cu2O(s)..
Characteristic behaviour of functional groups

Class of compound Tests Comments
Alkene 1. Br2 rapidly decolorised. Direct addition.
2. Brown ppt. with alkaline KMnO4. Brown MnO2(s) ppt.
Alkyne 1. Br2 rapidly decolorised. Direct addition.

2. White ppt. with [Ag(NH3)2]+NO3- and red ppt. Terminal alkyne group only.
with [Cu(NH3)2]+Cl-.
Alkanoic acid Liberates CO2 from aqueous NaHCO3.
Acid halide Hydrolysis to give X- ; Test with AgNO3(aq).
Amide Gives NH3 on warming with NaOH(aq).
Aliphatic 1º amine Gives N2 bubbles with cold 'HNO2'.
Aromatic 1º amine Does not give N2 bubbles with cold 'HNO2' but
can be coupled to a phenol to give orange diazo
dye.
1º alkanol 1. Steamy fumes of HCl with PCl5.

2. Ester with RCO2H. Fruity smell, (H+ catalyst)
3. Acidified orange dichromate(VI) goes green Aldehyde and acid product.
on warming.
2º alkanol 1. Steamy fumes with PCl5.

2. Acidified orange dichromate(VI) goes green Ketone product.
on warming.
3. Turns cloudy slowly with ZnCl2 in conc.
HCl(aq).
3º alkanol 1. Steamy fumes with PCl5.

2. No change with acidified orange 3º alcohol is resistant to oxidation.
dichromate(VI).
3. Turns cloudy quickly with ZnCl2 in conc.
HCl(aq).
Phenol 1. No CO2 with NaHCO3 solution.

2. White ppt. with bromine water.
3. Violet complex with neutral Fe3+(aq).
Aldehyde 1. Reduces Fehling's and Benedict's solutions to

orange/red Cu2O.
2. Ag mirror or grey ppt with Tollens' reagent.
3. Alkaline KMnO4 gives brown ppt.
4. DNPH gives orange ppt.
5. White ppt. with saturated aqueous
NaHSO3(aq).
Ketone 1. No reaction with alkaline KMnO4. Ketone is resistant to mild oxidation.

2. DNPH gives orange ppt.
3. White ppt. with saturated aqueous Methyl ketone only.
NaHSO3(aq).
Methyl ketone Yellow ppt. with I2 / NaOH(aq). +ve result with methyl ketone,
ethanol, ethanol and 2º alcohol with –
OH on 2nd C.
Test Reagents for functional groups

Reagent Used to test for
[Ag(NH3)2]+NO3- Diamminesilver(I) nitrate solution – 1. Mirror or ppt. with aldehyde.
Tollens' reagent 2. White ppt. with terminal alkynes.
Br2(aq) Bromine water 1. Decolorised by alkenes, alkynes quickly

and methane slowly under light.
2. White ppt. with phenol.
Cr2O72- Acidified aqueous potassium Orange solution goes green with 1º and 2º
dichromate(VI) alcohols and with aldehyde.
[Cu(NH3)2]+Cl- Diamminecopper(I) chloride solution Red ppt. with terminal alkynes.
DNPH 2,4-dinitrophenylhydrazine aqueous Yellow / orange ppt with aldehydes and ketones
solution
Fe3+ Neutral solution of iron(III) chloride Violet complex with phenols
Fehling's or Both contain complexed Cu2+(aq) Orange to red ppt. with aldehyde and reducing
Benedict's solution sugar.
'HNO2' A mixture of HCl(aq) and NaNO2. Used N2 evolved with aliphatic 1º amines. Aromatic
below 5ºC. 1º amines doesn't give N2 but give diazo dyes
when coupled with phenols.
I2 / NaOH Iodoform test. Aqueous I2 in KI Pale yellow ppt with methyl ketone, ethanol,
solution, made alkaline with NaOH. ethanal and
2º alcohol with –OH on 2nd C.
MnO4- Manganate(VII), i.e. KMnO4 solution Brown ppt. with alkenes, alkyne and aldehydes.
made alkaline with Na2CO3.
Na metal Used in the absence of water. Evolves H2 from –OH in alcohols and alkanoic
acid.
NaHCO3 Saturated sodium hydrogencarbonate Evolves CO2 with alkanoic acids.

solution
NaHSO3 Saturated sodium hydrogensulphite White ppt. with aldehyde and methyl ketone.
solution
NaOH Cold Acids and phenols dissolves. NH3 evolved from

NH4+ salts. Amines liberated from amine salts.
NH3 from NH4+ salts and amide.

Hot
PCl5 Phosphorous(V) chloride. Used as solid Steamy fumes of HCl from –OH in alcohols,
alkanoic acids and phenols.
ZnCl2 in conc. Luca's Test Turns cloudy with 3º alcohol quickly.

HCl(aq) Turns cloudy with 2º alcohol slowly.
Does not turn cloudy with 1º alcohol at all.
Glossary sodium fusion test ignition tube hexacyanoferrate(II) ion Prussian blue
sodium nitroprusside wet chemistry
Past Paper 90 1B 4 b i iii

93 2C 8 a ii iv
94 1B 4 b
95 2C 7 a iii
96 2C 7 c i
97 1A 4 d 97 1B 8 c i
98 1B 8 a iii 98 1A 4 b i ii
90 1B 4 b i iii
CH3
OH NH2
Br
X Y Z
b.p. 182°C b.p. 184°C b.p. 184°C
4b Outline tests involving observable colour changes to show that:

i X is a phenolic compound; 1
Add alcoholic FeCl3 solution. A colour change to red or blue denotes presence of phenol group. 1 mark
iii Z contains bromine. 1
Carry out a sodium fusion to resulting solution add HNO3 and aqueous AgNO3. A pale yellow ppt. sparingly
soluble in dil. NH3(aq) denotes presence of Br. 1 mark
C Few knew the Na fusion test. Some were able to devise a feasible procedure e.g. using the Grignard reagent and
testing the inorganic product—showing initiative for which they were rewarded in full.
91 2C 7 a iv
reactions.
iv Hexanal is treated with ammoniacal silver nitrate solution (Tollens’ reagent). 2
+
A silver mirror is formed on the surface of the test tube or some silver formed. Ag is reduced by hexanal to Ag
metal and deposits on the glass surface. 1 mark
O
CH3CH2CH2CH2CH2CHO Ag(NH3)2 CH3CH2CH2CH2CH2C + Ag
O-NH4+
1 mark
93 2C 8 a ii iv
ii CH3CH2CH2CH2CHO and CH3CH2COCH2CH3 3
Reagent: Fehling’s reagent / Tollen’s reagent 1 mark
Observation: Red ppt. / Formation of silver mirror 1 mark
Equation:
CH3CH2CH2CH2CHO + 2Cu2+ + 6OH- → CH3CH2CH2CH2COO- + 2Cu2O(red ppt.) + 3H2O
or
CH3CH2CH2CH2CHO + Ag(NH3)2+ + 2OH- → CH3CH2CH2CH2COO- + 2Ag(silver mirror) + H2O 1 mark
C A few candidates incorrectly stated that Ag2O was the product formed in the " Silver Mirror" test.
Some candidates could not give the formula of Tollen's reagent or Fehling's solution.
iv OH CH2OH 3
CH3 and
Reagent: Lucas reagent (ZnCl2 in conc. HCl) 1 mark

OH CH2OH
Observation: CH3 gives turbidity / cloudy / misty faster than 1 mark
Equation:
OH CH3 Cl
CH3 H+ + H2O Cl- CH3
1 mark
C Many candidates did not understand the chemistry involved in the Lucas test and the reason for observing
turbidity.
Many candidates incorrectly applied the Iodoform Test to distinguish the given pair of alcohols.
94 1B 4 b
4b You are provided with a sample of an aliphatic aldehyde. Describe, with experimental details, the silver mirror 3
test (Tollens’ test) that you would perform, in order to establish that the sample is an aldehyde. What hazard will
you face if you allow the reaction mixture to evaporate to dryness?
Clean test tube ½ mark
Add excess NH3 to AgNO3 in test tube until initial ppt. dissolves 1 mark
Add aldehyde ½ mark
Place the tube in a beaker of warm water (No direct gentle heating) ½ mark
Hazard : an explosion may occur ½ mark
C Candidates were reluctant to itemize the procedure, including experimental details. Frequent omissions included
the need to use a clean test tube; the steps in making Tollens' reagent; and the use of a water bath.
95 2C 7 a iii
iii CH3 3
and CH2OH
OH
Treat compound with MnO4-/H+ or Cr2O72-/H+ ½ + ½ mark

