J2 H2 Chemistry 2018 8.

INTRODUCTION TO ORGANIC CHEMISTRY

Introduction to Organic Chemistry

• Molecular, structural and empirical formulae
• Functional groups and the naming of organic compounds
• Characteristic organic reactions
• Shapes of organic molecules; σ and π bonds
• Isomerism: structural; geometrical; optical

Learning Outcomes

Candidates should be able to:

(a) interpret, and use the nomenclature, general formulae and displayed formulae of the
following classes of compound:
(i) alkanes, alkenes and arenes
(ii) halogenoalkanes and halogenoarenes
(iii) alcohols (including primary, secondary and tertiary) and phenols
(iv) aldehydes and ketones
(v) carboxylic acids, acyl chlorides and esters
(vi) amines, amides, amino acids and nitriles
(b) interpret, and use the following terminology associated with organic reactions:
(i) functional group
(ii) homolytic and heterolytic fission
(iii) free radical, initiation, propagation, termination
(iv) nucleophile, electrophile
(v) addition, substitution, elimination, hydrolysis
(vi) oxidation and reduction [in equations for organic redox reactions, the symbols [O]
and [H] are acceptable]
(c) describe sp3 hybridisation, as in ethane molecule, sp 2 hybridisation, as in ethene and
benzene molecules, and sp hybridisation, as in ethyne molecule
(d) explain the shapes of, and bond angles in, the ethane, ethene, benzene, and ethyne
molecules in relation to σ and π carbon-carbon bonds
(e) predict the shapes of, and bond angles in, molecules analogous to those specified in
(d)
(f) describe structural isomerism
(g) describe geometrical isomerism in alkenes, and explain its origin in terms of restricted
rotation due to the presence of π bonds [use of E, Z nomenclature is not required]
(h) explain what is meant by a chiral centre
(i) deduce whether a given molecule is optically active based on the presence or
absence of chiral centres and/or a plane of symmetry
(j) recognise that optical isomers have identical physical properties except in the direction
in which they rotate plane-polarised light
(k) recognise that optical isomers have identical chemical properties except in their
interactions with another chiral molecule
(l) recognise that different stereoisomers exhibit different biological properties, for
example in drug action
(m) deduce the possible isomers for an organic molecule of known molecular formula
(n) identify chiral centres and/or geometrical isomerism in a molecule of given structural
formula

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J2 H2 Chemistry 2018 8. INTRODUCTION TO ORGANIC CHEMISTRY

1. Introduction
Organic chemistry relates solely to the chemistry (structure, reaction, properties) of carbon
containing compounds. The topics that will be covered are:

1) Hydrocarbons: alkanes, alkenes, arenes

2) Halogeno-compounds: halogenoalkanes, halogenoarenes
3) Alcohols: primary, secondary and tertiary alcohols and phenols
4) Carbonyl compounds: aldehydes and ketones
5) Carboxylic acids and derivatives: carboxylic acids, acyl chlorides and esters
6) Organic nitrogen compounds: amines, amides, amino acids and nitriles

2. Classification
2.1 Arrangement of the carbon chain

A. Aliphatic molecules contain open (straight or branched) chains of carbon. The chains
may contain single or multiple bonds.

Straight Chained Branched Chain

Butane Butene 2-methylpropane

B. Alicyclic molecules consist of closed rings of cabon atoms. The rings may contain
single or multiple bonds.

Cyclohexane Cyclohexene

C. Aromatic molecules contain at least one benzene ring (ring of 6 carbon atoms where
electrons in p-orbitals are delocalized to form a π electron cloud) (In Chapter 12)

Benzene Phenol Methylbenzene

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J2 H2 Chemistry 2018 8. INTRODUCTION TO ORGANIC CHEMISTRY

4. Types of Formulae
Step 1: Naming the parent chain

1) Identify the longest unbranched carbon chain. This will be the parent chain.

2) The prefix in parent chain name denotes the number of carbon atoms in it.

Prefix Number of Carbon Prefix Number of Carbon

meth- 1 hex- 6
eth- 2 hept- 7
prop- 3 oct- 8
but- 4 non- 9
pent- 5 dec- 10

3) The suffix denotes the name of the functional group. If more than one functional group is
present, the compound is named after the functional group of highest precedence.
Rank Functional Prefix Suffix Example
Group
1 Propanoic acid
Carboxylic acid carboxy- -oic acid
(Highest) CH3 CH2 COOH
Methyl propanoate
2 Ester - R-R’-oate
CH3 CH2 COOCH3
Ethanoyl chloride
3 Acyl Halide - -noyl halide
CH3 COCl
Ethanamide
4 Amide - -amide
CH3 CONH2
Propanyl
5 Aldehyde formyl- -al
CH3 CH2 CHO
Propanone
6 Ketone oxo- -anone
CH3 COCH3
Propanol
7 Alcohol hydroxyl- -ol
CH3CH2CH2OH
Propanamine
8 Amine amino- -amine
CH3CH2CH2NH2
9 Arene phenyl- -benzene -
Propene
10 Alkene (alk)enyl- -ene
CH3 CH=CH2
Propane
11 Alkane (alk)yl- -ane
CH3CH2CH3
12 Halogen Chloropropane
(ha)lo- -
(Lowest) Compounds CH3CH2CH2Cl

Table 1

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J2 H2 Chemistry 2018 9. ALKANES

Alkanes
• Free radical reactions

Learning Outcomes

Candidates should be able to:

(a) recognise the general unreactivity of alkanes, including towards polar reagents

(b) describe the chemistry of alkanes as exemplified by the following reactions of ethane:

(i) combustion

(ii) substitution by chlorine and by bromine

(c) describe the mechanism of free-radical substitution at methyl groups with particular
reference to the initiation, propagation and termination reactions

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J2 H2 Chemistry 2018 9. ALKANES

To get the ratio of monosubstituted alkanes formed:

Consider the reaction of propane with Cl 2:

SAME REACTIVITY

If all the carbon atoms have the same reactivity, there is equal probability of Cl atoms
substituting any of the H atoms.

