UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

STUDENTS SHOULD KNOW HOW TO:

1. Define what a homologous series is

2. State the characteristics of a homologous series
3. Write molecular, fully displayed and condensed formulae of organic compounds
4. Name organic compounds with up to 6 carbon atoms
5. State what is structural isomerism
6. Deduce the number of isomers with a given molecular formula

OBJECTIVES:

1. To use the following terms to explain the wide variety of carbon compounds – high bond
energies, catenation, tetravalency, hybridization and resonance.
2. To deduce the homologous series of organic compounds based on the functional groups
present
3. To state the characteristics of a homologous series
4. To define and write empirical formula, molecular formula, fully displayed formula, condensed
formula and skeletal formula. To convert between different types of formulae.
5. To determine empirical and molecular formulae given mass data or combustion data
6. To apply IUPAC nomenclature to various organic compounds
7. To state the different types of isomerism
8. To deduce the various types of isomers from a given molecular formula

Introduction to organic chemistry

WHAT IS ORGANIC CHEMISTRY?

There is a common misconception that organic compounds are only naturally occurring compounds.
Naturally occurring compounds are considered as organic compounds because they contain carbon
as the main element. The carbon atoms are arranged in chains or rings and are surrounded by other
atoms. Because of this, the living organisms on this planet are called carbon-based lifeforms.

But there are many compounds, like urea, that are derived from living organisms and is also
considered an organic compound. Plastics, which are manmade, are organic compounds.

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

An organic compound is therefore a compound that contains carbon as its main element, which
can be bonded to other carbon atoms or other atoms like hydrogen, oxygen, nitrogen, sulphur,
chlorine, bromine, iodine and fluorine. Organic chemistry is the study of the structures and
properties of such compounds. It includes both naturally occurring substances like proteins,
carbohydrates, fats and ‘essential oils’ and synthetic ones like plastics, dyes, pharmaceuticals and
detergents.

If the organic compound contains carbon and hydrogen alone, it is also referred to
as a hydrocarbon.

CARBON IS AN UNIQUE ELEMENT

There are 5 unique features of carbon which enable it to form such extensive and various organic
compounds.

1. High Bond Energies – the bond energy for a C-C bond is 350kJmol-1. This means that the C-C
bond is relatively stable when compared to other bonds. For example N-N bond energy is
160kJmol-1 and O-O bond energy is 146kJmol-1. Therefore carbon chains are relatively stable
and hence the reason for the various organic compounds.

2. Catenation – this is the ability of carbon compounds to form chains and rings of multiple sizes
examples of such structures are shown below:

These chains and rings are the basis of carbon’s many stable compounds. This kinetic stability
is important because it means that fuels such as petroleum could be stored and the energy is
only released when they are oxidized (combusted).
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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

for a branched-chain organic compound, the alkyl

groups must be in the middle of the principle carbon chain. If the
alkyl groups are on the ends of the chain they are NOT
considered branched- chain compounds

3. Tetravalency – How many single covalent bonds can carbon form?

The bonds that carbon form can be single, double or triple.

Single Single
bonds:bonds: Double bonds: Triple bonds:

C–C C=C C≡C

This tetravalency of carbon atoms means that carbon can have 4 different groups around itself,
which leads to a wide diversity of organic compounds.

4. Hybridisation

HYBRIDISATION ACCOUNTS FOR THE TETRAVALENCY OF CARBON ATOMS

The electronic configuration of the carbon atom is 1s2 2s2 2p2.

In box notation form, the electronic configuration can be written as:
↑ ↑
Energy ↑ ↑↓

↑↓

1s 2s 2p

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

If there are only 2 electrons in the 2p orbitals, then how can carbon provide 4 electrons to make
4 covalent bonds?

This is because hybridization occurs:

In order to be more energetically stable, carbon promotes one of the 2s electrons to the vacant
2pz orbital:

↑ ↑ ↑
Energy ↑ ↑

↑↓

1s 2s 2p

The carbon atom is now said to be in an excited state. The s and p orbitals blend together to
form a hybrid.

The name of the hybrid would be dependent on the number of sigma bonds formed.

Table 1: the hybrid orbitals found in some organic compounds

Name of Structure of compound Orbitals involved in Name/ type of

compound sigma bonding hybrid
Methane
4 σ bonds around a sp3
carbon atom: 1s + 3p

Ethane 4 σ bonds around

each carbon atom: sp3
1s + 3p

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Ethane 3 σ bond around

each carbon atom (1 sp2
π bond): 1s and 2p

Benzene 3 σ bond around

each carbon atom (1 sp2
π bond): 1s and 2p

5. Resonance – this occurs when electrons move around a structure. Take for example the group
below:

C=O

In the double bond between carbon and oxygen, there is one σ and one π bond. Since oxygen is
the more electronegative atom between the two, the electrons in both bonds tend to move
closer to oxygen. This results in oxygen developing a more negative charge than carbon:

C+ - O-

In reality, the electron distribution is somewhere in between these two extremes. Sometimes it
may be a hybrid between the two canonical forms. This hybrid is called a resonance hybrid.
Resonance hybrids can be demonstrated as follows:

Note that a double headed

C=O ↔ C+ - O - arrow is used to demonstrate
resonance in organic
compounds.

ALIPHATIC VS. AROMATIC COMPOUNDS

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Some organic compounds have straight or branched chains only. These compounds are referred to as
aliphatic compounds. Then there are compounds which contain a ring structure with a delocalized pi
system as shown below. These compounds are called aromatic compounds.

Organic compounds that possess the pi

system shown on the right would be
referred to as aromatic compounds or
arenes

HOMOLOGOUS SERIES

Definition of ‘functional group’ – an atom or group of atoms that determine the homologous
series and by extension the chemical properties of the organic compound.
Organic compounds which have the same functional group, belong to the same homologous series.
Table 1 below lists the homologous series to which each functional group belongs.

Table 2: The Homologous Series to which an Organic Compound belongs based on its Functional Group

FUNCTIONAL GROUP NAME OF HOMOLOGOUS SERIES

FUNCTIONAL GROUP
C and H single bonds only Alkane
Carbon to carbon double Alkene
C=C bond

Hydroxyl Alcohol
C OH

Carbonyl carbon Aldehyde

(aldehyde group)

Carbonyl carbon (ketone Ketone

functional group)

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Carboxyl carbon Carboxylic acid

Amino group Amine

Halogen Halogenoalkane
C X

Where X is a halogen (F, Cl, Br, I)

Acyl chloride group (the Acyl chloride
OH of a carboxylic acid
is substituted by a Cl
group)

Ester linkage Ester (Polyester)

Ether linkage Ether

Amide linkage Amide (Polyamides)

Note that R denotes an alkyl group.

Members of a homologous series must have the following characteristics:

 They have the same general formula
 They have the same functional group

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

 They show similar chemical properties because they have the same functional
group
 Each member differs from the previous by CH2 or a mass of approximately 14
 They show a gradual change in density, viscosity, flammability, melting point and
boiling points.

FINDING FUNCTIONAL GROUPS

Students doing organic chemistry need to be able to locate the functional groups in a structure and
hence determine what reactions the structure would undergo and deduce what products will be
formed.

Exercise 1: Look at the structures below and circle and name the functional groups present:

Chocolate

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Caffeine

Oestrogen

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Testosterone

FORMULAE of organic compounds

There are 5 different types of formulae:

1. Empirical formula – this gives the ratio of the atoms present in an organic compound. Eg. CH3
2. Molecular formula – this shows the atoms and the number of atoms present in an organic
compound. Eg. C2H5
3. Structural formula/ displayed formula – this formula shows the bonds and all the atoms

present in an organic compound. Eg.

4. Condensed formula – this shows the arrangement of the atoms in an organic compound only.
It does not show the bond lines. Eg. CH3CH3
5. Skeletal formula – this formula shows the bonds only and the functional groups present in an organic

compound. Eg.

Look at the displayed structure below:

H3C – C – NH2

C2H5

The displayed condensed formula can be written as:

CH3CH(C2H5)NH2

The C2H5 group is written in brackets to indicate that it is below the carbon
atom. Deducing the formula

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Calculating empirical formulae

Example 1: Calculate the empirical formula of a compound containing 8.45% Carbon, 2.11%
hydrogen and 89.44% iodine.

Answer:

Atoms C H I
% 8.45 2.11 89.44
Mass in 100g 8.45 2.11 89.44
No. of moles 8.45 2.11 89.44
12 1 130

= 0.704 = 2.11 = 0.688

0.704 2.11 0.688
Ratio (divide
0.688 0.688 0.688
by lowest
number) = 1.02 = 3.06 =1

Empirical formula = CH3I

Example 2: 6.00g of a hydrocarbon contains 4.80g of carbon and 1.20g of hydrogen. The relative
molecular mass of the hydrocarbon is 30. Work out the molecular formula.

Answer:

Atoms C H
Mass 4.80 1.20
4.80 1.20
No. of moles
12 1

= 0.400 = 1.20
0.400 1.20
Ratio (divide
0.400 0.400
by lowest
number) =1 =3

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Empirical formula is CH3

Mass of empirical formula = 12 + 3 = 15.

30
=2
15

Multiply the atoms in the empirical formula by 2 and we get the molecular formula.

Molecular formula = C2H6

Example 3: Deduce the molecular formula of a hydrocarbon when 25cm3 of it reacts with exactly
125cm3 of oxygen to produce 75cm3 of carbon dioxide.

Answer:

Use the general equation to represent combustion of alkanes and alkenes:

𝑦 𝑦
CxHy + x + 4 O2  xCO2 + H2O
2

Write the volumes obtained 25cm3 125cm3 75cm3

from the question

25 125 75
Find the ratio by dividing by =1 =5 = 3
25 25 25
the smallest number:

So from the ratio, x = 3

𝑦
x + 4 = 5, so we solve for y:

𝑦
=5–3=2
4

y=2x4=8

So CxHy is C3H8

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Example 4: Suppose 10cm3 of a hydrocarbon is combusted with 80cm3 oxygen. After combustion, the
remaining gases were dissolved in sodium hydroxide, after which there was a reduction in the
volume of the gases by 30cm3. The excess oxygen was 30cm3. Determine the molecular formula of the
hydrocarbon.

To answer, we start with the general equation for combustion:

𝑦 𝑦
CxHy + x + 4 O2  xCO2 + H2O
2

Write the volumes obtained 10cm3 80 – 30 30cm3 Note that

from the question
CO2 is the only
= 50 cm3
acidic gas. So
the volume of

Find the ratio by dividing by

10
=1
50
=5
30
= 3 gas dissolved in
10 10 10
the smallest number: alkali would be
the volume of
CO2

So from the ratio, x = 3

𝑦
x + 4 = 5, so we solve for y:

𝑦
=5–3=2
4

y=2x4=8

So CxHy is C3H8

Example 5: Combustion analysis of a 0.18g organic compound containing carbon, hydrogen and
oxygen only was found to produce 0.396g of carbon dioxide and 0.216g of water. Determine its
empirical formula
12 0.108
Mass of carbon in CO2 = 44 x 0.396 = 0.108g. …. No of moles of carbon = = 0.009mol
12

2 0.024
Mass of hydrogen in H2O = 18 x 0.216 = 0.024g… No of moles of hydrogen = = 0.024mol
1

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

0.048
Mass of oxygen = 0.18 – (0.108 + 0.024) = 0.048g… No of moles of oxygen = = 0.003mol
16

Ratio of C : H : O
0.009 0.024 0.003
= : :
0.003 0.003 0.003

= 3 : 8 : 1

Empirical formula is C3H8O

NOMENCLATURE for organic compounds

Many organic compounds may have two names: one is the IUPAC name and the other is a common
name. The IUPAC name is one that is decided by The International Union of Pure and Applied
Chemistry (IUPAC) which is an international group of scientists who address issues concerning
chemistry. They have various rules on naming organic compounds. The rules are listed as follows:

1. Identify the principle carbon chain – this is the chain that contains the longest number of
carbon atoms. Write the prefix that corresponds with the number of carbon atoms.

Number of Carbon Atoms on Principle Prefix

Carbon Chain
1 Meth

2 Eth

3 Prop

4 But

5 Pent

6 Hex

7 Hept

8 Oct

9 Non

10 Dec

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

2. Deduce the main homologous series to which the molecule belongs. Write the
corresponding suffix.

Homologous series Suffix

Alkane -ane
Alkene -ene
Alcohol -anol
Ether Groups followed by the word ether
Aldehyde -anal
Ketone -anone
Carboxylic acid -anoic acid
Amine -amine

For some molecules, the position of the main functional group must be
indicated by a number. These include:

 Alkenes
 Alcohols
 Halogenoalkanes
 Ketones

For aldehydes and carboxylic acids, the functional groups are placed at the end
of the molecule so it is automatically assigned as C1.

In all cases, the main functional group must occupy the lowest possible
number.

3. Locate any secondary functional groups. These are assigned a corresponding prefix

Secondary functional group Prefix

Chlorine chloro
bromine Bromo
fluorine Fluoro
iodine Iodo

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Aromatic ring phenyl

Amine amino
Hydroxyl hydroxy

4. Look for any alkyl branches. These branches are composed of carbon and hydrogen and are
assigned a corresponding prefix based on their structures and the number of carbon atoms

Alkyl branch Prefix

Methyl

Ethyl

Propyl

Isopropyl

Butyl

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Isobutyl

sec-butyl

tert-butyl

5. If the organic compound has more than one different branches and secondary functional
groups, they are stated in alphabetical order along with their position numbers.

6. If the organic compound has more than one of the same functional group, the position
numbers are listed with a comma separating each number followed by a prefix denoting the
number of that group present:
2 – di
3 – tri
4 – tetra

Naming alkanes

1. The suffix ‘-ane’ is used.

2. Any substituents on the chain must be numbered and they must be given the lowest
possible number.
3. If there are more than one of the same substituents present, a prefix must be used to
indicate the amount. For example, if there are 2 then the prefix ‘di-‘must be used.
4. If there is more than one type of substituent, they are listed in alphabetical order
5. If the alkane is a ring structure, then ‘cyclo’ is written before the base name.

Examples:

Structure IUPAC Name Structure IUPAC Name

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

H H ethane Cl CH3 H 1-chloro-2-methyl

H C C C H propane
H C C H
H H H
H H
H H propane H3C 2-methylhexane
CH3
H C C H
CH3
H CH3
H CH3 H 2,2-dimethylpropane H3C CH3 3-phenylpentane
H C C C H
H CH3 H

Naming alkenes
1. The suffix for alkenes is ‘-ene’
2. If there are 2 double bonds, the suffix becomes ‘-adiene’. If there are 3 double bonds, the suffix
becomes ‘-atriene’.
3. The parent chain is the one that has the maximum number of double bonds.
4. The parent chain must be numbered so that the double bond is given the lowest possible
number.
5. If the alkene is a ring structure, then ‘cyclo-‘is included before the base name.