CH2OH COOH CHO
Cr2O72- / H+ or
½ mark
The solution changes colour from orange/yellow to green. ½ + ½ mark
CH3
No reaction with OH . ½ mark
OR
Treat compound with HCl and ZnCl2 ½ + ½ mark
CH3
CH2OH 1 mark
OH gives turbidity at a faster rate than
CH3 CH3
+ HCl + H2O 1 mark
OH Cl
C The Lucas test was generally used, but most candidates gave wrong observation : precipitation instead of
turbidity; they probably thought that the tertiary chloride was a solid. Some candidates gave incorrect reagents
such as Zn instead of ZnCl2; ZnCl2(aq) instead of anhydrous ZnCl2(s); dilute HCl instead of concentrated HCl. Some
gave the wrong formula ZnCl for zinc chloride. The simpler reagent, Cr2O72-/H+ only appeared occasionally. Some
candidates did not give the correct colour change involving this common oxidizing agent.
96 2C 7 c i
7c Suggest a chemical test to distinguish one compound from the other in each of the following pairs. Your answer
should include the reagents used and the observation expected.
i O 2
CHO
and
Treat compound with Tollen's reagent / ammoniacal silver(I) oxide / ammoniacal silver nitrate(V) / Ag(NH3)2+
1 mark
CHO
gives a silver mirror / silver deposit ½ mark
No reaction with ½ mark
Or
Treat compound with Fehling's reagent / a mixture of CuSO4,NaOH and sodium potassium tartarate (1 mark)
CHO
produces a (bright) red / orange / reddish brown ppt. (½ mark)
No reaction with (½ mark)
Or
Treat compound with Cr2O42-/H+ (cold MnO4-/H+) (1 mark)
CHO
changes the colour of the solution from orange to green (½ mark)
(changes colour of MnO4-/H+ from purple to colourless)
O
No reaction with (½ mark)
C Some candidates erroneously gave Brady's test for differentiation. One common mistake of the candidates
was to take CuSO4 as Fehling's reagent.
97 1A 4 d
4d Suggest, with explanation, a chemical reaction which would enable 4-methylbenzoic acid and 4-methylphenol to 2
be distinguished from each other.
97 1B 8 c i
8c For each of the following groups of compounds, suggest a chemical test which would enable each compound to be
distinguished from the other(s). In your answer also give the changes that you would expect to observe for each
compound.
i CH3CH2CH2OH, (CH3)2CHOH and (CH3)3COH 2
98 1A 4 b i ii
Alcohol E has the structure CH3CH(OH)C2H5.
4b i Draw the structures of three structural isomers of E, all of which are alcohols. 1½
ii Describe how the reagent Zn/concentrated HCl can be used to distinguish E from the three structural isomers. 1½
98 1B 8 a iii
iii distinguish between C6H5COCl and C6H5COBr using a chemical test. 1
Notes 27.4.0
Past Paper Questions of structural determination
Organic Chemistry, 6th Edition, Solomons, pg. 359-360, 742
Past Paper 90 2C 7 a b c
Question 91 2C 9 b i ii iii
92 1A 1 b
92 1A 1 f ii 92 2C 7 a b e
93 2C 9 a i
94 2C 7 b iii
95 2C 7 b i ii 95 2C 9 a i iii iv
96 2C 7 a i ii
98 2B 6 c ii
90 2C 7 a b c
7 Consider the following experimental information.
I. X (C9H11NO) gives on hydrolysis, two compounds with formulae CH5N and C8H8O2. When the latter
compound is added to sodium hydrogencarbonate solution, a colourless gas is evolved.
II. Y (C9H10) gives on vigorous oxidation, an acid with formula C7H6O2. Y decolourizes a solution of bromine
in tetrachloromethane.
III. Z is an optically active ester containing 64.6% carbon, 10.8% hydrogen and 24.6% oxygen, and has a relative
molecular mass between 120 and 140. Upon hydrolysis, Z gives propanoic acid.
(Relative atomic masses: H, 1.0; C, 12.0; O, 16.0)
7a Draw TWO possible structures for each of the compounds X, Y and Z. 9
X: Y:
O
C NHCH3 O
C NHCH3 H CH3 H H
C C C C
H CH3
CH3 CH3
Z: molecular formula calculated C7H14O2 3 marks

O CH3 O CH3
CH3CH2 C O C CH2CH3 CH3CH2 C O C H
H CH2CH3
1 mark for each structure
7b For each pair of possible structures, name the type of isomerism involved. 3
X: Structural isomerism 1 mark
Y: Geometric isomerism / cis-trans isomerism 1 mark
Z: Enantiomerism / optical isomerism / stereoisomerism 1 mark
7c Using only one of the possible structures for each of X, Y and Z, write equations for the reaction described above. 5
O
COOH
C NHCH3
hydrolysis + CH3NH2
CH3
CH3
2 marks
H CH3 COOH H CH3 Br
C C C C
H [O] H Br2 Br
1 mark each
O CH3 CH3
CH3CH2 C O C CH2CH3 H2O CH3CH2OOH + HO C CH2CH3
H H
1 mark
C The majority of the candidates could provide correct structures for X and Y, but not for Z.
O
C CH2NH2
One common incorrect structure for X was :

and the related reaction equation was incorrectly given as :
O O
C CH2NH2 hydrolysis C OH
+ CH3NH2
Common incorrect structures for Y were :

Although most candidates could work out the molecular formula for Z using the given analytical data, they failed
to provide the correct structures which would display optical activity i.e. a chiral centre.
Candidates had difficulty in drawing a 3 dimensional representation for Z properly.
Many candidates could not distinguish between different types of isomerism in (b).
It is suggested that terms like "chain isomerism", "functional group isomerism", "position isomerism" or
"metamerism" should be dropped and the more general term "structural isomerism" should be used to describe
different structures.
One other common mistake in isomerism for Y was regarding structures with the double bond at different
locations as geometric isomers, e.g.
CH CHCH3 CH2CH CH2
91 2C 9 b i ii iii
9b Suggest a possible structure for each of the compounds J, K, L, M, and N below and explain briefly your
deductions.
i J, C4H6O, on oxidation gives K, C4H6O2. 3
CHO [O] COOH
or
CHO [O] COOH
or
CHO [O] COOH
or
CHO [O] COOH
J K 1 mark for J, 1 mark for K

Oxidation increase the number of O atom on J 1 mark
ii L, C5H12O, can exist as a pair of enantiomers, and reacts with phosphorus pentachloride to give hydrogen 3
chloride.
OH Cl OH Cl
PCl5 PCl5
CH3 CH3 + HCl CH3 CH3 + HCl
H H H H
or 1 mark
L can exist as pair of enantiomers → chiral centre in L 1 mark
L gives out HCl on reaction with PCl5 → -OH group present 1 mark
C A few candidates did not realize the relation between the existence of enantiomers and chiral centre; hence they
gave an incorrect structure for L.
iii M, C6H10, on ozonolysis gives N, C6H10O2. 3
O3 CHO O3 O3 CHO
Zn/H2O O Zn/H2O
CHO Zn/H2O CHO CHO
or or
M N 1 mark for M, 1 mark for N
Ozonolysis of M without changing the carbon number → double bond forms part of a ring, i.e. cyclic alkene.
1 mark
C Many candidates could not account for the ring structure of M by relating the number of carbon atoms in M and
N.
92 1A 1 b
1b Compound X with formula C10H14 is optically active. On treatment with potassium manganate(VII), X gives 2
benzoic acid (C6H5COOH). Give the structure of X.
Me
CH
or Et
C Few commented on the 3-D aspect of the structure.

