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chemguide: helping you to understand Chemistry - Main Menu

chemguide
Helping you to understand Chemistry
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Atomic Structure and Bonding

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Covers basic atomic properties


(electronic structures, ionisation
energies, electron affinities, atomic
and ionic radii), bonding (including
intermolecular bonding) and
structures (ionic, molecular, giant
covalent and metallic).

chemguide: helping you to understand Chemistry - Main Menu

Inorganic Chemistry

Includes essential ideas about redox


reactions, and covers the trends in
Groups 2, 4 and 7 of the Periodic
Table. Plus: lengthy sections on the
chemistry of some important
complex ions, and of common
transition metals.

Physical Chemistry

Covers rates of reaction including


catalysis, an introduction to chemical
equilibria, redox equilibria, acid-base
equilibria (pH, buffer solutions,
indicators, etc) and phase equilibria
(including Raoult's Law and the use
of various phase diagrams).

Instrumental analysis

Explains how you can analyse


substances using machines - mass
spectrometry, infra-red spectroscopy
and NMR.

Basic Organic Chemistry

Includes help on bonding, naming


and isomerism, and a discussion of
organic acids and bases.

Properties of organic compounds

Covers the physical and chemical


properties of compounds on UK A
level chemistry syllabuses.

Organic Reaction Mechanisms

Covers all the mechanisms required


by the current UK A level chemistry
syllabuses.

About this site

Includes a contact address if you


have found any difficulties with the
site.

Chemistry Calculations

A description of the author's book on


calculations at UK A level chemistry
standard.

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chemguide: helping you to understand Chemistry - Main Menu

Textbook suggestions

Suggestions for textbooks and


revision guides covering the UK AS
and A level chemistry syllabuses,
with links to Amazon.co.uk if you
want to follow them up.

Download syllabuses

For UK A level students. Download a


copy of your current syllabus from
your Exam Board.

Test yourself

A link to Dr Phil Brown's website


where UK GCSE, AS and A level
chemistry students will find a wide
and growing range of multiple
choice, short answer and structured
questions.

An examiner's view

A link to Rod Beavon's chemistry


pages. Rod Beavon is chief
examiner for A level chemistry for
the UK exam board Edexcel. A close
look at what he has to offer is a must
for Edexcel students, but there is a
lot of good stuff whatever exam
system you are working in.

Latest additions and important updates

5/12/2004

There is now the beginnings of a section on phase


equilibria. I'm working on it at the moment and it is unlikely
to be finished before the end of January. It currently deals
with vapour pressure, phase diagrams for pure
substances and for solutions of non-volatile solutes
(including the effect of the solute on the boiling point and
freezing point of the solvent).

18/12/2004

An introduction to phase diagrams involving eutectic


mixtures is now available using the tin-lead system.

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chemguide: helping you to understand Chemistry - Main Menu

Jim Clark 2004

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Understanding Chemistry - Atomic Structure and Bonding Menu

Understanding Chemistry

ATOMIC STRUCTURE AND BONDING MENU

Basic atomic properties . . .


Includes a discussion of orbitals, electronic structures of atoms
and ions, ionisation energies, electron affinities, atomic and ionic
radii.
Bonding . . .
Includes ionic, covalent, co-ordinate (dative covalent) and metallic
bonding as well as intermolecular attractions like Van der Waals
forces and hydrogen bonding. Also includes full discussions of
electronegativity and shapes of molecules and ions.
Types of structure . . .
Describes and explains how the various types of structure (ionic,
giant covalent, metallic, and molecular) affect physical properties.

Go to Main Menu . . .

Jim Clark 2000

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Atomic properties menu

Understanding Chemistry

ATOMIC PROPERTIES MENU

Simple background . . .
Revises the simple knowledge you should already have about the
structure of atoms from introductory courses (e.g. GCSE).
Atomic orbitals . . .
Explains what atomic orbitals are and discusses their shapes and
relative energies. This is essential pre-reading before you go on to
any of the remaining topics in this section.
Electronic structures . . .
How to work out and write the electronic structures for atoms and
simple monatomic ions (containing only one atom - e.g. Cl- or Mg2
+) using s, p, d notation.
Ionisation energies . . .
Explains what ionisation energies are and how and why they vary
around the Periodic Table.
Electron affinities . . .
Explains what electron affinities are and how and why they vary
around the Periodic Table.
Atomic and ionic radii . . .

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Atomic properties menu

Looks at the various measures of atomic radius, and explains how


and why atomic radii vary around the Periodic Table. Also
considers how the radii of positive and negative ions differ from the
atoms they come from.

Go to atomic structure and bonding menu . . .


Go to Main Menu . . .

Jim Clark 2000

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a simple view of atomic structure

A SIMPLE VIEW OF ATOMIC STRUCTURE

This page revises the simple ideas about atomic structure that you will
have come across in an introductory chemistry course (for example,
GCSE). You need to be confident about this before you go on to the
more difficult ideas about the atom which under-pin A'level chemistry.

The sub-atomic particles


Protons, neutrons and electrons.

proton
neutron
electron

relative mass
1
1
1/1836

relative charge
+1
0
-1

Beyond A'level: Protons and neutrons don't in fact have


exactly the same mass - neither of them has a mass of
exactly 1 on the carbon-12 scale (the scale on which the
relative masses of atoms are measured). On the carbon-12
scale, a proton has a mass of 1.0073, and a neutron a mass
of 1.0087.

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a simple view of atomic structure

The nucleus
The nucleus is at the centre of the atom and contains the protons and
neutrons. Protons and neutrons are collectively known as nucleons.
Virtually all the mass of the atom is concentrated in the nucleus, because
the electrons weigh so little.

Working out the numbers of protons and neutrons


No of protons = ATOMIC NUMBER of the atom
The atomic number is also given the more descriptive name of proton
number.
No of protons + no of neutrons = MASS NUMBER of the atom
The mass number is also called the nucleon number.

This information can be given simply in the form:

How many protons and neutrons has this atom got?


The atomic number counts the number of protons (9); the mass number
counts protons + neutrons (19). If there are 9 protons, there must be 10
neutrons for the total to add up to 19.

The atomic number is tied to the position of the element in the Periodic
Table and therefore the number of protons defines what sort of element
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a simple view of atomic structure

you are talking about. So if an atom has 8 protons (atomic number = 8), it
must be oxygen. If an atom has 12 protons (atomic number = 12), it must
be magnesium.
Similarly, every chlorine atom (atomic number = 17) has 17 protons;
every uranium atom (atomic number = 92) has 92 protons.

Isotopes
The number of neutrons in an atom can vary within small limits. For
example, there are three kinds of carbon atom 12C, 13C and 14C. They all
have the same number of protons, but the number of neutrons varies.

carbon-12
carbon-13
carbon-14

protons
6
6
6

neutrons
6
7
8

mass number
12
13
14

These different atoms of carbon are called isotopes. The fact that they
have varying numbers of neutrons makes no difference whatsoever to
the chemical reactions of the carbon.
Isotopes are atoms which have the same atomic number but different
mass numbers. They have the same number of protons but different
numbers of neutrons.

The electrons
Working out the number of electrons
Atoms are electrically neutral, and the positiveness of the protons is
balanced by the negativeness of the electrons. It follows that in a neutral
atom:
no of electrons = no of protons

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a simple view of atomic structure

So, if an oxygen atom (atomic number = 8) has 8 protons, it must also


have 8 electrons; if a chlorine atom (atomic number = 17) has 17
protons, it must also have 17 electrons.
The arrangement of the electrons
The electrons are found at considerable distances from the nucleus in a
series of levels called energy levels. Each energy level can only hold a
certain number of electrons. The first level (nearest the nucleus) will only
hold 2 electrons, the second holds 8, and the third also seems to be full
when it has 8 electrons. At GCSE you stop there because the pattern
gets more complicated after that.
These levels can be thought of as getting progressively further from the
nucleus. Electrons will always go into the lowest possible energy level
(nearest the nucleus) - provided there is space.
To work out the electronic arrangement of an atom

Look up the atomic number in the Periodic Table - making sure


that you choose the right number if two numbers are given. The
atomic number will always be the smaller one.
This tells you the number of protons, and hence the number of
electrons.
Arrange the electrons in levels, always filling up an inner level
before you go to an outer one.

e.g. to find the electronic arrangement in chlorine

The Periodic Table gives you the atomic number of 17.

Therefore there are 17 protons and 17 electrons.

The arrangement of the electrons will be 2, 8, 7 (i.e. 2 in the first


level, 8 in the second, and 7 in the third).

The electronic arrangements of the first 20 elements

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a simple view of atomic structure

After this the pattern alters as you enter the transition series in the
Periodic Table.
Two important generalisations
If you look at the patterns in this table:

The number of electrons in the outer level is the same as the


group number. (Except with helium which has only 2 electrons.
The noble gases are also usually called group 0 - not group 8.)
This pattern extends throughout the Periodic Table for the main
groups (i.e. not including the transition elements).
So if you know that barium is in group 2, it has 2 electrons in its
outer level; iodine (group 7) has 7 electrons in its outer level; lead
(group 4) has 4 electrons in its outer level.

Noble gases have full outer levels. This generalisation will need
modifying for A'level purposes.

