6: Organic Chemistry I

6A. Introduction to Organic Chemistry

Basic definitions
Hydrocarbon is a compound consisting of hydrogen and carbon only to know

Saturated: Contain single carbon-carbon bonds only Unsaturated : Contains a C=C double bond

Molecular formula: The formula which shows the actual number of each type of atom

Empirical formula: shows the simplest whole number ratio of atoms of each element in the compound

General formula: algebraic formula for a homologous series e.g. CnH2n

Structural formula shows the minimal detail that shows the arrangement of atoms in a
molecule, eg for butane: CH3CH2CH2CH3 or CH3(CH2)2CH3,

Displayed formula: show all the covalent bonds present in a molecule

Drawing Displayed formulae Remember that the shape around the

carbon atom in saturated hydrocarbons is
H H H H tetrahedral and the bond angle is 109.5o
When drawing organic
H C C C C H compounds add the
hydrogen atoms so that H H
H H H
H C H each carbon has 4 bonds
H C C H
H

H H

Skeletal formula shows the simplified organic formula, shown by removing hydrogen atoms from alkyl chains,
leaving just a carbon skeleton and associated functional Groups.

OH

But-2-ene Butan-1-ol
2-methylbutane cyclohexane cyclohexene

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Homologous series are families of organic compounds with the same functional
group and same general formula.
•They show a gradual change in physical properties (e.g. boiling point).
• Each member differs by CH2 from the last.
• same chemical properties.

Functional group is an atom or group of atoms which when present in different molecules
causes them to have similar chemical properties

prefix / suffix
homologous functional example
(* = usual use)
series group
Alkane
C C CH3CH2CH2CH3
-ane Butane

H H
Alkenes C C suffix -ene C C propene
H
H C
H
H

suffix* -ol H H H Propan-1-ol

Alcohols prefix hydroxy-
C OH H C C C O H
OH
H H H

H H H
Halogenoalkanes C halogen prefix chloro-
1-chloropropane
H C C C Cl
bromo- Cl
H H H
iodo-

O suffix -al H O
Aldehydes O ethanal
C H prefix formyl- H C C H

O suffix* -one H O H
O Propanone
C
prefix oxo-
H C C C H
Ketones
H H

O suffix -oic acid

carboxylic acids H O O Ethanoic acid
C OH
H C C OH

H
OH
O
-yl –oate
O methylethanoate
C O
H O H
Esters
H C C O C H

H H
O

When compounds contain more than one functional group, the order of precedence determines which groups are
named with prefix or suffix forms. The highest precedence group takes the suffix (and the lowest number on the carbon
chain), with all others taking the prefix form. However, double and triple C-C bonds only take suffix form.
Order of priority highest first:
Carboxylic acids >aldehydes>ketones>alcohols>alkenes>halogenoalkanes

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 General rules for naming carbon chains no of
code
carbons
Count the longest carbon chain and name appropriately
meth 1
Find any branched chains and count how many carbons they contain
eth 2
 Add the appropriate prefix for each branch chain
prop 3
Eg -CH3 methyl or -C2H5 ethyl –C3H7 propyl
1 CH but 4
3
pent 5
2 CH2 hex 6
5 3,5-dimethylheptane
hept 7
H3 C CH CH2 CH CH3
3 oct 8
4
CH2 6 non 9

dec 10
CH3 7

Basic rules for naming functional groups

The functional group is named by a prefix or suffix. e.g. bromoethane, ethanol, propene

•When using a suffix, add in the following way :

If the suffix starts with a vowel- remove the –e from the stem alkane name
e.g. Propan-1-ol, butan-1-amine, ethanoic acid, ethanoylchloride, butanamide

If the suffix starts with a consonant or there are two or more of a functional group meaning di, or tri needs to be
used then do not remove the the –e from the stem alkane name
e.g. Propanenitrile, ethane-1,2-diol, propanedioic acid, propane-1,2,3-triol, Pentane-2,4-dione.

The position of the functional group on the carbon H H H O H

chain is given by a number – counting from the end
H C C 3 C2 C1 H Butan-1-ol
of the molecule that gives the functional group the 4
lowest number. For aldehydes, carboxylic acids &
H H H H
nitriles, the functional group is always on carbon 1.
H H H

We only include numbers, H C C C H

methylpropane CHCl3 trichloromethane
however, if they are needed H H
to avoid ambiguity. H C H

•The functional groups take precedence over branched 3-methylbut-1-ene is correct and not 2-methylbut-3-
chains in giving the lowest number ene
H H H H H

Where there are two or more of the same groups, di-, tri- , H C C C C C H 2,3-dibromopentane.
tetra-, penta- or hexa- are used. Note the point made above
H H Br H
about the addition of ‘e’ to the stem Br

Words are separated by numbers with dashes CH2FCCl2CH2CH3 2,2-dichloro-1-fluorobutane.

 numbers are separated by commas
CH2FCH2CHBrCH2CH3 3-bromo-1-fluoropentane
If there is more than one functional group or side chain, the
groups are listed in alphabetical order (ignoring any di, tri).

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Alkenes
2 4
1 3 Double bond between
The double bond will be between two carbons. Use the lower
C2 and C3 so But-2-ene
number of the two to show the position of the double bond

The name for alkenes may include E or Z at start to show Z-but-2-ene

the type of stereoisomer

If more than one double bond is present then suffix Penta-1,3-diene

ends diene or triene. The stem ends in a
The suffix -en for alkenes can go in front of other suffixes. CH2OHCHBrCH=CH2 2-bromobut-3-en-1-ol
The alcohol and carboxylic acid groups have higher priority OH
than the alkene group so take precedence with numbering
E-but-2-enoic acid
O

Halogenoalkanes H H Br H
Class the halogen as a substituent on the C chain and use 2-bromobutane
H C C C C H
the prefix -fluoro, -chloro, -bromo, or –iodo. (Give the
position number if necessary) H H H H
I
Cl

Br
Cl
F Br
2,3-dichloro-1-fluoro-3-methylpentane 5,5-dibromo-4-iodo-3-methylpent-1-ene