Since there are 6 positions Cl can substitute to get 1-chloropropane and 2 positions Cl can
substitute to get 2-chloropropane, the ratio of

1-chloropropane : 2-chloropropane
6:2 = 3:1

DIFFERENT REACTIVITY

At low temperatures, reactivity is not the same as the stability of halogenoalkanes increases
from primary < secondary < tertiary halogenoalkanes. Hence, the reactivity of carbon atoms
increases from primary < secondary < tertiary carbon atoms.

The reactivity of primary: secondary: tertiary = 1:4:5.

Hence, for the same reaction at low temperature, we expect 2-chloropropane to be formed
at 4 times the reactivity of 1-chloropropane.

The probability of getting 1-chloropropane is given by the frequency of getting 1-

chloropropane over the total frequency of getting 1-chloropropane and 2-chloropropane,
where frequency = reactivity x number of positions

probability of getting 1-chloropropane = 1 x 6 / (1 x 6 + 4 x 2) = 43%

probability of getting 2-chloropropane = 4 x 2 / (1 x 6 + 4 x 2) = 57%

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J2 H2 Chemistry 2018 9. ALKANES

Carbon Monoxide

Oxidation of carbon monoxide to carbon dioxide

CO + ½ O 2 → CO 2
Hydrocarbon

Complete combustion of hydrocarbon to carbon dioxide and water

C xHy → CO 2 + H2O

5. Ozone Layer Depletion

The ozone layer is a region of Earth's stratosphere that absorbs most of the Sun's ultraviolet
(UV) radiation. It arises from the use of chlorofluorocarbons (CFCs) in aerosols, air-
conditioning systems, refrigerants and in packaging.

CFCs are chemically inert and remain unchanged as they diffuse through the atmosphere.

When they reach the stratosphere, in the presence of UV light, they dissociate to produce
chlorine free radicals.

Step 1: Initiation

CF2Cl2 → Cl· + ·CF2Cl

Step 2: Propagation

The highly reactive Cl · attacks an ozone molecule to form a new radical.

Cl· + O3 → ·OCl + O2

· OCl formed then reacts with oxygen atoms formed from the decomposition of O 3 in the
presence of UV light (O 3 → O2 + O)

·OCl + O → Cl· + O2

Regeneration of Cl · continues to destroy other ozone molecules.

Step 3: Termination

Reaction is terminated when any two free radicals combine.

Cl· + ·Cl → Cl2

ClO· + ·NO2 → ClONO2

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J2 H2 Chemistry 2018 10. ALKENES

Alkenes
 Addition and oxidation reactions

Learning Outcomes

Candidates should be able to:

(a) describe the chemistry of alkenes as exemplified, where relevant, by the following
reactions of ethene:

(i) addition of hydrogen, steam, hydrogen halides and halogens

(ii) oxidation by cold, dilute manganate(VII) ions to form the diol

(iii) oxidation by hot, concentrated manganate(VII) ions leading to the rupture of the
carbon-to-carbon double bond in order to determine the position of alkene linkages
in larger molecules

(b) describe the mechanism of electrophilic addition in alkenes, using bromine/ethene as

an example

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J2 H2 Chemistry 2018 10. ALKENES

4. Physical Properties
Melting and Boiling Points

Trans isomers tend to have higher melting points than cis isomers due to more effective
packing.

Cis isomers tend to have higher boiling points than trans isomers due to stronger
permanent dipole-permanent dipole interactions.

Branching decreases the boiling point of alkenes since there are less contact points for
dispersion forces to act on.

5. Chemical Properties

The C=C bond is composed of a strong sigma bond and a relatively weaker pi bond. The
electrons in the pi bond protrude from the trigonal planar plane, creating a region of
electron cloud as shown below.

This region of high electron density readily attracts electrophiles.

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J2 H2 Chemistry 2018 10. ALKENES

5.1 Electrophilic Addition

The delocalized pi electrons in the C=C bond is electron rich and attracts electrophiles,
which are electron seeking species. These electrophiles are electron deficient and the pi
electrons are donated to form a sigma bond between the carbon in C=C and the
electrophile. This causes the product to be saturated.

+ →

Electrophilic Addition of Halogens (X – Y = X – X)

Reagents: X2 dissolved in CCl 4

Conditions: room temperature, absence of light
Observation: Reddish brown Br 2 decolorises (if X = Br)

Reagents: X2 (aq)
Conditions: room temperature
Observation: Orange Br2 (aq) decolorises (if X = Br)

*Note: To test for alkenes, it is better to use Br 2 (aq) instead of Br 2 in CCl 4 since aqueous Br 2
cannot cause free radical substitution, i.e. decolorisation of Br 2 (aq) is due to the presence of
C=C.

Electrophilic Addition of HX (X – Y = H – X)

Reagents: HX (where X = halogen = F, Cl, Br, I)

Conditions: room temperature

*Note: Rate increases from HF < HCl < HBr < HI because H – X bond strength decreases
down the group.