Dots-and-crosses diagrams
In any introductory chemistry course you will have come across the
electronic structures of hydrogen and carbon, for example, drawn as:

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a simple view of atomic structure

Note: There are many places where you could still make use
of this model of the atom at A'level. It is, however, a
simplification and can be misleading. It gives the impression
that the electrons are circling the nucleus in orbits like planets
around the sun. As you will find when you look at the A'level
view of the atom, it is impossible to know exactly how they
are actually moving.

The circles show energy levels - representing increasing distances from


the nucleus. You could straighten the circles out and draw the electronic
structure as a simple energy diagram.
Carbon, for example, would look like this:

Thinking of the arrangement of the electrons in this way makes a useful


bridge to the A'level view.

Note: If you have come to this page as a UK GCSE student


(or a student on a similar introductory chemistry course
elsewhere) and want some more help, you may be interested
in my GCSE Chemistry book. This link will take you to a page
describing it.

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a simple view of atomic structure

Where would you like to go now?


To the atomic properties menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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GCSE chemistry

Understanding Chemistry

GCSE CHEMISTRY
This book covers the chemistry
content of all the UK GCSE
Chemistry syllabuses - whether
as a part of dual award science,
or as a separate science. It is
aimed at students likely to
achieve grades from A* to B.
If you are working in another
system, GCSE in the UK is an
exam taken at the end of a
(usually) two year course at the
age of 16. Anyone taking a
similar introductory chemistry
course may find the book helpful.
On this page you will find a
description of how the book is organised, together with a summary of the
contents. You will also find direct links to the book on both the Longman
and the Amazon.co.uk sites.
Education in Chemistry, May 2003
"I was impressed with this new book, . . ."
"The text is clearly laid out with excellent diagrams and
illustrations."
"This is an excellent textbook."
School Science Review (issue 307)
". . will stretch and enthuse those with some ability in chemistry."
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GCSE chemistry

"It would certainly help to bridge the gap between GCSE and AS
level."

How to get hold of the book


Schools or colleges would probably find it best to go to the Longman
GCSE Chemistry website, but this site isn't really set up for individual
purchases.
You can, of course, buy the book through normal book sellers, but if you
want to buy online, you will find a direct link to Amazon.co.uk coming up.
Non-UK students can also buy the book from Amazon.co.uk, but will
obviously have to pay a slightly higher delivery charge.

Note: If your usual source of books is Amazon.com, you


should compare the price for the book (including delivery)
from Amazon.com with the price from Amazon.co.uk - even if
you live in North America.
You may well find that it is significantly cheaper to buy from
Amazon.co.uk and have it sent by air mail across the Atlantic,
than to buy it in America!

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GCSE chemistry

Have a look at the book on the Amazon site

What the book covers


The book is organised into 6 sections plus an important appendix. Each
section is made up of a number of related chapters.
There are questions at the end of each chapter to test understanding,
and a set of GCSE-style exam questions at the end of each section.
Answers to all the questions are provided on the supporting website although these are password-protected so that only teachers can get at
them!
Section A: Particles
This covers an introduction to atomic structure and bonding (including
metallic bonding and intermolecular forces) and the relationship between
the structures of elements and compounds and their physical properties.
There is also a chapter on how to write formulae and equations, and a
final one on the factors affecting rates of reaction together with
explanations.
Section B: Some essential background chemistry
This is a lengthy section which covers the important lab-based chemistry:

Reactivity series

Acids and their reactions

Salts

Simple analysis

Periodic Table: including some history, the structure of the table,


the noble gases, Groups 1 and 7, and an introduction to transition

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GCSE chemistry

metals

Electrolysis and electrochemical cells

Energy changes in reactions

Section C: Large scale chemistry


This covers the extraction of several metals, and the chemistry of salt
and limestone. It introduces reversible reactions leading to the Haber and
Contact Processes.
Section D: Air, water and earth
Discusses the atmosphere (including its evolution and some
environmental problems), water (including hardness, water treatment,
and an introduction to colloids) and types of rock.
Section E: Organic chemistry
An introductory look at the oil industry and some simple organic
compounds (alkanes, alkenes, alcohols, carboxylic acids, and a brief
look at esters). Structural isomerism is explained where it arises.
There are also chapters on food and drugs, and enzymes.
Section F: Sums
This section deals with all the calculations involving relative atomic
masses and moles up to and including simple titration and electrolysis
calculations.
Appendices
The most important appendix explains how to maximise your score when
writing up coursework practical investigations to satisfy the requirements
of UK GCSE examiners. The fully written out investigation is available
from the website accompanying the book. (See below.)
The website

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GCSE chemistry

There is a website to accompany the book which you can find by


following this link. You may find this useful even if you don't end up
buying the book!
You will find lots of links to other other useful chemistry web sites, a fully
written up example of a coursework investigation, and a set of
worksheets. Answers to all the questions in the book are available, but
only to teachers who have purchased the book from Longman. The
answers are password-protected for obvious reasons!

Go to Main Menu . . .

Jim Clark 2003

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atomic orbitals

ATOMIC ORBITALS

This page explains what an atomic orbital is. It explores s and p orbitals
in some detail, including their shapes and energies. d orbitals are
described only in terms of their energy, and f orbitals only get a passing
mention.

What is an atomic orbital?


Orbitals and orbits
When the a planet moves around the sun, you can plot a definite path for
it which is called an orbit. A simple view of the atom looks similar and you
may have pictured the electrons as orbiting around the nucleus. The truth
is different, and electrons in fact inhabit regions of space known as
orbitals.
Orbits and orbitals sound similar, but they have quite different meanings.
It is essential that you understand the difference between them.
The impossibility of drawing orbits for electrons
To plot a path for something you need to know exactly where the object
is and be able to work out exactly where it's going to be an instant later.
You can't do this for electrons.
The Heisenberg Uncertainty Principle (not required at A'level) says loosely - that you can't know with certainty both where an electron is and
where it's going next. That makes it impossible to plot an orbit for an
electron around a nucleus. Is this a big problem? No. If something is
impossible, you have to accept it and find a way around it.
Hydrogen's electron - the 1s orbital

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atomic orbitals

Note: In this diagram (and the orbital diagrams that follow),


the nucleus is shown very much larger than it really is. This is
just for clarity.

Suppose you had a single hydrogen atom and at a


particular instant plotted the position of the one
electron. Soon afterwards, you do the same thing,
and find that it is in a new position. You have no
idea how it got from the first place to the second.
You keep on doing this over and over again, and
gradually build up a sort of 3D map of the places that the electron is likely
to be found.
In the hydrogen case, the electron can be found anywhere within a
spherical space surrounding the nucleus. The diagram shows a crosssection through this spherical space.
95% of the time (or any other percentage you choose), the electron will
be found within a fairly easily defined region of space quite close to the
nucleus. Such a region of space is called an orbital. You can think of an
orbital as being the region of space in which the electron lives.

Note: If you wanted to be absolutely 100% sure of where the


electron is, you would have to draw an orbital the size of the
Universe!

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atomic orbitals

What is the electron doing in the orbital? We don't know, we can't know,
and so we just ignore the problem! All you can say is that if an electron is
in a particular orbital it will have a particular definable energy.
Each orbital has a name.
The orbital occupied by the hydrogen electron is called a 1s orbital. The
"1" represents the fact that the orbital is in the energy level closest to the
nucleus. The "s" tells you about the shape of the orbital. s orbitals are
spherically symmetric around the nucleus - in each case, like a hollow
ball made of rather chunky material with the nucleus at its centre.
The orbital on the left is a 2s orbital. This is
similar to a 1s orbital except that the region
where there is the greatest chance of
finding the electron is further from the
nucleus - this is an orbital at the second
energy level.
If you look carefully, you will notice that
there is another region of slightly higher
electron density (where the dots are thicker)
nearer the nucleus. ("Electron density" is another way of talking about
how likely you are to find an electron at a particular place.)
2s (and 3s, 4s, etc) electrons spend some of their time closer to the
nucleus than you might expect. The effect of this is to slightly reduce the
energy of electrons in s orbitals. The nearer the nucleus the electrons
get, the lower their energy.
3s, 4s (etc) orbitals get progressively further from the nucleus.
p orbitals

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atomic orbitals

Not all electrons inhabit s orbitals (in fact, very few


electrons live in s orbitals). At the first energy level,
the only orbital available to electrons is the 1s
orbital, but at the second level, as well as a 2s
orbital, there are also orbitals called 2p orbitals.
A p orbital is rather like 2 identical balloons tied
together at the nucleus. The diagram on the right is
a cross-section through that 3-dimensional region
of space. Once again, the orbital shows where
there is a 95% chance of finding a particular
electron.

Beyond A'level: If you imagine a horizontal plane through


the nucleus, with one lobe of the orbital above the plane and
the other beneath it, there is a zero probability of finding the
electron on that plane. So how does the electron get from
one lobe to the other if it can never pass through the plane of
the nucleus? For A'level chemistry you just have to accept
that it does! If you want to find out more, read about the wave
nature of electrons.

Unlike an s orbital, a p orbital points in a particular direction - the one


drawn points up and down the page.
At any one energy level it is possible to have three absolutely equivalent
p orbitals pointing mutually at right angles to each other. These are
arbitrarily given the symbols px, py and pz. This is simply for
convenience - what you might think of as the x, y or z direction changes
constantly as the atom tumbles in space.