92 1A 1 f ii
1f CO2H
CH3 CH NH3
V
ii Give the structure of the compound with a relative molecular mass of approximately 230, which on refluxing with 1½
dilute hydrochloric acid gives V as the only product.
(Relative atomic masses: H 1.0; C 12.0; N 14.0; O 16.0)
The structure of the compound is C9H17N3O4 with m.w. 231.
CONH CONH CO2H
NH2
Essential features (i) 2 peptide links: CONH

(ii) tripeptide 1½ mark
92 2C 7 a b e
7 A carboxylic acid P, with a relative molecular mass less than 100, contains C, 55.8%; H, 7.0%; and O, 37.2% by
mass . An attempt to convert P to its methyl ester Q by prolonged refluxing of P with methanol in the presence of
aqueous H2SO4 gave the desired ester Q but with much of the starting material P unchanged.
(Relative atomic masses : H 1.0; C 12.0; O 16.0)
7a Determine the molecular formula of P. 2
P : C4H6O2 2 marks
7b Give the structures of four carboxylic acids having the molecular formula you determined in (a). Give the 6
systematic names for any one of the carboxylic acids and its methyl ester.
COOH
but-3-enoic acid or 3-butenoic acid
H COOH
CH3 H
trans-but-2-enoic acid
H H
CH3 COOH
cis-but-2-enoic acid
COOH
2-methylpropenoic acid any 4 structures - 4 marks
COOH
cyclopropanecarboxylic acid name of acid - 1 mark
ester : methyl but-3-enoate etc. name of ester - 1 mark
C Many candidates did not show the structure of cis and trans isomer clearly, e.g.
H H
CH3 C C COOH for cis isomer, and
CH3 H
H C C COOH for trans isomer.
CH3 CH2
Many candidates treated CH2 C COOH and CH3 C COOH as two different structures.
Candidates were generally weak in naming; examples of common mistakes are :
CH3 CH CH COOH butan-2-enoic acid
CH3 CH CH COOCH3 methy but-2-enoate or methoxy but-2-enoate.
7e Show, using equations, how you would convert Q to P. 2

COOCH3 COO-K+
+ KOH Heat + CH3OH
Q
H+
COOH
P
2 marks
93 2C 9 a i
9a A compound W of relative molecular mass 121 has the elemental composition: C, 79.3%; H, 9.1%; N, 11.6%.
W reacts with nitric(III) acid to give a derivative X. X reacts with ethanoic anhydride to give a sweet-smelling
liquid Y which contains no nitrogen. Oxidation of X with chromic(VI) acid yields Z, C8H8O. Z reacts with iodine
and sodium hydroxide to produce a yellow precipitate and sodium benzoate.
i Deduce the structures of W, X, Y and Z, using all the given data. Explain your reasoning. 10
C H N
79.3 9.1 11.6
79.3 9.1 11.6
No. of atoms 12.0 1.008 14.01
= 6.61 : 9.1 : 0.828
≈ 8 : 11 : 1
Empirical formula of W is C8H11N 2 mark
Molecular formula is (C8H11N)n
Molecular mass = 121 ∴n=1 1 mark
X reacts with ethanoic anhydride to form a sweet-smelling liquid Y.
∴ X is an alcohol and Y is an ester 1 mark
W reacts with HNO2 to give an alcohol
∴ W carries an –NH2 group / 1º amine 1 mark
Z is obtained from oxidation of X (an alcohol) and it gives positive iodoform test. It is a methyl ketone. 1 mark
NH2 OH
C CH3 C CH3
W is X is
H H
CH3 O
O
C O C CH3
Y is Z is C CH3
H
(4 marks for structure, 6 marks for deduction)

C A number of candidates were able to give correct structures for the unknowns; however, they were unable to show
clearly and logically how these structures were deduced from the given information. Generally, candidates lacked
the necessary technique in presenting an answer for this type of problem.
Many candidates suggested X was a diazonium salt because X was formed from the reaction between an amine
and HNO2. They had ignored the fact that X gave an ester on reacting with anhydride.
94 2C 7 b iii
7b Give, with explanation, THREE possible structures for each of the compounds (G,H and J) below.
For (i) - (iii), 1 mark for the first correct structure, ½ mark for the second and ½ mark for the third structure.
iii J, C10H14O, reacts with PCl5 to give hydrogen chloride. Vigorous oxidation of J gives benzene-1,2-dicarboxylic 6
acid, but mild oxidation of J gives a ketone.
Suggest one chemical test, giving the expected observations, which would allow you to eliminate one of your
possible structures of J in (iii).
J reacts with PCl5 to give HCl, ∴ J carries a –OH group ½ mark
Stronge oxidation of J gives , J is a 1,2-disubstituted aromatic compound 1 mark
Mild oxidation of J gives a ketone, J is a 2º alcohol ½ mark
Possible structures of J
OH OH
OH
2 marks
Iodoform test / I2 in NaOH
Observation :
OH OH
OH
and will give a pale ppt., while will not. 2 marks
C Poorly-answered. Many candidates did not make use of all information to deduce that J was a secondary alcohol
as well as a 1,2-disubstituted benzene derivative.
95 2C 7 b i ii
7b An acidic compound D, C6H6O4, on heating to 140ºC dehydrates to give compound E, C4H2O3. D gives compound
F upon hydrogenation.
i Give the structures of D, E, F. 3
O
O
H C O H
C H C C
O
C
H C O H H C C
O O HOOCCH2CH2COOH
(1 or 0) mark each
D (must show the cis structure) E F
C Poorly answered. Few candidates gave the correct structure for D. Most candidates erroneously thought that
dehydration only involved the elimination of water from alkanols to give alkenes. Some gave both trans- and cis-
isomers for D probably because they did not realize that only cis-butenedioic acid would dehydrate to form an
anhydride at 140ºC. Most failed to appreciate geometrical isomerism and less than 5 % named D and E
correctly.
ii Give the systematic names for D and E. 2
D : cis-butenedioic acid 1 mark
E : butenedioic anhydride 1 mark
C Many candidates missed out the stereochemical prefix cis in the naming of D.
95 2C 9 a i iii iv
9a An acyclic hydrocarbon G, with relative molecular mass of between 60 and 80, contains 85.6% carbon and 14.4%
hydrogen by mass.
i Determine the molecular formula of G. 2
85.6
Mole % of C = 12.01 = 7.13
14.4
Mole % of H = 1.008 = 14.29
C : H = 7.13 : 14.29 = 1 : 2
∴ Empirical formula of G is CH2 1 mark
Since m.w. is between 60 and 80
The molecular formula of G must be C5H10 1 mark
iii G, on ozonlysis, yield H and J which both produce positive iodoform reactions. Give the structures of G, H and J. 3
O O
Structures of H and J : CH3 C CH3 and CH3 C H 1 + 1 mark

CH3 CH3
C C
∴ Structure of G : CH3 H 1 mark
C Although structures for H and J were given correctly, many candidates could not deduce the structure for G. Some
candidates could present G in (iii) but did not include it as one of the structures in (ii).
iv Give the systematic name of G. 1
2-methylbut-2-ene 1 mark
C G was frequently but erroneously named as 3-methylbut-2-ene.
96 2C 7 a i ii
7a Two compounds F and G. with the same molecular formula C4H8O, give the following results in four chemical
tests.
Reagent F G
H2NOH no reaction no reaction
Cr2O72-/H+ colour changes from orange to green no reaction
Br2 /CH3CCl3 decolorization no reaction
I2/NaOH yellow precipitate no reaction
i Give the structure for F. Explain your answer with reference to the result of each of the chemical tests. 5
F is CH2=CHCH(OH)CH3 1 mark
F does not form any oxime. ∴ F is not aldehyde or ketone ½ + ½ mark

or, Aldehyde or ketone will give the following reaction (½ mark)
O N OH
+ H2NOH
R C R' R C R'
(½ mark)
F can be oxidized by chromic(VI) acid ½ mark

∴ F is a (primary / secondary) alcohol / bears an –OH group ½ mark
or, alcohols can be oxidized by chromic(VI) acid (½ mark)
chromic acid
RR'CHOH RR'C O
(½ mark)
F gives addition reaction with Br2. ∴ C=C / C≡C / unsaturation is present ½ + ½ mark
or, compounds with C=C / C≡C form addition product with Br2 (½ + ½ mark)
C C Br
+ Br2
C C Br
(1 mark)
F gives positive reaction in iodoform test ∴ CH CH3

or C CH3
is present. ½ + ½ mark
OH O
H -
I2 / OH -
R C OH RCOO + CHI3
or, (1 mark)
CH3
C Candidates were weak in logical deduction. Many candidates missed the important hints and deduced the structure
without explanation or without referral to related reactions. They should learn how to summarize information,
reduce possibilities step by step, and then draw conclusions about the structure. Many candidates failed to give
oxime as the derivative of carbonyl compound with NH2OH. Some erroneously attributed the colour change with
chromic(VI) acid to the double bond. Some did not mention the words addition with Br2 and oxidation with
C CH3 CH CH3
chromic(VI) acid. Some wrongly concluded that OH
was present instead OH
for a positive iodoform
test.
ii Suggest a structure for G and explain your suggestion. 2
Any ONE of the following:
O
O O O OH
1 mark
Explanation:
O
G does not possess , C C , 1º or 2º alcohol / G is 3º alcohol ½ mark
C
it can only be ether / tertiary alcohol ½ mark
C Some candidates erroneously thought that cyclobutanol is a tertiary alcohol and assigned it as compound G.
98 2B 6 c ii
6c 2-Ethanoyloxybenzoic acid (aspirin) is one of the most common substances used to relieve pain. 4
CO2H
OCOCH3
2-ethanoyloxybenzoic acid
ii Suggest how you could show the presence of the two functional groups in 2-ethanoyloxybenzoic acid.
Reference 27.5
Assignment
Reading
Syllabus Introduction to IR and NMR spectroscopy