Electrophilic Addition of H2 (X – Y = H – H)

Reagents: H2 (g)
Conditions: Pt or Ni catalyst, high pressure and temperature

Electrophilic Addition of H2O (X – Y = H – OH)

Reagents: H2O (g)

Conditions: H3PO 4 catalyst, 300oC, 70 atm

OR

Reagents: conc. H 2SO 4, H2O

Conditions: heat

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J2 H2 Chemistry 2018 11. ARENES

Arenes
 Influence of delocalised π electrons on structure and properties
 Substitution reactions with electrophiles
 Oxidation of side-chain

Learning Outcomes

Candidates should be able to:

(a) describe the chemistry of arenes as exemplified by the following reactions of benzene
and methylbenzene:

(i) substitution reactions with chlorine and with bromine

(ii) nitration
(iii) oxidation of the side-chain to give a carboxylic acid

(b) (i) describe the mechanism of electrophilic substitution in arenes, using the mono-
nitration of benzene as an example

(ii) describe the effect of the delocalisation of electrons in arenes in such reactions

(c) predict whether halogenation will occur in the side-chain or aromatic nucleus in arenes
depending on reaction conditions

(d) apply the knowledge of positions of substitution in the electrophilic substitution

reactions of mono- substituted arenes

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J2 H2 Chemistry 2018 11. ARENES

1. Introduction
Arenes are known as aromatic hydrocarbons. They contain at least one benzene ring. The
simplest aromatic hydrocarbon is benzene (C 6H6).

1.1 Structure of Benzene Ring

In the benzene molecule, each carbon atom is sp2 hybridised and has a trigonal planar
geometry, making benzene planar. Each carbon atom has one unhybridised p-orbital
containing one remaining electron which lies perpendicular to the plane of the benzene
ring.

Each p orbital overlaps equally with each of its neighbours, resulting in 6 p electrons
completely delocalized in a two-lobed cloud above and below the ring of carbon atoms.

The six electrons are free to move throughout the delocalized cloud. The delocalization of
the pi electrons leads to extra stability (resonance stabilized) and all the C-C bonds are
identical. The circle in the structural formula of benzene indicates the delocalized cloud of
electrons.

2. Nomenclature

The benzene ring is considered the parent hydrocarbon and the name of the substituent
group is the prefix. In the case of monosubstituted benzenes, the position of the substituent
is understood to be on carbon 1.

Example

Chlorobenzene Methylbenzene Nitrobenzene

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J2 H2 Chemistry 2018 11. ARENES

3.1 Reaction Mechanism of Electrophilic Substitution

Step 1: Generation of electrophile

*Cl + or Br+ or R+ is the electrophile

*AlCl 3 or FeBr 3 “carries” the halogen, leaving behind a positively charged electrophile

Step 2: Formation of carbocation intermediate

Step 3: Restoration of stable ring structure and regenerate catalyst

Step 1: Generation of electrophile

2H2SO4 + HNO3 ⟶ 2HSO4– + NO2+ + H3O+

*NO 2+ is the electrophile

Step 2: Formation of carbocation intermediate

Step 3: Restoration of stable ring structure and regenerate catalyst

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J2 H2 Chemistry 2018 12. HALOGEN DERIVATIVES

Halogen Derivatives
• Halogenoalkanes and halogenoarenes
(i) Nucleophilic substitution
(ii) Elimination
• Relative strength of the C-Hal bond

Learning Outcomes

Candidates should be able to:

(a) recall the chemistry of halogenoalkanes as exemplified by

(i) the following nucleophilic substitution reactions of bromoethane: hydrolysis;

formation of nitriles; formation of primary amines by reaction with ammonia

(ii) the elimination of hydrogen bromide from 2-bromopropane

(b) describe the mechanism of nucleophilic substitutions (by both S N1 and S N 2

mechanisms) in halogenoalkanes

(c) interpret the different reactivities of halogenoalkanes and chlorobenzene with

particular reference to hydrolysis and to the relative strengths of the C-Hal bonds

(d) explain the uses of fluoroalkanes and fluorohalogenoalkanes in terms of their relative
chemical inertness

(e) recognise the concern about the effect of chlorofluoroalkanes (CFCs) on the ozone
layer [the mechanistic details of how CFCs deplete the ozone layer are not required]

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J2 H2 Chemistry 2018 12. HALOGEN DERIVATIVES

1. Introduction
Halogenoalkanes (or alkyl halides) are alkanes with one or more hydrogen atoms being
replaced by halogen atoms F, Cl, Br, I, where the halogen atoms are usually represented as
X.

General formula: CnH2n+1X

Halogenoarenes (or aryl halides) have one or more benzene rings in which one or more
hydrogen atoms on these rings have been replaced by halogen atoms.

More generally, halogen derivatives contain C – X bonds.

1.1 Classification of a Halogenoalkane

Halogenoalkanes can be classified according to the number of R groups attached to the C

atom bonded to the halogen, where R = any alkyl or aryl groups.

Primary (1o) Secondary (1o) Tertiary (1o)

No R groups or 1 R group 2 R groups 3 R groups

1.2 Physical Properties

Boiling points

The main intermolecular forces of interaction between halogenoalkanes are permanent

dipole-permanent dipole interactions and induced dipole - induced dipole interactions.

For halogenoalkanes of the same chain length but different halogens, the melting and
boiling points increase from R – F < R – Cl < R – Br < R – I as the number of electrons
increases from F to I, leading to stronger induced dipole - induced dipole interactions.

Comparing halogenoalkanes and their corresponding alkanes, halogenoalkanes have

higher melting and boiling points due to the polar C – X bonds which result in stronger
permanent dipole-permanent dipole interactions.

Solubility

Halogenoalkanes are generally immiscible with water as the weak permanent dipole -
permanent dipole interactions and induced dipole - induced dipole interactions with water do
not release enough energy to compensate the energy required to overcome the stronger
hydrogen bonds between water molecules.

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J2 H2 Chemistry 2018 12. HALOGEN DERIVATIVES

3.1.1 Reaction Mechanism

There are two reaction mechanisms for nucleophilic substitutions: S N1 (unimolecular

nucleophilic substitution) and S N2 (bimolecular nucleophilic substitution).