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atomic orbitals

The p orbitals at the second energy level are


called 2px, 2py and 2pz. There are similar
orbitals at subsequent levels - 3px, 3py, 3pz,
4px, 4py, 4pz and so on.
All levels except for the first level have p
orbitals. At the higher levels the lobes get
more elongated, with the most likely place to
find the electron more distant from the
nucleus.

d and f orbitals
In addition to s and p orbitals, there are two other sets of orbitals which
become available for electrons to inhabit at higher energy levels. At the
third level, there is a set of five d orbitals (with complicated shapes and
names) as well as the 3s and 3p orbitals (3px, 3py, 3pz). At the third level
there are a total of nine orbitals altogether.
At the fourth level, as well the 4s and 4p and 4d orbitals there are an
additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals are then
available at all higher energy levels as well.
For A'level purposes, you have to be aware that there are sets of five d
orbitals at levels from the third level upwards, but you will not be
expected to draw them or name them. Apart from a passing reference,
you won't come across f orbitals at all.

Fitting electrons into orbitals


You can think of an atom as a very bizarre house (like an inverted
pyramid!) - with the nucleus living on the ground floor, and then various
rooms (orbitals) on the higher floors occupied by the electrons. On the
first floor there is only 1 room (the 1s orbital); on the second floor there
are 4 rooms (the 2s, 2px, 2py and 2pz orbitals); on the third floor there
are 9 rooms (one 3s orbital, three 3p orbitals and five 3d orbitals); and so
on. But the rooms aren't very big . . . Each orbital can only hold 2
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atomic orbitals

electrons.
A convenient way of showing the orbitals that the electrons live in is to
draw "electrons-in-boxes".
"Electrons-in-boxes"
Orbitals can be represented as boxes with the electrons in them shown
as arrows. Often an up-arrow and a down-arrow are used to show that
the electrons are in some way different.

Beyond A'level: The need to have all electrons in an atom


different comes out of quantum theory. If they live in different
orbitals, that's fine - but if they are both in the same orbital
there has to be some subtle distinction between them.
Quantum theory allocates them a property known as "spin" which is what the arrows are intended to suggest.

A 1s orbital holding 2 electrons would be drawn as shown


on the right, but it can be written even more quickly as 1s2.
This is read as "one s two" - not as "one s squared".
You mustn't confuse the two numbers in this notation:

The order of filling orbitals


Electrons fill low energy orbitals (closer to the nucleus) before they fill
higher energy ones. Where there is a choice between orbitals of equal
energy, they fill the orbitals singly as far as possible.
This filling of orbitals singly where possible is known as Hund's rule. It
only applies where the orbitals have exactly the same energies (as with p
orbitals, for example), and helps to minimise the repulsions between
electrons and so makes the atom more stable.

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atomic orbitals

The diagram (not to scale) summarises the energies of the orbitals up to


the 4p level.

Notice that the s orbital always has a slightly lower energy than the p
orbitals at the same energy level, so the s orbital always fills with
electrons before the corresponding p orbitals.
The real oddity is the position of the 3d orbitals. They are at a slightly
higher level than the 4s - and so it is the 4s orbital which will fill first,
followed by all the 3d orbitals and then the 4p orbitals. Similar confusion
occurs at higher levels, with so much overlap between the energy levels
that the 4f orbitals don't fill until after the 6s, for example.
For A'level purposes you simply have to remember that the 4s orbital fills
before the 3d orbitals. The same thing happens at the next level as well the 5s orbital fills before the 4d orbitals. All the other complications are
beyond A'level.
Knowing the order of filling is central to understanding how to write
electronic structures. Follow the link below to find out how to do this.

Where would you like to go now?


To look at how to write electronic structures . . .
To the atomic properties menu . . .
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atomic orbitals

To the atomic structure and bonding menu . . .


To Main Menu . . .

Jim Clark 2000 (modified 2004)

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electronic structures of atoms

ELECTRONIC STRUCTURES

This page explores how you write electronic structures for atoms using s,
p, and d notation. It assumes that you know about simple atomic orbitals
- at least as far as the way they are named, and their relative energies. If
you want to look at the electronic structures of simple monatomic ions
(such as Cl-, Ca2+ and Cr3+), you will find a link at the bottom of the page.

Important! If you haven't already read the page on atomic


orbitals you should follow this link before you go any further.

The electronic structures of atoms


Relating orbital filling to the Periodic Table

Most A'level syllabuses stop at krypton when it comes to writing


electronic structures, but it is possible that you could be asked for
structures for elements up as far as barium. After barium you have to
worry about f orbitals as well as s, p and d orbitals - and that's a problem
beyond A'level. It is important that you look through past exam papers as
well as your syllabus so that you can judge how hard the questions are
likely to get.
This page looks in detail at the elements in the shortened version of the
Periodic Table above, and then shows how you could work out the
structures of some bigger atoms.

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electronic structures of atoms

Important! You must have a copy of your syllabus and


copies of recent exam papers. If you haven't got them, follow
this link to find out how to get hold of them.

The first period


Hydrogen has its only electron in the 1s orbital - 1s1, and at helium the
first level is completely full - 1s2.
The second period
Now we need to start filling the second level, and hence start the second
period. Lithium's electron goes into the 2s orbital because that has a
lower energy than the 2p orbitals. Lithium has an electronic structure of
1s22s1. Beryllium adds a second electron to this same level - 1s22s2.
Now the 2p levels start to fill. These levels all have the same energy, and
so the electrons go in singly at first.
B

1s22s22px1

1s22s22px12py1

1s22s22px12py12pz1
Note: The orbitals where something new is happening are
shown in bold type. You wouldn't normally write them any
differently from the other orbitals.

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electronic structures of atoms

The next electrons to go in will have to pair up with those already there.
O

1s22s22px22py12pz1

1s22s22px22py22pz1

Ne

1s22s22px22py22pz2

You can see that it is going to get progressively tedious to write the full
electronic structures of atoms as the number of electrons increases.
There are two ways around this, and you must be familiar with both.
Shortcut 1: All the various p electrons can be lumped together. For
example, fluorine could be written as 1s22s22p5, and neon as 1s22s22p6.
This is what is normally done if the electrons are in an inner layer. If the
electrons are in the bonding level (those on the outside of the atom), they
are sometimes written in shorthand, sometimes in full. Don't worry about
this. Be prepared to meet either version, but if you are asked for the
electronic structure of something in an exam, write it out in full showing
all the px, py and pz orbitals in the outer level separately.
For example, although we haven't yet met the electronic structure of
chlorine, you could write it as 1s22s22p63s23px23py23pz1.
Notice that the 2p electrons are all lumped together whereas the 3p ones
are shown in full. The logic is that the 3p electrons will be involved in
bonding because they are on the outside of the atom, whereas the 2p
electrons are buried deep in the atom and aren't really of any interest.
Shortcut 2: You can lump all the inner electrons together using, for
example, the symbol [Ne]. In this context, [Ne] means the electronic
structure of neon - in other words: 1s22s22px22py22pz2 You wouldn't do
this with helium because it takes longer to write [He] than it does 1s2.
On this basis the structure of chlorine would be written [Ne]
3s23px23py23pz1.
The third period

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electronic structures of atoms

At neon, all the second level orbitals are full, and so after this we have to
start the third period with sodium. The pattern of filling is now exactly the
same as in the previous period, except that everything is now happening
at the 3-level.
For example:
short version
Mg

1s22s22p63s2

[Ne]3s2

1s22s22p63s23px23py13pz1

[Ne]3s23px23py13pz1

Ar

1s22s22p63s23px23py23pz2

[Ne]3s23px23py23pz2

Note: Check that you can do these. Cover the text and then
work out these structures for yourself. Then do all the rest of
this period. When you've finished, check your answers
against the corresponding elements from the previous period.
Your answers should be the same except a level further out.

The beginning of the fourth period


At this point the 3-level orbitals aren't all full - the 3d levels haven't been
used yet. But if you refer back to the energies of the orbitals, you will see
that the next lowest energy orbital is the 4s - so that fills next.
K

1s22s22p63s23p64s1

Ca

1s22s22p63s23p64s2

There is strong evidence for this in the similarities in the chemistry of


elements like sodium (1s22s22p63s1) and potassium
(1s22s22p63s23p64s1)
The outer electron governs their properties and that electron is in the
same sort of orbital in both of the elements. That wouldn't be true if the
outer electron in potassium was 3d1.
s- and p-block elements

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electronic structures of atoms

The elements in group 1 of the Periodic Table all have an outer


electronic structure of ns1 (where n is a number between 2 and 7). All
group 2 elements have an outer electronic structure of ns2. Elements in
groups 1 and 2 are described as s-block elements.
Elements from group 3 across to the noble gases all have their outer
electrons in p orbitals. These are then described as p-block elements.
d-block elements

Remember that the 4s orbital has a lower energy than the 3d orbitals and
so fills first. Once the 3d orbitals have filled up, the next electrons go into
the 4p orbitals as you would expect.
d-block elements are elements in which the last electron to be added to
the atom is in a d orbital. The first series of these contains the elements
from scandium to zinc, which at GCSE you probably called transition
elements or transition metals. The terms "transition element" and "d-

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electronic structures of atoms

block element" don't quite have the same meaning, but it doesn't matter
in the present context.