Multiple functional group and side chains are listed The alkene group has higher priority than the
in alphabetical order (ignoring any di, tri). halogenoalkane group so it takes the lowest number
on the carbon chain

Alcohols
These have the ending -ol and if necessary the position OH

number for the OH group is added between the name Butan-2-ol

CH3 CH CH2 CH3
stem and the –ol 1 2 3 4

If there are two or more -OH groups then di, tri are HO CH2 CH2 OH Ethane-1,2-diol
used.
Add the ‘e’ on to the stem name though. H2C CH CH2 propane-1,2,3-triol
OH OH OH
Cl
The OH group has a higher priority than the
halogenoalkane group and alkene so takes
precedence in numbering. The OH is on carbon 1 OH
Cl
E-3,6-dichlorohex-4-en-1-ol
O
If the compound has an –OH group in addition to another
H3C CH C 2-hydroxypropanoic acid
functional group with a higher priority. The priority group gets
the suffix ending and the OH can be named with the prefix OH OH
hydroxy-:

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 H
Aldehydes O

An aldehyde’s name ends in –al

It always has the C=O bond on the first carbon of H C C

the chain so it does not need an extra number. It is

by default number one on the chain. H
H

Ethanal

If two aldehyde groups then di is put before –al and an O O

e is added to the stem.
pentanedial

O
Aldehydes have a higher priority than alcohol so the –OH HO
group uses the hydoxy prefix. 4-hydroxybutanal

Ketones H O H

Ketones end in -one H C C C H

When ketones have 5C’s or more in a chain then H H

it needs a number to show the position of the Propanone
double bond. E.g. pentan-2-one
H O H O H
If two ketone groups then di is put before – H C C C C C H
one and an e is added to the stem.
H H H
Pentane-2,4-dione

Carboxylic acids H H
O
These have the ending -oic acid but no number is
necessary for the acid group as it must always be H C C C Propanoic acid
at the end of the chain. The numbering always
starts from the carboxylic acid end. H H
O H

O O Ethanedioic acid
If there are carboxylic acid groups on both ends of the
C C
chain then it is called a - dioic acid Note the e in this name
HO OH

O
5-hydroxy-4-methylpentanoic acid

OH OH

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 Isomers
Structural isomers: same molecular formula different structures (or structural formulae)

Structural isomerism can arise from

EDEXCEL does not split structural
•Chain isomerism isomers into the different categories.
•Position isomerism They are all classed as structural
isomers.
•Functional group isomerism
Chain isomers: Compounds with the same molecular formula but different
structures of the carbon skeleton
H
H H H H H H H H H H C H
H H
H C C C C C H H C C C C H
H C C C H
H H H
H H H H H H C H H H
H C H
pentane H
H
2-methylbutane
2,2-dimethylpropane

Position isomers: Compounds with the same molecular formula but different structures
due to different positions of the same functional group on the same carbon skeleton

H H H H H H

H C C C H 1-bromopropane H C C C H 2-bromopropane

Br H H H Br H

Functional group isomers: Compounds with the same molecular formula but
with atoms arranged to give different functional groups

H H H H
Methoxymethane: an ether
H C C O H ethanol: an alcohol H C O C H

H H
H H

H H
H H
C
H C C H
Cyclohexane- cyclo alkane CH3CH2CH2CH2CH=CH2 hexene- alkene
H C C H
C
H H
H H Note: alkene and cyclo alkanes have the same general formula. Hexene
and cyclohexane have the same molecular formula but have a different
functional group

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Stereoisomerism

Stereoisomers have the same structural formulae Alkenes can exhibit a type of isomerism
but have a different spatial arrangement of atoms. called E-Z stereoisomerism

E-Z isomers exist due to restricted E-Z stereoisomers arise when:

rotation about the C=C bond (a) There is restricted rotation around the C=C double bond.
(b) There are two different groups/atoms attached both ends of
Single carbon-carbon covalent the double bond
bonds can easily rotate

H H

H H
two different groups H C C H But-1-ene
H C C H attached either end of
C C
the restricted double H H
C C H
bond- leads to EZ H two identical groups attached to
H H H H isomers one end of the restricted double
Z- but-2-ene bond – no E-Z isomers

But-1-ene is a structural isomer of But-2-

H
H These are two ene but does not show E-Z isomerism
C H isomers as the lack
H of rotation around Skeletal formulae can also represent E-Z isomerism
C C the double bonds
H
means one cannot Z-but-2-ene
H C
H
be switched to the
H other
E-but-2-ene
E -but-2-ene

Naming E-Z stereoisomers Priority Group: The atom with the bigger
atomic number is classed as the priority atom
First determine the priority groups on both sides of
the double bond

Priority Priority Cl H
group Cl Cl group
side 1 side 2 C C
C C
Z-1,2-dichloroethene
H H H Cl E-1,2-dichloroethene
If the priority atom is on the same side of the If the priority atom is on the opposite side of
double bond it is labelled Z from the german the double bond it is labelled E from the
zusammen (The Zame Zide!) german entgegen (The Epposite side!)

cis-trans isomerism is a special case of EIZ isomerism in

which two of the substituent groups are the same. H
H
H H C H
H C C H H
C C
H
C C
H C
H H H H H
H
Z- but-2-ene E- but-2-ene
Can also be called Can also be called
Cis- but-2-ene trans- but-2-ene

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6A Alkanes

Alkanes are saturated hydrocarbons Saturated: Contain single carbon-carbon bonds only

General formula alkane CnH2n+2 Hydrocarbon is a compound consisting of

hydrogen and carbon only

Fuels from crude oil

They are obtained from the crude oil in the order of fractional distillation, Alkanes are used as fuels
cracking and reformation of crude oil

Refining crude oil fuel gas (bottled)

20° C
Fractional Distillation: petrol/gasoline
40° C
Petroleum is a mixture consisting mainly naptha (chemicals)
of alkane hydrocarbons Crude 110° C
oil kerosene (jet fuel)
Petroleum fraction: mixture of hydrocarbons with 180° C
a similar chain length and boiling point range diesel oil
250° C
fuel oil
300° C
Furnace
lubricating oils
• Oil is pre-heated 340° C
• then passed into column.
• The fractions condense at different heights bitumen
• The temperature of column decreases upwards
• The separation depends on boiling point.
• Boiling point depends on size of molecules. This is a physical process
• The larger the molecule the larger the London forces involving the splitting of
weak London forces
• Similar molecules (size, bp, mass) condense together
between molecules
• Small molecules condense at the top at lower temperatures
• and big molecules condense at the bottom at higher temperatures.