The type of mechanism for nucleophilic substitution depends on the halogenoalkane that
undergoes nucleophilic substitution.

SN2 nucleophilic substitution

SN2 nucleophilic substitution involves two molecules (halogenoalkane and nucleophile)

in a single step mechanism. The single step reaction proceeds through a short-lived
transition state.

Reaction Pathway for Negatively Charged Nucleophile

transition state

 The nucleophile approaches the "+ carbon atom from the back directly opposite the
halogen leaving group to form a transition state.

 Since this is a single step reaction that involves two species, we describe this as a S N2
nucleophilic substitution reaction.

 The rate equation for this reaction is determined by the rate-determining step, which is
the single step reaction:

Rate = k [Nu] [halogenoalkane]

 In the transition state, the nucleophile is in the process of bond-forming while the
halogen is in the process of bond breaking with the carbon atom. These partial bonds
are represented with dashed lines ( ------ )

 The final product undergoes an inversion of configuration with the nucleophile

attached to the rear of the carbon instead of the front. If the halogenoalkane was chiral,
the optical isomerism of the product would be reversed.

 Generally, primary halogenoalkanes undergo SN2 mechanism, due to less steric

hindrance by the R groups, which increases the ease of attack by nucleophile on the "+
carbon atom.

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J2 H2 Chemistry 2018 13. HYDROXY COMPOUNDS

HYDROXY COMPOUNDS
• Alcohols (exemplified by ethanol)
(i) Formation of halogenoalkanes
(ii) Reaction with sodium; oxidation; dehydration
(iii) The tri-iodomethane test
• Phenol
(i) Its acidity; reaction with sodium
(ii) Nitration of, and bromination of, the aromatic ring

Learning Outcomes

Candidates should be able to:

(a) recall the chemistry of alcohols, exemplified by ethanol:

(i) combustion
(ii) substitution to give halogenoalkanes
(iii) reaction with sodium
(iv) oxidation to carbonyl compounds and carboxylic acids
(v) dehydration to alkenes

(b) (i) classify hydroxy compounds into primary, secondary and tertiary alcohols
(ii) suggest characteristic distinguishing reactions, e.g. mild oxidation

(c) deduce the presence of a CH3CH(OH)– group in an alcohol from its reaction with
alkaline aqueous iodine to form tri-iodomethane

(d) recall the chemistry of phenol, as exemplified by the following reactions:

(i) with bases
(ii) with sodium
(iii) nitration of, and bromination of, the aromatic ring

(e) explain the relative acidities of water, phenol and ethanol

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J2 H2 Chemistry 2018 13. HYDROXY COMPOUNDS

3. Reactions of Alcohols

There are 5 main reactions of alcohols:

(1) Nucleophilic substitution
(2) Elimination
(3) Acid-metal reaction
(4) Esterification
(5) Oxidation

3.1 Nucleophilic Substitution

3.1.1 Formation of Chloroalkanes

With phosphorous pentachloride PCl5 (s)

R–OH + PCl 5 → R–Cl + POCl 3 + HCl (g)

Reagents: anhydrous PCl 5 (s)

Conditions: Room temperature
Observations: Dense white fumes of HCl evolves

Note: This is a distinguishing test for alcohol.

With thionyl chloride SOCl2 (l)

R–OH + SOCl 2 → R–Cl + SO 2 + HCl (g)

Reagents: SOCl 2 (l)

Conditions: Room temperature
Observations: Dense white fumes of HCl evolves

Note: This is a distinguishing test for alcohol.

With phosphorous trichloride PCl3 (l)

3 R–OH + PCl 3 → 3 R–Cl + H3PO 4

Reagents: PCl 3 (l)

Conditions: Room temperature

With concentrated HCl

R–OH + HCl → R–Cl + H2 O

Reagents: concentrated HCl, anhydrous ZnCl 2(s)

Conditions: Room temperature

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J2 H2 Chemistry 2018 14. CARBONYL COMPOUNDS

CARBONYL COMPOUNDS
• Aldehydes (exemplified by ethanal)
(i) Oxidation to carboxylic acid
(ii) Reaction with hydrogen cyanide
(iii) Characteristic tests for aldehydes

• Ketones (exemplified by propanone and phenylethanone)

(i) Reaction with hydrogen cyanide
(ii) Characteristic tests for ketones

Learning Outcomes

Candidates should be able to:

(a) describe the formation of aldehydes and ketones from, and their reduction to, primary
and secondary alcohols respectively

(b) describe the mechanism of the nucleophilic addition reactions of hydrogen cyanide
with aldehydes and ketones

(c) describe the use of 2,4-dinitrophenylhydrazine (2,4-DNPH) to detect the presence of

carbonyl compounds

(d) deduce the nature (aldehyde or ketone) of an unknown carbonyl compound from the
results of simple tests (i.e. Fehling’s and Tollens’ reagents; ease of oxidation)

(e) describe the reaction of CH 3CO – compounds with alkaline aqueous iodine to give tri-
iodomethane

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J2 H2 Chemistry 2018 14. CARBONYL COMPOUNDS

1.4 Physical Properties

Boiling points

Aldehydes and ketones are polar molecules due to the permanent !+ and !- charges on C
and O atoms in the C=O bond. Hence, the intermolecular forces of attraction between
aldehydes and ketones are permanent dipole-permanent dipole interactions.

For molecules with similar relative molecular mass, Aldehydes and ketones have higher
boiling points than alkanes as alkanes only have weak dispersion forces but lower boiling
points than alcohols as alcohols have hydrogen bonding.

Solubility

Short-chain aldehydes and ketones are soluble in water as they are able to form hydrogen
bonds with water molecules due to lone pairs on O atom in C=O bond.

However, as the number of carbon atoms increases, solubility decreases as the non -polar
hydrocarbon chain is unable to form strong interactions with water.