If you are interested: A transition element is defined as one


which has partially filled d orbitals either in the element or
any of its compounds. Zinc (at the right-hand end of the dblock) always has a completely full 3d level (3d10) and so
doesn't count as a transition element.

d electrons are almost always described as, for example, d5 or d8 - and


not written as separate orbitals. Remember that there are five d orbitals,
and that the electrons will inhabit them singly as far as possible. Up to 5
electrons will occupy orbitals on their own. After that they will have to pair
up.
d5 means

d8 means

Notice in what follows that all the 3-level orbitals are written together,
even though the 3d electrons are added to the atom after the 4s.
Sc

1s22s22p63s23p63d14s2

Ti

1s22s22p63s23p63d24s2

1s22s22p63s23p63d34s2

Cr

1s22s22p63s23p63d54s1

Whoops! Chromium breaks the sequence. In chromium, the electrons in


the 3d and 4s orbitals rearrange so that there is one electron in each
orbital. It would be convenient if the sequence was tidy - but it's not!
Mn

1s22s22p63s23p63d54s2

Fe

1s22s22p63s23p63d64s2

(back to being tidy again)

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electronic structures of atoms

Co

1s22s22p63s23p63d74s2

Ni

1s22s22p63s23p63d84s2

Cu

1s22s22p63s23p63d104s1

Zn

1s22s22p63s23p63d104s2

(another awkward one!)

And at zinc the process of filling the d orbitals is complete.


Filling the rest of period 4
The next orbitals to be used are the 4p, and these fill in exactly the same
way as the 2p or 3p. We are back now with the p-block elements from
gallium to krypton. Bromine, for example, is
1s22s22p63s23p63d104s24px24py24pz1.

Useful exercise: Work out the electronic structures of all the


elements from gallium to krypton. You can check your
answers by comparing them with the elements directly above
them in the Periodic Table. For example, gallium will have the
same sort of arrangement of its outer level electrons as boron
or aluminium - except that gallium's outer electrons will be in
the 4-level.

Summary
Writing the electronic structure of an element from hydrogen to
krypton

Use the Periodic Table to find the atomic number, and hence
number of electrons.
Fill up orbitals in the order 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p - until you
run out of electrons. The 3d is the awkward one - remember that
specially. Fill p and d orbitals singly as far as possible before
pairing electrons up.
Remember that chromium and copper have electronic structures
which break the pattern in the first row of the d-block.

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electronic structures of atoms

Writing the electronic structure of big s- or p-block elements

Note: We are deliberately excluding the d-block elements


apart from the first row that we've already looked at in detail.
The pattern of awkward structures isn't the same in the other
rows. This isn't an A'level problem.

First work out the number of outer electrons. This is quite likely all you
will be asked to do anyway.
The number of outer electrons is the same as the group number. (The
noble gases are a bit of a problem here, because they are normally
called group 0 rather then group 8. Helium has 2 outer electrons; the rest
have 8.) All elements in group 3, for example, have 3 electrons in their
outer level. Fit these electrons into s and p orbitals as necessary. Which
level orbitals? Count the periods in the Periodic Table (not forgetting the
one with H and He in it).
Iodine is in group 7 and so has 7 outer electrons. It is in the fifth period
and so its electrons will be in 5s and 5p orbitals. Iodine has the outer
structure 5s25px25py25pz1.
What about the inner electrons if you need to work them out as well? The
1, 2 and 3 levels will all be full, and so will the 4s, 4p and 4d. The 4f
levels don't fill until after anything you will be asked about at A'level. Just
forget about them! That gives the full structure:
1s22s22p63s23p63d104s24p64d105s25px25py25pz1.
When you've finished, count all the electrons to make sure that they
come to the same as the atomic number. Don't forget to make this check
- it's easy to miss an orbital out when it gets this complicated.
Barium is in group 2 and so has 2 outer electrons. It is in the sixth
period. Barium has the outer structure 6s2.
Including all the inner levels: 1s22s22p63s23p63d104s24p64d105s25p66s2.
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electronic structures of atoms

It would be easy to include 5d10 as well by mistake, but the d level


always fills after the next s level - so 5d fills after 6s just as 3d fills after
4s. As long as you counted the number of electrons you could easily spot
this mistake because you would have 10 too many.

Note: Don't worry too much about these complicated


structures. You need to know how to work them out in
principle, but your examiners are much more likely to ask you
for something simple like sulphur or iron.

Where would you like to go now?


To working out electronic structures for ions . . .
To the atomic properties menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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Understanding Chemistry - A' level syllabuses

Understanding Chemistry

UK A and AS LEVEL CHEMISTRY SYLLABUSES


I assume that you want to get the best grade you possibly can with the
minimum of effort! Getting a good A level grade is rather like playing a
game with your examiners - in which they make up the rules (and
occasionally change them). You aren't going to win unless you know
those rules.
Before you do anything else:

Get a copy of your syllabus if you haven't already got one. Details
of how to do this are given below.
Syllabuses are often quite difficult to interpret, so you need to
know exactly what questions your examiners are asking, and how
they are marking them.
Explore your Exam Board web site. They all offer free downloads
of specimen papers (including mark schemes), but you might have
to pay for recent exam papers and mark schemes, and other
support material. If they don't offer these free, find out how to order
them and invest a small amount of money in your future!
If you want the best possible grade, you should be working with
exam papers all the way through your course. Leaving looking at
exam papers until your last minute revision is too late.
Be careful, though! Syllabuses change and so do examiners.
Make sure that the question papers and mark schemes you get
relate to your current syllabus and are as recent as possible. A
new chief examiner can make a lot of difference to the style of a
question paper.

How to download a copy of your syllabus

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Understanding Chemistry - A' level syllabuses

Finding your way to the right syllabus


The following links take you to the front pages of each of the Exam Board
web sites and you will then have to find your own way to your syllabus.
This is because these sites are liable to change.
Be aware that the syllabuses are known as specifications. You want
GCE Advanced and Advanced Subsidiary (A and AS) Chemistry.
Finding the syllabuses is very straightforward - finding other information
may take you longer!
The Exam Boards:

OCR
This includes both the standard OCR syllabus and the Salters
syllabus.

Edexcel
This includes both the standard Edexcel syllabus and the Nuffield
syllabus.

AQA
AQA have free downloadable versions of all their recent exam
papers and mark schemes. Once you get to the chemistry page,
look for it under "Assessment Material". You can also get
Examiners' Reports (another link from the chemistry page). These
are essential if you want to avoid common mistakes.

WJEC
This link should take you directly to the correct chemistry page to
download a syllabus. At the time of writing, you will have to pay if
you want past papers or mark schemes.

Problems reading the downloaded syllabus?


The syllabuses are available only in pdf format. You need software such
as Adobe Acrobat Reader to access it. You have almost certainly got this
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Understanding Chemistry - A' level syllabuses

(or the equivalent) software on your computer, but if your computer is


old, you may not have the latest version.
If your downloaded syllabus won't open, it may be that the syllabus was
created in a newer version of the Reader than you've got. You will have
to download a new version of Reader.
Each of the Exam Board web sites provides a link to Adobe, but these
links are often easy to miss.
Use this link:

www.adobe.com
This will take you to Adobe's front page where you will find a link
enabling you to download the Reader. Be warned that this is a
seriously large bit of software and could take a long time to
download on a dial-up connection.

Go to Main Menu . . .

Jim Clark 2000 (modified 2004)

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electronic structures of ions

ELECTRONIC STRUCTURES OF IONS

This page explores how you write electronic structures for simple
monatomic ions (ions containing only one atom) using s, p, and d
notation. It assumes that you already understand how to write electronic
structures for atoms.

Important! If you have come straight to this page via a


search engine, you should read the page on electronic
structures of atoms before you go any further.

Working out the electronic structures of ions


Ions are atoms (or groups of atoms) which carry an electric charge
because they have either gained or lost one or more electrons. If an
atom gains electrons it acquires a negative charge. If it loses electrons, it
becomes positively charged.
The electronic structure of s- and p-block ions
Write the electronic structure for the neutral atom, and then add (for a
negative ion) or subtract electrons (for a positive ion).
To write the electronic structure for Cl -:
Cl

1s22s22p63s23px23py23pz1

Cl-

1s22s22p63s23px23py23pz2

but Cl- has one more electron

To write the electronic structure for O2-:


O

1s22s22px22py12pz1

but O2- has two more electrons

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electronic structures of ions

O2-

1s22s22px22py22pz2

To write the electronic structure for Na+:


Na

1s22s22p63s1

Na+

1s22s22p6

but Na+ has one less electron

To write the electronic structure for Ca2+:


Ca

1s22s22p63s23p64s2

Ca2+

1s22s22p63s23p6

but Ca2+ has two less electrons

The electronic structure of d-block ions


Here you are faced with one of the most irritating facts in A'level
chemistry! You will recall that the first transition series (from scandium to
zinc) is the result of the 3d orbitals being filled after the 4s orbital.
However, once the electrons are established in their orbitals, the energy
order changes - and in all the chemistry of the transition elements, the 4s
orbital behaves as the outermost, highest energy orbital. The reversed
order of the 3d and 4s orbitals only applies to building the atom up in the
first place. In all other respects, the 4s electrons are always the electrons
you need to think about first.
You must remember this:

When d-block elements form ions, the 4s electrons are lost first.