Examples:

Structure Name Structure Name

H3C 2,4-hexadiene H3C 4,4-dimethyl
CH3
pent-1-ene
H3C C CH2 CH CH2

H3C
3-chlorocyclopentene CH3CH=CClCH2CH3 3-chloropent-2-ene

Cl
H H But-2-ene H3C F 2-chloro-3-fluoro-
but-2-ene
H3C CH3 C C

Cl CH3

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Naming alcohols
1. The suffix used for alcohols is ‘-anol’
2. If there are two OH groups, then the suffix ‘-anediol’ is used. If there are 3 OH groups then the
suffix ‘-anetriol’ is used.
3. The hydroxyl group takes precedence over any alkyl groups, halogens or double bonds in the
structure.
4. If there are double bonds present in the alcohol, the suffix becomes ‘-enol’.

Examples:

Structure Name
OH 3-methylpentan-2-ol
H3C CH CH CH2 CH3
CH3
OH 2,3-butanediol
H3C
CH3
OH
OH 2-cyclopenten-1-ol

Naming aldehydes
1. The suffix ‘-anal’ is used.
2. If there are 2 CHO groups present, then the suffix becomes ‘-anedial’.
3. CHO groups must occupy the ends of the chain. It is therefore not necessary to number the
position of the CHO group.
4. If there are double bonds present in the aldehyde, the suffix becomes ‘-enal’.
5. The parent chain is therefore the one that possesses the CHO group.
6. When numbering the aldehyde, the carbonyl functional group is given the lowest possible
number.

Examples:

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Structure Name Structure Name

O Propanal O Benzaldehyde
H3C
H

H3C O 3-methylbutanal H3C CH Ethanal (common

O name: acetaldehyde)
CH3
H2C O 3-methyl-3-butenal O Methanal (common
C name: formaldehyde)
H H
CH3

Naming ketones
1. The suffix for ketones is ‘-anone’.
2. If there are 2 C=O groups present, the suffix is ‘-anedione’. If there are 3 C=O groups present
the suffix is ‘-anetrione’.
3. The position of the C=O group must be written and must have the lowest number possible.
4. If both double bonds and C=O groups are present, the suffix becomes ‘-enone’.

Examples:

Structure Name Structure Name

O Propanone (common H3C O 3-methylpentan-2-one
name: acetone)
C H3C CH3
H3C CH3
O 4,4-dichlorobutan-2- O 3-methyl-3-buten-2-
one H2C one
C CH3
H3C CH2
H3C
CH
Cl Cl
H3C Butan-2-one H3C CH3 2,4-pentanedione
CH3
O O O

Naming carboxylic acids

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

1. The suffix is ‘-anoic acid’.

2. If there are 2 acid groups present then the suffix becomes ‘-anedioic acid’.
3. The COOH groups occupy the ends of the chain and therefore must be given the lowest
possible number. It is not necessary to include the position of the COOH group.
4. If double bonds are present then the suffix ‘-enoic acid’ is used.
5. If the COOH group is attached to a ring, the ring is named and the suffix ‘carboxylic acid’ is
used.

Examples:

Structure Name Structure Name

O Methanoic acid O Benzoic acid
HC (common name: formic
OH acid) OH

O Ethanoic acid OH 2-hydroxybenzoic acid

H3C C (common name: acetic (common name:
OH acid) O salicylic acid)

OH
Cl 3,3-dichloropropanoic H3C O 3-methylbutanoic acid
CH CH2 acid
Cl C OH CH3 OH

O
HO O Ethanedioic acid O 3-butenoic acid
C C (common name: oxalic
O OH acid) HO CH2

Naming esters

1. There are 2 groups attached to the ester linkage. One is the alkyl group and the other is the
acyl group.

2. The alkyl group is written first with the suffix ‘-yl’ being used.

3. The acyl group is written after with the suffix ‘-oate’.

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

O
C R
R O
alkyl group
acyl group

Examples:

Structure Name Structure Name

O Methylpropanoate O ethylbenzoate
H3C CH2 C O CH3
O CH3

H3C CH2 O CH3 ethylbutanoate O

phenylpropanoate
CH2 C CH2
CH3
O O

Naming amines
1. There are groups attached to the amine functional group. They are listed in alphabetical order.
2. If there are more than one of the same alkyl groups attached, then the corresponding prefix is
used.

Examples:

Structure Name Structure Name

H Methylamine CH3 Dimethylamine
N CH3 N
H3C H
H
CH3 Ethylmethylamine CH3 trimethylamine
H3C N N
H H3C CH3

Naming ethers
1. Alkyl groups that are attached to the ether functional group are listed in alphabetical order.
2. If there are more than one of the same alkyl groups present, then the corresponding prefix is
used.

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Examples:

Structure Name
H3C O CH2 CH3 ethylmethylether
H3C O CH3 Dimethylether

Isomerism
There are 2 main types of isomerism – structural isomerism and stereoisomerism. Each type can be
further divided.

STRUCTURAL ISOMERISM – this type of isomerism occurs when organic molecules have the same
molecular formula but different spatial arrangements. There are three types:

1. CHAIN ISOMERISM – there is a difference in the chain length due to branching. For example,
C4H10 can be:

Or

Name: butane Name: 2-methylpropane

2. POSITION ISOMERISM – there is a difference in the position of the functional group. For
example:

Or
Name: propan-2-ol Name: propan-1-ol

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

3. FUNCTIONAL GROUP ISOMERISM

These compounds have the same molecular formula but different functional groups. Take for
example the two compounds below. The molecular formula for each is C2H4O. However, one
has a C=O functional group which makes it a ketone. The second molecule has the –OH
functional group as well as the C=C functional group which makes it an enol. The keto and
enol forms are interchangeable. This type of functional group isomerism is also called keto-
enol tautomerism.

STEREOISOMERISM – stereoisomerism occurs when the sequence of atoms joined on the

structure is the same but the spatial arrangement is different. There are two types of
stereoisomerism – geometric isomerism and optical isomerism.

1. GEOMETRIC ISOMERISM
Consider an organic compound which has only single bonds. These bonds can rotate freely.
For example:

And
Both are considered the same structure.

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

However, for organic compounds in which there is restriction in rotation of a bond,

they become fixed in space. This is applicable to alkenes which have a double bond in their
structure. It is also applicable to ring structures.

Geometrical Isomerism in Alkenes:

The π bond of the double bond restricts rotation of the double bond. Therefore the groups can
either lie above or below the double bond. There are 2 types of isomers: cis and trans.

Cis (Z) isomer: Trans (E) isomer:

Same atoms/ groups of atoms Same atoms/ groups of atoms

are on the same side of the on different sides of the double
double bond bond

Cis-1,2-dichloroethene Trans-1,2-dichloroethene

Geometrical Isomerism in Ring structures:

The ring is locked in a specific configuration. Groups can either be above or below the plane of
the ring.

Geometrical isomers of 1, 2-dimethylcyclobutane:

H3C CH3 cis-1,2-dimethylcyclobutane

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

H3C CH3 trans-1,2-dimethylcyclobutane

2. OPTICAL ISOMERISM
Optical isomers have the same structural formula and the same spatial arrangements,
however, they rotate a plane of polarized light in different directions. In order for a
compound to be considered as optically active, it must have 4 different groups around a
central carbon atom. This carbon atom is referred to as an asymmetrical chiral centre. It is
denoted by an *.

Draw two examples of optical isomers:

1 1
R R

4 C C
R 2 4
R 2 R
3 R 3
R R

These optical isomers are also referred to as enantiomers. They are mirror images of each
other.
A plane of polarized light is light that vibrates in one plane. This is made by passing a beam of
light through a polarizer like a Polaroid sheet.
Enantiomers have similar chemical properties because they have the same groups.
However, their physical properties are different. All naturally occurring glucose molecules are
the D isomers or (+) isomers. Enzymes would be able to recognize the D isomer, however, they
cannot recognize the L isomer. If glucose were to be synthesized in a lab, it would be isomers
in equal amounts. This is called a racemic mixture.

Example

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

OH OH
H3C C* CH2 CH3 H3C CH2 * C CH3
H H

The chiral carbon is the second carbon atom and it is denoted by the symbol *. The enantiomers are
mirror images of each other.

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Name and draw all isomers of the molecular formula C 4H9OH

H H H H

H C C C C OH
butan-1-ol

H H H H

H H H H

H C C C C H

butan-2-ol

H H OH H

H H3C H

H C C C H

2-methylpropan-1-ol
H H OH

H CH3 H

H C C C H

2-methylpropan-2-ol

H OH H

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 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – INTRODUCTION TO ORGANIC CHEMISTRY

Reactions and mechanisms

The reactions of organic compounds do not always go to completion. This is because the rate is
very slow or because dynamic equilibrium is established. Many organic compound are susceptible to
attack in different ways or by different reagents. The conditions and reagents that are present in the
reaction will critically affect the products formed at the end of the reaction. It is not always possible to
write a balanced stoichiometric equation to represent organic reactions. The equations are mostly
used to depict transformations. Conditions and reagents are included on the arrows.

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 NOMENCLATURE for organic compounds
Many organic compounds may have two names: one is the IUPAC name and the
other is a common name. The IUPAC name is one that is decided by The
International Union of Pure and Applied Chemistry (IUPAC) which is an
international group of scientists who address issues concerning chemistry. They have
various rules on naming organic compounds. The rules are listed as follows:

1. Identify the principle carbon chain – this is the chain that contains the
longest number of carbon atoms. Write the prefix that corresponds with the
number of carbon atoms.

Number of Carbon Atoms on Principle Prefix

Carbon Chain
1 Meth

2 Eth

3 Prop

4 But

5 Pent

6 Hex

7 Hept

8 Oct

9 Non

10 Dec

2. Deduce the main homologous series to which the molecule belongs. Write
the corresponding suffix.

Homologous series Suffix

Alkane -ane

Alkene -ene

Alcohol -anol
 Ether Groups followed by the word ether

Aldehyde -anal

Ketone -anone

Carboxylic acid -anoic acid

Amine -amine

3. Locate any secondary functional groups. These are assigned a

corresponding prefix

Secondary functional group Prefix

Chlorine chloro

bromine Bromo

fluorine Fluoro

iodine Iodo

Aromatic ring phenyl

Amine amino
 Hydroxyl hydroxy

4. Look for any alkyl branches. These branches are composed of carbon and
hydrogen and are assigned a corresponding prefix based on their structures
and the number of carbon atoms

Alkyl branch Prefix

Methyl

Ethyl

Propyl

Isopropyl

Butyl

Isobutyl
 sec-butyl

tert-butyl

5. If the organic compound has more than one different branches and
secondary functional groups, they are stated in alphabetical order along
with their position numbers.

6. If the organic compound has more than one of the same functional group,
the position numbers are listed with a comma separating each number
followed by a prefix denoting the number of that group present:
2 – di
3 – tri
4 – tetra
 UNIT 2 CHEMISTRY – ALKANES & ALKENES

General formula CnH2n+2

Functional group Single bonds only

All C-C bonds and C-H bonds are σ bonds. Hence alkanes are said to be saturated. They

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all arrange themselves for maximum separation around the carbon atom, so there is a
tetrahedral arrangement of atoms bound to each carbon atom.
K
R

USES OF ALKANES
1. Fuel – when alkanes are combusted, they produce a high amount of energy.
When sufficient oxygen is present, alkanes would undergo complete combustion,
producing carbon dioxide and water. This is the main use of alkanes. The
combustion of alkanes is useful in all internal combustion engines (those of cars,
planes and ships etc.) A mixture of alkanes is obtained from crude oil and natural
gas.
2. Solvent - Alkanes are non-polar compounds. This means that they can dissolve
non-polar substances (these substances cannot dissolve in water).
3. Chemical Feedstock - alkanes (especially larger ones) can be cracked to form
smaller alkanes and alkenes which can be used to make a variety of organic
compounds.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

PHYSICAL PROPERTIES OF ALKANES

1. ALKANES ARE NON-POLAR – the electronegativities of C and H are 2.5 and
2.1 respectively. There is only a very weak dipole moment that is formed, and
hence alkanes are considered as non-polar substances. They are therefore unable
to form hydrogen bonds with water and are said to be immiscible with water.
This physical property is responsible for the use of alkanes as a non-polar
solvent.
2. ALKANES HAVE LOWER MELTING AND BOILING POINTS – because of
the similar electronegativities that exist between C and H atoms, there is only a

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weak dipole moment that will form. Also, only van der Waals forces will exist
between the atoms of alkanes. This is a weak intermolecular force of attraction
and as such, alkanes would have lower melting and boiling points that other
organic compounds.
As the chain length of alkanes increases, the melting/ boiling points would also
increase as there would be more van der Waals forces.
The attractive forces are so weak that the lower alkanes (C1 – C4) are gases at
room temperature and pressure. Linear molecules of higher homologous series
can align themselves in parallel arrangement so that dipole-dipole and Van der
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Waals forces can operate along the whole molecule. Therefore alkanes from C5 to
C17 are liquids. Alkanes greater than C 17 exist as solids.
Branched- chain alkanes have a lower melting point/boiling point than
straight-chained alkanes. This is because there are less points of contact in
branched alkanes, and as such there would be less van der Waals forces
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3. LIQUID ALKANES ARE LESS DENSE THAN WATER – this is why oil floats
on water. The higher members are more viscous liquids, as there are more
attractive forces between the molecules.

CHEMICAL PROPERTIES OF ALKANES

Because all alkanes are saturated molecules, bond breaking must occur before reaction
with any other reagent can take place. C-C bonds and C-H bonds are also strong and
weakly polar. They require high activation energies which results in alkanes being
unreactive to polar reagents. There are only three reactions which alkanes undergo –
combustion, cracking and halogenation (only in the presence of UV light).

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

COMBUSTION
Alkanes burn exothermically in oxygen. The flame becomes more luminous as the
number of carbon atoms in the alkane increases. If sufficient oxygen is present,
complete combustion occurs. The products are carbon dioxide and water.

If there is insufficient oxygen present, then incomplete combustion occurs. Along with

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carbon dioxide and water, other products are formed such as carbon monoxide and
solid carbon (called soot). Combustion and the release of energy is employed in
internal combustion engines. The high temperatures in the internal combustion engines
lead to nitrogen and oxygen combining to form oxides of nitrogen which are
environmental pollutants.