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J2 H2 Chemistry 2018 14. CARBONYL COMPOUNDS

Note:
• Since the carbonyl carbon is trigonal planar, CN – can attack the carbon from either the
top or bottom at equal probability. Hence, solution formed is racemic and optically
inactive.

• The reaction is a step-up reaction as the number of carbon atoms increase.

• The nitrile group –CN can further react in the following ways:

(1) Acid hydrolysis

R – CN + 2 H2O + H+ → R–COOH + NH4+

Reagents: H2SO 4 (aq)

Conditions: Heat under reflux

(2) Base hydrolysis

R – CN + H2O + OH– → R–COO– + NH3

Reagents: NaOH (aq)

Conditions: Heat under reflux

(3) Reduction
R – CN + 4 [H] → R–CH2NH2

Reagents: LiAlH4 in dry ether

Conditions: Room temperature
OR
Reagents: H2, Pt catalyst
Conditions: high pressure and temperature

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J2 H2 Chemistry 2018 15. CARBOXYLIC ACIDS AND DERIVATIVES

CARBOXYLIC ACIDS AND DERIVATIVES

• Carboxylic acids (exemplified by ethanoic acid and benzoic acid)
(i) Formation from primary alcohols and nitriles
(ii) Salt, ester and acyl chloride formation

• Acyl chlorides (exemplified by ethanoyl chloride)

(i) Ease of hydrolysis compared with alkyl and aryl chlorides
(ii) Reaction with alcohols, phenols and primary amines

• Esters (exemplified by ethyl ethanoate and phenyl benzoate)

(i) Formation from carboxylic acids and from acyl chlorides
(ii) Hydrolysis (under acidic and under basic conditions)

Learning Outcomes

Candidates should be able to:

(a) describe the formation of carboxylic acids from alcohols, aldehydes and nitriles

(b) describe the reactions of carboxylic acids in the formation of

(i) salts
(ii) esters on reaction with alcohols, using ethyl ethanoate as an example
(iii) acyl chlorides, using ethanoyl chloride as an example

(c) explain the acidity of carboxylic acids and of chlorine-substituted ethanoic acids in
terms of their structures

(d) describe the hydrolysis of acyl chlorides

(e) describe the reactions of acyl chlorides with alcohols, phenols and primary amines

(f) explain the relative ease of hydrolysis of acyl chlorides, alkyl chlorides and aryl
chlorides

(g) escribe the formation of esters from acyl chlorides, using phenyl benzoate as an
example

(h) describe the acid and base hydrolyses of esters

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J2 H2 Chemistry 2018 15. CARBOXYLIC ACIDS AND DERIVATIVES

2. Preparation of Carboxylic Acids

2.1 Oxidation of Primary Alcohols or Aldehydes

+ 2[O] → + H2O

+ [O] → + H2O

Reagents: K2Cr2O 7 (aq), H2SO 4 (aq)

Conditions: Heat
Observations: Orange Cr 2O 72– turns green

OR

Reagents: KMnO 4 (aq), H2SO 4 (aq)

Conditions: Heat
Observations: Purple MnO 4– decolorises

2.2 Oxidative Cleavage of Alkenes

Example:

Reagents: KMnO 4 (aq), H2SO 4 (aq)

Conditions: Heat under reflux
Observations: Purple MnO 4– decolorizes

2.3 Hydrolysis of Nitrile Groups (C≡N)

R – CN + 2 H2O + H+ → R–COOH + NH4+

Reagents: H2SO 4 (aq)

Conditions: Heat under reflux

2.4 Hydrolysis of Acyl Chlorides (RCOCl)

RCOCl + H2O → RCOOH + HCl

Reagents: H2O
Conditions: Room temperature
Observations: White fumes of HCl evolved
J2 H2 Chemistry 2018 16. NITROGEN COMPOUNDS

NITROGEN COMPOUNDS
• Amines (exemplified by ethylamine and phenylamine)
(i) Their formation
(ii) Salt formation
(iii) Other reactions of phenylamine
• Amides (exemplified by ethanamide)
(i) Their formation from acyl chlorides
(ii) Their hydrolysis
• Amino acids (exemplified by aminoethanoic acid)
(i) Their acid and base properties
(ii) Zwitterion formation
• Proteins
(i) Protein structure: primary; secondary; tertiary; quaternary structures
(ii) The hydrolysis of proteins
(iii) Denaturation of proteins

Learning Outcomes

Candidates should be able to:

(a) describe the formation of ethylamine and of phenylamine (by the reduction of
nitrobenzene)
(b) explain the basicity of amines
(c) explain the relative basicities of ammonia, ethylamine and phenylamine in terms of
their structures
(d) describe the reaction of phenylamine with aqueous bromine
(e) describe the formation of amides from the reaction between RNH 2 and R'COCl
(f) describe amide hydrolysis on treatment with aqueous alkali or acid
(g) describe the acid/base properties of amino acids and the formation of zwitterions
(h) describe the formation of peptide (amide) bonds between amino acids and, hence,
explain protein formation
(i) list the major functions of proteins in the body
(j) describe the hydrolysis of proteins
(k) explain the term primary structure of proteins
(l) recognise that the twenty amino acids that make up all the proteins in the body are α -
amino acids with the general formula RCH(NH2)CO2H, and be able to interpret the
properties of α-amino acids in terms of the nature of the R group
(m) describe the secondary structure of proteins: α-helix and β-pleated sheet and the
stabilisation of these structures by hydrogen bonding
(n) state the importance of the tertiary protein structure and explain the stabilisation of the
tertiary structure with regard to the R groups in the amino acid residues (ionic
linkages, disulfide bridges, hydrogen bonds and van der Waals’ forces)
(o) describe
(i) the quaternary structure of proteins
(ii) the protein components of haemoglobin
(p) explain denaturation of proteins by heavy metal ions, extremes of temperature and pH
changes
(q) apply the knowledge of the loss and formation of secondary and tertiary structures to
interpret common everyday phenomena

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J2 H2 Chemistry 2018 16. NITROGEN COMPOUNDS

3. Amides
Amides can be classified as primary (1 o), secondary (2 o) and tertiary (3 o) according to the
number of R groups attached to it.