Cracking Cracking: conversion of large hydrocarbons to smaller molecules by breakage of C-C bonds

High Mr alkanes  smaller Mr alkanes+ alkenes + (hydrogen)

Economic reasons for catalytic cracking

• The petroleum fractions with shorter C chains (e.g. petrol and This is a chemical process
naphtha) are in more demand than larger fractions. involving the splitting of
• To make use of excess larger hydrocarbons and to supply demand strong covalent bonds so
for shorter ones, longer hydrocarbons are cracked. requires high temperatures.
• The products of cracking are more useful and valuable than the
starting materials (e.g. ethene used to make poly(ethene) and
ethane-1,2-diol, and ethanol) The smaller alkanes are used for motor
fuels which burn more efficiently.

Reforming Turns straight chain alkanes into branched and cyclic

alkanes and Aromatic hydrocarbons

Branched and cyclic hydrocarbons burn more cleanly and are used to Used for making motor fuels
give fuels a higher octane number.

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Alkanes as Fuels
Alkanes readily burn in the
Fuel : releases heat energy when burnt presence of oxygen. This
combustion of alkanes is highly
Complete Combustion exothermic, explaining their use
In excess oxygen alkanes will burn with complete combustion as fuels.

The products of complete combustion are CO2 and H2O.

C8H18(g) + 12.5 O2(g)  8CO2(g) + 9 H2O(l)

Incomplete Combustion Incomplete combustion produces

less energy per mole than
If there is a limited amount of oxygen then incomplete combustion
complete combustion.
occurs, producing CO (which is very toxic) and/or C (producing a sooty
flame)
Carbon (soot)/particulates can
CH4(g) + 3/2 O2(g)  CO(g) + 2 H2O(l)
cause global dimming- reflection of
CH4(g) + O2(g)  C(s) + 2 H2O(l)
the sun’s light

Carbon monoxide is an highly toxic but odourless CO is toxic to humans as CO can from a strong bond
gas. It can cause death if it builds up in a enclosed with haemoglobin in red blood cells. This is a stronger
space due to faulty heating appliances. bond than that made with oxygen and so it prevents the
oxygen attaching to the haemoglobin.
Pollution from Combustion
Sulfur containing impurities are found in petroleum fractions which
Coal is high in sulfur content, and
produce SO2 when they are burned.
large amounts of sulfur oxides are
S+ O2  SO2 CH3SH+ 3O2  SO2 + CO2 + 2H2O emitted from power stations.

SO2 is acidic and will dissolve in atmospheric water and can produce acid rain.
Nitrogen Oxides NOx
Nitrogen oxides form from the reaction between N2 and O2 inside the car engine.
The high temperature and spark in the engine provides sufficient energy to break strong N2 bond

N2 + O2  2NO N2 + 2O2  2NO2

Pollutant Environmental consequence

Nitrogen oxides (formed when N2 in the air reacts at NO is toxic and can form smog
the high temperatures and spark in the engine) NO2 is toxic and acidic and forms acid rain
Carbon monoxide toxic
Carbon dioxide Contributes towards global warming
Unburnt hydrocarbons (not all fuel burns in the Contributes towards formation of smog
engine)
Soot/particulates Global dimming and respiratory problems

Catalytic converters
These remove CO, NOx and unburned hydrocarbons (e.g. octane,
C8H18) from the exhaust gases, turning them into ‘harmless’ CO2, N2 Converters have a ceramic
and H2O. honeycomb coated with a thin
layer of catalyst metals
2 CO + 2 NO  2 CO2 + N2 platinum, palladium, rhodium
– to give a large surface area.
C8H18 + 25 NO  8 CO2 + 12½ N2 + 9 H2O

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Biofuels

Most fossil fuels come from crude oil, which is a non- Alcohols such as ethanol can be produced
renewable resource. Fossil fuel reserves will eventually from the fermentation of sugars from
run out plants.
Alternative fuels have been developed from renewable Biodiesel is produced by reacting
resources. Alcohols and biodiesel, which can both be vegetable oils with a mixture of alkali and
made from plants, are two examples of renewable plant- methanol
based fuels

Advantages of using Biofuels Disadvantages of Biofuels

Reduction of use of fossil fuels which are finite resources Less food crops may be grown
biofuels are renewable Land not used to grow food crops
Use of biodiesel is more carbon-neutral Rain forests have to be cut down to
Allows fossil fuels to be used as a feedstock for organic provide land
compounds Shortage of fertile soils
No risk of large scale pollution from exploitation of fossil
fuels

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 Introduction to Mechanisms
To understand how the reaction proceeds we must first understand how bonds are broken in organic mechanisms
There are two ways to break a covalent bond:
1.HOMOLYTIC FISSION:
each atom gets one electron from the covalent bond
one headed arrow shows
movement of one electron
Y X Y
X

The bond has broken in a process called homolytic fission.

