Chapter 1.6.

Introduction to
Organic Chemistry
21.1 What is Organic Chemistry?
21.2 The Unique Nature of Carbon
21.3 Classification of Organic Compounds
21.4 Factors Affecting the Physical
Properties of Organic Compounds

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2 New Way Chemistry for Hong Kong A-Level Book 3A
28.1 Types of Reactive Species in Organic Chemistry (SB p.82)

FreeRadicals
Free Radicals

• Electrically neutral atoms or groups of atoms possessing an

unpaired electron

• Highly reactive because of the unstable electronic configuration

e.g.

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28.1 Types of Reactive Species in Organic Chemistry (SB p.82)

Electrophilesand
Electrophiles andNucleophiles
Nucleophiles

Electrophiles
• electron-deficient species that tend to accept electron(s)
• possess an empty orbital to receive the electron pair
• cations or free radicals seeking electron-rich centres

Nucleophiles
• electron-rich species that tend to seek an electron-
deficient site for reaction
• possess lone pairs of electrons
• anions or molecules with lone pairs of electrons
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28.1 Types of Reactive Species in Organic Chemistry (SB p.83)

Electrophile Nucleophile
Molecule
Nature with lone
Cation Free radical Anion
pair of
electrons
Br+, Cl+, H•, Br•, Cl•, Cl–, Br–, I–, H2O, ROH,
NO2+, R+, I•, R•, HO•, RO–, CN–, ROR, NH3,
RCO+, CH2=CHCH2•, OH–, RNH2,
Example RCOO–
SO3H+ R2NH, R3N

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28.1 Types of Reactive Species in Organic Chemistry (SB p.83)

Check Point 28-1

Identify the following chemical species as electrophiles,
nucleophiles, or one that could act as both an electrophile
and a nucleophile.
(a) Cl– (a) (d)
Nucleophile
CH3Cl
(b) Electrophile
(b) C2H5+ (e) NO2 +

(c) Nucleophile Answer

(c) NH3 (d) CH3OH
(d) Electrophile and nucleophile

(e) Electrophile

(f) Electrophile and nucleophile

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28.2 Ways of Breaking Covalent Bond (SB p.83)

Homolysis
Homolysis

A curly arrow with half an arrow head ‘ ’ is used

to indicate the movement of a single electron.

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28.2 Ways of Breaking Covalent Bond (SB p.84)

Energy must be supplied in, either in form of heat or

irradiation with light.

e.g. chlorine undergoes homolysis readily when heated, or

when irradiated with light of a wavelength that can be
absorbed by the molecule to form two chlorine
radicals

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28.2 Ways of Breaking Covalent Bond (SB p.84)

General equation of homolysis of a bond to carbon:

e.g. methane undergoes homolysis to form a methyl

radical and a hydrogen radical

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28.2 Ways of Breaking Covalent Bond (SB p.84)

Heterolysis
Heterolysis

• a curly arrow with a full arrow head ‘ ’ is

used to indicate the movement of an electron pair.

• 2 charged fragments or ions formed

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28.2 Ways of Breaking Covalent Bond (SB p.85)

Heterolysis of a bond requires the bond to be polarized

The greater the difference in electronegativity between

the atoms, the greater is the polarization of the bonds.

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28.2 Ways of Breaking Covalent Bond (SB p.85)

The product of heterolysis of a bond to carbon depends on

the electronegativity of the atom that is bonded to the
carbon atom.

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28.2 Ways of Breaking Covalent Bonds (SB p.85)

Check Point 28-2

Which type of bond fission, homolysis or heterolysis, is most
likely to occur in:
(a) a bond between identical atoms?
(b) a bond between atoms having widely different
electronegativities?
(c) a bond between atoms having similar
(a) Homolysis
electronegativities?
(b) Heterolysis
Answer

(c) Homolysis

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28.3 Inductive and Resonance Effects (SB p.86)

InductiveEffect
Inductive Effect

Due to the difference in electronegativity between two

atoms linked up by  bonds, the bonding electrons will
displace towards the more electronegative atom. The
atom exhibits a partial negative charge.

The electronic effect of a group that is transmitted by the

polarization of electrons in  bonds is called an inductive
effect.