Provided you remember that, working out the structure of a d-block ion is
no different from working out the structure of, say, a sodium ion.

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electronic structures of ions

To write the electronic structure for Cr3+:


Cr

1s22s22p63s23p63d54s1

Cr3+

1s22s22p63s23p63d3

The 4s electron is lost first followed by two of the 3d electrons.

To write the electronic structure for Zn2+:


Zn

1s22s22p63s23p63d104s2

Zn2+

1s22s22p63s23p63d10

This time there is no need to use any of the 3d electrons.

To write the electronic structure for Fe3+:


Fe

1s22s22p63s23p63d64s2

Fe3+

1s22s22p63s23p63d5

The 4s electrons are lost first followed by one of the 3d electrons.


The rule is quite simple. Take the 4s electrons off first, and then as many
3d electrons as necessary to produce the correct positive charge.

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electronic structures of ions

Note: You may well have the impression from GCSE that
ions have to have noble gas structures. It's not true! Most
(but not all) ions formed by s- and p-block elements do have
noble gas structures, but if you look at the d-block ions we've
used as examples, not one of them has a noble gas structure
- yet they are all perfectly valid ions. Getting away from a
reliance on the concept of noble gas structures is one of the
difficult mental leaps that you have to make at the beginning
of A'level chemistry.

Where would you like to go now?


To the atomic properties menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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first ionisation energy

IONISATION ENERGY

This page explains what first ionisation energy is, and then looks at the
way it varies around the Periodic Table - across periods and down
groups. It assumes that you know about simple atomic orbitals, and can
write electronic structures for simple atoms. You will find a link at the
bottom of the page to a similar description of successive ionisation
energies (second, third and so on).

Important! If you aren't reasonable happy about atomic


orbitals and electronic structures you should follow these
links before you go any further.

Defining first ionisation energy


Definition
The first ionisation energy is the energy required to remove the most
loosely held electron from one mole of gaseous atoms to produce 1 mole
of gaseous ions each with a charge of 1+.
This is more easily seen in symbol terms.

It is the energy needed to carry out this change per mole of X.

Worried about moles? Don't be! For now, just take it as a


measure of a particular amount of a substance. It isn't worth
worrying about at the moment.

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first ionisation energy

Things to notice about the equation


The state symbols - (g) - are essential. When you are talking about
ionisation energies, everything must be present in the gas state.
Ionisation energies are measured in kJ mol-1 (kilojoules per mole). They
vary in size from 381 (which you would consider very low) up to 2370
(which is very high).
All elements have a first ionisation energy - even atoms which don't form
positive ions in test tubes. The reason that helium (1st I.E. = 2370 kJ mol1) doesn't normally form a positive ion is because of the huge amount of
energy that would be needed to remove one of its electrons.

Patterns of first ionisation energies in the Periodic Table


The first 20 elements

First ionisation energy shows periodicity. That means that it varies in a


repetitive way as you move through the Periodic Table. For example,
look at the pattern from Li to Ne, and then compare it with the identical
pattern from Na to Ar.
These variations in first ionisation energy can all be explained in terms of
the structures of the atoms involved.

Factors affecting the size of ionisation energy


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first ionisation energy

Ionisation energy is a measure of the energy needed to pull a particular


electron away from the attraction of the nucleus. A high value of
ionisation energy shows a high attraction between the electron and the
nucleus.
The size of that attraction will be governed by:
The charge on the nucleus.
The more protons there are in the nucleus, the more positively charged
the nucleus is, and the more strongly electrons are attracted to it.
The distance of the electron from the nucleus.
Attraction falls off very rapidly with distance. An electron close to the
nucleus will be much more strongly attracted than one further away.
The number of electrons between the outer electrons and the
nucleus.
Consider a sodium atom, with the electronic structure 2,8,1. (There's no
reason why you can't use this notation if it's useful!)
If the outer electron looks in towards the nucleus, it doesn't see the
nucleus sharply. Between it and the nucleus there are the two layers of
electrons in the first and second levels. The 11 protons in the sodium's
nucleus have their effect cut down by the 10 inner electrons. The outer
electron therefore only feels a net pull of approximately 1+ from the
centre. This lessening of the pull of the nucleus by inner electrons is
known as screening or shielding.

Warning! Electrons don't, of course, "look in" towards the


nucleus - and they don't "see" anything either! But there's no
reason why you can't imagine it in these terms if it helps you
to visualise what's happening. Just don't use these terms in
an exam! You may get an examiner who is upset by this sort
of loose language.

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first ionisation energy

Whether the electron is on its own in an orbital or paired with


another electron.
Two electrons in the same orbital experience a bit of repulsion from each
other. This offsets the attraction of the nucleus, so that paired electrons
are removed rather more easily than you might expect.

Explaining the pattern in the first few elements


Hydrogen has an electronic structure of 1s1. It is a very small atom, and
the single electron is close to the nucleus and therefore strongly
attracted. There are no electrons screening it from the nucleus and so
the ionisation energy is high (1310 kJ mol-1).
Helium has a structure 1s2. The electron is being removed from the
same orbital as in hydrogen's case. It is close to the nucleus and
unscreened. The value of the ionisation energy (2370 kJ mol-1) is much
higher than hydrogen, because the nucleus now has 2 protons attracting
the electrons instead of 1.
Lithium is 1s22s1. Its outer electron is in the second energy level, much
more distant from the nucleus. You might argue that that would be offset
by the additional proton in the nucleus, but the electron doesn't feel the
full pull of the nucleus - it is screened by the 1s2 electrons.

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first ionisation energy

You can think of the electron as feeling a net 1+ pull from the centre (3
protons offset by the two 1s2 electrons).
If you compare lithium with hydrogen (instead of with helium), the
hydrogen's electron also feels a 1+ pull from the nucleus, but the
distance is much greater with lithium. Lithium's first ionisation energy
drops to 519 kJ mol-1 whereas hydrogen's is 1310 kJ mol-1.

The patterns in periods 2 and 3


Talking through the next 17 atoms one at a time would take ages. We
can do it much more neatly by explaining the main trends in these
periods, and then accounting for the exceptions to these trends.
The first thing to realise is that the patterns in the two periods are
identical - the difference being that the ionisation energies in period 3 are
all lower than those in period 2.

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first ionisation energy

Explaining the general trend across periods 2 and 3


The general trend is for ionisation energies to increase across a period.
In the whole of period 2, the outer electrons are in 2-level orbitals - 2s or
2p. These are all the same sort of distances from the nucleus, and are
screened by the same 1s2 electrons.
The major difference is the increasing number of protons in the nucleus
as you go from lithium to neon. That causes greater attraction between
the nucleus and the electrons and so increases the ionisation energies.
In fact the increasing nuclear charge also drags the outer electrons in
closer to the nucleus. That increases ionisation energies still more as you
go across the period.

Note: Factors affecting atomic radius are covered on a


separate page.

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first ionisation energy

In period 3, the trend is exactly the same. This time, all the electrons
being removed are in the third level and are screened by the 1s22s22p6
electrons. They all have the same sort of environment, but there is an
increasing nuclear charge.
Why the drop between groups 2 and 3 (Be-B and Mg-Al)?
The explanation lies with the structures of boron and aluminium. The
outer electron is removed more easily from these atoms than the general
trend in their period would suggest.
Be

1s22s2

1st I.E. = 900 kJ mol-1

1s22s22px1

1st I.E. = 799 kJ mol-1

You might expect the boron value to be more than the beryllium value
because of the extra proton. Offsetting that is the fact that boron's outer
electron is in a 2p orbital rather than a 2s. 2p orbitals have a slightly
higher energy than the 2s orbital, and the electron is, on average, to be
found further from the nucleus. This has two effects.

The increased distance results in a reduced attraction and so a


reduced ionisation energy.
The 2p orbital is screened not only by the 1s2 electrons but, to
some extent, by the 2s2 electrons as well. That also reduces the
pull from the nucleus and so lowers the ionisation energy.

The explanation for the drop between magnesium and aluminium is the
same, except that everything is happening at the 3-level rather than the 2level.
Mg

1s22s22p63s2

1st I.E. = 736 kJ mol-1

Al

1s22s22p63s23px1

1st I.E. = 577 kJ mol-1

The 3p electron in aluminium is slightly more distant from the nucleus


than the 3s, and partially screened by the 3s2 electrons as well as the
inner electrons. Both of these factors offset the effect of the extra proton.

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first ionisation energy

Warning! You might possibly come across a text book which


describes the drop between group 2 and group 3 by saying
that a full s2 orbital is in some way especially stable and that
makes the electron more difficult to remove. In other words,
that the fluctuation is because the group 2 value for ionisation
energy is abnormally high. This is quite simply wrong! The
reason for the fluctuation is because the group 3 value is
lower than you might expect for the reasons we've looked at.

Why the drop between groups 5 and 6 (N-O and P-S)?


Once again, you might expect the ionisation energy of the group 6
element to be higher than that of group 5 because of the extra proton.
What is offsetting it this time?
N

1s22s22px12py12pz1

1st I.E. = 1400 kJ mol-1

1s22s22px22py12pz1

1st I.E. = 1310 kJ mol-1

The screening is identical (from the 1s2 and, to some extent, from the 2s2
electrons), and the electron is being removed from an identical orbital.
The difference is that in the oxygen case the electron being removed is
one of the 2px2 pair. The repulsion between the two electrons in the
same orbital means that the electron is easier to remove than it would
otherwise be.
The drop in ionisation energy at sulphur is accounted for in the same way.