When a bond breaks by homolytic fission it forms two Free Radicals. DEFINITION

Free Radicals do not have a charge and are represented by a A Free Radical is a reactive species
which possess an unpaired electron

2. HETEROLYTIC FISSION: (one atom gets both electrons)

X Y X: - Y+
two headed arrow shows
movement of pair of
OR - electrons
X Y X+ Y:

+ -
xx xx
x

xx
xx

Cl Cl Cl + Cl
x

xx xx

Heterolytic fission produces IONS

Most organic reactions occur via heterolytic fission, producing ions

The Mechanism:
To understand a reaction fully we must look in detail at how it proceeds step
by step. This is called its mechanism

HO:-
H H The carbon has a small
H H
positive charge because
of the electronegativity
H C C δ+ X δ- H C C OH + X- difference between the
H H carbon and the halogen
H H

We use curly arrows in mechanisms to

A curly arrow will always start
show the movement of an electron pair
from a lone pair of electrons or
showing either breaking or formation of a
covalent bond; the centre of a bond

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 Free Radical Substitution Reactions of Alkanes
Reaction of alkanes with bromine / chlorine in UV light
In general, alkanes do not react
In the presence of UV light alkanes react with chlorine to form a with many reagents.
mixture of products with the halogens substituting hydrogen atoms. This is because the C-C bond
and the C-H bond are relatively
Overall Reaction strong.
This is the overall reaction, but
CH4 + Cl2  CH3Cl + HCl a more complex mixture of
products is actually formed
methane chloromethane
It proceeds via a series of steps:
The mechanism for this reaction is called a free radical Step one: Initiation
substitution Step two: Propagation
Step three: Termination

Step one Initiation The UV light supplies the energy to break the Cl-Cl bond. It is
Essential condition: UV light broken in preference to the others as it is the weakest.

Cl2  2Cl
.
UV light does not have enough energy to break the C-H bond

The bond has broken in a process called homolytic fission.

Cl Cl Cl each atom gets one electron from the covalent bond

Cl

DEFINITION
When a bond breaks by homolytic fission it forms Free Radicals.
A Free Radical is a reactive species which
Free Radicals do not have a charge and are represented by a
possess an unpaired electron

Step two Propagation

The chlorine free radicals are very reactive and remove
CH4 + Cl.  HCl + .CH3
an H from the methane leaving a methyl free radical

.CH + Cl  CH Cl + Cl. The methyl free radical reacts with a Cl2 molecule to
3 2 3
produce the main product and another Cl free radical

All propagation steps have a free radical in the reactants and in the products.

As the Cl free radical is regenerated, it can react with several more

alkane molecules in a chain reaction

Step three Termination Collision of two free radicals does not generate further free radicals:
the chain is terminated.
.CH + Cl .  CH Cl
3 3
.CH + .CH  CH CH Minor step leading to impurities of ethane in product.
3 3 3 3 Write this step using structural formulae and
Cl . + Cl .  Cl 2
don’t use molecular formulae

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 Applying the mechanism to other alkanes
The same mechanism is used: Learn
Example: Write mechanism of Br2 and Propane the patterns in the mechanism

STEP ONE Initiation

Essential condition: UV light
Br2  2Br
. Br2 splits in the same way as Cl2

STEP TWO Propagation

.
CH3CH2CH3 + Br  HBr + CH3CH2CH2
.
Remove one H from the alkane to produce a radical
.
CH3CH2CH2 + Br2  CH3CH2CH2Br + Br
.
To the radical produced in the previous step add a Br
STEP THREE Termination
.
CH3CH2CH2 + Br  CH3CH2CH2Br
.
. .
CH3CH2CH2 + CH3CH2CH2  CH3CH2CH2CH2CH2CH3

Propagation steps for substituting a halogen on a ‘middle’ carbon

.
CH3CH2CH3 + Br  HBr + CH3CH CH3
.
If the question asks for the halogen to be substituted
.
CH3CH CH3 + Br2  CH3CH2BrCH3 + Br
. onto a middle carbon in the chain, it is important to
put the free radical ‘dot’ on the correct carbon in the
propagation stages.

Further substitution
Excess Cl2 present will promote further substitution and could produce CH2Cl2, CHCl3 and CCl4

These reactions could occur Example propagation steps that would lead to
further substitution
CH3Cl + Cl2  CH2Cl2 + HCl
CH2Cl2 + Cl2  CHCl3 + HCl CH3Cl + Cl.  HCl + .CH2Cl
CHCl3 + Cl2  CCl4 + HCl . CH Cl + Cl  CH Cl + Cl .
2 2 2 2

Overall reaction equations

You should be able to write overall reaction equations for various reactions
Example 1. Write the overall reaction equation for the formation of CCl4 from CH4 + Cl2

CH4 + 4 Cl2  CCl4 + 4 HCl

Example 2. Write the overall reaction equation for the formation of CFCl3 from CH3F + Cl2
CH3F + 3 Cl2  CFCl3 + 3 HCl

Note HCl is always the side product – never H2

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6C Alkenes
Alkenes contain a carbon-
Alkenes are unsaturated hydrocarbons General formula is CnH2n carbon double bond
somewhere in their structure
H H H H

C C C H
C C Ethene Propene
H H H
H H

H H H H
Numbers need to be H
added to the name when H C C C C H But-2-ene
C C C C H But-1-ene
positional isomers can
occur H H H H H H H H

π bonds are exposed and have high

C=C double covalent bond electron density.
consists of one sigma (σ)
bond and one pi (π) bond. They are therefore vulnerable to attack
by species which ‘like’ electrons: these
C-C sigma bond C-C pi bond species are called electrophiles.

Formation of σ bond

C C

One sp2 orbital from each carbon overlap to

form a single C-C bond called a sigma σ bond sigma σ bond

Rotation can occur around a sigma bond

Formation of π bond
p orbitals

The π bond is formed by

sideways overlap of two p
orbitals on each carbon atom
forming a π-bond above and
below the plane of molecule.

C-C sigma bond The π bond is weaker than

C-C pi bond the σ bond.

The pi bond leads to resultant high electron density above

There is Restricted rotation about a pi bond and below the line between the two nuclei

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 Addition Reactions of Alkenes Addition reaction: a reaction where two molecules react
together to produce one

1. Reaction of Alkenes with Hydrogen

Change in functional group: alkene  alkane H H

H H
Reagent: hydrogen
Conditions: Nickel Catalyst C C + H2  H C C H
Type of reaction: Addition/Reduction
H H H H
ethene ethane

Electrophilic Addition: Reactions of Alkenes

A π bond is weaker than a σ bond so less energy is needed to break π bond Definition Electrophile: an
The π bonds in alkenes are areas with high electron density. This is more electron pair acceptor
accessible to electrophilic attack by electrophiles. Alkenes undergo addition
reactions.