For example:
K
2C2H6 (g) + 7 O2 (g) 🡪 4CO2 (g) + 6H2O (l)

C3H8 (g) + 5O2 (g) 🡪 3CO2 (g) + 4H2O (l)

Combustion and the release of energy is employed in internal combustion engines.

R

Liquid alkanes, such as octane, must be vapourised before they can be combusted. The
high temperatures of internal combustion engines would ensure this (the hydrocarbons
in gasoline have a boiling point around 150˚C). The high temperatures in the internal
combustion engines lead to nitrogen and oxygen combining to form oxides of nitrogen
which are environmental pollutants.

The hot gases that are formed from combustion of gasoline forces the piston down
which drives the wheels. To obtain maximum energy from the fuel, the ignition of
gasoline vapour must occur when the piston is at the right point, and that all the petrol
vapour is burnt. Because of the high pressures in the system, this might lead to
premature ignition of fuel which will lead to knocking. It is therefore essential that fuels
must have some sort of resistance to knocking. This resistance to knocking is called the
octane rating. Branched hydrocarbons have a higher octane rating than unbranched

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

ones. Tetraethyllead (Pb (C2H5)4) was used to reduce the knocking in unbranched
hydrocarbons. With TEL, dibromoethane must also be added. The combination of these
two resulted in hazardous lead and bromine compounds being emitted from exhaust
pipes. Now, unbranched hydrocarbons are being converted to branched-chain
hydrocarbons using cracking.

CRACKING
At times, there are large alkanes which are relatively not as useful as smaller
fractions. Unfortunately the availability of the smaller fractions rarely meets the

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demands. To rectify this, many of the longer chain hydrocarbons are cracked. Higher
molecular mass alkanes are broken down into lower molecular mass alkanes and
short-chained alkenes. Both C-C and C-H bonds are broken in the process. Bond
breaking is a random process and a variety of products are formed which includes
smaller alkanes, alkenes and hydrogen.

There are 2 types of cracking:

1. Thermal or steam cracking – steam is added to the fractions to be cracked. The

mixture is heated for a fraction of a second and then quenched (cooled very
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quickly). The products are separated by fractional distillation. The temperature
used in cracking will determine the proportions of different chemicals obtained.
For example:
- Cracking of naphtha at 700˚C produces 15% ethene, 15% propene and 30%
high grade gasoline in the products.
- Cracking of naphtha at 900˚C produces 30% ethene and 25% high grade
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gasoline in the products.

The desired products will determine the temperature to be used for thermal
cracking.

2. Catalytic or ‘cat’ cracking – occurs at a lower temperature of 400-500˚C using a

catalyst of SiO2 and Al 2O3.

Examples:

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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Cracking has some advantages:

1) Shorter chained hydrocarbons are produced which are more useful.

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2) Some products are alkenes. Alkenes are more reactive and more suitable for use
as a chemical feedstock for conversion to other useful compounds.
3) Hydrogen gas is produced which has a variety of uses.

HALOGENATION
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Alkanes contain only single bonds and are therefore said to be saturated. Because of
this they are considered unreactive and only undergo substitution reactions.

Alkanes can only react with halogens except iodine under ultraviolet (UV) light.
Because of this dependency on light, the reaction is referred to as a photochemical
reaction. As an example, the reaction between methane and chlorine will be used.

The reaction has three main steps:

1. INITIATION - The bonds between the halogens are broken. Homolytic fission
occurs in the presence of UV light which results in one electron from the covalent
bond moving towards each atom. Each halogen atom is a highly reactive atom
which is called a free radical.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

2. PROPAGATION – Once the free radicals are generated, they react with other
compounds. Any reaction that occurs in which a free radical has reacted and
another free radical is formed at the end of the reaction is part of the propagation
step.

M
K
CH4 (g) + Cl. (g) 🡪 CH3. (g) + HCl(g)

CH3. (g) + Cl2(g) 🡪 CH3Cl (g) + Cl. (g)

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And hence there is substitution of methane to form monochloromethane. This process is

repeated over and over until all four hydrogens are substituted by Cl.

For every photon of light absorbed to generate two Cl˙ free radicals, thousands of CH3Cl
molecules are formed, which then continues the process. The reaction is said to be a
chain reaction.

3. TERMINATION - This describes any reaction in which two free radicals collide
to produce a neutral molecule.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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1 termination reaction occurs for every 10 000 propagation reactions. Since free radicals
are present in very low concentrations compared to other molecules, it is more likely
that a free radical will collide with a molecule than another free radical.
K
Note the following:

1. The C-H and C-Cl bonds are very strong (410 and 350 kJmol-1) respectively as
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compared to the weaker C-Cl bond (240kJmol-1). It is unlikely that a Cl˙ free
radical would take away a Cl from a C-Cl bond to form a weak Cl-Cl bond.
Hemolytic fission of the C-H bond only becomes kinetically feasible if it is
replaced by an even stronger H-Cl bond. Therefore H˙ free radicals are never
formed. So H2(g) is never a product.
2. The wavelength of light used to initiate this process is 400kJmol-1, much stronger
than the 240kJmol-1 required to cleave the Cl-Cl bond. The reaction rate is
therefore determined by the intensity of light (i.e. the number of photons) and
not the energy in the photons. So the greater the intensity of light, the more free
radicals would be generated.
3. In the free radical substitution of methane using chlorine, only a small amount of
ethane would be formed.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

4. Free radical substitution occurs rapidly at 300˚C or in the sunlight at room

temperature. It cannot occur in the dark at room temperature.

General formula CnH2n

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Functional group carbon to carbon double bond (C=C)

Prior to bond formation, three of the four valence electrons in each carbon atom
undergoes hybridization to form sp2 hybrids. The three hybrids arrange themselves
symmetrically about the nucleus in a plane at an angle of 120˚ from each other. The
fourth unhybridised electron occupies a 2p orbital which lies perpendicular to the
plane.
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The two carbon atoms bond with each other using one of the hybrid orbitals. The other
hybrid orbitals combine with other groups. The unhybridised electrons in the 2p
orbitals bond by a sideways overlap forming a π molecular bond.
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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

The double bond consists of both one σ bond and one π bond between two carbon
atoms. The atoms are drawn closer to each other by two bonds while the repulsive
forces between the two nuclei remain the same. Consequently, the C=C bond length is
shorter than the C-C bond length. It is also stronger, however if it is assumed that the σ
bond is the same as for saturated compounds (350 kJmol-1), then the strength of the π
bond is only 260 kJmol-1. Therefore the π bond is weaker than the σ bond.

PHYSICAL PROPERTIES OF ALKENES

● Non-polar compounds due to the presence of carbon and hydrogen atoms only

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and are therefore immiscible with water.
● Going down the homologous series, there is an increase in boiling points and
the alkenes move from gases to solids.
● Alkenes have slightly lower boiling points than their corresponding alkanes.

Why is this so?

● The boiling points of alkenes increase as one goes down the series. The first 3
K
members are colourless gases at r.t.p. The solid alkenes start from C18 onwards.

CHEMICAL PROPERTIES OF ALKENES

COMBUSTION (OXIDATION) OF ALKENES

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Alkenes burn in oxygen exothermically and will burn in excess oxygen to form carbon
dioxide and water.

Alkenes contain a higher proportion of carbon to hydrogen than their corresponding

alkanes. Therefore they tend to burn with a luminous, sometimes smoky flame due to
the incomplete combustion of carbon.

The general equation for the combustion of alkanes by volume can also be
used to determine the formula of an alkene. Recall combustion of alkanes.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

Exercise 2: Write balanced equations to show the combustion of:

1. C2H4(g) + 3 O2(g) 🡪 2CO2(g) + 2 H2O(l)

2. 2C5H10(l) + 15O2(g) 🡪 10CO2(g) + 10H2O(l)

M REACTION WITH H2 (HYDROGENATION OF ALKENES)

When an alkene is mixed with H2, there is no appreciable reaction. However, in the
presence of a catalyst, a rapid reaction occurs in which hydrogen is added to the
structure of the alkene, forming its corresponding alkane. The catalyst is usually either
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nickel, platinum or palladium. The catalyst must be in a finely divided (or powdered
form) to provide a large surface area to adsorb the hydrogen molecules. Often the
catalyst is supported on the surface of an inert material such as charcoal, alumina or
silica.
This process is used in the partial hydrogenation of polyunsaturated fats. Plant oils such
as sunflower seed oil or peanut oil contain many C=C bonds and form a soft margarine.
R

Hydrogenation is done and the process is called hardening, which increases the degree
of saturation of the molecules, producing solids called trans-fats which are harmful and
lead to deposits in the arteries.

Write the product of the hydrogenation of the following alkenes:

1. C4H8 🡪 C4H10

2. CH3CHCH2 🡪 CH3CH2CH3

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

3.

REACTION WITH HALOGENS, HYDROGEN HALIDES AND SULPHURIC ACID

The reactions of alkenes with halogens (such as Cl2, Br2, F2), hydrogen halides (HF, HCl
and HBr) and conc. H2SO4 all follow the same basic mechanism:

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1. The reagent becomes polarized as it approaches the electron dense region of the
double bond. Recall that the double bond has one σ and one π bond.
2. The electrons of the π bond move toward the slightly positive halogen atom. The
bond in the reagent is broken. The result is the formation of a carbocation and the
rest of the reagent is left with a negative charge.
3. The positive carbon atom of the carbocation bonds with the negative part of the
reagent.
4. Since the reagent reacts with an electron rich region in an organic molecule, it is
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termed an electrophile. As the reagent is simply added to the organic molecule,
the reaction is termed as an electrophilic addition.

REACTION WITH HALOGENS (HALOGENATION)

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Alkenes would react with halogens even in the dark because it is an unsaturated
molecule which is trying to become saturated and it has an electron dense region which
attracts electrophiles. The procedure includes bubbling the alkene (or adding liquid
alkene) to a solution of the halogen in a suitable solvent. The solvent can be an inert
solvent (organic solvent) or a polar solvent (such as water). Different products are made
depending on the solvent.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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K
- REACTION WITH Br2(l) IN AN INERT SOLVENT
R

An inert solvent can be an organic non polar solvent. One example is trichloromethane.
The bromine atoms are added to the double bond. The mechanism was illustrated
above.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

REACTION WITH Br2 (aq)

Hydroxide ions are also produced from the dissociation of water, which can substitute
for the Br- ions in the mechanism.

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NOTE: Bromine is a brown liquid whether it is in an inert solvent or aqueous solvent.
Once there is a reaction with bromine, one would observe that it will decolourise (i.e.
from brown to colourless). If the organic compound is immiscible with water and it
reacts with Br2 (aq), one would observe two layers separating. If it reacts with Br2 (l)
then one would observe that there is no separation of layers occurring.
K
R

REACTION OF ALKENES WITH HYDROGEN HALIDES

(HYDROHALOGENATION).

The mechanism for the reaction of an alkene with a hydrogen halide is similar to that of
halogenation wherein a carbocation intermediate is formed. It is also an example of
electrophilic addition.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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K
R

ADDITION OF HYDROGEN HALIDES TO ASYMMETRIC ALKENES

An asymmetric alkene is one in which the molecules differ on either side of the
double bond. When an asymmetric molecule adds to an asymmetric alkene, there are
always 2 possible products – a major product and a minor product. To determine which
is the major and which is the minor product which forms, Markovnikov’s rule is used.
Markovnikov’s rule states:

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

Carbocations can be primary (1°), secondary (2°) or tertiary (3°).

As the number of alkyl groups on the carbocation increases, the relative stability
increases. This is because alkyl groups are electron donating groups and would end up
stabilizing the positive charge on the carbocation. Take for example the reaction of

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propene with HBr:

To which carbon atom would the H add to and which would the Br add to?
K
Answer: H would be added to C1 and Br would be added to C2

REACTION OF ALKENES WITH CONC. SULPHURIC ACID (HYDRATION)

The structural formula of sulphuric acid (H2SO4) is shown below:

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This is another type of electrophilic addition.

The product that is formed is an ester of sulphuric acid. This ester can then be easily
hydrolysed to form ethanol. This reaction is used in petroleum industry to remove small
amounts of alkenes from saturated hydrocarbons. This method is also used in the
manufacture of alkyl sulphate detergents (soapless detergents).

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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K
R

Another set of conditions and reagents can be used to convert an alkene to an alcohol. A
concentrated phosphoric acid catalyst (H3PO4) at a temperature of 300˚C and a pressure
of 60atm. This is an important process in the manufacture of ethanol for laboratory
uses.

In most organic reactions, concentrated sulphuric acid can also be used as a

catalyst and a drying agent. Concentrated sulphuric acid reacts with the organic
compound, but it is reformed at the end of the reaction. Hence, it is termed as a catalyst.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

REACTION WITH ACIDIFIED POTASSIUM MANGANATE (VII)

When KMnO4 is in an acidic environment (KMnO4/H+) it acts as an oxidizing agent. In

organic chemistry, oxidation is easily shown in the addition of oxygen to the compound
(or the removal of hydrogen). Recall that oxidation is also a loss of electrons. As a
general rule of thumb, alkenes can be oxidized to alcohols and then to carbonyl
compounds and then to the carboxylic acid.

[O]
Alkenes Alcohols [O]

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UNDER COLD CONDITIONS

Under cold conditions, KMnO4/H+ is a weaker oxidizing agent. Therefore the alkene is
oxidized and 2OH groups are added across the double bond. This forms a diol
compound. The MnO4- is reduced to colourless Mn2+ or to a brown suspension of
K
MnO2(s) as the purple colour is discharged. This decolourisation of the MnO4- solution
under cold conditions is also a test for the C=C bond, as few organic compounds are
oxidized by this weak oxidizing agent.

For example, the reaction of ethene with KMnO4/H+ under cold conditions:
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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

UNDER HOT CONDITIONS

Under hot conditions, KMnO4/H+ becomes a stronger oxidizing agent. This causes
fission of the C-C double bond to produce a variety of products, such as aldehydes,
ketones and carboxylic acid. CH2 groups attached to the C=C are oxidized to
ethanedioic acid and then to CO2 and H2O

For example:

M
K
R

Describe 2 simple laboratory tests to distinguish between an alkane and an alkene

1. Add Br2 (l) – to a small amount of alkane and alkene in test tubes, add a small amount of
Br2 (l). In the alkene, Br2 (l) would decolourise (colour changes from brown to colourless).
With the alkane there would be no colour change.
2. Add KMnO4/H+ - to a small amount of alkane and alkene in a test tube, add a small
amount of KMnO4/H+. With the alkene, the colour would change from purple to
colourless, while there would be no colour change with the alkane.