Trends in ionisation energy down a group


As you go down a group in the Periodic Table ionisation energies
generally fall. You have already seen evidence of this in the fact that the
ionisation energies in period 3 are all less than those in period 2.
Taking Group 1 as a typical example:

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first ionisation energy

Why is the sodium value less than that of lithium?


There are 11 protons in a sodium atom but only 3 in a lithium atom, so
the nuclear charge is much greater. You might have expected a much
larger ionisation energy in sodium, but offsetting the nuclear charge is a
greater distance from the nucleus and more screening.
Li

1s22s1

1st I.E. = 519 kJ mol-1

Na

1s22s22p63s1

1st I.E. = 494 kJ mol-1

Lithium's outer electron is in the second level, and only has the 1s2
electrons to screen it. The 2s1 electron feels the pull of 3 protons
screened by 2 electrons - a net pull from the centre of 1+.
The sodium's outer electron is in the third level, and is screened from the
11 protons in the nucleus by a total of 10 inner electrons. The 3s1
electron also feels a net pull of 1+ from the centre of the atom. In other
words, the effect of the extra protons is compensated for by the effect of
the extra screening electrons. The only factor left is the extra distance
between the outer electron and the nucleus in sodium's case. That
lowers the ionisation energy.
Similar explanations hold as you go down the rest of this group - or,
indeed, any other group.

Trends in ionisation energy in a transition series

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first ionisation energy

Apart from zinc at the end, the other ionisation energies are all much the
same.
All of these elements have an electronic structure [Ar]3dn4s2 (or 4s1 in
the cases of chromium and copper). The electron being lost always
comes from the 4s orbital.

Note: Confusingly, once the orbitals have electrons in them,


the 4s orbital has a higher energy than the 3d - quite the
opposite of their order when the atoms are being filled with
electrons. That means that it is a 4s electron which is lost
from the atom when it forms an ion. It also means that the 3d
orbitals are slightly closer to the nucleus than the 4s - and so
offer some screening.
You will find this commented on in the page about electronic
structures of ions.

As you go from one atom to the next in the series, the number of protons
in the nucleus increases, but so also does the number of 3d electrons.
The 3d electrons have some screening effect, and the extra proton and
the extra 3d electron more or less cancel each other out as far as
attraction from the centre of the atom is concerned.
The rise at zinc is easy to explain.
Cu

[Ar]3d104s1

1st I.E. = 745 kJ mol-1

Zn

[Ar]3d104s2

1st I.E. = 908 kJ mol-1

In each case, the electron is coming from the same orbital, with identical
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first ionisation energy

screening, but the zinc has one extra proton in the nucleus and so the
attraction is greater.

Ionisation energies and reactivity


The lower the ionisation energy, the more easily this change happens:

You can explain the increase in reactivity of the Group 1 metals (Li, Na,
K, Rb, Cs) as you go down the group in terms of the fall in ionisation
energy. Whatever these metals react with, they have to form positive
ions in the process, and so the lower the ionisation energy, the more
easily those ions will form.
The danger with this approach is that the formation of the positive ion is
only one stage in a multi-step process.
For example, you wouldn't be starting with gaseous atoms; nor would
you end up with gaseous positive ions - you would end up with ions in a
solid or in solution. The energy changes in these processes also vary
from element to element. Ideally you need to consider the whole picture
and not just one small part of it.
However, the ionisation energies of the elements are going to be major
contributing factors towards the activation energy of the reactions.
Remember that activation energy is the minimum energy needed before
a reaction will take place. The lower the activation energy, the faster the
reaction will be - irrespective of what the overall energy changes in the
reaction are.
The fall in ionisation energy as you go down a group will lead to lower
activation energies and therefore faster reactions.

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first ionisation energy

Note: You will find a page discussing this in more detail in


the inorganic section of this site dealing with the reactions of
Group 2 metals with water.

Where would you like to go now?


To look at second (and successive) ionisation energies . . .
To the atomic properties menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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atomic and ionic radius

ATOMIC AND IONIC RADIUS

This page explains the various measures of atomic radius, and then looks
at the way it varies around the Periodic Table - across periods and down
groups. It assumes that you understand electronic structures for simple
atoms written in s, p, d notation.

Important! If you aren't reasonable happy about electronic


structures you should follow this link before you go any further.

ATOMIC RADIUS
Measures of atomic radius
Unlike a ball, an atom doesn't have a fixed radius. The radius of an atom
can only be found by measuring the distance between the nuclei of two
touching atoms, and then halving that distance.

As you can see from the diagrams, the same atom could be found to have
a different radius depending on what was around it.
The left hand diagram shows bonded atoms. The atoms are pulled closely
together and so the measured radius is less than if they are just touching.
This is what you would get if you had metal atoms in a metallic structure,
or atoms covalently bonded to each other. The type of atomic radius being
measured here is called the metallic radius or the covalent radius
depending on the bonding.

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atomic and ionic radius

The right hand diagram shows what happens if the atoms are just
touching. The attractive forces are much less, and the atoms are
essentially "unsquashed". This measure of atomic radius is called the van
der Waals radius after the weak attractions present in this situation.

Note: If you want to explore these various types of bonding


this link will take you to the bonding menu.

Trends in atomic radius in the Periodic Table


The exact pattern you get depends on which measure of atomic radius
you use - but the trends are still valid.
The following diagram uses metallic radii for metallic elements, covalent
radii for elements that form covalent bonds, and van der Waals radii for
those (like the noble gases) which don't form bonds.
Trends in atomic radius in Periods 2 and 3

Trends in atomic radius down a group


It is fairly obvious that the atoms get bigger as you go down groups. The
reason is equally obvious - you are adding extra layers of electrons.
Trends in atomic radius across periods
You have to ignore the noble gas at the end of each period. Because
neon and argon don't form bonds, you can only measure their van der
Waals radius - a case where the atom is pretty well "unsquashed". All the
other atoms are being measured where their atomic radius is being
lessened by strong attractions. You aren't comparing like with like if you

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atomic and ionic radius

include the noble gases.

Leaving the noble gases out, atoms get smaller


as you go across a period.

If you think about it, the metallic or covalent radius is going to be a


measure of the distance from the nucleus to the electrons which make up
the bond. (Look back to the left-hand side of the first diagram on this page
if you aren't sure, and picture the bonding electrons as being half way
between the two nuclei.)
From lithium to fluorine, those electrons are all in the 2-level, being
screened by the 1s2 electrons. The increasing number of protons in the
nucleus as you go across the period pulls the electrons in more tightly.
The amount of screening is constant for all of these elements.

Note: You might possibly wonder why you don't get extra
screening from the 2s2 electrons in the cases of the elements
from boron to fluorine where the bonding involves the p
electrons.
In each of these cases, before bonding happens, the existing s
and p orbitals are reorganised (hybridised) into new orbitals of
equal energy. When these atoms are bonded, there aren't any
2s electrons as such.
If you don't know about hybridisation, just ignore this comment
- you won't need it for UK A level purposes anyway.

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atomic and ionic radius

In the period from sodium to chlorine, the same thing happens. The size of
the atom is controlled by the 3-level bonding electrons being pulled closer
to the nucleus by increasing numbers of protons - in each case, screened
by the 1- and 2-level electrons.

Trends in the transition elements

Although there is a slight contraction at the beginning of the series, the


atoms are all much the same size.
The size is determined by the 4s electrons. The pull of the increasing
number of protons in the nucleus is more or less offset by the extra
screening due to the increasing number of 3d electrons.

Note: Confusingly, once the orbitals have electrons in them,


the 4s orbital has a higher energy than the 3d - quite the
opposite of their order when the atoms are being filled with
electrons. That means that it is the 4s electrons which can be
thought of as being on the outside of the atom, and so
determine its size. It also means that the 3d orbitals are
slightly closer to the nucleus than the 4s - and so offer some
screening.
You will find this commented on in the page about electronic
structures of ions.

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atomic and ionic radius

IONIC RADIUS
Ions aren't the same size as the atoms they come from. Compare the
sizes of sodium and chloride ions with the sizes of sodium and chlorine
atoms.

Positive ions
Positive ions are smaller than the atoms they come from. Sodium is 2,8,1;
Na+ is 2,8. You've lost a whole layer of electrons, and the remaining 10
electrons are being pulled in by the full force of 11 protons.
Negative ions
Negative ions are bigger than the atoms they come from. Chlorine is
2,8,7; Cl- is 2,8,8. Although the electrons are still all in the 3-level, the
extra repulsion produced by the incoming electron causes the atom to
expand. There are still only 17 protons, but they are now having to hold 18
electrons.

Where would you like to go now?


To the atomic properties menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

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atomic and ionic radius

Jim Clark 2000 (modified 2004)

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Bonding menu

Understanding Chemistry

BONDING MENU

Ionic bonding . . .
Includes a simple view of ionic bonding and the way you need to
modify this for A'level purposes.
Covalent bonding . . .
Includes a simple view of covalent bonding (single and double)
and the modifications needed for A'level purposes.
Co-ordinate (dative covalent) bonding . . .
Explains what co-ordinate (dative covalent) bonding is, and looks
at a wide range of examples.
Electronegativity . . .
Explains what electronegativity is and how it varies around the
Periodic Table. Describes and explains how electronegativity
differences determine the type of bond formed. Looks at polar
bonds and molecules.
Shapes of simple molecules and ions . . .
Explains how to work out the shapes of a wide range of simple
molecules and ions.
Metallic bonding . . .
A simple explanation of the forces holding metals together.
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Bonding menu

van der Waals forces . . .