2. Reaction of Alkenes with bromine/chlorine

H H
Change in functional group: H H
alkene  dihalogenoalkane
C C + Br2  H C C H
Reagent: Bromine (dissolved in organic solvent)
Conditions: Room temperature (not in UV light) H H Br Br
Mechanism: Electrophilic Addition 1,2-dibromoethane
Type of reagent: Electrophile, Br+
Type of Bond Fission: Heterolytic

As the Br2 molecule H H

H H H H
approaches the alkene,
the pi bond electrons + The INTERMEDIATE
C C H C C H H C C H formed, which has a
repel the electron pair in
the Br-Br bond. This δ+ H positive charge on a
H Br Br carbon atom is called a
INDUCES a DIPOLE. Br2 Br Br
becomes polar and :Br - CARBOCATION
ELECTROPHILIC (Brδ+). Brδ-

3. Reaction of Hydrogen Bromide with alkenes

Change in functional group: H H H H H H

alkene halogenoalkane
H C C C C H + HBr  H C C C C H
Reagent: HCl or HBr
Conditions: Room temperature H H H H H H Br H

Mechanism: Electrophilic Addition But-2-ene 2-bromobutane

Type of reagent: Electrophile, H+
Type of Bond Fission: Heterolytic

HBr is a polar molecule H H H H

H H
because Br is more +
H3C C C CH3
electronegative than H. H3C C C CH3 H3C C C CH3
The H δ + is attracted to δ+
H H H
the electron-rich pi bond. -
Br
Brδ :Br -

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 If the alkene is unsymmetrical, addition of hydrogen bromide can lead to two isomeric products.
But-1-ene will form a mixture of 1-bromobutane and 2-bromobutane on reaction with hydrogen
bromide :Br -
H
+ H H H H
C CH2
Major
H C C C C H
H3C CH3 product
δ+ δ- 90%
H Br H H Br H

:Br -
H2C CH CH2 CH3 H H
+
C C CH2 CH3 CH2 CH2 CH2 CH3 Minor
product
H Br 10%
H

WHY? In electrophilic addition to alkenes, the major product is

This carbocation intermediate H H H formed via the more stable carbocation intermediate.
is more stable because the
methyl groups on either side H C C C H In exam answers
of the positive carbon are +
•Draw out both carbocations and identify as primary, secondary
electron releasing and reduce and tertiary
H H
the charge on the ion which •State which is the more stable carbocation e.g. secondary more
stabilises it. stable than primary
•State that the more stable carbocation is stabilised because the
The order of stability for carbocations is methyl groups on either (or one) side of the positive carbon are
electron releasing and reduce the charge on the ion.
tertiary > secondary >primary •(If both carbocations are secondary then both will be equally
stable and a 50/50 split will be achieved)

4. Reaction of Potassium Manganate(VII) with Alkenes

Change in functional group: alkene  diol H H H H H

Reagent: KMnO4 in an acidified solution KMnO4
C C C H H C C C H
Conditions: Room temperature
Type of reaction: Oxidation
H H H OH OH H
Observation: purple colour of MnO4- ion will propene Propane-1,2-diol
decolourise to colourless
This reaction with its colour change can be used as a test
for the alkene functional group. It would not change colour
with alkanes

5. Reaction of Bromine Water with Alkenes

Reagent: Bromine dissolved in water H H H H

Conditions: Room temperature
Type of reaction: Addition C C + BrOH H C C H
Observation: Orange colour of bromine water H H Br OH
will decolourise to colourless

This reaction with its colour change is used as a test for the
alkene functional group.

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Hydration of alkenes to form alcohols This reaction can be called
Industrially alkenes are converted to alcohols in one step rather than the hydration: a reaction where
two in the above sulfuric acid reaction. They are reacted with water in the water is added to a molecule
presence of an acid catalyst.
Essential Conditions

CH2=CH2 (g) + H2O (g)  CH3CH2OH High temperature 300 to 600°C

(l)
High pressure 70 atm
Catalyst of concentrated H3PO4

The high pressures needed mean this cannot be done in the laboratory. It is preferred industrially, however,
as there are no waste products and so has a high atom economy. It would also mean separation of products
is easier (and cheaper) to carry out. See equilibrium chapter for more on the industrial conditions for this
reaction.

Addition Polymers
Addition polymers are formed from alkenes Poly(alkenes) like alkanes are unreactive due to
the strong C-C and C-H bonds.
This is called addition polymerisation

be able to recognise the repeating unit in a poly(alkene)

n

Monomer H H H H H H
Polymer
Ethene Poly(ethene) C C C C C C
H H
H H
CH3 H CH3 H CH3 H
C C
C C
n
H CH3 H CH3
n Add the n’s if writing an equation showing the
propene reaction where ‘n’ monomers become ‘n’ repeating
poly(propene)
units
Poly(propene) is recycled

Poly(ethene): is used to make plastics bags,

Poly(propene) is a stiffer polymer, used in
buckets, bottles. It is a flexible, easily moulded,
utensils and containers and fibres in rope
waterproof, chemical proof, and low density
and carpets.
plastic.

It is best to first draw out H CH3

You should be able e.g. For but-2-ene the monomer with groups H CH3
to draw the polymer of atoms arranged around
H3C CH CH CH3 the double bond C C C C
repeating unit for any
alkene H3C H
CH3 H

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Methods of disposal of waste polymers

Incineration
Rubbish is burnt and energy produced is used to generate electricity.
Some toxins can be released on incineration. (e.g. Combustion of halogenated plastics (ie PVC) can
lead to the formation of toxic, acidic waste products such as HCl.) Modern incinerators can burn more
efficiently and most toxins and pollutants can be removed. Greenhouse gases will still be emitted
though.
Volume of rubbish is greatly reduced.