Interpretation of IR spectrum
Notes V. Introduction to IR and NMR spectroscopy
Other than wet chemistry, infra-red spectroscopy and nuclear magnetic resonance (NMR) are modern instrumental
techniques in helping chemists to understand the structures of molecules.
IR spectrum
Infra-red spectroscopy depends on the vibrations of atoms with respect to each other in the molecule. The infra-red
spectrum can tell us whether particular functional groups are present in a molecule
IR spectrum of octane
N.B. The actual structure cannot be deduced from the IR spectrum alone, other tests are required to confirm the
result.
NMR spectrum
Nuclear magnetic resonance depends on the magnetic properties of the atomic nuclei (e.g. hydrogen nuclei) in a
molecule. The proton NMR spectrum can tell us the number of hydrogen nuclei present in the molecule and give
information about the structural environment of the hydrogen.
NMR spectrum of 1,1,2-chloroethane

On an IR spectrum, different functional groups have characteristic absorption wavenumbers, therefore, the
functional group(s) present in an organic compound can be identified from a given IR spectrum.
The frequency of infra-red spectrum is usually measured in wavenumber (cm-1). This means the number of
wavelength in each cm. The wavenumber is directly proportional to the frequency.
An IR spectrum can be divided into several region :
1. 4000 – 2500 cm-1 Absorption of single bonds formed by H and other elements. e.g. C–H, O–H, N–H
2. 2500 – 2000 cm-1 Absorption of triple bonds. e.g. C≡C, C≡N
3. 2000 – 1500 cm-1 Absorption of double bonds e.g. C=C, C=O
4. 1500 – 500 cm-1 Fingerprint region, consists of complicated bands and is unique to each compound.
IR spectrum of octane CH3(CH2)6CH3
In A-Level, we only focus on the identification of functional groups. Therefore, only the region from
4000 cm-1 to 1500 cm-1 will be studied.
Characteristic group absorption wavenumbers of covalent bonds in organic molecules

1
The following examples show how to make use of the characteristic absorption wavenumbers to identify the
functional groups present in organic compounds.
Fig. 1 shows a portion of the IR spectrum of ethanol.
The peak at 2950 cm-1 corresponds to the absorption of

C–H group and that at 3340 cm-1 corresponds to the
absorption of O–H group. Hence, a O–H group is
present in the ethanol.
Fig. 1 IR spectrum of ethanol
Fig. 2 shows a portion of the IR spectrum of methanoic

acid.
The peak at 1710 cm-1 corresponds to the absorption of

C=O group and that at 3100 cm-1 corresponds to the
absorption of O–H group. Hence. both the C=O and
O–H groups are present in the methanoic acid.
It should be noted that the absorption of the O–H group

in alcohols and carboxylic acids does not usually appear
as a sharp peak. Instead. a broad band is observed
because the vibration of O–H group is complicated by
the hydrogen bonding.
Fig. 2 IR spectrum of methanoic acid

1. More examples
H H H H O H
Peak / cm-1 Bond
a. Hex-5-en-2-one H C C C C C C H 3080 C–H
H H H 1720 C=O
1635 C=C
H H H H
Peak / cm-1 Bond
b. Hex-1-yne H C C C C C C H 3300 C–H*
H H H H 2900 to 2950 C–H
2200 C≡C
* Absorption at
3300 cm-1 is due to
C–H bond in terminal
C≡C triple bond, which
is weaker.
H H H H O H
Peak / cm-1 Bond
c. Butyl ethanoate H C C C C O C C H 2900 to 2950 C–H
H H H H H 1740 C=O
O CH3
Peak / cm-1 Bond
d. 3-methylbutan-2-one CH C C CH
3 3 2880 to 2980 C–H
1720 C=O
H H H H H
Peak / cm-1 Bond
e. Butylamine H C C C C N H 3300 to 3400 N–H
H H H H 2850 to 2950 C–H
H H
Peak / cm-1 Bond
f. Propanenitrile H C C C N 2900 to 3000 C–H
H H 2250 C≡N
Glossary infra-red (IR) spectroscopy nuclear magnetic resonance (NMR) spectroscopy spectrum / spectra
wavenumber fingerprint region absorption peak
Past Paper 97 2B 6 c
Question 98 1B 8 a ii
99 2B 6 a iii
Sample question
7b An organic compound Z, with relative molecular mass below 100, has the following composition by mass. 11
C 66.7%, H 11.1% and O 22.2%.
i Determine the molecular formula of Z.
no. of mole of C : no. of mole of H : no. of mole of O
66.7 11.1 22.2
= 12.0 : 1.0 : 16.0
= 5.56 : 11 : 1.39
= 4.00 : 7.91 : 1.00
≈4:8:1
Empirical formula of Z is C4H8O.
Formula mass of C4H8O = 12.0 × 4 + 1.0 × 8 + 16.0 = 72.
Since the molecular mass of Z is below 100, the molecular mass of Z should be 72.
ii A portion of the infra-red (IR) spectrum of Z is shown below:
Using the IR spectrum and the result from (i), deduce two possible structures of Z, each belonging to a different
homologous series.
Given :
Characteristic Group Absorption Wavenumbers of
Covalent Bonds in Infra-red Spectra (stretching modes)
Bond Characteristic Range
Wavenumber / cm-1
C=C Alkenes 1610 to 1680
C=O Aldehydes, ketones, acids, esters 1680 to 1750
C–C Alkynes 2070 to 2250
C≡N Nitriles 2200 to 2280
O–H Acids (hydrogen-bonded) 2500 to 3300
C–H Alkanes, alkenes, arenes 2840 to 3095
O–H Alcohols, phenols (hydrogen-bonded) 3230 to 3670
N–H Primary amines 3350 to 3500
From the molecular formula C4H8O, the degree of unsaturation of the molecule is 1.
The peak at 1700 cm-1 and absence of a board peak at 3100 cm-1 indicate the presence of C=O bond.
Z may be butanal (an aldehyde) or butan-2-one (a ketone).
H H H O H H O H
H C C C C H H C C C C H
H H H H H H
butanal butan-2-one
iii Suggest one chemical test, giving the expected observation(s), that can be used to distinguish the two compounds
having the structures as deduced in (ii) above.
By iodoform reaction, when I2(aq) and NaOH(aq) are added, only butan-2-one will give yellow precipitate of CHI3(s)
but butanal has no reaction.
Sample question
1 The infrared spectra in figure 1 and 2 represent an ester and an alkyne. Identify the peaks which are starred on
each spectrum and so decide which spectrum represents which type of compounds.
Figure 1 Figure 2
Figure 1 : an ester
Figure 2 : an alkyne
2 An alkene A (C5H10), on ozonolysis, gave two different compounds, B and C with molecular formulae C3H6O and
C2H4O respectively. Compound B has an infrared spectrum as shown in figure 3 below.
Figure 3 IR spectrum of compound B
When B and C were separately treated with acidified dichromate(VI), B did not react but C gave D with molecular
formula C2H4O2, D gave effervescence with sodium hydrogencarbonate.
Deduce possible structure for A, B, C and D based on above information.
A : 2-methylbut-2-ene
B : propanone
C : ethanal
D : ethanoic acid
97 2B 6 c
6c Compound H. C3H6O2, does not react with NaBH4 and displays the following infra-red spectrum. Deduce all
possible structures of H.
98 1B 8 a ii
ii distinguish between propan-2-ol and propanone using spectroscopy,
99 2B 6 a iii
6a O
Cl NH2 Cl NH CCH3
iii Suggest how to show the presence of the amide group in N-(4-chlorophenyl)ethanamide by
(I) a chemical test and
(II) a spectroscopic method.
Organic synthesis
A. Chain length
1. Carbon chain
B. Degree of unsaturation
D. Position of functional group

IV. Examples
Organic Synthesis Page 1
Topic Organic Synthesis
Reference 28
Reading Organic Chemistry, Solomons, 5th Edition pg. 157
Organic Chemistry, Stanley H. Pine, 5th Edition pg. 722–723
Assignment Organic Chemistry, 6th Edition, Solomons, pg. 169-171
Syllabus Organic Synthesis
Notes Synthesis is the real test of our ability to use and control organic reactions. Before attempting any synthesis, you
must be familiar with all kinds of conversion available first.
Besides the knowledge about the conversion (organic reaction), the following analysis may help you to plan the
synthesis.
Retro- means working backwards.
1. It is better to begin with the target molecule and work backwards from it. The no. of ways of preparing a
target molecule is usually fewer than the no. of way that a starting molecule can react.
If we start from the starting molecule, the no. of possible synthetic path may be numerous.
The molecule from which the target molecule is prepared is called precursor.
Target molecule ⇒ 1st Precursor ⇒ 2nd Precursor ⇒ ⇒ Starting molecule
For a beginner, it may be quite difficult to plan the complete path at once. The structural analysis may
help you to identify some of the precursors (and reagents) required, therefore a long path can be broken
into several shorter pathways.
2. The no. of steps involved should be as few as possible. Try not to use path with more than 4 steps. If the
yield of each step is 80%, a 4 steps conversion means merely (80%)4 = 41% overall yield.
3. Use a precursor (or a reagent) which will give a higher yield.

