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CHEMISTRY A LEVEL NOTES

Section 3: Organic Chemistry

Luca Seemungal1

February 25, 2017

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Many thanks to Mr Holt #bae
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Contents

1 Introduction to Organic Chemistry 5


1.1 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.1 Formulae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.2 Homologous Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.1.3 IUPAC Nomenclature Convention . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2 Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.1 Free-Radical Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.2.2 Nucleophilic Substitution Mechanism in Halogenoalkanes . . . . . . . . . . . . . . 7

2 Alkanes 9
2.1 Fractional Distillaion of Crude Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.1 Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 Crude Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.1.3 Fractional Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2 Modificaton of Alkanes by Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.1 Thermal Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2.2 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Combustion of Alkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.1 Complete Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3.2 Incomplete Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

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4 CONTENTS
Chapter 1

Introduction to Organic Chemistry

1.1 Nomenclature
Organic chemistry studies millions of covalent compounds based on the element carbon, and so scientists
have devised an algorithm to name every possible type of compound (thus far discovered) with a distinct
name. This means that compounds that have not been discovered yet, but whose structure can be
predicted, and is therefore of an already known type, can be named. It also means that online databases
can use computers to name any compound given certain pieces of information.

1.1.1 Formulae
Organic compounds can be represented by:
Empirical Formulae: the simplest whole number ratio between the atoms of each element in a
compound.
Molecular Formulae: the formula that shows the actual number of atoms of each element that
make up the molecule of a compound.
General Formulae: the molecular formula that contains a variable n that shows the pattern of
the number of atoms of each element that make up any molecule in a certain homologous series
Structural Formulae: the formula that shows the unique arrangement of atoms in a molecule in
a simplified form, without showing all the bonds.
Displayed Formulae: the formula that draws out the molecule showing every atom and every
bond in the molecule.
H H

e.g. C2 H4 (ethene): C C

H H
Skeletal Formulae: the formula that is used to represent carbon chains; the carbon atoms are
not shown but:
each straight line is a C C bond
each double line is a C C double bond
each triple line is a C C triple bond
the end of each line is a CH3 group
where two lines meet is a CH2 group
where three lines meet is a CH group

e.g. C2 H4 :
Ethene
e.g. C3 H6 :
Propene

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6 CHAPTER 1. INTRODUCTION TO ORGANIC CHEMISTRY

1.1.2 Homologous Series


Homologous Series: A series of compounds containing the same functional group.

Members of a homologous series have a general formula.


Each adjacent member of a homologous series differ by one CH2 group.
Different homologous series differ by their functional group, which is the group which has a
certain structure, and will therefore react similarly no matter what chain it is attached to.
The length of the carbon chain has little effect on the chemical reactivity of the functional
group.
The length of the carbon chain affects physical properties. As the length of the straight chain
increases,
the melting point increases,
the boiling point increases.
This is because there are more electrons in each molecule, and so the intermolecular forces
also increase.
Branching on a chain reduces melting points because the molecules pack toghter less easily
thus the intermolecular forces do not superimpose as symmetrically, and so the intermolecular
forces are weaker.

1.1.3 IUPAC Nomenclature Convention


In chemistry, a number of prefixes, suffixes and infixes are used to describe the type and position of
functional groups in the compound.
The steps for naming an organic compound are:

1. Identification of the parent hydrocarbon chain. This chain must obey the following rules, in order
of precedence:

(a) It should have the maximum number of the suffix functional group. By suffix, it is meant that
the parent should have a suffix, unlike halogen substituents. If more than one functional group
is present, the one with highest precedence should be used.
(b) It should have the maximum number of multiple bonds.
(c) It should have the maximum number of single bonds.
(d) It should have the maximum length.

2. Identification of the parent functional group, if any, with the highest order of precedence.

3. Identification of the side-chains. Side chains are the carbon chains that are not in the parent chain,
but are branched off from it.

4. Identification of the remaining functional groups, if any, and naming them by their ionic prefixes.

5. Identification of double/triple bonds.

6. Numbering of the chain. This is done by first numbering the chain in both directions, then choosing
the numbering which follows these rules, in order of precedence:

(a) Has the lowest-numbered locant for the suffix functional group. Loncants are the numbers on
the carbons to which the substituent is directly attached.
(b) Has the lowest-numbered locants for multiple bonds. The locant of a multiple bond is that
number of the adjacent carbon which has a lower number.
(c) Has the lowest-numbered locants for prefixes.

7. Numberig of the various substituents and bonds with their locants. If there is more than one of the
same type of substituent/double bond, then a prefix is added showing how many there are (di, tri,
tetra, etc).
1.2. REACTION MECHANISMS 7

1.2 Reaction Mechanisms


In chemistry, certain reactions of organic compounds can be explained by showing how the species interact
- that is, explaining their reaction mechanisms.