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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

INDUSTRIAL IMPORTANCE OF ALKENES

Because of the ease at which alkenes react, they are very important feedstock materials:

1. The wide variety of polymers of alkenes and the derivatives have many uses and
life without them would be very difficult to imagine.
2. Alkenes are easily converted into alcohols which are important industrial
solvents and starting materials to make other products.
3. Ethene and higher straight-chained alkenes are converted to detergents.
4. Ethene can be used to make ethane-1, 2-diol (an engine coolant), ethanoic acid

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(vinegar) and ethanoic anhydride (used in aspirin manufacture).
5. Propene is used to manufacture propanone (acetone) which is another important
solvent.
6. In the manufacture of lubricants whose viscosity do not vary with temperature
K
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 UNIT 2 CHEMISTRY – ALKANES & ALKENES

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K
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 1
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

Halogenoalkanes are organic compounds where at least 1 hydrogen atom is substituted

by a hydrogen atom on an alkane chain. Halogen atoms can be fluorine (F), chlorine
(Cl), bromine (Br) and iodine (I).

Halogenoalkanes can be further divided into three structures – primary, secondary, and
tertiary.

➢ Primary (1˚) halogenoalkanes – where there is 1 alkyl group attached to the

carbon atom bearing the halogen.
➢ Secondary (2˚) halogenoalkanes – where 2 alkyl groups are attached to the
carbon bearing the halogen.
➢ Tertiary (3˚) halogenoalkane – 3 alkyl groups are attached to the carbon atom
bearing the halogen.

Primary Secondary
Secondary Tertiary

Alkyl groups are electron pushing groups. The more alkyl groups the
halogenoalkane has, the more electrons are pushed towards the C-X bond. Therefore,
the halogenoalkane becomes less stable. Therefore 1˚ halogenoalkanes are more stable
than 2˚ which are more stable than 3˚.

1˚ > 2˚ > 3˚
 2
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

PHYSICAL PROPERTIES OF HALOGENOALKANES

• The large electronegativity difference between C and X (the halogen) leads to
their bonds being strongly polar with C-F being the most polar and C-I the least
polar. The number and placement of the bonds determines its overall polarity.
• Boiling temperatures of chloroalkanes and fluoroalkanes are higher than those
of alkanes of similar molecular mass. However, the boiling temperatures of
bromoalkanes and iodoalkanes are lower than those of alkanes of similar
molecular mass.
The halogen atom is an electronegative atom. Therefore, the C-X bond is a polar
one. This leads to permanent dipole-dipole interactions as well as induced
dipole-dipole interactions. These forces do not significantly increase the boiling
point as compared to the corresponding alkanes, which only have van der Waals
forces. This is because as the chain length increases, the influence of the halogen
diminishes, and the boiling points become similar to that of the alkane.
• Halogenoalkanes are slightly soluble in water.
The polar ends of the compounds can interact with water, but the attractive
forces that occur (dipole interactions) are not as strong as hydrogen bonds
present in water. The non-polar ends will not dissolve in water. Therefore,
although they dissolve more than alkanes, they are only slightly soluble.
• Halogenoalkanes have a sweet, slightly sickly smell.
• The vapour of chloro and iodo compounds can be toxic and can be absorbed
through the skin.
• Chloroalkanes are less dense than water, while bromoalkanes and iodoalkanes
are denser than water.
• Halogenoalkanes have a low flammability.

Chemical properties of halogenoalkanes

Because of the polarity of the C-X bond in halogenoalkanes, the C attached to the
halogen has a δ+ charge and is susceptible to nucleophilic attack. Suitable nucleophiles
include molecules like NH3 and H2O and anions like OH- and C≡N- all of which have
lone pairs of electrons.
 3
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

Hydrolysis

Hydrolysis (reaction with water) of halogenoalkanes is a typical one. Usually water has
no effect, but when it is in the presence of a strong alkali (such as NaOH or KOH in
ethanol (as an alcoholic base)), the OH- ion replaces the halogen atom. The
halogenoalkane is refluxed with aqueous alkali for 1 hour. The mechanism of the
reaction depends on the structure of the halogenoalkane. The general equation to
represent the reaction is as follows:

OH - + R-X → R-OH + X -

Hydrolysis of primary halogenoalkanes

- Description of the reaction
1. The C-X bond is a polar one where the halogen atom bears a slight negative charge,
and the carbon atom has a slight positive charge.
2. The lone pairs of electrons on the OH- group from the alkali are attracted to the
carbon atom and attacks it from the opposite side from the halogen atom. This is to
minimise repulsion.
3. A transition state (also called an activated complex) is formed where both the
halogen and the OH group are attached to the carbon atom. This step is the slowest
step of the reaction and hence it is referred to as the rate determining step. The C-X
bond weakens
4. Since the halogen is a weaker nucleophile than OH group, it will leave the structure
and combine with the cation of the base.
5. The result is an ionic salt, and the corresponding alcohol is formed.

• Since the halogen atom is being substituted by an OH group, the reaction is said
to be a nucleophilic substitution reaction. The transition state is bimolecular (as
carbon is attached to both OH and halogen at the same time) and the entire
reaction occurs in a stepwise manner. Such a mechanism is referred to as an SN2
mechanism. (Substitution Nucleophilic Bimolecular).
• The ease of hydrolysis by means of alkali increases as the strength of the C-X
bond decreases. As such, hydrolysis of C-I bond occurs with ease, while
hydrolysis of C-F bond occurs with great difficulty.
 4
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

- The mechanism of the reaction

NaOH → Na+ + OH-

Na+ + Cl- → NaCl

Energy

Reactants

CH3CH2Cl + OH- Products

CH3CH2OH + Cl-

Progress of Reaction
 5
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

NOTE: 100% conversion does not occur, so the reaction is reversible

The rate of the reaction is dependent on both the nucleophile and the
halogenoalkane.

HYDROLYSIS OF TERTIARY HALOGENOALKANES

- DESCRIPTION OF THE REACTION

1. Kinetic studies show that the rate of reaction depends only on the
halogenoalkane and not the nucleophile. The rate determining step must
therefore involve the halogenoalkane alone and not the nucleophile.
2. Because 3˚ carbocations are very stable, it can be formed easily from the
halogenoalkane by eliminating the halogen.
3. The carbocation now combines with the OH- ion.
4. The rate determining step involves only 1 entity, and it occurs in a concerted
manner. This mechanism is therefore an SN1 mechanism (Substitution
Nucleophilic Unimolecular).

- THE MECHANISM
In the space below, illustrate the mechanism of reaction between 2 methyl-2-chloro
propane and sodium hydroxide in ethanol:

NaOH → Na+ + OH-

CH3 CH3
slow + – –
H3C C CH3
rds
H3C C CH3 + Cl + HO

Cl
fast

CH3

H3C C CH3

OH
 6
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

Na+ + Cl- → NaCl

Energy profile diagram:

Uses of halogenoalkanes
1. Solvents – chloroalkanes are widely used as solvents because of their high
solvent power, low volatilities, and low flammability. Both tetracholoroethane
and tetracholoromethane are widely used as dry-cleaning solvents and for
degreasing.
2. Pesticides – bromoethane is a widely used nematocide (pesticide for nematodes
and roundworms).
3. Anaesthetics – chloromethane, chloroethane and trichloromethane (chloroform)
are widely used local anaesthetics. Halothane which has the formula CF3CHBrCl
is a widely used anaesthetic because it has a high volatility, non-flammability
and chemical stability and high potency.
4. Refrigerant – CF2Cl2 (also called CFC) was used as a replacement for ammonia as
a refrigerant gas. It was found that such compounds can lead to destruction of
the ozone layer. Countries like the US banned ‘non-essential uses’ of such
compounds in 1979.
5. Petrol additives – chloroethane is used in the manufacture of tetraethyl lead
which is added to petrol to improve its octane rating. Such compounds are
banned in some countries because of environmental dangers they pose. 1, 2-
dichloro and 1, 2-dibromoethanes act as lead scavengers in fuel. During
 7
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

combustion, they form volatile halides and oxyhalides which are vented through
the car’s exhaust, preventing the accumulation of the lead in engines.

The behaviour of secondary halogenoalkanes is intermediate between

primary and tertiary halogenoalkanes, depending on the nature of the halogenoalkane
and the solvent.

ALCOHOLS
General formula CnH2n+1OH
Functional group OH (hydroxyl group)

Alcohols can be primary, secondary or tertiary.

1˚ alcohol – if the carbon attached the OH group has 1 alkyl group attached to it.

2˚ alcohol – if the carbon attached to the OH group has 2 alkyl groups attached to it.

3˚ alcohol – if the carbon attached to the OH group has 3 alkyl groups attached to it.

Look at the following structures and label them as primary, secondary and
tertiary:

Primary Secondary Tertiary

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

Alcohols with 1 OH group – monohydric alcohols

2 OH groups – dihydric alcohols (diols)

3 OH groups – trihydric alcohols (triols)

More than 3 OH groups – polyhydric alcohols

Physical properties of alcohols

• Alcohols are weak acids. Acidity refers to the ability of a compound to give up
H+ ion. The oxygen atom of the OH group is more electronegative than the
hydrogen – consequently, the O-H bond is polarised and destabilises the bond
and facilitates the loss of the H+ ion. The H+ bears a partial positive charge and is
susceptible to attack by negatively charges species such as the oxygen in water
molecules. As a result, alcohols are weak acids. They can therefore react with
highly reactive metals, such as sodium and potassium to produce a salt and
hydrogen gas.
H H
1 1 –
R C OH R C O
+ H+
H H

It should be noted that alcohols are not strong enough to reaction with bases.

As one moves along the homologous series, the acidity of alcohols decrease.
Also, the few alcohols that actually liberate H+ ions are so mild that they referred
to as being neutral.

• Alcohols are good solvents. Lower alcohols are soluble in water. Molecules of
alcohol can displace molecules of water in the hydrogen-bonded association of
water molecules. The polar OH group enables them to dissolve sodium
hydroxide. The non-polar hydrocarbon part of the molecule enables alcohols to
dissolve non-polar substances like hexane. As the chain length increases the
influence of the OH group on the structure decreases and they become less
soluble in water.
• Boiling points of alcohols are higher than their corresponding alkanes as
increases as one goes down the homologous series. Methanol, ethanol are
 9
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

colourless volatile liquids. Higher members are viscous liquids. The first solid
occurs at C11.
The boiling points are substantially higher than their corresponding alkanes/
halogenoalkanes. This is due to the extensive hydrogen bonding that occurs.

Draw a diagram to show the hydrogen bonding that occurs between two ethanol molecules:

As the number of OH groups increase, so does the degree of hydrogen bonding,

and hence the boiling points and viscosities.

Chemical properties of alcohols

Oxidation

- WITH ACIDIFIED POTASSIUM MANGANATE (VII) AND

ACIDIFIED POTASSIUM DICHROMATE (VI)
 10
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

H H H H H OH
-2[H] [O]
H C C OH H C C H C C

H H O H O
E.g.: H
 11
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

H OH H H O H
-2[H]
H C C C H H C C C H

E.g.: H H H H H

Tertiary alcohols are very difficult to oxidise. With very powerful oxidising agents,
they form a mixture of acids.

Acidified potassium manganate (VII) (KMnO4/H+) is an oxidising agent. A colour

change is observed where the purple manganate (VII) ions are converted to the brown
manganate (IV) ions. After some time, the solution becomes colourless when Mn is
further reduced to the manganate (II) ions

For example: when ethanol reacts with acidified potassium manganite (VII) it is
oxidised to ethanal:

5CH3CH2OH + 2MnO4- + 6H+ warm 5CH3CHO + 2Mn2+ + 8H2O

Further oxidation can occur where ethanol is oxidised to ethanoic acid.

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

With acidified potassium dichromate, the solution changes from orange to green.

For example: ethanol is oxidised by acidified potassium dichromate (VI) to ethanol:

3CH3CH2OH + Cr2O72- + 8H+ warm 3CH3CHO + 2Cr3+ + 7H2O

The chromium (VI) ion which is orange is reduced to the chromium (III) ion which is
green.

Ethanal can also be further oxidised by acidified potassium dichromate (VI) to ethanoic
acid. The reaction of ethanol with acidified potassium dichromate (VI) is the basis of
the breathalyser test.

Esterification
THIS IS A REACTION WITH CARBOXYLIC ACID.
CONDITIONS: CONC. H2SO4 AND HEAT UNDER REFLUX.

Alcohol + Carboxylic acid Ester + Water

Examples:

Methanol + Propanoic acid → Methyl propanoate + water

O H H
O H H
H H C C C H
Δ
C C C H
H C OH + conc. H2SO4 H C O H H + H2O
H HO H H
H
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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

Butanol + methanoic acid → butylmethanoate + water

H
H H
C O O
H
C H Δ H H H H
H C H
H
C
C
+ C H
conc. H2SO4 + H2O
H OH HO H C C C C O
H
H H H H

Esters typically have a sweet smell/ fruity aroma.

Dehydration

REACTION WITH CONC. H2SO4 AT 170˚C

Alcohol + Conc. H2SO4 Alkene

Strong acids can protonate alcohols:

CH2 + H
H3C CH2 + H3C O
OH + H
H

H H H
H
CH2 + H +
H
H3C O H C
+
C + H2O C C +
H
H H H
H

Example:
 14
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

H H
H H
C H C H
OH conc. H2SO4
C 170°C
H H C C
C
H H
H H
H

NOTE: At a lower temperature, an ether is produced.

Cold H2SO4 reacts with a primary alcohol to form an alkylhydrogensulphate

Eg. C2H5OH + H2SO4 → C2H5HSO4 + H2O

If excess H2SO4 is used, and the mixtyre is heated to 170ºC, an alkene is produced.

Eg. C2H5HSO4 → C2H4 + H2SO4

If excess alcohol is used and the mixture is heated to 140ºC, an ether is formed

Eg. C2H5HSO4 + C2H5OH → C2H5OC2H5 + H2SO4

Iodoform reaction

REACTION WITH I2 AND NaOH

A mixture of NaOH and I2 produces the iodate ion (IO-) which is an oxidising agent.

NaOH + I2 H+ + Na+ + I- + IO-

The iodate ion only reacts with a methyl group attached to carbon atom of the following
groups:
 15
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

OR

The resulting compound is oxidised to its corresponding compound which contains 1

less carbon atom.

For example:

Triiodomethane (CHI3) is a pale-yellow precipitate with an antiseptic odour.