e.g. bromoalkane instead of alcohol in nucleophilic substitution
acyl halide instead of carboxylic acid in nucleophilic addition-elimination
4. Even a conversion seems to be simple may not be so simple.

e.g. Direct conversion of acyl bromide (RCOBr) to bromoalkane (RCH2Br) is impossible.
This is the feasible way : acyl bromide → carboxylic acid → alcohol → bromoalkane

(The following guideline is only applicable to A-Level where the choices of conversion are limited.)
Before planning of any organic synthesis, it is important to know the difference between the starting molecule
and the target molecule.
A. Chain length
1. Carbon chain
If the no. of C is increased by 1
i. Substitution reaction with CN- (haloalkane precursor)
ii. Addition reaction with CN- (carbonyl compound precursor)
If the no. of C is decreased by 1

i. Haloform reaction (methyl ketone or methyl alcohol precursor)
ii. Hoffman degradation (1º amide precursor)
If the chain length is increased.

i. Acylation by acylating agent e.g. RCOCl (nucleophile precursor e.g. RNH2 or ROH)
ii. Substitution reaction with RI (nucleophile precursor e.g. RNH2 or ROH)
B. Degree of unsaturation (consider C=C and C≡C bond only)
If the degree of unsaturation is increased → Elimination with strong base e.g. CH3CH2ONa+ (haloalkane or
dihaloalkane precursor)
If the degree of unsaturation is decreased → Catalytic hydrogenation (alkene or alkyne precursor)
If it is oxidized to
i. Carboxylic acid (methyl ketone, aldehyde, 1º alkanol or alkyl benzene precursor)
ii. Ketone (2º alkanol precursor)
If it is reduced to
i. Alkanol (any acid derivatives except amide precursor)
ii. Amine (amide, nitrile or aromatic nitro compound precursor)
D. Position of the functional group
If there is no change in the position of the functional group, it may be converted by direct conversion.
If there is change in the position, the functional group may be converted by elimination followed by addition.
1. Name all the functional groups on the original and target molecule, must be specific e.g. 1º or 2º.
2. Identify if there is any change in length of carbon chain.
3. Identify if the molecule is oxidized or reduced.
4. Identify if there is any change in degree of unsaturation.
5. Figure out the possible intermediate (precursor).
6. Repeat step 1 to 5 until all the intermediates are figured out.
7. Assign reagent to each conversion.
IV. Examples
Example 1
CH3CH2CH2COOH CH3CH2CH2CH2COOH
Round 1
1 – Naming Starting molecule : CH3CH2CH2COOH (carboxylic acid)
Target molecule : CH3CH2CH2CH2COOH (carboxylic acid)
2 – Chain length The no. of C is increased by one.
3 – Redox N.A.
4 – Unsaturation No double or triple bond involved.
5 – Intermediate Since the chain is lengthened by 1, nitrile should be the intermediate which can be hydrolyzed
to carboxylic acid.
CH3CH2CH2COOH CH3CH2CH2CH2CN CH3CH2CH2CH2COOH
Round 2
1 – Naming Starting molecule : CH3CH2CH2COOH (carboxylic acid)
Target molecule : CH3CH2CH2CH2CN (nitrile)
2 – Chain length No change on the main C chain.
3 – Redox Carboxylic acid is reduced.
5 – Intermediate Carboxylic acid has to be reduced to alkanol first.
CH3CH2CH2COOH CH3CH2CH2CH2OH CH3CH2CH2CH2CN
Round 3
1 – Naming Starting molecule : CH3CH2CH2CH2OH (1º alkanol)
Target molecule : CH3CH2CH2CH2CN (nitrile)
3 – Redox N.A.
5 – Intermediate –OH group is not a good leaving group. This makes alkanol not a good substrate for
nucleophilic substitution by CN- ion. –OH has to be converted to a good leaving group first,
e.g. –Br.
CH3CH2CH2CH2OH CH3CH2CH2CH2CH2Br CH3CH2CH2CH2CN
7 Overall conversion
CH3CH2CH2COOH LiAlH4 CH3CH2CH2CH2OH PBr3 CH3CH2CH2CH2CH2Br KCN / H+ CH3CH2CH2CH2CN H3O+ CH3CH2CH2CH2COOH

Example 2
+ -
(CH3)2CHCH2COOH (CH3)2CHCH2CH2N (CH3)3I
Round 1
1 – Naming Starting molecule : (CH3)2CHCH2COOH (carboxylic acid)
Target molecule : (CH3)2CHCH2CH2N+(CH3)3I- (quartenary ammonium iodide)
5 – Intermediate Quartenary ammonium salt can only be prepared from alkylation of amine, therefore, the
intermediate may be a 1º amine, (CH3)2CHCH2CH2NH2.
+ -
(CH3)2CHCH2COOH (CH3)2CHCH2CH2 NH2 (CH3)2CHCH2CH2N (CH3)3I
Round 2
Target molecule : (CH3)2CHCH2CH2NH2 (1º amine)
5 – Intermediate Amine has 3 possible precursors :
Nitrile (by reduction), amide (by reduction or Hoffman degradation) or haloalkane (by
alkylation of ammonia)
Since there is no change in the length of C chain, nitrile intermediate and Hoffman degradation
of amide can be ruled out.
1. (CH3)2CHCH2COOH (CH3)2CHCH2CH2 Br (CH3)2CHCH2CH2 NH2
(Remark : Only 1º amine can be prepared by alkylation of ammonia)
O
2. (CH3)2CHCH2COOH (CH3)2CHCH2C NH2 (CH3)2CHCH2CH2 NH2
Round 3
Target molecule : 1. (CH3)2CHCH2CH2–Br (haloalkane)
2. (CH3)2CHCH2CONH2 (1º amide)
3 – Redox 1. haloalkane – Carboxylic acid is reduced.
2. 1º amide – Carboxylic acid is neither oxidized nor reduced.
5 – Intermediate 1. Carboxylic acid has to be reduced first before it can be converted to haloalkane.
Therefore, the intermediate may be alkanol.
(CH3)2CHCH2COOH (CH3)2CHCH2CH2 OH (CH3)2CHCH2CH2 Br
2. Carboxylic acid can be converted to amide through acid chloride intermediate. Because
ammonia is a base which forms a salt RCOO-NH4+ with carboxylic acid, it does not form
amide with acid directly.
O O
(CH3)2CHCH2COOH (CH3)2CHCH2C Cl (CH3)2CHCH2C NH2
7 Overall conversion
Path 1
LiAlH4 PBr3 excess NH3 excess CH3I
(CH3)2CHCH2COOH (CH3)2CHCH2CH2 OH (CH3)2CHCH2CH2 Br (CH3)2CHCH2CH2 NH2 +
(CH3)2CHCH2CH2N (CH3)3I
-
Path 2
O
(CH3)2CHCH2COOH SOCl2 (CH3)2CHCH2COCl NH3
(CH3)2CHCH2C NH2 LiAlH4 (CH3)2CHCH2CH2 NH2 excess CH3I (CH3)2CHCH2CH2N+(CH3)3I-
Glossary organic synthesis retrosynthetic analysis target molecule precursor structural analysis
Past Paper 90 2C 9 b i ii
Question 91 2C 8 a b d
93 2C 7 b i ii
94 2C 8 a i ii
95 1A 3 e ii 95 2C 8 b i ii iii
98 2B 6 c i
99 2B 7 b ii
90 2C 9 b i ii
9b Using equations, show the reactions you would employ for the following conversions in the laboratory. Give the
reagent(s) for each step and structures of all intermediate compounds.
i O 3
C CH2OH
CH3
O
1. I2, NaOH COOH CH2OH
C LiAlH4
CH3 2. H+(aq)
3 marks
ii CH2CH2Br C CH
3
Br
CH2CH2Br NaOEt Br2 NaOEt C CH
Br
3 marks
91 2C 8 a b d
8 Using equations, show the reactions you would employ for the following conversions in the laboratory. Give the
reagent(s) for each step and the structures of all intermediate compounds.
8a OH 3
conc. HNO3 NO2 NH2 OH