1.2.1 Free-Radical Mechanisms


A free-radical reaction is more precisely known as a free-radical substitution chain reaction
Free Radical: A highly reactive particle with an unpaired electron.

For example: CH4 + Cl2 CH3 Cl + HCl

1. Initiation
Cl2 + 2Cl

Homolytic fission occurs between the two Cl atoms, that is the Cl Cl bond is broken
symmetrically, such that 2Cl are produced and not only one Cl
The Cl free-radical has one unpaired electron.

2. Propogation
CH4 + Cl HCl + CH3
CH3 + Cl2 CH3 Cl + Cl

This process continues in a chain because each equation produces another free radical which
can produce another free radical.

3. Termination
When any two free radicals meet, they react with each other to form a stable molecule, and
so those two particular chains stop.

Cl + Cl Cl2
Cl + CH3 CH3 Cl
CH3 + CH3 C 2 H6

Traces of ethane provides very strong evidence for this mechanism.

1.2.2 Nucleophilic Substitution Mechanism in Halogenoalkanes


A nucleophile can be attracted to an atom which carries a partial positive charge, and use its lone pair
to form a covalent bond to that atom. The nucleophile is also commonly referred to as a lone pair donor.
Each of the following species can act as a nucleophile:
hydroxide ion OH

cyanide ion CN
ammonia molecule NH3
water molecule H2 O

Some nucleophiles have a positive charge, and others are neutral molecules, but they always have
a lone pair, and it must be drawn.

Sometimes the charge is draw on the atom which provides that charge.
A curly arrow shows the movement of a pair of electrons, either a lone pair or a bond pair.
When nucleophilic substitution occurs, the nucleophile takes the place of the leaving group.
8 CHAPTER 1. INTRODUCTION TO ORGANIC CHEMISTRY
Chapter 2

Alkanes

2.1 Fractional Distillaion of Crude Oil


2.1.1 Alkanes
Alkanes are saturated hydrocarbons, because they have only single bonds (saturated) and con-
tain only carbon and hydrogen (hydrocarbons).

The general formula of alkanes is Cn H2n+2 . There are three types of structures of alkanes:

Straight / Unbranches Chain Straight chain alkanes consist of a CH3 group at either end of
the chain and only CH2 groups in the middle of the chain. They are called straight because
each carbon not on the end of the chain is bonded to 2 other carbons, but the bond angle is
109.5 .
Branched chain Branched chain alkanes are isomers of straight-chain alkans with the same carbon
number, and because they are branched certain carbon atoms in the are bonded to 3 or 4 other
carbon atoms. The number of isomers increases rapidly with the number of carbons in the
molecules, because there are many more configurations of the same number of carbon atoms.
Ring Ring alkanes have the general formula Cn H2n because the 2 carbons that would have been
on the end of the straight chain do not bond with 1 hydrogen each but rather with each other.

Physical Properties of Alkanes


Polarity and Intermolecular Forces Alkanes are almost non-polar because the electronegativities of
carbon (2.5) and hydrogen (2.1) are so similar, and many symmetrically-structured alkanes such as
straight chain and ring alkanes are such that the partial charges cancel out so there is no net charge
on any large area of the alkane. Van der Waals forces, however, get increasingly more potent as
the number of carbons in the alkane increases because there is a higher electron density. The van
der Waals forces in branched chain alkanes are much weaker, however, because they are much less
symmetrical and so the electron density is not as great.

Boiling Points As the chain length increases, so do the boiling points of the molecules. This is due
to the stronger van der Waals forces explained above. The shorted chains are gases at room
temperature, and the solids have a very waxy feel.

Solubility Alkanes are insoluble in water, because the hydrogen bonds between water molecules are
much stronger than the van der Waals forces that act between alkanes. However, alkanes do mix
with relatively non-polar liquids.

Reactivity
Alkanes are very inert. They do not react with acids, bases, oxidising agents, and reducing agents. Alka-
nes, however, burn vigorously and will react with halogens under suitable conditions. When combusted,
alkanes produce CO2 , and when incompletely combusted, alkanes produce CO.

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10 CHAPTER 2. ALKANES

2.1.2 Crude Oil


Crude oil is a mixture consisting mainly of alkane hydrocarbons that can be separated by fractional
distillation. The length of the chains vary greatly, from gaseous hydrocarbons which exist above
the reserve of crude oil, to chain lengths tens of carbons long.
Crude oil is formed over millions years by the breakdown of plant and animal remains at high
temperatures and pressures deep below the Earths surface.
Crude oil contains small amounts of other compounds dissolved in it from the plants and animals
from which the oil was formed. These impurities can cause harmful effects to the environment when
the hydrocarbons are burned - for example, sulfur impurities can for SO2 when burned, which is
acidic and can cause acid rain.