A description of van der Waals forces (temporary fluctuating dipole
and dipole-dipole interactions) causing attractions between
individual molecules.
Hydrogen bonding . . .
An explanation of how hydrogen bonding arises and its effect on
boiling points.

Bonding in organic compounds . . .


This leads you to the bonding menu in the organic section of this
site in case you are only interested in bonding in organic
compounds.

Go to atomic structure and bonding menu . . .


Go to Main Menu . . .

Jim Clark 2000

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ionic (electrovalent) bonding

IONIC (ELECTROVALENT) BONDING

This page explains what ionic (electrovalent) bonding is. It starts with a
simple picture of the formation of ions, and then modifies it slightly for
A'level purposes.

A simple view of ionic bonding


The importance of noble gas structures
At a simple level (like GCSE) a lot of importance is attached to the
electronic structures of noble gases like neon or argon which have eight
electrons in their outer energy levels (or two in the case of helium).
These noble gas structures are thought of as being in some way a
"desirable" thing for an atom to have.
You may well have been left with the strong impression that when other
atoms react, they try to organise things such that their outer levels are
either completely full or completely empty.

Note: The central role given to noble gas structures is very


much an over-simplification. We shall have to spend some
time later on demolishing the concept!

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ionic (electrovalent) bonding

Ionic bonding in sodium chloride


Sodium (2,8,1) has 1 electron more than a stable noble gas structure
(2,8). If it gave away that electron it would become more stable.
Chlorine (2,8,7) has 1 electron short of a stable noble gas structure
(2,8,8). If it could gain an electron from somewhere it too would become
more stable.
The answer is obvious. If a sodium atom gives an electron to a chlorine
atom, both become more stable.

The sodium has lost an electron, so it no longer has equal numbers of


electrons and protons. Because it has one more proton than electron, it
has a charge of 1+. If electrons are lost from an atom, positive ions are
formed.
Positive ions are sometimes called cations.
The chlorine has gained an electron, so it now has one more electron
than proton. It therefore has a charge of 1-. If electrons are gained by an
atom, negative ions are formed.
A negative ion is sometimes called an anion.
The nature of the bond
The sodium ions and chloride ions are held together by the strong
electrostatic attractions between the positive and negative charges.
The formula of sodium chloride
You need one sodium atom to provide the extra electron for one chlorine
atom, so they combine together 1:1. The formula is therefore NaCl.

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ionic (electrovalent) bonding

Some other examples of ionic bonding


magnesium oxide

Again, noble gas structures are formed, and the magnesium oxide is held
together by very strong attractions between the ions. The ionic bonding is
stronger than in sodium chloride because this time you have 2+ ions
attracting 2- ions. The greater the charge, the greater the attraction.
The formula of magnesium oxide is MgO.
calcium chloride

This time you need two chlorines to use up the two outer electrons in the
calcium. The formula of calcium chloride is therefore CaCl2.
potassium oxide

Again, noble gas structures are formed. It takes two potassiums to


supply the electrons the oxygen needs. The formula of potassium oxide
is K2O.
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ionic (electrovalent) bonding

THE A'LEVEL VIEW OF IONIC BONDING

Electrons are transferred from one atom to another resulting in the


formation of positive and negative ions.
The electrostatic attractions between the positive and negative
ions hold the compound together.

So what's new? At heart - nothing. What needs modifying is the view that
there is something magic about noble gas structures. There are far more
ions which don't have noble gas structures than there are which do.
Some common ions which don't have noble gas structures
You may have come across some of the following ions in a basic course
like GCSE. They are all perfectly stable , but not one of them has a noble
gas structure.
Fe3+

[Ar]3d5

Cu2+

[Ar]3d9

Zn2+

[Ar]3d10

Ag+

[Kr]4d10

Pb2+

[Xe]4f145d106s2

Noble gases (apart from helium) have an outer electronic structure


ns2np6.

Note: If you aren't happy about writing electronic structures


using of s, p and d notation, follow this link before you go on.
Return to this page via the menus or by using the BACK
button on your browser.

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ionic (electrovalent) bonding

Apart from some elements at the beginning of a transition series


(scandium forming Sc3+ with an argon structure, for example), all
transition elements and any metals following a transition series (like tin
and lead in Group 4, for example) will have structures like those above.
That means that the only elements to form positive ions with noble gas
structures (apart from odd ones like scandium) are those in groups 1 and
2 of the Periodic Table and aluminium in group 3 (boron in group 3
doesn't form ions).
Negative ions are tidier! Those elements in Groups 5, 6 and 7 which form
simple negative ions all have noble gas structures.
If elements aren't aiming for noble gas structures when they form ions,
what decides how many electrons are transferred? The answer lies in the
energetics of the process by which the compound is made.

Warning! From here to the bottom of this page goes beyond


anything you are likely to need for A'level purposes. It is
included for interest only.

What determines what the charge is on an ion?


Elements combine to make the compound which is as stable as possible
- the one in which the greatest amount of energy is evolved in its making.
The more charges a positive ion has, the greater the attraction towards
its accompanying negative ion. The greater the attraction, the more
energy is released when the ions come together.
That means that elements forming positive ions will tend to give away as
many electrons as possible. But there's a down-side to this.
Energy is needed to remove electrons from atoms. This is called
ionisation energy. The more electrons you remove, the greater the total
ionisation energy becomes. Eventually the total ionisation energy needed
becomes so great that the energy released when the attractions are set
up between positive and negative ions isn't large enough to cover it.

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ionic (electrovalent) bonding

The element forms the ion which makes the compound most stable - the
one in which most energy is released over-all.
For example, why is calcium chloride CaCl2 rather than CaCl or CaCl3?
If one mole of CaCl (containing Ca+ ions) is made from its elements, it is
possible to estimate that about 171 kJ of heat is evolved.
However, making CaCl2 (containing Ca2+ ions) releases more heat. You
get 795 kJ. That extra amount of heat evolved makes the compound
more stable, which is why you get CaCl2 rather than CaCl.
What about CaCl3 (containing Ca3+ ions)? To make one mole of this, you
can estimate that you would have to put in 1341 kJ. This makes this
compound completely non-viable. Why is so much heat needed to make
CaCl3? It is because the third ionisation energy (the energy needed to
remove the third electron) is extremely high (4940 kJ mol-1) because the
electron is being removed from the 3-level rather than the 4-level.
Because it is much closer to the nucleus than the first two electrons
removed, it is going to be held much more strongly.

Note: It would pay you to read about ionisation energies if


you really want to understand this.
You could also go to a standard text book and investigate
Born-Haber Cycles.

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ionic (electrovalent) bonding

A similar sort of argument applies to the negative ion. For example,


oxygen forms an O2- ion rather than an O- ion or an O3- ion, because
compounds containing the O2- ion turn out to be the most energetically
stable.

Where would you like to go now?


To explore the physical properties of ionic compounds . . .
To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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ionic structures

IONIC STRUCTURES

This page explains the relationship between the arrangement of the ions
in a typical ionic solid like sodium chloride and its physical properties melting point, boiling point, brittleness, solubility and electrical behaviour.

Note: If you need to revise how ionic bonding arises, then


you might like to follow this link. It isn't important for
understanding this page, however.

The structure of a typical ionic solid - sodium chloride


How the ions are arranged in sodium chloride
Sodium chloride is taken as a typical ionic compound. Compounds like
this consist of a giant (endlessly repeating) lattice of ions. So sodium
chloride (and any other ionic compound) is described as having a giant
ionic structure.
You should be clear that giant in this context doesn't just mean very
large. It means that you can't state exactly how many ions there are.
There could be billions of sodium ions and chloride ions packed together,
or trillions, or whatever - it simply depends how big the crystal is. That is
different from, say, a water molecule which always contains exactly 2
hydrogen atoms and one oxygen atom - never more and never less.
A small representative bit of a sodium chloride lattice looks like this:

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ionic structures

If you look at the diagram carefully, you will see that the sodium ions and
chloride ions alternate with each other in each of the three dimensions.
This diagram is easy enough to draw with a computer, but extremely
difficult to draw convincingly by hand. We normally draw an "exploded"
version which looks like this:

Only those ions joined by lines are actually touching each other. The
sodium ion in the centre is being touched by 6 chloride ions. By chance
we might just as well have centred the diagram around a chloride ion that, of course, would be touched by 6 sodium ions. Sodium chloride is
described as being 6:6-co-ordinated.
You must remember that this diagram represents only a tiny part of the
whole sodium chloride crystal. The pattern repeats in this way over
countless ions.

How to draw this structure


Draw a perfect square:

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ionic structures

Now draw an identical square behind this one and offset a bit. You might
have to practice a bit to get the placement of the two squares right. If you
get it wrong, the ions get all tangled up with each other in your final
diagram.