NOTE: only a few compounds give a positive iodoform test. These are:

➢ Methylketones :

➢ Secondary alcohols which contain a methyl branch:

➢ Ethanol:
 16
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

➢ Ethanal:

➢ Dimethyl ketone:

Substitution reactions
Few compounds can substitute OH groups because OH groups are not easily displaced.
There are 3 conditions under which substitution occurs:
1. With phosphorus pentachloride (PCl5):

R-OH + PCl5 R-Cl + HCl + POCl3

For example: CH3OH(l) + PCl5(l) → CH3Cl(l) + HCl(g) + POCl3(l)

One can observe fumes of gas being evolved. This gas is HCl vapour which is
acidic.

2. With phosphorus trichloride (PCl3)

3R-OH + PCl3 3R-Cl + H3PO3

For example: 3C2H5OH(l) + PCl3(l) → 3C2H5Cl(l) + H3PO3(aq)

In this case, phosphorous acid is produced which will turn blue litmus red

3. With SOCl2:

R-OH + SOCl2 R-Cl + SO2 + HCl

For example: C3H7OH(l) + SOCl2(l) → C3H7Cl(l) + SO2(g) + HCl(g)

 17
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS –
HALOGENOALKANES & ALCOHOLS

One can observe a gas with an irritating odour being evolved. This gas is SO2, and
it is acidic.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

Carbonyl compounds
Functional group: C=O

There are two major types of carbonyl compounds:

1. ALDEHYDES – the carbonyl carbon is attached to at least one hydrogen atom.
2. KETONES – the carbonyl carbon is not attached to any hydrogen atoms.

PHYSICAL PROPERTIES OF CARBONYL COMPOUNDS

● The boiling points of carbonyl compounds are higher than their corresponding
alkanes or alkenes, but lower than their corresponding alcohols. This is because
there is a permanent dipole-dipole interaction due to the presence of the carbonyl
(C=O) group. However, hydrogen bonding does not occur as there is no
hydrogen directly attached to the electronegative oxygen atom, unlike with
alcohols.
● Methanal (formaldehyde) is the simplest aldehyde and it is used to preserve
biological specimens.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

● C1 – C4 members are miscible with water, but after C5 they become increasingly
immiscible with water. This is because the influence of the hydrocarbon chain
has more influence than the polar carbonyl group.
● The simplest ketone is propanone (acetone) and it mixes readily with water.
KETO-ENOL TAUTOMERISM
Tautomers are structural isomers which can be inter-converted. Ketones and their
corresponding enol (alkene with an OH group) are tautomers of each other. They have
the same molecular formula, however the C=O bond breaks to give C=C as well as the
C-H bond becomes a C-OH group. *Recall isomerism*

Chemical properties of carbonyl compounds

In a C=C double bond, both the σ and π electrons are symmetrically distributed
between the carbon atoms. In the C=O double bond, the electrons are distributed
unequally between the carbon and oxygen atoms. This is because the oxygen atom is
more electronegative than the carbon atom. This results in a permanent polarisation of
the bond which can be represented as follows:

The carbon atom is therefore susceptible to nucleophilic attack, where nucleophiles can
donate a lone pair of electrons to form a new bond. The oxygen atom is then susceptible
to electrophilic attack, and in most cases, this attack is protonation (i.e. a reaction with
H+).

Aldehydes are generally more reactive than ketones. The reason is chiefly that the
presence of two alkyl groups in ketones hinder the approach of attacking reagents to the
carbonyl group. Another factor is that the alkyl groups are electron donating and reduce
the partial positive charge on the carbonyl carbon.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH HCl (NUCLEOPHILIC ADDITION)

Both aldehydes and ketones react with HCl. Chlorine attacks the carbonyl carbon while
the H combines with the oxygen of the carbonyl group.

Below is the generalised mechanism of the reaction between a typical carbonyl

compound and HCl:

STEPS OF THE MECHANISM

1. HCl dissociates in solution producing H+ and Cl- .
2. Cl- acts as a nucleophile and donates electrons to the δ+ carbon in the carbonyl
group, forming a bond with it. Simultaneously, the pi bond in the C=O group is
broken and the electrons migrate to oxygen, giving it a negative charge.
3. The O- now bonds with the H+ ions in solution.
4. The result is the formation of a chloro-alcohol
5. The name of the mechanism above is nucleophilic addition.
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH HCN (NUCLEOPHILIC ADDITION)

Both aldehydes and ketones can react with HCN. The cyano group attacks the
carbonyl carbon. The hydrogen combines with the oxygen of the carbonyl group.

Below is the mechanism of the reaction between a typical carbonyl compound and
HCN:

POINTS TO NOTE:
1. HCN firstly dissociates in solution, forming H+ and CN-
2. CN-, being a nucleophile, donates electrons to the δ+ C atom of the C=O group
and bonds with it. Simultaneously, the pi bond in the C=O group breaks as the
electrons move to the oxygen, giving it a negative charge.
3. O- donates electrons and bonds with the H+ ion forming OH group
4. The end product is a cyanoalcohol.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

5. This mechanism is very similar to that of carbonyl compounds with HCl. It is

also called nucleophilic addition.

NOTE: The chain is lengthened by one more carbon atom.

Cyanohydrin can be readily converted to a carboxylic acid or a hydroxylamine.

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH 2,4-DNPH (BRADY’S REAGENT).

Brady’s reagent is a solution of 2,4-dinitrophenyl hydrazine in methanol and sulphuric
acid. It reacts with both aldehydes and ketones to produce 2,4-dinitrophenyl hydrazone
which separates rapidly. Aliphatic carbonyl compounds produce an orange or yellow
precipitate while those of aromatic carbonyl compounds are darker in colour. Brady’s
reagent is often used to test for the presence of carbonyl compounds. The reaction is
quantitative and therefore can be used to determine the amount of carbonyl compounds
present.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

Write the reaction between ethanal and 2,4-DNPH:

REACTION WITH TOLLEN’S REAGENT (OXIDATION)

This is also called the silver mirror test. Tollen’s reagent is a solution of silver nitrate in
an excess of ammonia and it contains the diamine silver ion – [Ag(NH3)2]+. Aldehydes
are oxidised to their corresponding carboxylic acids while the silver ion is reduced to
solid silver. The metallic silver precipitates and if the test tube is clean enough, it is
deposited as a shilling silver mirror on the walls of the test tube. Ketones do not react
with Tollen’s reagent. This is because they are resistant to oxidation by mild oxidising
agents so the reduction of the silver ion does not occur.
The oxidation of a typical aldehyde by Tollen’s reagent can be summarised in the
following equation:

R-CHO + 2[Ag(NH3)2]+ + OH- R-COO- + 2Ag + 2NH4+ + 2NH3

Write the reaction of ethanal with Tollen’s reagent:
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH FEHLING’S SOLUTION (OXIDATION)

Fehling’s solution is made by adding sufficient sodium hydroxide to a solution of
copper sulphate and potassium sodium 2,3-dihydroxybutanedioate (Rochelle’s salt) to
make a deep blue solution. Fehling’s solution is a complex containing Cu2+ ions. When
aldehydes react with Fehling’s solution, it becomes oxidised to the corresponding
carboxylic acid. The Cu2+ ions becomes Cu2O and a brick red precipitate forms. Ketones
do not react with Fehling’s solution.
The oxidation of a typical aldehyde with Fehling’s solution can be summarised by the
following equation:
R-CHO + 2Cu2+ + 5OH- R-COO- + Cu2O + 3H2O
Write the reaction between methanal and Fehling’s solution:

NOTE: One aldehyde which does not give a positive Fehling’s test is benzaldehyde.

+
REACTION WITH KMnO4/H (OXIDATION)
Like with the previous oxidising agents, aldehydes would react while ketones would
not. Aldehydes are oxidised to their corresponding carboxylic acids while ketones are
resistant to oxidation. If ketones are heated strongly with KMnO4/H+ the molecule
ruptures to produce two carboxylic acids.
Illustrate the reaction between KMnO4/H+ and a typical aldehyde:

REACTION WITH H2/Pt (REDUCTION)

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

Hydrogen and platinum mixture forms a reducing agent. Aldehydes would be reduced
to their primary alcohols while ketones are reduced to their secondary alcohols.

REACTION WITH LiAlH4 (REDUCTION)

LiAlH4 (tetrahydroalumina) in ether is a very powerful reducing agent. This can also
therefore reduce aldehydes to their corresponding primary alcohols while ketones are
reduced to their corresponding secondary alcohols.
Reduction of a typical carbonyl compound:

Reduction of ethanal:

Reduction of propanone:

SUMMARY OF REACTIONS OF CARBONYL COMPOUNDS

Complete the following table by drawing the organic product that forms along with any
expected observations:

Reagents

HCl
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

HCN

2,4-DNPH

Tollen’s reagent

Fehling’s solution

H2/ Pt or LiAlH4 in
ether:

KMnO4/H+
UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

CARBOXYLIC ACIDS
General formula CnH2n+1COOH
Functional group

PHYSICAL PROPERTIES OF CARBOXYLIC ACIDS

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

● They are weak organic acids. This means that they do not dissociate completely
in solution. Despite the number of hydrogen atoms in the structure of the
carboxylic acid, only the hydrogen that is attached to the functional group
(COOH) is protonated. Therefore if a carboxylic acid has 1COOH group, it is
monobasic. If it has 2 COOH groups (like oxalic acid) it is dibasic. If it has
3COOH groups (like citric acid) it is tribasic.
● Some of the larger members of carboxylic acids are called fatty acids. This is
because they are the constituents (in the form of esters) of naturally occurring
vegetable oils and animal fats.
● Some of the middle members have very unpleasant odours. For example,
butanoic acid is found in sweat and smells of rancid butter.
● Lower members are colourless liquids with pungent smells.
● Lowest members are very soluble in water. This is due to the extensive hydrogen
bonding that occurs. As the chain length increases, the solubility in water
decreases as the effect of the COOH group on the solubility become less
significant. Acids which contain more than 9 carbon atoms become waxy and
insoluble and have a low volatility with no smell.
● The boiling points of carboxylic acids are substantially higher than
corresponding alkanes. This is due to the hydrogen bonding that occur between
carboxylic groups of different compounds. The acids usually exist as dimers
which will result in a relative molecular mass to be determined as twice the
amount it should be.
In the space below, draw the hydrogen bonding that occurs between two typical
carboxylic acids:

THE ACIDITY OF CARBOXYLIC ACIDS

Carboxylic acid are weak acids. They dissociate in water to yield H+ ions as well as
carboxylate or alkanoate ions.
 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

This is attributed to the polarization of the OH bond which destabilizes the bond
allowing it to break easily.
The negative charge on the carboxylate ion is stabilised because the electronic charge
spreads out or it is delocalised between two oxygen atoms.

REACTION WITH NaOH (ACID-BASE REACTION)

Write the reaction between ethanoic acid and sodium hydroxide:

REACTION WITH NaHCO3 (ACID-BASE REACTION)

Write the reaction between propanoic acid and sodium hydrogencarbonate:

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH METALS

The metals replace the H of the COOH group.

Write the reaction between the following:

(a) Ethanoic acid and sodium:

(b) Ethanoic acid and potassium:

(c) Propanoic acid and magnesium:

(d) Butanoic acid and calcium:

(e) Ethanoic acid and aluminium:

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

REACTION WITH ALCOHOLS (ESTERIFICATION)

- CONDITIONS: conc. H2SO4 + heat (reflux)

Write the reaction that occurs between the following:

(a) Ethanoic acid and methanol:

Ethanoic acid + methanol 🡪 methylethanoate + water

(b) Propanoic acid and methanol:

propanoic acid + methanol 🡪 methyl propanoate + water

(c) Butanoic acid and ethanol:

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

Butanoic acid + ethanol 🡪 ethyl butanoate + water

REACTION WITH PCl5 (SUBSTITUTION REACTION)

The OH group of the carboxyl group acts just as that of an alcohol. The OH group is
substituted by Cl. This forms an acyl chloride. A typical reaction can be illustrated by
the following equation:

One would observe fumes of gas being evolved. This gas is HCl and it is acidic.
Write the reaction between ethanoic acid and PCl5:

REACTION WITH PCl3 (SUBSTITUTION REACTION)

 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – CARBONYL COMPOUNDS

Phosphorus acid is produced which can be detected by dipping blue litmus paper in the
acid. The blue litmus paper will turn red.
Write the reaction between propanoic acid and PCl3:

REACTION WITH SOCl2 (SUBSTITUTION REACTION)

One would observe a gas being evolved which has an irritating smell. This gas is SO2
which is acidic. One can also observe dense white fumes being evolved which is HCl(g).
Write the reaction between butanoic acid and SOCl2:
 1

UNIT 2 CHEMISTRY - ESTERS & AMINES

ESTERS

FUNCTIONAL GROUP: - COO

The functional group in an ester is called the ester linkage

PHYSICAL PROPERTIES OF ESTERS

1. They are known to have pleasant odours. Esters can also have unpleasant
odours. Because of this, esters are widely used in the flavor and fragrance
industries. Below show the structures of some common esters

2. They are non-polar liquids. Esters are oily liquids. They are not miscible with
water, but are miscible with non-polar solvents.

1
 2

UNIT 2 CHEMISTRY - ESTERS & AMINES

3. They have lower boiling points than their corresponding carboxylic acids.
Hydrogen bonding occurs between molecules of carboxylic acids, while Van der
Waals forces exist between ester molecules. Van der Waals forces are weaker
than hydrogen bonds, so the boiling points of esters are lower.

CHEMICAL PROPERTIES OF ESTERS

1. ACID HYDROLYSIS

In the presence of a strong acid, the ester linkage breaks and the carboxylic acid and
alcohol are formed. A strong mineral acid is typically used, such as concentrated H 2SO4
or HCl.

ESTER  CARBOXYLIC ACID + ALCOHOL

In the space below, write an equation to represent acid hydrolysis of methyl

propanoate:

2
 3

UNIT 2 CHEMISTRY - ESTERS & AMINES

2. Hydrolysis can also occur under alkaline conditions. This is called alkaline
hydrolysis. In such cases, a strong alkali is used, such as NaOH or KOH. The salt
of the carboxylic acid and an alcohol are produced.