2.1.3 Fractional Distillation


Crude oil is a mixture of many different sizes of hydrocarbons, and so to separate the hydrocarbons
into classes of similarly sized molecules fractional distillation is carried out. The different fractions
are then further separated for more specific uses, or they are used as-is. Fractional distillation works
because there is a correlation between chain length and boiling point, and so the different fractions can
be separated out by distilling them in a fractionating tower. Below is outlined the process of fractional
distillation:
1. The crude oil is heated in a furnace.
2. A mixture of liquid and vapour passes into a tower that is cooler at the top than at the bottom.
3. The vapours pass up the tower via a series of trays containing bubble caps, until they arrive at
a tray that is sufficiently cool as to be below that molecules boiling point, and so the molecules
condense into a liquid and are siphoned off through pipes.
As is possible to deduce, the chorter chain hydrocarbons will have higher boiling points and so the first
tray which is below their boiling point will be higher than longer chain hydrocarbons, the first tray which
is below whose boiling point will be lower down. Therefore the fractions are separated by boiling point.
The thick residue that collects at the base of the tower is called bitumen or tar, and can be use for road
surfacing.
diagramme of fractionating column.

2.2 Modificaton of Alkanes by Cracking


Cracking involves breaking CC bonds in alkanes.

Cracking involves breaking C C bonds in alkanes in order to produce smaller-chained alkanes and
alkenes.
Long-chained hydrocarbons are in very low demand, but high supply.
Short-chained hydrocarbons are in very high demand, but low supply.
Therefore long-chained alkanes can be cracked into two shorted hydrocarbons, one an alkane and
the other an alkene. This will increase the supply of shorter-chained hydrocarbons and satisfy
customer demand.
Shorter length alkanes are used for fuel; the high demand comes from gasoline for cars which
are alkanes of length 5-10 carbon atoms, and also from cooking gas which are hydrocarbons
of length 1-4 carbon atoms.
Alkenes are very reactive as they have c c double bonds (they are unsaturated and so are in
high demand for feedstock - that is, alkenes are used to make many other organic compounds
such as paints, plastic, and medicinal drugs.
The products of cracking are often separated using fractional distillation.
There are 2 types of cracking, thermal cracking and catalytic cracking:
2.3. COMBUSTION OF ALKANES 11

2.2.1 Thermal Cracking


In thermal cracking, the long-chain alkanes are put under high temperatures, 700-1200 K, and high
pressures, up to 7000 kPa. A C C bond in the long chain molecule is split, producing 2 shorted chain
hydrocarbons. One electron from the bond goes to one of the species, and the other electron goes to
the other species. Each species has one unpaired electron hence they are free radicals. This is incredibly
unstable, and so one of the free radicals has one of its hydrogen atoms removed, and so there are now 2
unpaired electrons in the species. These 2 electrons form a double bond (a bond) between the outer
carbon and the next carbon along. Now there is a and a bond between 2 carbons, and so that species
is an alkene. The remaining H+ and free radical react and form an C H. Hence this other species is now
a shorter alkane. diagramme

2.2.2 Catalytic Cracking


Catalytic cracking takes place at a lower temperature, 720 K, and a lower pressure, 1 atm, using a zeolite
catalyst. Zeolites have a honeycomb structure and so they have an enormous surface area, an they are
also acidic. This form of cracking is used mainly to produce motor fuels, which are branched alkanes,
cycloalkanes, and aromatic compounds. laboratory cracking diagramme

2.3 Combustion of Alkanes


Alkanes are used as fuels, because despite being inert with most other chemical compounds, they combust
vigorously. Combustion reactions give out large amounts of heat, and therefore have large negative
enthalpies. The longer the chain, the larger the heat output. Alkanes therefore contain a large amount
of energy per gramme, and so are store energy very efficiently, and are the main global fuel source.

2.3.1 Complete Combustion


Shorter chain alkanes burn completely in a plentiful supply of oxygen to give carbon dioxide and water:
CH4(g) + 20 2(g) CO2(g) + 2 H2 O(l)

2.3.2 Incomplete Combustion


In a limited supply, of oxygen, alkanes will burn incompletely and produce carbon monoxide and water:
C3 H8(g) + 3.50 2(g) 3 CO(g) + 4 H2 O(l)
The internal combustion engine produces a number of pollutants including NOx , CO, carbon and
unburned hydrocarbons. These gaseous pollutants from internal combustion engines can be removed
using catalytic converters. Combustion of hydrocarbons containing sulfur leads to sulfur dioxide that
causes air pollution. Students should be able to explain why sulfur dioxide can be removed from flue
gases using calcium oxide or calcium carbonate.