[H+]
HNO2
conc. H2SO4 Sn, HCl
3 marks
8b (CH3)2CHCH2COOH → (CH3)2CHCH2CH2COOH 4
H2O, H+
(CH3)2CHCH2COOH LiAlH4 (CH3)2CHCH2CH2OH PBr3 (CH3)2CHCH2CH2Br KCN (CH3)2CHCH2CH2CN (CH3)2CHCH2CH2COOH
hydrolysis
4 marks
C Some common mistakes were : ROH  
→ RCN KCN
(without going through RX)
RX  
→ RCN HCN
(wrong reagent; should use KCN)
8d O CH3 3
CH3CH2CH2 C NH2 CH3CH2CH2CH2 N CH3
O CH3
LiAlH4 CH3CH2CH2CH2NH2 CH3I
CH3CH2CH2 C NH2 CH3CH2CH2CH2 N CH3
3 marks
C O
Zn / Hg
Some common mistakes were : R C NH2 HCl RCH2NH2 (wrong reagent)
93 2C 7 b i ii
7b Show how you would carry out the following conversions in the laboratory, giving the structures of intermediate
compounds and the reagents for each step.
i CH
O O 3
3
C C
O
CH3 COOH COCl

MnO4- / OH-, heat PCl5
O O
C C
O
COOH
3 marks
C Common mistakes revealed in the candidates' synthetic conversions were :
O O
RCOOH  →
heat
R C O C R (without dehydrating agent);
ii CH3CH2CH2COOH CH3CH2CH2CH2COOH 3
LiAlH4 PBr3 +
CH3CH2CH2COOH CH3CH2CH2CH2OH CH3CH2CH2CH2CH2Br KCN / H+ CH3CH2CH2CH2CN H3O CH3CH2CH2CH2COOH
3 marks
C Common mistakes revealed in the candidates' synthetic conversions were :
ROH  
→ RCN
KCN
(without going through RX)
RCOOH  → RCHO
LiAlH 4
94 2C 8 a i ii
8a Show how you would carry out the following multi-step conversions. For each step, give the structure of the
intermediate compound and the necessary reagent(s).
i CH2CH2OH C CH 3
Br Br
CH2CH2OH C CH
conc. H2SO4 Br2 C C H KOH / EtOH
H H
3 marks
C Common mistakes of the candidates included :
RCH2CH2OH   → RCH=CH2
alc . NaOH
RCH=CH2 → RC≡CH directly

ii CH2OH
O 3
CH2CH2 O C CH3
CH2OH PBr3 Br KCN CN H3O+, heat

(or PCl5)
O O
OH CH2CH2 O C CH3
COOH LiAlH4 Cl
3 marks
C Common mistakes of the candidates included :
ROH  
→ RCN
KCN or HCN
95 1A 3 e ii
3e Use equations to show how you would carry out the following conversions in the laboratory. For each
conversion, give the reagent(s), conditions and structure of the intermediate compound(s) formed.
ii O O 3
CH2=CH2 to COCH2CH2OC
O
C Cl O O
MnO4- CH2 CH2
CH2 CH2 COCH2CH2OC
OH- OH OH
3 marks
C Some candidates did not state that concentrated sulphuric(VI) acid is needed for the acid-catalyzed esterification if
benzenecarboxylic acid is used.
95 2C 8 b i ii iii
8b Each of the following conversions can be completed in not more than three steps. Use equations to show how you
would carry and each of these conversions in the laboratory. For each conversion, give the reagent(s), conditions,
and structure of the intermediate compound(s)
1 mark for reagents
1 mark for intermediate
C All the conversions could be accomplished in two steps. Many candidates did not state the experimental
conditions for the transformations, e.g., reaction temperature, concentration of the acid or base etc. Common
mistakes were as follows :
i NO2 OH 3
CH3 CH3
NO2 Fe or Zn in dil. HCl NH2 OH

Sn in conc. HCl NaNO2, HCl
LiAlH4 or HNO2
Na or K in EtOH 0 - 5 °C
CH3 H2 with Pt or Ni CH3 CH3
3 marks
C HNO3 instead of HNO2 was given. Direct conversion of the nitrobenzene into the phenol without going through
the amine stage was erroneously given.
ii CH3CHCH3 3
CH3CH2CH2OH
OH
conc. H2SO4 or Al2O3 H3O+ or H+ or H2O, heat CH3CHCH3

CH3CH2CH2OH CH3 CH CH2
heat or conc. H2SO4, H2O OH
3 marks
C NaOH was wrongly used as the dehydrating agent. Aqueous KOH or NaOH was wrongly used for the
dehydrohalogenation, but alcoholic metal hydroxide for the substitution reaction. Nucleophilic displacement of
secondary alkyl halides is not of high preparative value because the reaction is generally low-yielding due the
competing yet facile elimination. Heating is necessary in the dehydration of alkanol with concentrated H2SO4 and
in the hydrolysis of alkene. Some candidates wrongly used H+ as the reagent for acid hydrolysis instead of H2O/H+
or H3O+. They did not realize that the reactant for the hydrolysis is water and H+ is just a catalyst. The following
examples should illustrate the point.
+ OH
H2O / H
CH3CH CH2 CH3CHCH3
+ OCH3
CH3OH / H
CH3CH CH2 CH3CHCH3
iii OH 3
CHO
H C CO2H
NO2
NO2
OH OH
CHO
H C CN H C CO2H
NaCN / H+ H3O+ or H+ / H2O
or HCN heat
NO2
NO2 NO2
3 marks
C Again H+ was used as the reagent for acid hydrolysis of the nitrile group and the important condition, heating, was
omitted.
98 2B 6 c i
6c 2-Ethanoyloxybenzoic acid (aspirin) is one of the most common substances used to relieve pain.
CO2H
OCOCH3
2-ethanoyloxybenzoic acid
i Outline a synthetic route for preparing 2-ethanoyloxybenzoic acid from 2-methylphenol.
99 2B 7 b ii
7b With no more than four steps, outline a synthetic route to accomplish each of the following transformations. In
each step, give the reagent(s) used, the conditions required and the structure of the product.
ii OH
CH2NH2
C CH3
H
CH3O
CH3O
Organic Laboratory Technique
I. Purification of organic compound
B. Steam distillation
C. Chromatography
II. Use of quickfit apparatus
B. Different setup of quickfit apparatus
1. Reflux setup
2. Distillation setup
III. Testing for purity

Organic Laboratory Techniques Unit 1 Page 1
Topic Organic Laboratory Techniques Unit 1
Reference 29.1.1
Reading Modern Physical Chemistry ELBS pg.
Chemistry in Context, 3rd Edition ELBS pg.
Physical Chemistry, Fillans pg.
Assignment
Reading
Syllabus solvent extraction
Notes I. Purification of organic compound
Technique of solvent extraction is commonly used to purify organic compound. It has an

advantage that no heating is required. This is particularly important to some heat sensitive
compounds which decompose easily upon heating.
Water and ether are the solvents commonly used. They are immiscible with each other.
Moreover, ether is a very volatile solvent which can be evaporized by a warm water bath / at
reduced pressure to obtain the pure solute dissolved in it.
Precaution : Since ether is very volatile, a pressure may build up inside the separating funnel
while being shaken. The pressure should be released occasionally by opening
the tap, especially, at the beginning of the extraction process when there is a lot
of air inside the flask.
Theoretically, in solvent extraction, a solute will partition between the two solvents.
Practically, the solute is usually more soluble in one solvent than another.
For example, if a brown iodine solution in KI(aq) is shaken with ether. The brown aqueous
layer will turn to pale yellow while the ethereal layer will turn to deep purple. This is because
iodine is much more soluble in ether than in KI(aq).
The following are the solubilities of some organic compounds :
More soluble in aqueous (polar) solvent More soluble in organic (non-polar) solvent
Salt of an organic acid Organic acid
e.g. sodium benzoate, sodium phenoxide e.g. benzoic acid, phenol
Salt of an organic base Organic base
e.g. benzenammonium chloride e.g. benzenamine
Small alkanol Large alkanol
e.g. ethanol e.g. phenol, decan-1-ol
Solvent extraction separates different components in a

solution by their difference in solubility.
For an aqueous solution containing ethanol(more water

soluble) and benzoic acid(more ether soluble), benzoic
acid can be extracted by shaking the solution with ether.
Eventually, the ether layer is evaporated to obtain pure
solid benzoic acid.
However, if the two solutes have similar solubility in

both aqueous and organic solvent, the solutes must be
converted to other derivatives with different solubility
first.
For example, both benzoic acid and phenol are very soluble in ether but not very soluble in water. However,
benzoic acid is more acidic than phenol, benzoic acid reacts with sodium carbonate but phenol does not. Benzoic
acid and phenol in an ethereal solution can be separated by converting benzoic acid to sodium benzoate first. This
can be done by shaking the ethereal solution with aqueous sodium carbonate solution.
An insoluble organic acid can

easily be converted to a
soluble salt by reacting with
an alkali. For a relatively
strong acid, e.g. benzoic acid,
a weak base, like sodium
hydrogencarbonate, is usually
used to neutralized the acid.
For a very weak acid, e.g.
phenol, a very strong base,
like sodium hydroxide, must
be used.
After the separation have

been done, the benzoic acid
can be regenerated by adding
hydrochloric acid to sodium
benzoate. And the benzoic
acid is then extracted with
ether again.
Glossary solvent extraction partition ethereal layer aqueous layer
Past Paper 90 1B 4 a
Question 91 1B 5 a i
92 1B 5 b
94 1A 3 a i
96 1A 3 e
97 1B 8 b
98 1B 8 c
99 2B 6 a ii
90 1B 4 a
CH3
OH NH2
Br
X Y Z
b.p. 182°C b.p. 184°C b.p. 184°C
4a Outline a chemical method to separate X, Y and Z from each other. 4