- In the space below, write an equation to illustrate alkaline hydrolysis of ethyl

butanoate using sodium hydroxide

C3H7COOC2H5  C3H7COOH + C2H5OH

- In the space below, write an equation to illustrate the alkaline hydrolysis of ethyl
methanoate using potassium hydroxide:

3
 4

UNIT 2 CHEMISTRY - ESTERS & AMINES

HCOOC2H5  HCOOK + C2H5OH

FATS/ OILS

Fats or oils are triesters of long-chained carboxylic acids (also called fatty acids) and
glycerol. When such an ester is a liquid at room temperature, it is known as an oil.
When it is a solid at room temperature, it is known as a fat. Below is the general
structure of a fat or oil:

4
 5

UNIT 2 CHEMISTRY - ESTERS & AMINES

SAPONIFICATION OF FATS/ OILS

When fats/ oils undergo alkali hydrolysis, the reaction is also called saponification. If
sodium hydroxide was used, the products would be the sodium salt of the fatty acids
and glycerol. The sodium salt of the fatty acid is known as soap. If potassium hydroxide
was used, then the potassium salt of the fatty acid would be produced. This is known as
soft soap.

5
 6

UNIT 2 CHEMISTRY - ESTERS & AMINES

Note that the R groups indicated above represent long carbon chains that may or may
not have the same length.

The structure of a typical soap molecule is shown below:

The hydrophobic tail would attach onto oil and grease on the surface of the object being
washed. The hydrophilic head (also called the ionic head) would move towards water
molecules. This would pull onto the soap molecules which would in turn pull the oils
and grease away.

TRANSESTERIFICATION

Transesterification is the process by which the alcohol in an ester is replaced by another

alcohol. In this case, the glycerol molecule in a fat/ oil is replaced by methanol
molecules. This reaction is usually catalyzed by a strong alkali, like sodium hydroxide.
Although, strong acids, like HCl may be used as well.

6
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UNIT 2 CHEMISTRY - ESTERS & AMINES

The methyl esters that are produced can be used as biodiesel. Biodiesel can be used as
fuel for diesel engines, without the need to modify the engines. Biodiesel can also be
blended with diesel fuel. For example, a B40 blend will contain 40% biodiesel and 60%
diesel. A B100 blend will contain 100% biodiesel. Biodiesel is made from renewable
resources, such as fats or oils that come from any natural life. Even waste oils may be
used to produce biodiesel. However, such oils must be cleaned first, and any free fatty
acids must be removed. Otherwise they will react with the sodium hydroxide to form
soap instead.

Biodiesel is considered a cleaner fuel than diesel produced from crude oil.
Although carbon dioxide is produced (which is a greenhouse gas), along with water
vapour, there is little to no production of other wastes like carbon monoxide, oxides of
Sulphur or nitrogen. Biodiesel may also be consumed quicker than diesel, resulting in
the need to refill tanks more often.

7
 8

UNIT 2 CHEMISTRY - ESTERS & AMINES

AMINES

Amines are formed when one or more hydrogens in the ammonia is replaced by an
alkyl group. There are 3 types of amines:

1. Primary amines - these are formed when one hydrogen is replaced by an alkyl
group. The functional group of primary amines is NH 2.

For example:

2. Secondary amines – these are formed when two hydrogens are replaced by alkyl
groups. The functional group of secondary amines is NH

8
 9

UNIT 2 CHEMISTRY - ESTERS & AMINES

For example:

3. Tertiary amines – these are formed when all three hydrogens are replaced by
alkyl groups. The functional group of tertiary amines is N.

For example:

9
 10

UNIT 2 CHEMISTRY - ESTERS & AMINES

PHYSICAL PROPERTIES OF AMINES

1. Amines would generally have higher boiling points than their corresponding
alkanes. This is due to the NH groups forming hydrogen bonding with each
other. However tertiary amines are not capable of forming hydrogen bonds. The
boiling points decrease going from primary to tertiary amines
2. Amines are generally soluble in water due to the polarity of the NH bonds. The
solubility in water decreases as one moves from primary to tertiary amines. Also
as the alkyl groups increase in size, the solubility in water decreases.
3. Aliphatic amines tend to have a fishy odour, while aromatic amines have an
odour similar to urea.
4. Phenylamine can easily penetrate the skin.

CHEMICAL PROPERTIES OF PRIMARY AMINES

1. REACTION OF ALIPHATIC AMINE WITH NITROUS ACID

Aliphatic Amine + Nitrous acid Alcohol + N2 + H2O

10
 11

UNIT 2 CHEMISTRY - ESTERS & AMINES

2. REACTION OF PHENYLAMINE WITH NITROUS ACID

3. REACTION WITH CARBOXYLIC ACIDS

Amine + Carboxylic acid N-substituted amide + Water

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1 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

AROMATIC HYDROCARBONS
The simplest aromatic hydrocarbon is benzene (C6H6). The term ‘aromatic’ was initially
used to describe such compounds because many of their derivatives have pleasant
smells. However, it is now found that many have unpleasant smells, and, in some cases,
the aromatic vapours are toxic or carcinogenic. The term ‘aromatic’ is now used to
describe certain chemical characteristics which such chemicals possess. Such
compounds are also referred to as arenes.

There are two types of structures that can be drawn for benzene. Draw these two types
of structures below:

NAMES OF SOME COMMON ARENES

Apart from numbering positions, names are assigned to certain positions on the π ring:

- Positions 2,6 – ortho

- Positions 3,5 – meta
- Position 4 – para

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 2 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

BENZENE
Benzene is the most important arene industrially. It is used to make many items
including detergents, polystyrene, nylon and insecticides. It is usually manufactured by
catalytic reforming of C6 – C8 hydrocarbons in which the atoms are rearranged to form
the ring structure.

PHYSICAL PROPERTIES OF BENZENE:

 It is a colourless liquid at room temperature with a pleasant odour.
 It is immiscible with water because it is entirely non-polar. It is soluble, therefore,
in non-polar solvents.
 It is highly toxic and carcinogenic.

CHEMICAL PROPERTIES OF BENZENE

Benzene is usually quite unreactive due to the stability of the delocalised π electrons in
the ring. Therefore, it is unfeasible to break up the ring structure in order to add atoms
to the compound. Therefore, benzene does not undergo addition reactions. Under
certain conditions, benzene is able to undergo substitution reactions. Since such
substitution reactions involve the electron dense region of the ring, benzene is said to
undergo electrophilic substitution reactions.

NITRATION OF BENZENE
CONDITIONS: conc. HNO3 + conc. H2SO4 @ 50˚C

EQUATION:
NO2

conc. H2SO4
+ HNO3
50°C
+ H2O

THE MECHANISM

1. An acid base reaction occurs between HNO3 and H2SO4. This forms the nitryl
cation or nitronium cation which acts as an electrophile.
2. The nitronium ion acts as an electrophile and it is attracted to the electron dense
region of the π ring system.
3. Resonance stabilisation of the ring occurs.
4. A proton is removed and the π ring system is restored.

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3 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

5. The proton combines with HSO4-. Since H2SO4 is reformed at the end, it is
considered a catalyst.
Write the mechanism of nitration of benzene below:

STEP 1: FORMATION OF THE NITRYL CATION

This occurs in three steps:

1. Protonation of nitric acid:

H2SO4 + HNO3 HSO4- + H2NO3+

2. Formation of the nitryl cation:

H O O
+ +
O N H2O + N
O
H O

3. Ionisation of H2SO4 with water formed:

H2SO4 + H2O  H3O+ + HSO4-

Overall reaction:

HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4-

STEP 2: ELECTROPHILIC SUBSTITUTION ON BENZENE

H NO2 NO2

slow +
+ NO2+ +
fast
+ H

STEP 3: REFORMATION OF THE CATALYST

HSO4- + H+  H2SO4

Note: If temperatures above 50˚C are used, a second substitution occurs, and the
following compound is obtained:

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4 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

HALOGENATION, ALKYLATION AND ACYLATION OF BENZENE

Alkylation, acylation and halogenation of benzene all involve respective halogen

compounds and halogen carriers. Halogen carriers are also called Friedel-crafts
catalysts. They can be either: AlCl3, AlBr3, BF3 or FeBr3

HALOGENATION OF BENZENE
FOR EXAMPLE, BROMINATION OF BENZENE
CONDITIONS: AlBr3 and Br2(l)

EQUATION:
Br
AlBr3
+ Br2 rtp + HBr

MECHANISM:

1. AlBr3 reacts with Br2 forming Br+ and AlBr4-.

2. Br+ is attacked by the π system of the ring.
3. Resonance stabilisation of the ring system occurs.
4. A proton is removed from the benzene ring in order to restore the π system.
5. The proton combines with one Br from AlBr-4 to form HBr and AlBr3. The
catalyst is regenerated.
Write the mechanism for the bromination of benzene
STEP 1: FORMATION OF THE Br+ CATION
Br Br
Br
–
Br Al Br –
Br Al + Br Br Br Al Br + Br+

Br Br
Br Br

STEP 2: ELECTROPHILIC SUBSTITUTION

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5 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

H Br Br

slow +
fast
+ Br+ + + H

STEP 3: REFORMATION OF THE CATALYST

H+ + AlBr4-  AlBr3 + HBr (steamy white fumes)

ALKYLATION OF BENZENE
FOR EXAMPLE, ADDITION OF CH3 TO BENZENE
CONDITIONS: CH3Cl + AlCl3

EQUATION:
CH3

AlCl3
+ CH3Cl rtp + HCl

MECHANISM

1. AlCl3 reacts with CH3Cl forming CH3+ and AlCl4-.

2. CH3+ is attacked by the π system of the ring.
3. Resonance stabilisation of the ring system occurs.
4. A proton is removed from the benzene ring in order to restore the π system.
5. The proton combines with one Cl from AlCl-4 to form HCl and AlCl3. The
catalyst is regenerated.

Write the mechanism of the reaction of the addition of CH3 to benzene

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6 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

Cl Cl
Cl Cl
H
– – +
Cl Al + C Cl Al Cl Cl Al Cl + CH3
H CH3
Cl
H
Cl Cl

H+ + AlCl4-  AlCl3 + HCl (steamy white fumes)

ACYLATION OF BENZENE
FOR EXAMPLE, THE FORMATION OF A PHENYL ESTER (METHYL BENZOATE).
CONDITIONS: METHANOYL CHLORIDE AND AlCl3

EQUATION:
O
O
AlCl3
+Cl C
CH3 rtp + HCl

MECHANISM

1. AlCl3 reacts with CH3COCl forming CH3CO+ and AlCl4-.

2. CH3CO+ is attacked by the π system of the ring.
3. Resonance stabilisation of the ring system occurs.
4. A proton is removed from the benzene ring in order to restore the π system.

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7 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

5. The proton combines with one Cl from AlCl-4 to form HCl and AlCl3. The
catalyst is regenerated.

Write the mechanism of the reaction of the addition of CH3CO to benzene

Cl Cl
Cl Cl O
– – +
Cl Al + C Cl Al Cl Cl Al Cl + C CH3
O CH3 C O
Cl
Cl H3C Cl

O
O
H
O
+
C slow +
fast
+ CH3 + + H

H+ + AlCl4-  AlCl3 + HCl

DERIVATTIVES OF BENZENE
DIRECTING GROUP INFLUENCE
Substituents that are directly attached to the benzene ring can affect the positions to
which the electrophile can attach.

Activating groups direct electrophiles to the ortho or para positions. This is because
they increase the electron density toward the ring. Such groups include:

 OH (strong)
 NH2 (strong)
 OR (moderate)
 CH3 (weak)

Deactivating groups direct electrophiles to the meta positions as they decrease the
electron density of the ring. Such groups include:

 NO2 (strong)

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8 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

 NH3+ (strong)
 COOH (moderate)

METHYLBENZENE

REACTIONS WITH THE CH3 GROUP:

CH3 reacts as an alkyl group would. In the presence of UV light, the hydrogens are
substituted by halogens. Just as with alkanes, the mechanism of such reactions is a free
radical substitution.

For example:
CH2Cl
CH3

UV light
+ Cl2 + HCl

REACTIONS WITH THE AROMATIC RING:

The CH3 group has a positive inductive effect on the aromatic ring. This means that it
pushes electrons towards the ring. Resonance stabilisation occurs:

+ + +
CH3 CH3 CH3 CH3
– –
CH HC

–
CH

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9 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

The negative charge appears on positions 2, 4 and 6. Hence, substitution occurs in the
ortho and para positions.

BROMINATION OF METHYLBENZENE

Reagents: Br2(l)

Conditions: Friedel-Crafts catalyst e.g., FeBr3

CH3 CH3
CH3
FeBr3 Br
+ Br Br
OR + HBr
Br

NITRATION OF METHYL BENZENE

CH3 CH3
CH3
68% conc. HNO3/ conc. H2SO4 NO2
50°C for 1 hr OR

NO2

CH3
CH3
68% conc. HNO3/ conc. H2SO4 NO2
70°C for 30 mins

NO2

CH3 CH3
NO2 NO2
fuming HNO3 (90%)/ conc. H2SO4

120°C for 5 hrs

NO2

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10 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

PHENOL

The simplest phenols are liquids or solids with low melting points. Because of hydrogen
bonding, they have higher boiling points than their corresponding alkane. Phenol is
slightly soluble in water as it forms hydrogen bonds with water molecules. Derivatives
of phenol are insoluble in water. Phenol is colourless, but its derivatives are capable of
producing a colour. when phenol is dissolved in water, it is known as carbolic acid
which is a powerful antiseptic. 2,4,6-trichlorophenol is the antiseptic that is present in
Dettol.

THE ACIDITY OF PHENOL

Phenol dissociate in water to produce H+ ions due to the polarizing of the O-H bond.
As such, phenols are much stronger acids than alcohols.

Ka for C6H5OH = 1.3 x 10-10 moldm-3, pKa = 9.89

Ka for C2H5OH = 1 x 10-16 moldm-3, pKa = 16

This occurs primarily because the phenoxide ion is much more stable than the alkoxide
ion.

OH –
O

+
H
+

The lone pair of electrons from the oxygen becomes incorporated into the giant pi
system of the aromatic ring. The negative charge on the phenoxide ion is therefore
delocalized through the entire aromatic ring. This significantly stabilizes the phenoxide
ion and consequently phenol with react with:

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11 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

1. Highly reactive metals to produce a salt and hydrogen gas.

2. Alkalis to produce a salt and water.

NOTE: phenols are not strong enough to react with carbonates or bicarbonates.

REACTIONS WITH THE OH GROUP:

NEUTRALISATION

Phenol can react with strong bases such as NaOH. The hydrogen atom from the OH
group gets displaced

–
OH O Na+

+ NaOH + H2O

Because of the benzene ring, which is insoluble in water, phenol is only very slightly
soluble in water. It will completely dissolve in NaOH.

While phenol can react with strong bases, it cannot react with weaker bases such as
carbonates/ hydrogen carbonates.