3.1 Physical Properties of Amides

Volatility

Primary and secondary amides have relatively high melting and boiling points due to
extensive intermolecular hydrogen bonding. Most primary amides (except methanamide)
exist as crystalline solids at room temperature.

Tertiary amides have lower boiling points than primary and secondary amides because there
are no N – H bonds available for hydrogen bonding. As such, tertiary amides only have
permanent dipole- permanent dipole interactions and it is easier to overcome this interaction,
hence the lower boiling point.

Solubility

Amides are soluble in water as they form extensive hydrogen bonds with water molecules
due to presence of lone pairs on N atom as well as N–H bonds. As the number of non-polar
groups attached increases, solubility decreases.

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J2 H2 Chemistry 2018 16. NITROGEN COMPOUNDS

Buffer Solution

Amino acids can act as a buffer to resist pH changes.

When a small amount of acid is added, NH 2 group can react with H +:

RNH2 + H+ → RNH3+

When a small amount of base is added, COOH group can react with OH –:

RCOOH + OH– → RCOO – + H2O

4.3 Formation of Peptide Bonds

Amino acids can form peptide bonds (or amide linkage) with another amino acid through the
condensation reaction between the COOH group of one amino acid and the NH 2 group of
another amino acid, with the loss of one water molecule.

The product formed from two amino acids is a dipeptide.

The product formed from three amino acids is a tripeptide.

When many amino acids are joined by peptide bonds, they are called polypeptides.

Proteins are naturally occurring polypeptides formed from over 100 amino acids

Conventionally, we draw the amino acid from the N-terminus to the C-terminus (i.e. NH2
group on the left and COOH group on the right).

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 J2 H2 Chemistry 2018 17. GROUP II

GROUP II
 Similarities and trends in the properties of the Group II metals magnesium to barium and
their compounds

Learning Outcomes

Candidates should be able to:

(a) describe the reactions of the elements with oxygen and water

(b) describe the behaviour of the oxides with water

(c) interpret and explain qualitatively the trend in the thermal stability of the nitrates in
terms of the charge density of the cation and the polarisability of the large anion

(d) interpret, and make predictions from, the trends in physical and chemical properties of
the elements and their compounds

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J2 H2 Chemistry 2018 17. GROUP II

1. Physical Properties of Group II Metals

1.1 Atomic Radii and Ionic Radii

Be Mg Ca Sr Ba
Atomic radius/ nm 0.106 0.140 0.174 0.191 0.198
Ionic radius/ nm 0.030 0.064 0.094 0.110 0.134

Down the group, atomic radii and ionic radii increase.

Nuclear charge increases due to increase in protons. Shielding effect increases due to
increase in number of core electrons. Effective nuclear charge remains relatively constant.
Size of atom increases due to increase in number of principal quantum shell.

1.2 Ionisation Energy

Be Mg Ca Sr Ba
st -1
1 IE (kJ mol ) 899 738 590 550 500

Down the group, first ionization energy decreases.

Size of atom increases due to increase in number of principal quantum shell, resulting in
weaker attraction between the nucleus and valence electron. Less energy is required to
remove the electron from the nucleus.

1.3 Melting and Boiling Points

Be Mg Ca Sr Ba
o
Melting Point ( C) 1283 650 850 770 710

Down the group, melting and boiling points generally decrease.

Ionic radii of metal increases down the group but number of delocalized electrons remain the
same. Weaker electrostatic attraction between the larger cations and the same sea of
delocalized electrons. Hence, less energy is required to overcome the weak metallic bonds.

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J2 H2 Chemistry 2018 18. GROUP VII

GROUP VII
• The similarities and trends in the physical and chemical properties of chlorine, bromine
and iodine
(i) Characteristic physical properties
(ii) The relative reactivity of the elements as oxidising agents
(iii) Some reactions of the halide ions
(iv) The reactions of chlorine with aqueous sodium hydroxide

Learning Outcomes

Candidates should be able to:

(a) describe the trends in volatility and colour of chlorine, bromine and iodine

(b) analyse the volatility of the elements in terms of van der Waals’ forces

(c) describe and deduce from E values the relative reactivity of the elements as oxidising
agents

(d) describe and explain the reactions of the elements with hydrogen

(e) (i) describe and explain the relative thermal stabilities of the hydrides, (ii) interpret
these relative stabilities in terms of bond energies

(f) describe and explain the reactions of halide ions with:

(i) aqueous silver ions followed by aqueous ammonia,

(ii) concentrated sulfuric acid

(g) describe and analyse in terms of changes of oxidation number the reaction of chlorine
with cold, and with hot, aqueous sodium hydroxide

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J2 H2 Chemistry 2018 18. GROUP VII

1.6 Bond Energy

F Cl Br I
Bond Energy of X-X
158 242 193 151
(kJ mol–1)

The bond energy decreases down the group as the atomic size of X increases and bond
length increases.

Exception: F-F bond is weaker than Cl-Cl bond due to interelectronic repulsion experienced
by F atoms due to their small sizes, resulting in a lesser extent of orbital overlap.

2. Chemical Properties
2.1 Oxidising Strength and Reducing Strength

F2 + 2e– ⇌ 2F– E⦵ = + 2.87 V

Cl2 + 2e– ⇌ 2Cl– E⦵ = + 1.36 V
Br2 + 2e– ⇌ 2Br– E⦵ = + 1.07 V
l2 + 2e– ⇌ 2l– E⦵ = + 0.54 V

Reduction potential of X2 decreases down the group.