Recycling
Saves raw materials- nearly all polymers are formed from compounds sourced/produced from
crude oil. Saves precious resources.
Polymers need collecting/ sorting- expensive process in terms of energy and manpower.
Polymers can only be recycled into the same type – so careful separation needs to be done.
Thermoplastic polymers can be melted down and reshaped.

feedstock for cracking

Polymers can be cracked into small molecules which can be used to make other chemicals and new
polymers- Saves raw materials-

Chemists have designed ways to remove toxic waste products like HCl before they are emitted into the
atmosphere. The waste gases from the incinerator are scrubbed/reacted with a base or carbonate. The
base reacts with the acidic HCl gas, neutralising it (eg CaO + 2HCl  CaCl2 + H2O)

Chemists have also develop biodegradable and compostable polymers. Biodegradable polymers can
be made from substances such as maize and starch

18
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 6D Halogenoalkanes
H
Naming Halogenoalkanes H H H
H C H
H H H
Based on original alkane, with a prefix indicating halogen atom: H C C C H
H C C C C H
Fluoro for F; Chloro for Cl; Bromo for Br; Iodo for I.
Br H H H Cl H H
Substituents are listed alphabetically
1-bromopropane 2-chloro-2-methylbutane
Classifying Halogenoalkanes

Halogenoalkanes can be classified as primary, secondary or tertiary depending

on the number of carbon atoms attached to the C-X functional group.
H
H H H H H H
H C H
H H H
H C C C H H C C C H
H C C C C H
Br H H H Br H
H Cl H H

Primary halogenoalkane Secondary halogenoalkane Tertiary halogenoalkane

One carbon attached to the Two carbons attached to the Three carbons attached to the
carbon atom adjoining the carbon atom adjoining the carbon atom adjoining the
halogen halogen halogen

Halogenoalkanes undergo either

Reactions of Halogenoalkanes
substitution or elimination reactions
Nucleophilic substitution reactions
Substitution: swapping a halogen atom for another atom or groups of atoms

Nucleophile: electron pair donator e.g. :OH-, :NH3, CN-

:Nu represents any nucleophile – they
The Mechanism: We draw (or outline) mechanisms to always have a lone pair and act as
show in detail how a reaction proceeds electron pair donators

Nu:-
The nucleophiles
H H The carbon has a small
attack the positive H H positive charge because
carbon atom
of the electronegativity
H C C δ+ X δ- H C C Nu + X- difference between the
carbon and the halogen
H H
H H

We use curly arrows in mechanisms (with

A curly arrow will always start
two line heads) to show the movement of
from a lone pair of electrons or
two electrons
the centre of a bond

The rate of these substitution reactions depends on the strength Bond enthalpy /
of the C-X bond kJmol-1
The weaker the bond, the easier it is to break and the faster the reaction.
C-I 238
C-Br 276
The iodoalkanes are the fastest to substitute and the
fluoroalkanes are the slowest. The strength of the C-F bond is C-Cl 338
such that fluoroalkanes are very unreactive
C-F 484

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 Comparing the rate of hydrolysis reactions

Hydrolysis is defined as the splitting of a molecule ( in this Water is a poor nucleophile but it can
case a halogenoalkane) by a reaction with water react slowly with halogenoalkanes in a
substitution reaction
CH3CH2X + H2O  CH3CH2OH + X- + H+

Aqueous silver nitrate is added to a halogenoalkane and the CH3CH2I + H2O  CH3CH2OH + I- + H+
halide leaving group combines with a silver ion to form a
Ag+ (aq) + I-(aq)  AgI (s) - yellow precipitate
silver halide precipitate.
The precipitate only forms when the halide ion has left the The iodoalkane forms a precipitate with
halogenoalkane and so the rate of formation of the precipitate the silver nitrate first as the C-I bond is
can be used to compare the reactivity of the different weakest and so it hydrolyses the quickest
halogenoalkanes.

The quicker the precipitate is formed, the faster the AgI (s) - yellow precipitate
substitution reaction and the more reactive the haloalkane AgBr(s) – cream precipitate forms faster
The rate of these substitution reactions depends on the strength AgCl(s) – white precipitate
of the C-X bond . The weaker the bond, the easier it is to break
and the faster the reaction.

Nucleophilic substitution with aqueous hydroxide ions

Change in functional group: halogenoalkane  H H H
H H H
alcohol
Reagent: potassium (or sodium) hydroxide
H C C C Br + KOH  H C C C OH + KBr
Conditions: In aqueous solution; Heat under reflux H H H H H H
Mechanism: Nucleophilic substitution
1-bromopropane propan-1-ol
Role of reagent: Nucleophile, OH-

The OH– is a stronger nucleophile than water as it has a full negative The aqueous conditions needed
charge and so is more strongly attracted to the Cδ+ is an important point. If the
solvent is changed to ethanol an
elimination reaction occurs

SN2 nucleophilic substitution mechanism for halogenoalkanes

H CH3 H - H
δ+ δ-
H3C C Br HO C Br H3C C OH + :Br -
-
HO:
H H
H
transition state.

This mechanism occurs with primary halogenoalkanes

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SN1 nucleophilic substitution mechanism for tertiary halogenoalkanes

Tertiary haloalkanes undergo nucleophilic substitution in a different way

Tertiary halogenoalkanes
CH3 CH3 CH3 undergo this mechanism as the
+ - tertiary carbocation is stabilised
H3C C Br H3C C :OH H3C C OH
by the electron releasing methyl
CH3 CH3 CH3 groups around it. (See alkenes
topic for another example of this).
The Br first breaks Also the bulky methyl groups
The hydroxide prevent the hydroxide ion from
away from the
nucleophile then attacking the halogenoalkane in
halogenoalkane to
attacks the positive the same way as the mechanism
form a carbocation
carbon above
intermediate

Primary halogenoalkanes do not do the SN1 mechanism because they would only form an unstable primary
carbocation.

Nucleophilic substitution with ammonia

Change in functional group: halogenoalkane 

amine H H H
H H H

Reagent: NH3 dissolved in ethanol

H C C C Br + 2NH3  H C C C NH2 + NH4Br
Conditions: Heating under pressure in a sealed
tube H H H
H H H

Mechanism: Nucleophilic substitution propylamine

Type of reagent: Nucleophile, :NH3

Naming amines:
In the above example
H H H propylamine, the propyl shows
δ+ δ- the 3 C’s of the carbon chain.
CH3 CH2 C Br
+ :Br -
CH3 CH2 C N H Sometimes it is easier to use the
3HN: IUPAC naming for amines e.g.
H H H Propan-1-amine
:NH3

CH3 CH2 C NH2 + NH4Br

H

Further substitution reactions can occur between the halogenoalkane and the amines
formed leading to a lower yield of the amine. Using excess ammonia helps minimise this.