Two methods are possible:
Method I
Dissolve the mixture in diethyl ether, place in a separating funnel and shake with dil. HCl and separate. The ether
layer will contain X and Z, the aqueous layer will contain Y. 1 mark
To aqueous layer add dil. alkali (NaOH), ether and separate - the ether layer on evaporation will yield the amine
Y. 1 mark
To ether layer containing X and Z, add dil. alkali, and shake, separate. Ether layer will contain Z. 1 mark
Neutralize alkaline layer with acid (dil. HCl) and extract with ether which on evaporation will yield X. 1 mark
Method II
Dissolve the mixture in diethyl ether using a separating funnel. Shake with NaOH and separate. 1 mark
Acidify (HCl) the aqueous layer and extract with ether to obtain X. 1 mark
Acidify (dil. HCl) the other layer (from NaOH extraction), shake and separate. The ether layer will contain Z.
1 mark
Add NaOH or alkali to this aqueous layer and extract with ether. The ether layer contains Y. 1 mark
Answers which separate by fractional distillation of X, Y, Z. (0 mark)
If no solvent (-1 mark)
If in doubt, ask ‘will separation succeed?”. If yes award mark, if maybe award ½ mark, if no then 0 mark.
C Some extraordinary answers were given (e.g. using Na or HNO2, or not using any solvent in the separation
process) showing absolutely no training in this basic technique.
91 1B 5 a i
5a CH3 CH3
NH2 NO2
X Y
i If, in this reaction, some Y remains unreacted, suggest a procedure to isolate pure X from the reaction mixture. 4
The reaction mixture would contain X, Y, HCl and Sn which need to be separated. 1 mark
Firstly remove Sn by filtration and Y by extraction with ether. 1 mark
Followed by basification with NaOH of the aqueous layer and extraction with ether 1½ mark
(Instead of ether extraction, distillation / steam distillation may be used.)
Evaporation of ether gives X. ½ mark
C This kind of basic organic process is still not well answered.
92 1B 5 b
5b An incomplete reaction of an amine with ethanoic anhydride gave a liquid mixture on cooling. Briefly outline a 3
procedure, using a separating funnel and appropriate reagent(s), to isolate the ethanoylation product.
The mixture contains phenylamine, ethanoic acid, ethanoic anhydride and N-phenylethanamide.
Use acid/base separation technique and hydrolyse all anhydride to acid.
Procedure:
Shake mixture with dil. HCl and ether. Remove ether layer, it contains N-phenylethanamide and ethanoic acid.
All ethanoic anhydride have been converted to ethanoic acid with phenylamine forming a salt which is water
soluble.
Shake resultant ether layer with dil. alkali (or Na2CO3 or NaHCO3). The alkali forms a salt with ethanoic acid
which is water soluble. Remove ether layer which contains only N-phenylethanamide. In this way,
N-phenylethanamide is isolated from other parts present in the mixture. ½ mark for each underlined
C Use of separating funnel - very weak. This basic organic technique had obviously never been experienced by
students. Every student should do at least one separation. Most answers had no solvent (ether) for example.
Candidates can learn more about the separation of mixtures either through laboratory work or by the use of flow
charts.
94 1A 3 a i
OH and
C D
i Explain how you would separate a mixture of C and D making use of the difference in their chemical properties 3
and solubility.
Add dil.(aq) HCl and (diethyl) ether to C + D 1 mark
Separate the layers (using a separating funnel ½ mark
In aq. HCl layer – D 1 mark
In ether layer – C ½ mark
In place of HCl, H2SO4 can be used
In place of ether, CHCl3, CH2Cl2
OR
If D forms salts with HCl and soluble in H2O while C does not only 2 marks
If D may be recovered by addition of alkali (extracting with ether, drying and evaporation) ½ bonus mark
C Quite a number of candidates did not realize the difference in the basicity of the two compounds. Some did not
even know how to carry out a solvent extraction.
96 1A 3 e
3e The structures of compounds A and B are shown below : 3
OH OH
A B
Outline a laboratory method, based on a difference in their chemical properties, to separate a mixture of A and B .
mixture of A and B
shake with NaOH(aq)

and ether / CHCl3 / CCl4 / CH3CCl3
O-Na+ OH
aqueous layer ether layer
add acid evaporate / distill ether

OH OH
A B
(Accept answer in form of paragraph.)
C Generally well-answered, except that some candidates erroneously used NaHCO3 instead of NaOH for the
separation, and some gave a test to distinguish between A and B instead of a method to separate them from a
mixture.
97 1B 8 b
8b You are provided with a mixture of two liquids, hexan-1-amine (U) and ethyl ethanoate (W).
Outline an experimental procedure, based on a solvent extraction process, to enable U to be separated from W.
98 1B 8 c
8c You are provided with a mixture of two liquids, heptanoic acid and hexan-3-one. Outline an experimental
procedure, based on a solvent extraction process, to isolate pure heptanoic acid in good yield.
99 2B 6 a ii
6a O
Cl NH2 Cl NH CCH3
ii Based on the fact that the amino group of 4-chlorophenylamine is more basic than the amide group of N-(4-
chlorophenyl)ethanamide, outline a procedure to separate a mixture of the two compounds.
Reference 29.1.2–29.1.5
Assignment
Reading
Syllabus Steam distillation

Chromatography
Recrystallization
Filtration and suction filtration
Notes B. Steam distillation (Refer to Phase Equilibria – Unit 4)
Setup of steam distillation
Steam distillation is used in the purification of organic compound which is insoluble in water. The presence of
water lowers the boiling point of the mixture to avoid decomposition of the compound.
C. Chromatography (Refer to Phase Equlibria – Unit 5)
Paper chromatography is usually used to separate a mixture of compounds for identification purpose. Nevertheless,
chromatography can also be used for separation purpose in larger scale. However, gas chromatography or column
chromatography would be used instead.
A solute starts to crystallize from a solution if the solution is saturated. The amount of solute that can be dissolved
in a solvent is depending on the amount of solvent and the temperature of the solvent. Therefore, it is possible to
make a solution saturated by reducing the amount of solvent (by evaporation) or by lowering the temperature
(lowering the solubility by cooling).
The size of the crystal is depending on the speed of crystallization, not the method of crystallization. Although a
large crystal are usually prepared by evaporation, indeed, if a saturated solution is allowed to cool down very
slowly, a large crystal can also be obtained.
Recrystallization enhances the purity of a crystal. For example, a crystal containing 95% sodium chloride and 5%
sugar can be purified by using a minimium amount of hot water to dissolve the crystal and recrystallizing the
crystal. The solution prepared would have a very high concentration of sodium chloride (95%) and a very low
concentration of sugar (5%). Upon recrystallization, the solution will become saturated with sodium chloride but
not with sugar. The sugar will remain in solution form. And the purity of the sodium chloride crystal obtained
would be higher, say (99.5%).
Filtration is used to separate an insoluble

substance from a liquid. However, the
speed of filtration may be very slow if the
solid to be filtered is very fine. The process
can be speeded up by using suction i.e.
suction filtration.
The suction flask is connected to a filter

pump to generate a partial vacuum. A filter
paper is placed onto the Buchner funnel
with a few drops of solvent sticking the
filter paper in place. The pump is switched
on and the mixture to be filtered is placed Suction filtration
in the Buchner funnel.
When the filtration is done, it is important to disconnect the filter pump from the suction flask before switching off
the water tap. Otherwise, the partial vacuum in the suction flask may draw the water from the tap into the flask and
contaminate the filtrate.
Glossary steam distillation chromatography gas chromatography column chromatography

recrystallzation suction filtration filter pump Buchner flask
Past Paper 92 1B 5 a iii