Consequently,

Oxidising strength of X2 decreases down the group.

Reducing strength of X– increases down the group.

2.2 Reactivity of Halogens

Reactivity of X2 decreases down the group.

Down the group, reduction potential of X2 decreases, hence, it is less likely for X2 to become
X–.

A more reactive halogen can displace a less reactive one from its ion form.

F2 Cl2 Br2 I2
–
Reaction with F No reaction
– –
Reaction with Cl F2 displaces Cl No reaction
– – –
Reaction with Br F2 displaces Br Cl2 displaces Br No reaction
No
Reaction with I– F2 displaces l– Cl2 displaces I– Br2 displaces l– reaction

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J2 H2 Chemistry 2018 18. GROUP VII

Worked Example 1
When aqueous chlorine was added to an unknown sample and the aqueous mixture was
shaken with tetrachloromethane, a violet organic layer was observed. Identify the violet
organic layer and explain the observations.

Worked Example 2
Aqueous potassium iodide is added to a solution of bromine in hexane in a test-tube and the
mixture is shaken. Describe and explain the observations in the above experiment.

2.3 Reaction with Thiosulfate, S2O32–

I2 can oxidise S2O32– to S4O62– as oxidation number changes from +2 to +2.5.

I2 (aq) + 2S2O32– (aq) → 2I– (aq) + S4O62–(aq)

Since Br2 and Cl2 are stronger oxidizing agents, they can oxidise S2O32– to SO42– instead.
Oxidation number changes from +2 to +6.

4Cl2 (aq) + S2O32– (aq) + 5H2O(l) → 2SO42–(aq) + 10H+(aq) + 8Cl–(aq)

4Br2 (aq) + S2O32– (aq) + 5H2O(l) → 2SO42–(aq) + 10H+(aq) + 8Br–(aq)

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J2 H2 Chemistry 2018 19. PERIODICITY

Periodicity
• Periodicity of physical properties of the elements: variation with proton number across
the third Period (sodium to argon) of:
(i) atomic radius and ionic radius
(ii) melting point
(iii) electrical conductivity
(iv) ionization energy

• Periodicity of chemical properties of the elements in the third Period

(i) Reaction of the elements with oxygen and chlorine
(ii) Variation in oxidation number of the oxides (sodium to sulfur only) and of the
chlorides (sodium to phosphorus only)
(iii) Reactions of these oxides and chlorides with water
(iv) Acid/base behaviour of these oxides and the corresponding hydroxides

Learning Outcomes

Candidates should be able to:

(a) describe qualitatively (and indicate the periodicity in) the variations in atomic radius,
ionic radius, melting point and electrical conductivity of the elements (see the Data
Booklet)
(b) explain qualitatively the variation in atomic radius and ionic radius
(c) interpret the variation in melting point and in electrical conductivity in terms of the
presence of simple molecular, giant molecular or metallic bonding in the elements
(d) explain the variation in first ionisation energy
(e) describe the reactions, if any, of the elements with oxygen (to give Na2O; MgO; Al2O3;
P4O6; P4O10; SO2; SO3), and chlorine (to give NaCl; MgCl2; AlCl3; SiCl4; PCl3; PCl5)
(f) state and explain the variation in oxidation number of the oxides and chlorides
(g) describe the reactions of the oxides with water [treatment of peroxides and
superoxides is not required]
(h) describe and explain the acid/base behaviour of oxides and hydroxides, including,
where relevant, amphoteric behaviour in reaction with sodium hydroxide (only) and
acids
(i) describe and explain the reactions of the chlorides with water
(j) interpret the variations and trends in (f), (g), (h), and (i) in terms of bonding and
electronegativity
(k) suggest the types of chemical bonding present in chlorides and oxides from
observations of their chemical and physical properties

In addition, candidates should be able to:

(l) predict the characteristic properties of an element in a given Group by using
knowledge of chemical periodicity
(m) deduce the nature, possible position in the Periodic Table, and identity of unknown
elements from given information of physical and chemical properties

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J2 H2 Chemistry 2018 19. PERIODICITY

1.5 Electrical Conductivity

Na, Mg and Al
• Na, Mg and Al are metals with metallic bonds and they have high conductivity due to
the delocalized sea of electrons
• Electrical conductivity increases from Na to Al due to greater number of delocalized sea
of electrons

Si
• Si exists as a giant covalent structure and is a semi-conductor
• It has a lower conductivity than metals but higher than non-metals

P, S, Cl, Ar
• P, S, Cl and Ar exist as simple molecules and have no mobile charged particles to
conduct electricity.

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J2 H2 Chemistry 2018 19.PERIODICITY

2. Chemical Properties of Elements Across Period

2.1 Diagonal Relationships

A diagonal relationship is said to exist between certain pairs of diagonally adjacent elements
in the second and third periods of the periodic table due to similar charge densities.

Considering the ionic radii, charge density and electronegativity of Li, Mg, Be and Al:

Be Al
Ionic Radii (nm) 0.031 0.050
Charge density 64.5 60
(nm-1)
Electronegativity 1.57 1.61

On moving across a period of the periodic table, the size of the atoms decreases, and on
moving down a group the size of the atoms increases.

Similarly, on moving across the period, the elements become progressively more
covalent, less basic and more electronegative, whereas on moving down the group the
elements become more ionic, more basic and less electronegative.

Thus, on both descending a group and crossing the period by one element, the changes
"cancel" each other out, and diagonal elements have similar chemistry.