ESTERIFICATION

Because of conjugation with the ring, the C-O bond is stronger in phenol than in
alcohols. Esterification is difficult and can only be brought about using acyl chlorides

In an acyl chloride molecule, there are 2 very electronegative elements, Cl and O. There
is a large δ+ charge on the carbon atom as a result. Any reaction with acyl chlorides
would de a nucleophilic attack.

d-
O
d+
R C
d-
Cl

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12 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

Which acyl chloride would you expect the be the most reactive?
Ans: The one containing less alkyl groups. More alkyl groups present would push
electrons towards the δ+ carbon decreasing its positive nature and making it less
reactive.

O
OH
O CH3
O
+ H3C C + HCl
Cl

Alkaline solutions of phenols (which contain the phenoxide ion) are used instead of
phenol. Under these conditions, the nucleophile is the phenoxide ion and NaCl is the
other product formed.
O
+
- O Na
O CH3
O
+ H3C C + Na Cl
Cl

SUBSTITUTION IN THE RING

The oxygen atom in the OH group has lone pairs of electrons that are directly attached
to the C atom of benzene. This increases the electron density and activates the ring. The
OH group will have a positive inductive effect on the ring. This will cause resonance
stabilisation (conjugative effect) along the ring. Phenol will undergo electrophilic attack
more readily than benzene

+ + +
OH OH OH OH
– –
CH HC

–
CH

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13 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

The negative charge appears on positions 2,4 and 6. Therefore substitution will occur
along the ortho and para positions

Bromination

With aqueous bromine, phenol rapidly forms a white precipitate of 2,4,6-

tribromophenol, and the Br2(aq) is decolourised. A side product formed is HBr which is
a colourless solution. This reaction is often used as a test for the presence of phenol

OH OH

Br
+ 3Br2 Br + 3HBr
Colourless solution
Br
White
ppt

NITROBENZENE

REACTIONS WITH NO2 GROUP

The most common reaction of the NO2 group is the conversion of nitrobenzene to
phenylamine in which the NO2 becomes NH2.
CONDITIONS: Sn + HCl under reflux

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14 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

EQUATION:
NO2 NH2
Sn/ HCl
reflux

The reactions occur in two steps:

1. Nitrobenzene is reduced to phenylammonium ions using a mixture of Sn and

conc. HCl. The mixture is heated under reflux. Phenylammonium ions are
formed.
NO2 +
NH3
Sn/ HCl
reflux

2. A proton is removed from the NH3+ group. Sodium hydroxide is added and
phenylamine is formed. The end product is a mixture of phenylamine with other
complexes formed between Sn and other compounds. To separate phenylamine,
one has to perform steam distillation, solvent extraction and a final distillation.

SUBSTITUTION ALONG THE RING

Nitrogen bears a partial positive charge which withdraws electrons from the ring. It
therefore deactivates the ring structure and substitution occurs in the meta positions.
– – –
O O O O –
+ – – –
N N O O O O
N N
+
CH
+
HC

+
CH

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15 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

Halogenation
–
O + O –
N O + O
N

AlCl3
+ Cl Cl + HCl

Cl

Nitration
–
O + O –
N O + O
N
conc. H2SO 4

+ HNO3 50°C + H2O

NO2

PHENYLAMINE

SUBSTITUTION ALONG THE RING

The lone pair of electrons on the nitrogen increases the electron density of the ring and
thereby activates it. Therefore, substitution occurs on the ortho and para positions. As it
is a strong directing group, a tri-substituted product is normally achieved.

15
16 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

NH2 NH2
Br Br

+ 3Br2 3HBr
+

Br

REACTION OF THE NH2 GROUP

Phenylamine is also a primary amine. Therefore, it can react with sodium nitrite and
conc. hydrochloric acid. Recall that sodium nitrite reacts with conc. HCl to produce
nitrous acid. The reaction between nitrous acid and phenylamine produces the
diazonium salt.

EQUATION:

This reaction is usually carried out under 10˚C to avoid the decomposition of both the
nitrous acid and the diazonium salt.

Diazonium salts can be isolated, but they are unstable and explosive in the solid state.
They are used in solution to prepare other substances.

SUBSTITUTION REACTIONS OF DIAZONIUM COMPOUNDS

Once the diazonium compound is warmed to 100˚C with an appropriate reagent and
catalyst, the group is replaced by other groups.

On warming with water, phenol is produced, and nitrogen gas is evolved:

+ –
N N Cl OH

Δ
+ H2O
+ HCl + N N

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17 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

Diazonium compounds make it possible to obtain derivatives of benzene which cannot

be made directly from benzene.

COUPLING REACTIONS OF DIAZONIUM COMPOUNDS

Diazonium compounds can act as electrophiles. The diazonium cation can be attacked
by the ring system of phenol or aromatic amines. the diazonium compound is
substituted on the para position and the bond –N=N- forms between the two. This
compound is called an azo compound and the reaction is known as azo coupling. Azo
compounds are coloured compounds and are widely used as dyes.

One example is the formation of aniline yellow:

NH2
+ –
N NCl NH2

+ + HCl
N
N

Aniline yellow

Other azo compounds:

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18 UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – AROMATIC HYDROCARBONS

1.

USES OF AZO COMPOUNDS:

1. Dyes – the electrons in the azo compounds are delocalised over both benzene
rings and nitrogen atoms. Therefore, such a compound will have more closely
spaced energy levels available for the electrons, so the electrons can absorb
specific wavelengths of light in their visible range. The colours that are reflected
product the various colours of the compounds. Therefore, azo compounds are
very popular as dyes in the clothing, paint and fashion industry. Some azo
compounds have sulphonic acid groups (R-SO3) which allow polymerisation and
hence integration into fabrics. Congo red, aniline yellow, methyl red and methyl
orange are examples of dyes.
2. pH indicators – for example, methyl red and methyl orange are popular
indicators used in acid-base titrations.
3. Concerns – over recent years, there has been some concerns over the possible
carcinogenicity of some azo compounds. The azo dye 4-dimethylaminobenzene
or butter yellow was once used as a food colouring, but it is now a suspected
carcinogen by the FDA.

18
 1
UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

SPECIFIC OBJECTIVES EXPLANATORY NOTES

explain the difference in acidity of Include chlorosubstituted acids. Reference
alcohols, phenols, and carboxylic acids; should be made to the relationship
between acid strength, pH and pKa.
Inductive and conjugative effects.
explain differences in basic character of pH and pKb. Inductive and conjugative
aliphatic amines, amides, and aromatic effects.
amines;
explain the acid-base properties of amino Formation of zwitterions.
acids.

INDUCTIVE EFFECT AND CONJUGATIVE EFFECT

1. The inductive effect – this is the process whereby electrons are pulled along a
bond to make it polar. If a group pulls electrons away from a carbon atom, it is
said to have a negative inductive effect (-I) on the bond. If a group tends to push
electron density towards the carbon atom, it is said to have a positive inductive
effect (+I)
2. The conjugative effect – this occurs in molecules that have alternating single and
double bonds such as benzene. The electrons are free to move in the delocalized
π system which results in the sideways overlap of p orbitals. This gives
additional stability to the benzene molecule.

An acid can be defined as a substance that produced H+ in solution.

HA(aq) H+ (aq) + A-(aq)

Recall that the H+ ion becomes attached to a water molecule to form the H3O+ ion.

H+(aq) + H2O(l) H3O+(aq)

Organic acids are weak acids because they do not dissociate completely. So, at any
given time we may find some undissociated acid molecules present in the solution. For
example, with a dilute ethanoic acid solution, 99% of the acid molecules are
undissociated, so only 1% of the acid have ionized. The position of equilibrium lies
considerably to the left.
1
 2
UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

Any organic molecule that contains the OH group would have some acidic properties.
This is because the OH group dissociates forming the H+ ion:

R-O-H(aq) H+(aq) + R-O-(aq)

The ionisation results from the acceptance of a pair of electrons by the oxygen atom:

R H R – +
O O + H

ACIDITY OF CARBOXYLIC ACIDS

When carboxylic acids dissociate, they produce the alkanoate ion and H+.

O O

C +

R
C
O
H
R O
– + H

Recall that the double bond in the C=O group is composed of a sigma bond and a pi
bond. The lone pair of electrons that are on the O- ion can become incorporated into this
pi bond. This causes the COO- group to become delocalized, much like what occurs for
benzene:

O
R C –
O

Note that the dotted line represents delocalization. The negative charge is drawn in the
centre of the group to show that it isn’t localized to one of the oxygen atoms. This
results in the alkanoate ion being very stable and therefore unwilling to accept H+ to
reform the acid.

EFFECT OF LENGTH OF CARBON CHAIN ON ACIDITY

Alkyl groups tend to push electrons towards the COOH groups. This is called the
positive inductive effect, and it is given the symbol +I.

More alkyl groups that are present (i.e., the longer the principal carbon chain) the more
electrons will be pushed to the COOH group.

2
 3
UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

This would make it more and more difficult for the oxygen atom in the O-H group to
accept a pair of electrons and break the bond. Hence, it will be more difficult for the
acid to ionize.

In short, the longer the principal carbon chain of the acid, the weaker the carboxylic acid
would become. This can also be shown using the pKa values:

pKa
HCOOH 3.75
CH3COOH 4.76
CH3CH2COOH 4.87

CH3CH2CH2COOH 4.82

As the chain length increases, the pKa values also increases. This means that the
carboxylic acid becomes weaker.

CHLOROSUBSTITUTED ACIDS

Adding electronegative atoms, such as chlorine, to the carboxylic acid would pull
electrons away from the COOH group. This is called the negative inductive effect (-I).
This will make it easier for the oxygen atom of the O-H group to accept the bond pair of
electrons and break the bond. Hence it becomes easier for the carboxylic acid to ionize.

Adding electronegative atoms, such as chlorine, to a carboxylic acid would strengthen

it.

The more chlorines are attached to the acids, the stronger the acid will be.

3
 4
UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

pKa
CH3COOH 4.76

CH2ClCOOH 2.86
CHCl2COOH 1.29
CCl3COOH 0.65

If the halogen is further away from the group, its effect will be less on the COO-
group.

pKa
CH3CH2CH2COOH 4.82
CH3CH2CHClCOOH 2.84
CH3CHClCH2COOH 4.06

CH2ClCH2CH2COOH 4.52

Therefore, chlorine will be most effective when it is next to the COO- group.

Attaching different halogens will influence the strength of the acid. Fluorine is the most
electronegative, so it will pull most of the charge away from the COO- group and
strengthen the acid even more.

ACIDITY OF ALCOHOLS

Because alcohols have the OH group, they are also considered acidic. They are,
however, very mildly
acidic.
R H R – +
O O + H

4
 5
UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

When the alcohol has lost the H atom, it has formed the alkoxide ion. There is no
stabilization of the negative charge on the alkoxide ion, so it is very easy for it to
combine with H+ and reform the alcohol.

THE EFFECT OF CHAIN LENGTH ON THE ACIDITY OF ALCOHOLS

Alkyl groups tend to push electrons to the OH group. This is called the positive
inductive effect (+I). This will make it more difficult for the OH group to ionize, which
is the same for carboxylic acids. Therefore, as the chain length increases, the acidity of
the alcohols will decrease, and the pKa values would also increase.

THE EFFECT OF ELECTRONEGATIVE GROUPS ON ALCOHOLS

As with carboxylic acids, adding electronegative groups on to the principal carbon

chain would tend to pull electrons away from the OH group. This is called the negative
inductive effect (-I). This would make it easier for the OH group to ionize and the
alcohol would become more acidic.

The further away the electronegative group is from the OH group, its effect on the OH
group would be less.

More electronegative atoms, like F, would have a greater effect on the acidity of the OH
group and make the alcohol more acidic.

ACIDITY OF PHENOL

When phenol is in solution, it loses the H+ and forms the phenoxide ion.

OH –
O

+
H
+

The negative charge on the phenoxide ion becomes incorporated into the delocalized pi
system in the benzene ring.

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

– O O
O O
– –
CH HC

–
CH

This is called the conjugative effect. The pi system becomes distorted toward the
negative charge on the phenoxide ion which makes it easy to accept H+ ion and reform
phenol.

COMPARING THE ACIDITY OF ALCOHOLS, PHENOL AND CARBOXYLIC

ACIDS

When comparing the acidity of alcohols, phenol and carboxylic acids, the stability of the
negative ion formed is compared. Recall that they are all weak acids, which means that
the dissociation is reversible. If the anion readily accepts H+, then the acid is considered
weaker.

When alcohols dissociate, they form the alkoxide ion. There is no stabilization of the
negative charge, so it can readily accept H+. This makes alcohols very weak acids. It is
the weakest of the three homologous series.

When phenol dissociates, it forms the phenoxide ion. Although the negative charge is
incorporated into the pi system of the benzene ring, and there is some stabilization, it
mostly distorts the system toward itself. This causes the oxygen ion to retain most of its
negative charge and it can still accept H+. Phenol therefore is a stronger acid than
alcohols.

When carboxylic acids dissociate, they form the alkanoate ions. The negative charge is
stabilised due to the presence of the C=O group. This makes it more difficult to accept
H+. Hence, carboxylic acids are the strongest acids of the three homologous series.

The strengths of acids can be measured using the pKa scale:

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

The pKa value of ethanoic acid is the lowest, so it is the strongest acid. The pKa value of
ethanol is the highest, so it is the weakest acid.

We can also use reactions to compare the acidic strengths of these compounds:

Homologous Series Reaction with:

Bases/ Alkalis Carbonates/ Metals
hydrogen
carbonates
Alcohols No No Yes
Phenol Yes No Yes
Carboxylic Acids Yes Yes Yes

In using the reactions, we can see that carboxylic acids are the strongest acids because
they can react with all three substances. Alcohols are considered the weakest acids
because they can only react with highly reactive metals like sodium or potassium.

The order of acidic strength from lowest to highest is:

ALCOHOLS < PHENOL < CARBOXYLIC ACIDS

A base can be defined as a compound that accepts H+ ions.

In organic compounds, H+ ions can be accepted by the NH2 group to form the NH3+ ion:

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

H H
+ +
R N + H H N H
H R

This occurs when the N atom donates a lone pair of electrons to bond with H+.

BASIC CHARACTER OF ALIPHATIC AMINES

As shown above, the aliphatic amines would be basic because the NH2 group can accept
a lone pair of electrons.