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28.3 Inductive and Resonance Effects (SB p.86)

Inductive effect is represented by an arrow head in the

middle of the covalent bond pointing in the direction of
the displacement of electrons.

Electron-withdrawing Electron-donating group

group (X) exerts a (Y) exerts a positive
negative inductive inductive effect.
effect.

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28.3 Inductive and Resonance Effects (SB p.87)

1. Groups which exert negative inductive effects (i.e.

electron-withdrawing groups):
e.g.

–NO2 > –F > –COOH > –Cl > –Br > –I

2. Groups which exert positive inductive effects (i.e.

electron-releasing groups):
e.g.

alkyl groups like –CH3, –C2H5, –C3H7

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28.3 Inductive and Resonance Effects (SB p.87)

tert-butyl carbocation is the most stable because electron-

donating groups exert positive inductive effects to
reduce the positive charge on the carbon atom.

The greater the number of alkyl groups attached to the

central carbon atom, the more stable is the carbocation.

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28.3 Inductive and Resonance Effects (SB p.87)

ResonanceEffect
Resonance Effect

Resonance effect is an electronic effect involving  bond

electrons or electrons present in unhybridized p
orbitals.

The ion become more stable when the charge of the ion
can be reduced or dispersed.

Resonance structures

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28.3 Inductive and Resonance Effects (SB p.88)

The actual structure of carboxylate ion is the resonance

hybrid of the resonance structures.

• The negative charge of the anion is dispersed

• This resonance stabilization is responsible for the high

acidity of carboxylic acids

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28.3 Inductive and Resonance Effects (SB p.88)

Another example:

Carbocation with the positively charged carbon atom

directly bonded to a benzene ring

Its actual structure is represented by four resonance

structures shown below:

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28.3 Inductive and Resonance Effects (SB p.88)

Example 28-1
The following equations represent the ionizations of two
organic acids:

Solution:
(a) Conjugate base 2 is more stable. The anion is stabilized
by resonance effect and the negative charge of the anion
is dispersed over two oxygen atoms. The two resonance
structures of the anion are shown below:

(a) Which conjugate base is more stable? Explain your answer.

Answer

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28.3 Inductive and Resonance Effects (SB p.88)

Example 28-1 (cont’d)

(b) Which conjugate base is less stable? Explain your answer.
(c) Which is a stronger acid?

Solution:
(b) Conjugate base 1 is less stable because there is no
resonance effect stabilizing the anion. Moreover, the
positive inductive effect of the electron-releasing
CH3CH2– group further destabilizes the anion.

Answer
(c) Acid 2 is a stronger acid than acid 1.

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28.3 Inductive and Resonance Effects (SB p.89)

Check Point 28-3

(a) Draw the two resonance structures for propanoate ion
(CH3CH2COO–).
(b) State whether the following species exhibit positive or
negative inductive effects.
(a)
(i) –I
(ii) –NO2(b) (i) Negative inductive effect
(iii) –COOH (ii) Negative inductive effect Answer

(iv) –C2H5 (iii) Negative inductive effect

(iv) Positive inductive effect

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28.4 Types of Organic Reactions (SB p.90)

SubstitutionReactions
Substitution Reactions

• An atom or a group of atoms of the reactant molecule

is replaced by another atom or group of atoms

• Characteristic reactions of saturated compounds

e.g.
H2O
CH3 – Cl + NaOH  CH3 – OH + NaCl

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28.4 Types of Organic Reactions (SB p.90)

AdditionReactions
Addition Reactions

• Two molecules react to give a single product

• Characteristic reactions of compounds with multiple

bonds

e.g.

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28.4 Types of Organic Reactions (SB p.90)

EliminationReactions
Elimination Reactions

• Atoms or groups of atoms are removed from two

adjacent atoms of the reactant molecule

• Method for preparing compounds with multiple bonds

e.g.

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28.4 Types of Organic Reactions (SB p.91)

CondensationReactions
Condensation Reactions

• Two or more molecules join together, with a small

molecule being removed

e.g.

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28.4 Types of Organic Reactions (SB p.91)

RearrangementReactions
Rearrangement Reactions

• A molecule undergoes reorganization of its constituent

atoms or groups of atoms

e.g.

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 The END

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