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J2 H2 Chemistry 2018 20. TRANSITION METALS

TRANSITION METALS
• General physical and characteristic chemical properties of the first set of transition
elements, titanium to copper
• Colour of complexes

Learning Outcomes

Candidates should be able to:

(a) explain what is meant by a transition element, in terms of d-block elements forming
one or more stable ions with incomplete d orbitals

(b) state the electronic configuration of a first row transition element and of its ions

(c) state that the atomic radii, ionic radii and first ionisation energies of the transition
elements are relatively invariant

(d) contrast, qualitatively, the melting point; density; atomic radius; ionic radius; first
ionisation energy and conductivity of the transition elements with those of calcium as a
typical s-block element

(e) describe the tendency of transition elements to have variable oxidation states

(f) predict from a given electronic configuration, the likely oxidation states of a transition
element

(g) describe and explain the use of Fe3+/Fe2+, MnO4–/Mn2+ and Cr2O72–/Cr3+ as examples
of redox systems

(h) (i) explain the reactions of transition elements with ligands to form complexes,
including the complexes of copper(ΙΙ) ions with water and ammonia
(ii) describe the formation, and state the colour of, these complexes

(i) predict, using E values, the likelihood of redox reactions

(j) explain qualitatively that ligand exchange may occur, including CO/O2 in haemoglobin

(k) explain how some transition elements and/or their compounds can act as catalysts

(l) explain, in terms of d orbital splitting, why transition element complexes are usually
coloured

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J2 H2 Chemistry 2018 20. TRANSITION METALS

(2) When filling a subshell, each orbital must be occupied singly before they are occupied in
pairs.

(3) Each orbital can hold a maximum of 2 electrons with opposite spins.

EXCEPTION:
Half-filled d orbitals are more stable as electronic repulsion is minimized between singly
occupied orbitals. E.g. for Cr atom, electronic configuration should be [Ar] 3d5 4s1 instead of
[Ar] 3d5 4s2.

Instead of

Fully-filled d orbitals are more stable as the subshell has symmetric charge distribution.
E.g. for Cu atom, electronic configuration should be [Ar] 3d10 4s1 instead of [Ar] 3d9 4s2.

Instead of

Example
The electronic configuration of Ti would contain fully filled subshells preceding the 3d
subshell it is in.

1s2 2s2 2p6 3s2 3p6 3d2 4s2

Since Cr is the fourth element of the 3d orbital, the 3d orbital contains 4 electrons.

1s2 2s2 2p6 3s2 3p6 3d4 4s2

Since 3d4 4s2 is the exception stated above, we correct it to 3d5 4s1.

1s2 2s2 2p6 3s2 3p6 3d5 4s1

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J2 H2 Chemistry 2018 20. TRANSITION METALS

4.1.1 Stability of M2+/M3+

The reduction potential of M3+/M2+ can be used to reflect the relative stabilities of the +3 and
+2 oxidation states of the transition elements in aqueous medium. The higher the E⦵, the
more stable M2+ is.

The E⦵ value generally becomes more positive, i.e. metal of +2 oxidation state is more stable
across the period. This is because as nuclear charge increases, it becomes increasingly
difficult for M2+ to lose its 3rd electron.

Anomaly: Fe2+/Fe3+

The dip in E⦵ for Fe is an anomaly, i.e. Fe3+ is more stable than expected.

Fe2+ : [Ar] 3d6

Fe3+ : [Ar] 3d5

It is easier to remove the 3rd electron from Fe2+ because of inter-electronic repulsion in the d6
configuration. Also, a half-filled d subshell is formed in Fe3+ which is more stable.

Anomaly: Cr2+/Cr3+

The dip in E⦵ for Cr is an anomaly, i.e. Cr3+ is more stable than expected.

Cr2+ : [Ar] 3d4

Cr3+ : [Ar] 3d3

Cr3+ has a d3 configuration which is more stable. (Not required in A-level syllabus)

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J2 H2 Chemistry 2018 20. TRANSITION METALS

4.3.6 Effect of Ligand Exchange on Color

Different ligands split the d-orbitals differently, resulting in different energy levels for dd
transition and hence, the color observed would also be different.

4.3.7 Effect of Ligand Exchange on Reduction Potential

Fe3+ + e– ⇌ Fe2+ E⦵ = + 0.77 V

[Fe(CN)6]3– + e– ⇌ [Fe(CN)6]4– E⦵ = + 0.36 V

With the replacement of water ligands by the stronger CN– ligands, the reduction potential
becomes less positive, i.e. tendency for reduction is lower.

This is because reduction involves a gain of electrons and it is energetically less feasible for
a negatively charged species to gain electrons. Furthermore, CN– ligands stabilize the +3
oxidation state of iron, reducing its oxidizing power.

4.3.8 Effect of Ligand Exchange on Biological Functions

Haemoglobin is the iron containing protein that transports oxygen in blood. It contains iron
in the +2 oxidation state.

A haemoglobin molecule (deoxyhaemoglobin) in the lungs picks up an O 2 molecule which is

datively bonded to iron to form a species called oxyhaemoglobin. The bonding is reversible
and enables haemoglobin to transport oxygen around the body.

Carbon monoxide, CO, binds irreversibly with the Fe2+ in haemoglobin to form a stable
complex called carboxyhaemoglobin. The affinity of haemoglobin for CO is about 210 times
stronger than for O2. Hence, a relatively small quantity of CO can inactivate a substantial
fraction of haemoglobin for oxygen transport. If the concentration of CO is high, the level of
carboxyhaemoglobin becomes too high and oxygen transport shuts down resulting in
suffocation. Treatment involves breathing pure oxygen to reverse the binding so that
concentration of O2 overrides the stability factor.

Cyanide ions, on the other hand, bind even more strongly than CO and prevent haemoglobin
from taking up oxygen. Hence, cyanide is considered a poison.

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