THE EFFECT OF CHAIN LENGTH ON BASIC CHARACTER

Alkyl groups tend to push electrons to the NH2 group. This is called the positive
inductive effect (+I). this would make it easier for the N atom to donate its lone pair of
electrons to accept H+. Therefore, as the chain length increases, the amine becomes more
basic. However, the difference is not that large.

pKb
CH3NH2 3.36
CH3CH2NH2 3.27
CH3CH2CH2NH2 3.16

CH3CH2CH2CH2NH2 3.39

This is also applicable for different types of amines. Tertiary amines have three alkyl
groups attached to the nitrogen atom. These all push electrons towards the N atom.
This makes it easier for the N atom to donate its lone pair of electrons and bond with
H+. So, the order of the basic strength of amines, from the lowest to the highest is:

PRIMARY AMINES < SECONDARY AMINES < TERTIARY AMINES

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

EFFECT OF ELECTRONEGATIVE GROUPS ON THE BASIC CHARACTER OF

AMINES

Because electronegative atoms tend to pull electrons from the NH2 group (the negative
inductive effect), they would make it more difficult for N to donate its lone pair of
electrons. So, the presence of electronegative groups on amines would make them
weaker bases. This effect is greater the closer the electronegative atom is to the NH2
group and with more electronegative atoms.

BASIC CHARACTER OF PHENYLAMINE

The N atom of phenylamine can also accept H+

+
NH2 NH3

+
H
+

The lone pair of electrons on the N atom would become incorporated into the pi system.
This would make it difficult for it to donate the lone pair of electrons. Therefore,
phenylamine is considered a weaker base than aliphatic amines.

BASIC CHARACTER OF AMIDES

GENERAL FORMULA:

C N

In an amide, a pi bond is made by the sideways overlap between the p orbitals on the
carbon and the oxygen. The lone pair of electrons on nitrogen is almost parallel to these

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

p orbitals and overlap with them. The lone pair is therefore unavailable to accept a
proton as they are used in the delocalized electron cloud generating greater stability.
Amides show little or no tendency to accept a proton and hence are very weak bases,
almost neutral.

DIFFERENCES IN THE BASIC CHARACTER OF ALIPHATIC AMINES,

AROMATIC AMINES AND AMIDES

The strengths of weak bases are measured on the pKb scale:

Structure pKb
Methylamine 3.36
Phenylamine 9.38
Ethanamide 15

In comparing the basic character of organic compounds, the ease at which the lone pair
of electrons can be donated from the nitrogen atom is compared. For aliphatic amines,
like methylamine, this is easy, not only because there is no incorporation of the lone
pair of electrons, but also because of the presence of alkyl groups which tend to push
electrons.

With phenylamine, the lone pair of electrons on the N atom become incorporated into
the pi system. But this can also distort the system towards the N atom. So, while it can
donate the lone pair of electrons but not as easily as for aliphatic amines. Phenylamine
is a weaker base than aliphatic amines.

For amides, the lone pair of electrons become incorporated into the C=O group.
Therefore, the electrons are not easily donated. This results in amides being the weakest
base of all three, almost neutral.

In comparing the pKb values, this is also evident. Methylamine has the lowest pKb
value which makes it the strongest base. Ethanamide has the highest pKb value, which
makes it the weakest base.

The order of increasing basic character is:

AMIDES < PHENYLAMINE < ALIPHATIC AMINES.

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

GENERAL FORMULA:

O H H

C C N

HO R H

The variation in the R group accounts for 20 amino acids. Amino acids have abnormally
high melting points. This suggests that they have some form of ionic character. Amino
acids exist as dipolar ions in aqueous solution, known as zwitterions:

O H H O H H
in H2O +
C C N C C N H
–
HO R H O R H

The negative end of one amino acid is attracted to the positive end of another amino
acid generating electrostatic attractions. This accounts for the high melting point of
amino acids.

NEUTRAL AMINO ACIDS

For example: Alanine

O H H O H H
in H2O +
C C N C C N H
–
HO CH3 H O CH3 H

There is an equal number of COOH and NH2 groups. So, the pH of alanine is 7.

In acidic solution:

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

O H H H H
O
+ H+ +
C C N H C C N H
–
O CH3 H HO CH3 H

In alkaline solution:

O H H H
O H
+ OH-
C C N H
–
C C N + H2O
O –
CH3 H O CH3 H

ACIDIC AMINO ACIDS

Some amino acids have more COOH groups than NH2 groups. These amino acids
would have a pH of <7.

For example, aspartic acid:

H H – H H
HO O O O
in H 2O
C C C C C C C C
+ –
O H NH2 OH O H NH3 O

In acidic solution:

– H H
O O HO H H O
C C C C H+
C C C C
+ – –
O H NH3 O O + O
H NH3

In alkaline solution:

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

– H H –
O O O H H O
-
C C C C OH
+ –
C C C C
–
+ H2O
O H NH3 O O O
H NH2

BASIC AMINO ACIDS

These amino acids would have more NH2 groups than COOH groups. As a result, the
pH of these would be >7.

For example, lysine:

+
NH2 H H H H NH3 H H H H O
O
in H 2O
H C C C C C C H C C C C C C
+ –
OH H H H H NH3 O
H H H H NH2

In acidic solution:

+ +
NH3 H H H H O NH3 H H H H O
+
H
H C C C C C C H C C C C C C
+ – +
H H H H NH3 O H H H H NH3 OH

In alkaline solution:

+
NH3 H H H H O NH2 H H H H O
OH-
H C C C C C C
+ –
H C C C C C C
–
+ H2O
O + O
H H H H NH3 H H H H NH3

Amino acids can therefore maintain their pH even when small amounts of acid or alkali
are added to them.

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UNIT 2 CHEMISTRY – ACID/ BASE CHARACTER OF ORGANIC COMPOUNDS

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

MACROMOLECULES
SPECIFIC OBJECTIVES EXPLANATORY NOTES
describe the characteristics of addition Examples to include polyethene;
polymerization; polyvinyl chloride; polytetrafluoroethene.
describe the characteristics of Terylene; nylon 6.6; proteins, starch.
condensation polymerisation;
predict types of polymer formed from
given monomers;
deduce the repeat unit of a polymer;
identify proteins as naturally Treat amino acids as monomeric
occurring macromolecules; molecules.
identify carbohydrates as naturally Include the following: cellulose, starch and
occurring macromolecules; pectin. Treat simple sugars as monomeric
materials.
illustrate the connection between
carbohydrates and their monomers.

Definition of monomer: a molecule that can undergo polymerization, thereby

contributing constitutional units to the essential structure of a macromolecule.

Definition of polymer: a large macromolecule which has a relatively high molecular

mass which is comprised of repeating units, each having a relatively small molecular
mass.

Polymers may be natural or synthetic. Polymers may also be formed either through
addition or condensation polymerisation.

The structure of the monomers would determine the type of polymerization that would
occur. If the monomer has multiple bonds, then they would undergo addition
polymerization. If there is OH and/or NH2 present in the monomer, then it would
undergo condensation polymerization.

Determine whether the compounds below would undergo addition polymerization or

condensation polymerization.

Structure Type of Polymerisation

H H Addition
C C

H H

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

O H O Condensation
C C C
HO H OH
F Addition
H
H C
C C
H
H H
O O
H OH Condensation
C C + HO C C H
HO OH
H H

ADDITION POLYMERISATION
Addition polymerization involves the linking together of monomers with double or
triple bonds. Such monomers may be alkenes or alkynes. These unsaturated monomers
have π bonds which are able to break easily and hence link up with other monomers to
form a repeating chain. The reactions are not simple addition reactions, but usually
involve free radicals. Like all free radical reactions, it occurs in 3 stages:

1. Initiation – free radicals are formed, usually from the decomposition of organic
peroxides.
2. Propagation – the free radical adds onto one monomer molecule. One electron
from the pi bond is used to bond with the free radical, the other forms a free
radical. Then the chain is lengthened by addition of more monomer units. This is
a rapid reaction.
3. Termination – two radicals react with each other.

At the end of the reaction, the organic peroxides are restored and can be recycled.

Nothing is lost from the monomers and so the polymer is made up of a large number of
units simply adding to each other.

EXAMPLES OF ADDITION POLYMERISATION

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

POLYETHENE/ POLYTHENE

Monomer: Ethene

H H

C C

H H

Structure of polymer:

H H H H H H

C C C C C C

H H H H H H

Repeating unit:

H H

C C

H H
n

Uses: Low density polythene:

Plastic bags, insulation for electric cables, wraps for food and clothing. Requires high
pressure and temperature to make.

High density polythene:

Buckets, tanks, crates, bowls and bottles. Requires lower temperature and pressure with
a catalyst.

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

POLYVINYL CHLORIDE

Monomer: 1-chloroethene (vinyl chloride)

H H

C C

H Cl

Structure of polymer:

H H H H H H

C C C C C C

H Cl H Cl H Cl

Repeating Unit:

H H

C C

H Cl
n

Uses: Pipes, window frames, electrical conduits gloves, dialysis equipment.

POLYTETRAFLUOROETHENE (PTFE)

Monomer: Tetrafluoroethene

F F

C C

F F

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

Structure of polymer:

F F F F F F

C C C C C C

F F F F F F

Repeating Units:

F F

C C

F F
n

Uses: Nonstick coating in pans, heat shields in spacecrafts, lubricants in machines

CONDENSATION POLYMERISATION
These types of polymers are produced from a condensation reaction in which
monomers are joined together with the loss of small molecules such as water or
hydrogen halide. The product of condensation polymerization depends on the number
of functional groups in the monomer:
1 functional group – ends the growing chain.
2 functional groups – form linear polymers.
3 or more functional groups – form three dimensional polymers with cross linkages.

Condensation polymers are classified according to the type of linkages present in the
polymer. For example:
- Ester linkage – polyester
- Amide linkage – polyamide

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

- Glycosidic linkage - polysaccharide

Unlike additional polymers, condensation polymers are biodegradable and can be

broken down via acid hydrolysis or bacterial enzymes.

POLYESTERS

Polyesters are polymers which contain many ester linkages. Polyesters can be naturally
occurring or artificially produced. One example of a naturally occurring polyester is a
fat. One example of an artificially produced polyester is terylene.

TERYLENE

Type of polymer: Polyester.

Monomers: ethane-1,2-diol + benzene-1,4-dicaboxylic acid

Terylene is a condensation polymer that is synthetic. Since it is made up of two

monomers, it is referred to as a copolymer. Water is removed in the joining of the diol
and diacid to form the ester linkage.

O O H H

+ HO C C OH
HO OH
H H

O O
H H
O O C C O + H2O

H H

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

Uses of terylene:

✓ Also called Dacron

✓ Fabrics for clothing and draperies.

POLYAMIDES

Polyamides are polymers which contain many amide linkages. Naturally occurring
polyamides are polypeptides and one example of an artificially produced polyamide is
nylon 6,6

NYLON 6,6

Type of Polymer: Polyamide

Monomers: diamines and diacids (1, 6-diaminohexane + hexane-1, 6-dioic acid).

Nylon 6,6 is a copolymer that is made up of a diamine and a diacid. Water molecule is
removed in linking the two monomers and an amide linkage is formed.

O O H H
C CH2 C + N CH2 N
6 H 6 H
HO OH

O O H
C CH2 C N CH2 N + H2O
6 H 6
O

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

Uses of Nylon:

✓ An early substitute for silk.

✓ Ropes, clothing, carpets, parachutes and combat uniforms.

PROTEINS

Monomers: Amino acids

Linkage: Peptide linkage (naturally occurring amide linkage)

Proteins are naturally occurring polyamides. They are formed from the condensation
reactions between amino acids. Amino acids possess two functional groups: an amine
and a carboxylic acid functional group.
The general structure of an amino acid can be illustrated as follows:

2 amino acids form a dipeptide.

Many amino acids form a polypeptide.
Polypeptides fold into complex networks forming primary, secondary, tertiary and
quaternary structures of proteins.

Formation of a dipeptide:

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

2
1 2 H R OH
H R H H R O H 1
R
N C C + N C C
H N C C
N C C H O
H H O H H O
H H O

+ H2O

The primary protein structure is defined as the specific sequence of amino acids in the
protein. The dipeptide consisting of two different amino acids alanine and glycine can
either have the sequence gly-ala or ala-gly. Each sequence can give rise to different
properties of proteins. The sequence of amino acids in proteins is guided by genetics
(DNA and RNA).

CARBOHYDRATES (aka POLYSACCHARIDES)

Monomer: monosaccharide
Linkage: glycosidic linkage
Carbohydrates are also naturally occurring polymers with the general formula Cx(H2O)
y.

Monosaccharide – e.g.: glucose, fructose

Disaccharide – e.g.: maltose, sucrose
Polysaccharides – e.g. cellulose, starch, pectin.

The structure of glucose

Open chain structure of glucose:

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

H O
C
H C OH
HO C H
H C OH
H C OH
H C H
OH

Ring structures of glucose:

Intramolecular cyclisation occurs in the open chain structure which forms the ring
structure of glucose. Carbon 1 is a chiral carbon. It is also called an anomeric carbon and
it allows glucose to exist in 2 forms:
1. The α form – the hydrogen on carbon 1 is above the plane of the ring:
2. The β form – the hydrogen on carbon 1 is below the plane of the ring:

This Photo by Unknown Author is licensed under CC BY-NC

Formation of a glycosidic bond

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

A water molecule is eliminated between 2 monosaccharides resulting in the formation

of 1, 4 glycosidic linkages.

Starch

Starch is the major carbohydrate reserve in plants. It consists of two types of polymers:
amylose and amylopectin.

Amylose:

Monomer: α- glucose

Linkage: α-1, 4 glycosidic linkage

Amylose is a linear chain (i.e., there are no branches in this structure).

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

Amylopectin (Pectin)

Monomer: α-glucose

Linkage: α-1, 4 glycosidic linkage and α-1, 6 glycosidic linkage

About one in every 20 glucose units is linked by a α-1, 6 glycosidic bond which forms
branch points. e

α-1,6-glycosidic linkage

α-1,4-glycosidic linkage

Cellulose

Cellulose is also found in plants and is a major constituent of cell walls. It is also made
up of glucose units.

Monomer: β-glucose

Linkage: β-1, 4 glycosidic linkage

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UNIT 2 CHEMISTRY – THE CHEMISTRY OF CARBON COMPOUNDS – MACROMOLECULES

Because of this type of bonding that occurs in cellulose, it is a structural polymer which
gives rigidity and strength to plant cell walls. Cellulose in indigestible by humans
because the enzyme which breaks down its structure (cellulase) is absent in humans.
Cellulose forms microfibrils which form macrofibrils and provide tensile strength.

Pectin

Pectin is found between the walls of plant cells. It is used commercially in place of
gelatin to make foods set. The monomer to make pectin is methylglucuronic acid.

Structure of Pectin

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