H R
Further reactions H H
RX RX
RX R N:
H N: H N: R N:

H R R R

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Elimination reaction of halogenoalkanes Elimination: removal of small molecule
(often water) from the organic molecule
Elimination with alcoholic hydroxide ions
H H H H H H
Change in functional group: halogenoalkane 
alkene H C C C H + KOH  H C C C + KBr + H2O
Reagents: Potassium (or sodium) hydroxide H H Br H H

Conditions: In ethanol ; Heat 1-bromopropane propene

Mechanism: Elimination
Role of reagent: Base, OH-

Note the importance of the solvent to the type of reaction here.

Aqueous: substitution
Alcoholic: elimination

Often a mixture of products from both elimination and substitution occurs

2-methyl -2- H
chlorobutane can give
H H C H
With unsymmetrical secondary 2-methylbut-1-ene and H H H
and tertiary halogenoalkanes H C H 2-methylbut-2-ene
H H H C C C C H
two (or sometimes three)
H C C C C H H
different structural isomers can H H
H
be formed H Cl H H
H C H
H H H

H C C C C H

H H

The structure of the halogenoalkane also has an effect on the

degree to which substitution or elimination occurs in this reaction.
Primary tends towards substitution
Tertiary tends towards elimination

Uses of halogenoalkanes
Halogenoalkanes have been used as refrigerants, fire retardants, pesticides and aerosol propellants.

Chloroalkanes and chlorofluoroalkanes can be used as solvents. Some halogenoalkanes

CH3CCl3 was used as the solvent in dry cleaning have low flammability.

Many of these uses have now been stopped due to the toxicity of
halogenoalkanes and also their detrimental effect on the ozone layer.

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6E Alcohols
General formula alcohols CnH2n+1OH

Naming Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4

O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-): OH OH

HO CH2 CH2 OH Ethane-1,2-diol

If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH

H2C OH

Bond angles in alcohols

H The H-O- C bond is 104.5o (bent line
All the H-C-H bonds and C- H shape), because there are 2 bond
C-O are 109.5o (tetrahedral O H pairs of electrons and 2 lone pairs
shape), because there are 4
109.5O C 104.5O
C repelling to a position of minimum
bond pairs of electrons H
repulsion. Lone pairs repel more than
repelling to a position of H bond pairs so the bond angle is
minimum repulsion. H reduced.

Different types of alcohols

H

H H H O
H H H H H

H C C C H
H C C C O H H C C C H

H H H H O H H H
H C H
Propan-1-ol H
H
Primary Propan-2-ol
Secondary methylpropan-2-ol
Tertiary
Primary alcohols are alcohols Secondary alcohols are alcohols Tertiary alcohols are alcohols
where 1 carbon is attached to where 2 carbon are attached to where 3 carbon are attached to
the carbon adjoining the the carbon adjoining the oxygen the carbon adjoining the oxygen
oxygen

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1. Combustion of Alcohols
CH3CH2OH + 3O2  2CO2 + 3H2O
Alcohols combust with a clean flame

2. Reaction of Alcohols with Sodium Observations:

• effervescence,
Sodium reacts with alcohols • the mixture gets hot,
• sodium dissolves,
2CH3CH2OH + 2Na  2CH3CH2O-Na+ + H2 • a white solid is produced.
This reaction can be used as a test for alcohols

3. Substitution reactions of Alcohols to form Halogenoalkanes

Various halogenating compounds can be used to
substitute the –OH group for a halogen PCl5 / PCl3 / conc HCl / SOCl2 / mixture of NaCl +
H2SO4 can all be uses for substituting a Cl
Reaction with phosphorous (V) halide
This reaction with PCl5
CH3CH2OH + PCl5  CH3CH2Cl + POCl3 + HCl (phosphorous(V)chloride) can be used as a
test for alcohols. You would observe misty
fumes of HCl produced.

For Br use KBr, 50% concentrated

CH3CH2OH + HBr  CH3CH2Br + H2O
H2SO4 to produce HBr

Reaction with phosphorous (III) iodide

The phosphorous (III) Iodide is produced in situ by
PI3 + 3 CH3CH2OH  3CH3CH2I + H3PO3 reacting red phosphorus and Iodine.

The reaction of KI and conc H2SO4 can’t be used to produce HI because the
sulfuric acid will oxidise the hydrogen halides to other products.

4. Oxidation reactions of the alcohols

The exact reaction, however, depends on
Potassium dichromate K2Cr2O7 is an oxidising agent the type of alcohol, i.e. whether it is primary,
that causes alcohols to oxidise. secondary, or tertiary, and on the
conditions.
Partial Oxidation of Primary Alcohols H
O
An aldehyde’s name ends
Reaction: primary alcohol  aldehyde in –al
Reagent: potassium dichromate (VI) solution and dilute H C C It always has the C=O bond
sulfuric acid. on the first carbon of the
Conditions: (use a limited amount of dichromate) warm H
H chain so it does not need
gently and distil out the aldehyde as it forms: Ethanal an extra number

H H O
H H H Observation: the
+ [O] H C C C + H2O orange dichromate ion
H C C C O H
(Cr2O72-) reduces to
H H H
H H H the green Cr 3+ ion
OH + [O] O + H2O

CH3CH2CH2OH + [O]  CH3CH2CHO + H2O

propan-1-ol
propanal

Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent
When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO

N Goalby chemrevise.org 24
 Full Oxidation of Primary Alcohols
Reaction: primary alcohol  carboxylic acid H H
O
Reagent: potassium dichromate(VI) solution and dilute
sulfuric acid H C C C
Conditions: use an excess of dichromate, and heat
under reflux: (distil off product after the reaction H H
O H
has finished)
Propanoic acid