Question 95 1B 4 b i
92 1B 5 a iii
iii Suggest one method for the isolation of the product from the reaction mixture. 2
I Throw the mixture into ice-water. The product with m.p. 114ºC which is insoluble in water will precipitate.
Filter and wash with cold water. 2 marks
or
II. Boil off all the reagent and by-product, leaving the high boiling (304ºC) product. 2 marks
95 1B 4 b i
4b i Describe the experimental procedure by which you would recrystallize a sample of impure benzoic acid 3
Dissolve in minimium quantity of hot (boiling) water using boiling tube / conical flask. ½ + ½ mark
Filter the solution while it is hot through fluted filter paper into beaker / conical flask. ½ mark
Leave for crystals to form (scratch side, seed..) ½ mark
Filter crystals off and wash with minimium amount of cold water. ½ mark
Dry between filter papers until not damp ½ mark
C The recrystallization of benzoic acid requires the minimum quantity of hot water. Many candidates . confused
solvent extraction and fractional distillation with recrystallization.
Reference 29.2
Assignment
Reading
Notes II. Use of quickfit apparatus
Quickfit apparatuses of the same set have identical junction size. All joints are finished with ground glass. When
different pieces are connected, the junctions are air tight.
Names of different pieces quickfit apparatus
1. Pear shaped flask

2. Stillhead
3. Liebig condenser
4. Screwcap adapter
5. Receiver adapter
6. Thermometer
7. Dropping funnel with Rotaflo tap
8. Stopper
9. Air leak / steam inlet tube
10. Round bottom flask
11. Air condenser / drying tube
12. Sintered glass funnel
13. Drying tube
14. Pear shaped flask with angled side neck
15. Air leak / steam inlet tube
16. Adapter with 'T' connection
17. Screwcap adapter
Cleaning
See that the ground surfaces are absolutely free from dirt before use.
Lubrication
For many preparations ground glass joints can be used unlubricated, but for reactions at high temperature apply a
small amount of lubricant to the top portion of the cone only to ensure easily disassembly of the setup.
Methods of Heating
Use direct heating with a small flame whenever possible. Adjust the bunsen flame to a height of about 2 cm. Keep
the tip of the flame about 3 cm from the base of the flask so that heaing is, in effect, by an air bath.
Smooth boiling can be induced, if necessary, by adding antibumping granules.
Clamping
Supporting rather than clamping should always be the principle with assemblies of glassware. The clamping should
not be too tight since the glassware will expand upon heating. Where more than one clamp has to be used, a hint is
always to adjust and tighted the bosshead on the clamp, and finally on the stand.
It is advisable is fix the flask to be heated first because its position is depending on the position of the bunsen
burner.
Seizure – sticking of joints

Strong alkali should never be allowed to remain in contact with a joint face. Its attack on the matt surface is quite
rapid and it left between two ground surfaces sticking them together very effectively.
Disassembly of the joints while apparatus is still warm and application of a little lubricant are recommended for
prevention of seizure.
If the joints are stuck together, they may be separated by i) rocking the cone in the socket,
ii) tapping the socket flange on a wooden surface,
iii) heating the socket and not the cone in a localized
flame.
C. Different setup of quickfit apparatus
1. Reflux setup 2. Distillation setup

Glossary quickfit apparatus ground surface seizure
Past Paper 92 1B 5 a i
Question
92 1B 5 a i
i With the aid of a labelled diagram, show the laboratory apparatus required to carry out the above reaction. 2
½ mark for each piece of apparatus

C Many did not know the difference between reflux and fractional distillation. Generally very poorly answered.
Experimental knowledge and labelling poor. It is obvious that few have used the apparatus in a laboratory.
Reference 29.3
Assignment
Reading
Syllabus Melting point determination

Boiling point determination
Notes III. Testing for purity
A pure substance has a sharp melting point but a mixture

does not melts sharply. According to this behaviour, the
purity of a substance can be tested. Furthermore, the
presence of impurity will also lower the melting point of the
mixture.
Example 1
Pure ice melts at 0ºC but a mixture of salt and ice melts at
about -20ºC to 25ºC . This phenomenon is called depression
of melting point by an impurity.
Example 2
Pure octadecan-1-ol melts at 58ºC and pure napth-1-ol melts
at 120ºC.
Experimentally, pure octadecan-1-ol will start to melts at
57.5ºC and when the temperature reaches 58.5ºC, all solid
will be melted.
If it is mixed with a little napth-1-ol, the mixture will start to
melts at 50ºC and will melts completely at 55ºC.
By knowing whether a substance melts sharply or not, the purity of the substance can be tested. A pure substance
only has a very narrow melting range.
Unlike melting point determination, a sharp boiling

point may not represent a pure sample. A constant
boiling liquid may be an azeotropic mixture of two
substances.
However, boiling point can be used as a kind of positive

confirmation of the identity of an unknown sample.
For example, if the boiling point of a liquid is 103ºC,

the liquid must not be water.
Glossary determination of melting point depression of melting point determination of boiling point
Past Paper 95 1B 4 b i ii 95 1B 4 c
Question
95 1B 4 b i ii
4b i Describe the experimental procedure by which you would recrystallize a sample of impure benzoic acid 3
Dissolve in minimium quantity of hot (boiling) water using boiling tube / conical flask. ½ + ½ mark
Filter the solution while it is hot through fluted filter paper into beaker / conical flask. ½ mark
Leave for crystals to form (scratch side, seed..) ½ mark
Filter crystals off and wash with minimium amount of cold water. ½ mark
Dry between filter papers until not damp ½ mark
C The recrystallization of benzoic acid requires the minimum quantity of hot water. Many candidates . confused
solvent extraction and fractional distillation with recrystallization.
ii How would you test the purity of the product obtained in (i) ? 1
Use melting point determination, compare with literature value ½ + ½ mark
or the crystals should have sharp melting point ½ + ½ mark
or mix with pure benzoic acid, and determine the m.p. of the mixture ½ + ½ mark
or carry out further recrystallization, until the products obtained have a consistent m.p. ½ + ½ mark

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Topic Reference Reading from Solomons, Organic Chemistry 6th edition

Acid-Base Theory (Unit 1) 90-93, 96-101

Chain propagation (chain propagating step)

Chain termination (chain terminating step)

A mixture of products would be obtained.

II. Alkenes and alkynes

1. Reaction with bromine in CCl4

2. Reaction with bromine water

3. Reaction with hydrogen bromide

4. Reaction with conc. sulphuric(VI) acid

5. Reaction with water

6. Catalytic hydrogenation of oil

C. Oxidation cleavage of double bond

3-ethyl-2-methylpent-2-ene pentan-3-one propanone

a) Reaction with cold acidic or alkaline permanganate solution

Chain propagating step

Chain terminating step

III. Aromatic hydrocarbons

benzenesulphonic acid sodium phenoxide phenol

alkylbenzene benzenecarboxylic acid

1. Reaction with sodium hydroxide

2. Reaction with potassium cyanide

3. Reaction with ammonia

4. Reaction with alkoxide

5. Reaction with carboxylate ion

1. Reaction with alcoholic sodium hydroxide to form alkene

2. Reaction with alcoholic sodium hydroxide to form alkyne

b) by heating with halide salt in acidic medium

7. Distinction between primary, secondary and tertiary alcohols

a) With potassium dichromate(VI)

1. Reaction with sodium

2. Reaction with sodium hydroxide

4. Reaction with bromine

VI. Carbonyl compounds

1. Reaction with hydrogen cyanide

2. Reaction with sodium hydrogensulphate(IV)

1. Reaction with hydroxylamine

Note : 1. A test for aldehyde or ketone.

2. Reaction with 2,4-dinitrophenylhydrazine

C. Oxidation and reduction

1. Oxidation of aldehyde with potassium dichromate(VI)

2. Oxidation of aldehyde with Tollens' reagent

3. Oxidaton of aldehyde with Fehling's reagent

4. Resistance of ketones to oxidation

5. Reduction with sodium tetrahydridoborate / lithium tetrahydrioaluminate

VII. Carboxylic acids and their derivatives

alkylbenzene benzenecarboxylic acid

B. Reactions of carboxylic acid

2. Formation of acyl chloride

6. Reduction with lithium tetrahydridoaluminate

C. Reactions of acyl chlorides and anhydrides

1. Reaction with water

2. Reaction with alcohol

3. Reaction with ammonia

4. Reaction with amine

1. Acid and base-catalysed hydrolyses

2. Reduction with lithium tetrahydridoaluminate

3. Hofmann degradation of non-substituted amide

4. Reduction with lithium tetrahydridoaluminate

VIII. Nitrogen compounds

3. 1º, 2º, 3º amines and quaternary ammonium compounds by alkylation

4. Phenylamine from nitrobenzene

1) Sn, conc. HCl(aq)