H H H H H O
+ 2 [O] H C C C + H2O Observation: the
H C C C O H
orange dichromate
H H H H H O H
ion (Cr2O72-) reduces
OH + 2[O] OH to the green Cr 3+ ion
+ H2O

O
CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O
propan-1-ol Propanoic acid

Oxidation of Secondary Alcohols

Ketones end in -one
H O H
Reaction: secondary alcohol  ketone When ketones have 5C’s
Reagent: potassium dichromate(VI) solution and H C C C H or more in a chain then it
dilute sulfuric acid. needs a number to show
H H
Conditions: heat under reflux the position of the double
Propanone bond. E.g. pentan-2-one

H H H
H O H
H C C C H
+ [O] Observation: the
H C C C H
+ H2O orange dichromate
H O H ion (Cr2O72-) reduces
H H
to the green Cr 3+ ion
H

propan-2-ol Propanone

There is no further oxidation of the ketone under these conditions.

Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group

Distinguishing between Aldehydes and Ketones

The fact that aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised
is the chemical basis for tests that are commonly used to distinguish between aldehydes and ketones

Fehling’s (Benedict’s) solution

Reagent: Fehling’s solution containing blue Cu 2+ ions.
The presence of a carboxylic acid
Conditions: heat gently
can be tested by addition of
Reaction: aldehydes only are oxidised by Fehling’s solution into a carboxylic
acid and the copper (II) ions are reduced to copper(I) oxide
sodium carbonate. It will fizz and
Observation: Aldehydes :Blue Cu 2+ ions in solution change to a red produce carbon dioxide
precipitate of Cu2O. Ketones do not react

CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

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Reaction of Alcohols with Dehydrating Agents

Reaction: Alcohol  Alkene

Dehydration Reaction: removal of a
water molecule from a molecule
Reagents: Concentrated phosphoric acid
Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination
H
H
H H H
H C
H C C C O H H
C C
+ H2O
H H H
H H
propan-1-ol Propene

CH3CH2CH2OH  CH2=CHCH3 + H2O

H H
H C
Some 2o and 3o Butan-2-ol But-1-ene
alcohols can give H H H H C C C H
more than one
product, when the H C C C C H H
H H
double bond H H
forms between H H O H H H
different carbon C C
atoms H
H H
C C
Butan-2-ol can form both alkenes
although more but-2-ene would be But-2-ene
H H
formed
But-2-ene could also exist as E and Z
isomers

Producing alkenes from alcohols provides a possible route to polymers without using monomers derived from oil

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 Organic techniques
It’s important to be able to
draw and label this
Distillation apparatus accurately.
thermometer Don’t draw lines between
In general used as separation technique to separate an flask, adaptor and
organic product from its reacting mixture. Need to condenser.
collect the distillate of the approximate boiling point
range of the desired liquid.

Classic AS reaction using distillation Liebig condenser

Reaction: primary alcohol  aldehyde
Reagent: potassium dichromate (VI) solution and
dilute sulfuric acid.
Conditions: use a limited amount of dichromate
and warm gently and distil out the aldehyde as it
forms [This prevents further oxidation to the Water
carboxylic acid] out
CH3CH2CH2OH + [O]  CH3CH2CHO + H2O
Round Water in
Observation
bottomed
Orange dichromate solution changes to green
flask
colour of Cr3+ ions
Heat

Reflux
Reflux is used when heating organic reaction mixtures for long Water out
periods. The condenser prevents organic vapours from escaping
by condensing them back to liquids.
condenser
Never seal the end of the condenser as the build up of gas
pressure could cause the apparatus to explode. This is true of any
apparatus where volatile liquids are heated

Classic AS reaction using reflux

Reaction: primary alcohol  carboxylic acid Water in
Reagent: potassium dichromate(VI) solution and dilute
sulfuric acid
Conditions: use an excess of dichromate, and heat
under reflux: (distil off product after the reaction Round
has finished using distillation set up) bottomed
CH3CH2CH2OH + 2[O]  CH3CH2CO2H + H2O flask
Observation
Orange dichromate solution changes to green colour of
Cr3+ ions
Heat

Anti-bumping granules are added to the flask in both distillation and reflux to prevent vigorous,
uneven boiling by making small bubbles form instead of large bubbles

It’s important to be able to draw and label this apparatus accurately.

• Don’t draw lines between flask and condenser. Electric heaters are often used to heat
• Don’t have top of condenser sealed organic chemicals. This is because
• Condenser must have outer tube for water that is sealed at top and bottom organic chemicals are normally highly
• Condenser must have two openings for water in and out that are open flammable and could set on fire with a
naked flame.

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Purifying an organic liquid
• Put the distillate of impure product into a separating funnel
Sodium hydrogencarbonate will
• wash product by adding either neutralise any remaining reactant acid.
• sodium hydrogencarbonate solution , shaking and
releasing the pressure from CO2 produced. Sodium chloride will help separate the
• Saturated sodium chloride solution organic layer from the aqueous layer

•Allow the layers to separate in the funnel, and then run and
discard the aqueous layer.
The drying agent should
•Run the organic layer into a clean, dry conical flask and add •be insoluble in the organic liquid
three spatula loads of drying agent (anhydrous sodium • not react with the organic liquid
sulfate) to dry the organic liquid.

• Carefully decant the liquid into the distillation flask

•Distil to collect pure product

Separating funnel

Solvent extraction

Mix organic solvent and oil-water mixture in a

separating funnel then separate the oil layer.
Distil to separate oil from organic solvent
Add anhydrous CaCl2 to clove oil to dry oil
Decant to remove CaCl2
Separating funnel

Measuring boiling point

Purity of liquid can be determined by measuring a boiling point. This can be
done in a distillation set up or by simply boiling a tube of the sample in an To get a correct measure
heating oil bath. of boiling point the
thermometer should be
Pressure should be noted as changing pressure can change the boiling above the level of the
point of a liquid surface of the boiling liquid
and be measuring the
temperature of the
Measuring boiling point is not the most accurate method of identifying a saturated vapour.
substance as several substances may have the same boiling point.

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