Turn this into a perfect cube by joining the squares together:

Now the tricky bit! Subdivide this big cube into 8 small cubes by joining
the mid point of each edge to the mid point of the edge opposite it. To
complete the process you will also have to join the mid point of each face
(easily found once you've joined the edges) to the mid point of the
opposite face.

Now all you have to do is put the ions in. Use different colours or different
sizes for the two different ions, and don't forget a key. It doesn't matter
whether you end up with a sodium ion or a chloride ion in the centre of
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ionic structures

the cube - all that matters is that they alternate in all three dimensions.

You should be able to draw a perfectly adequate free-hand sketch of this


in under two minutes - less than one minute if you're not too fussy!

Why is sodium chloride 6:6-co-ordinated?


The more attraction there is between the positive and negative ions, the
more energy is released. The more energy that is released, the more
energetically stable the structure becomes.
That means that to gain maximum stability, you need the maximum
number of attractions. So why does each ion surround itself with 6 ions of
the opposite charge?
That represents the maximum number of chloride ions that you can fit
around a central sodium ion before the chloride ions start touching each
other. If they start touching, you introduce repulsions into the crystal
which makes it less stable.

Note: If the positive ion is big enough, you can fit 8 chloride
ions around it. For example, caesium ions are significantly
bigger than sodium ions, and so caesium chloride is 8:8-coordinated. It can gain stability from the extra attractions
without any problems because of repulsion due to ions with
the same charge touching each other.
The structure of caesium chloride isn't on any current A'level
syllabuses.

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ionic structures

The physical properties of sodium chloride


Sodium chloride has a high melting and boiling point
There are strong electrostatic attractions between the positive and
negative ions, and it takes a lot of heat energy to overcome them. Ionic
substances all have high melting and boiling points. Differences between
ionic substances will depend on things like:

The number of charges on the ions


Magnesium oxide has exactly the same structure as sodium
chloride, but a much higher melting and boiling point. The 2+ and
2- ions attract each other more strongly than 1+ attracts 1-.

The sizes of the ions


If the ions are smaller they get closer together and so the
electrostatic attractions are greater. Rubidium iodide, for example,
melts and boils at slightly lower temperatures than sodium
chloride, because both rubidium and iodide ions are bigger than
sodium and chloride ions. The attractions are less between the
bigger ions and so less heat energy is needed to separate them.

Sodium chloride crystals are brittle


Brittleness is again typical of ionic substances. Imagine what happens to
the crystal if a stress is applied which shifts the ion layers slightly.

Ions of the same charge are brought side-by-side and so the crystal
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ionic structures

repels itself to pieces!

Sodium chloride is soluble in water


Many ionic solids are soluble in water - although not all. It depends on
whether there are big enough attractions between the water molecules
and the ions to overcome the attractions between the ions themselves.
Positive ions are attracted to the lone pairs on water molecules and coordinate (dative covalent) bonds may form. Water molecules form
hydrogen bonds with negative ions.

Note: The bonding in hydrated metal ions is covered in the


page on co-ordinate bonding. The bonding between negative
ions like chloride ions and water molecules is covered in the
page on hydrogen bonding.

Sodium chloride is insoluble in organic solvents


This is also typical of ionic solids. The attractions between the solvent
molecules and the ions aren't big enough to overcome the attractions
holding the crystal together.

The electrical behaviour of sodium chloride


Solid sodium chloride doesn't conduct electricity, because there are no
electrons which are free to move. Molten sodium chloride undergoes
electrolysis, which involves conduction of electricity because of the
movement of the ions. In the process, sodium and chlorine are produced.
This is a chemical change rather than a physical process.

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Where would you like to go now?


To the structures menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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co-ordinate (dative covalent) bonding

CO-ORDINATE (DATIVE COVALENT) BONDING

This page explains what co-ordinate (also called dative covalent)


bonding is. You need to have a reasonable understanding of simple
covalent bonding before you start.

Important! If you are uncertain about covalent bonding


follow this link before you go on with this page.

Co-ordinate (dative covalent) bonding


A covalent bond is formed by two atoms sharing a pair of electrons. The
atoms are held together because the electron pair is attracted by both of
the nuclei.
In the formation of a simple covalent bond, each atom supplies one
electron to the bond - but that doesn't have to be the case. A co-ordinate
bond (also called a dative covalent bond) is a covalent bond (a shared
pair of electrons) in which both electrons come from the same atom.
For the rest of this page, we shall use the term co-ordinate bond - but if
you prefer to call it a dative covalent bond, that's not a problem!

The reaction between ammonia and hydrogen chloride


If these colourless gases are allowed to mix, a thick white smoke of solid
ammonium chloride is formed.

Ammonium ions, NH4+, are formed by the transfer of a hydrogen ion from
the hydrogen chloride to the lone pair of electrons on the ammonia
molecule.
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co-ordinate (dative covalent) bonding

When the ammonium ion, NH4+, is formed, the fourth hydrogen is


attached by a dative covalent bond, because only the hydrogen's nucleus
is transferred from the chlorine to the nitrogen. The hydrogen's electron
is left behind on the chlorine to form a negative chloride ion.
Once the ammonium ion has been formed it is impossible to tell any
difference between the dative covalent and the ordinary covalent bonds.
Although the electrons are shown differently in the diagram, there is no
difference between them in reality.
Representing co-ordinate bonds
In simple diagrams, a co-ordinate bond is shown by an arrow. The arrow
points from the atom donating the lone pair to the atom accepting it.

Dissolving hydrogen chloride in water to make hydrochloric acid


Something similar happens. A hydrogen ion (H+) is transferred from the
chlorine to one of the lone pairs on the oxygen atom.
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co-ordinate (dative covalent) bonding

The H3O+ ion is variously called the hydroxonium ion, the hydronium ion
or the oxonium ion.
In an introductory chemistry course (such as GCSE), whenever you have
talked about hydrogen ions (for example in acids), you have actually
been talking about the hydroxonium ion. A raw hydrogen ion is simply a
proton, and is far too reactive to exist on its own in a test tube.
If you write the hydrogen ion as H+(aq), the "(aq)" represents the water
molecule that the hydrogen ion is attached to. When it reacts with
something (an alkali, for example), the hydrogen ion simply becomes
detached from the water molecule again.
Note that once the co-ordinate bond has been set up, all the hydrogens
attached to the oxygen are exactly equivalent. When a hydrogen ion
breaks away again, it could be any of the three.

The reaction between ammonia and boron trifluoride, BF3


If you have recently read the page on covalent bonding, you may
remember boron trifluoride as a compound which doesn't have a noble
gas structure around the boron atom. The boron only has 3 pairs of
electrons in its bonding level, whereas there would be room for 4 pairs.
BF3 is described as being electron deficient.
The lone pair on the nitrogen of an ammonia molecule can be used to
overcome that deficiency, and a compound is formed involving a coordinate bond.
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co-ordinate (dative covalent) bonding

Using lines to represent the bonds, this could be drawn more simply as:

The second diagram shows another way that you might find co-ordinate
bonds drawn. The nitrogen end of the bond has become positive
because the electron pair has moved away from the nitrogen towards the
boron - which has therefore become negative. We shan't use this method
again - it's more confusing than just using an arrow.

The structure of aluminium chloride


Aluminium chloride sublimes (turns straight from a
solid to a gas) at 178C. If it contained ions it would
have a very high melting and boiling point because of
the strong attractions between the positive and
negative ions. The implication is that it must be
covalent. The dots-and-crosses diagram shows only
the outer electrons.
AlCl3, like BF3, is electron deficient. There is likely to be a similarity,
because aluminium and boron are in the same group of the Periodic
Table, as are fluorine and chlorine.

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co-ordinate (dative covalent) bonding

Measurements of the relative formula mass of aluminium chloride show


that its formula in the solid is not AlCl3, but Al2Cl6. It exists as a dimer
(two molecules joined together). The bonding between the two molecules
is co-ordinate, using lone pairs on the chlorine atoms. Each chlorine
atom has 3 lone pairs, but only the two important ones are shown in the
line diagram.

Note: The uninteresting electrons on the chlorines have


been faded in colour to make the co-ordinate bonds show up
better. There's nothing special about those two particular lone
pairs - they just happen to be the ones pointing in the right
direction.

Energy is released when the two co-ordinate bonds are formed, and so
the dimer is more stable than two separate AlCl3 molecules.

The bonding in hydrated metal ions


Water molecules are strongly attracted to ions in solution - the water
molecules clustering around the positive or negative ions. In many cases,
the attractions are so great that formal bonds are made, and this is true
of almost all positive metal ions. Ions with water molecules attached are
described as hydrated ions.

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co-ordinate (dative covalent) bonding

Although aluminium chloride is covalent, when it dissolves in water, ions


are produced. Six water molecules bond to the aluminium to give an ion
with the formula Al(H2O)63+. It's called the hexaaquaaluminium ion which translates as six ("hexa") water molecules ("aqua") wrapped
around an aluminium ion.
The bonding in this (and the similar ions formed by the
great majority of other metals) is co-ordinate (dative
covalent) using lone pairs on the water molecules.

Aluminium is 1s22s22p63s23px1. When it forms an Al3+ ion it loses the 3level electrons to leave 1s22s22p6.
That means that all the 3-level orbitals are now empty. The aluminium reorganises (hybridises) six of these (the 3s, three 3p, and two 3d) to
produce six new orbitals all with the same energy. These six hybrid
orbitals accept lone pairs from six water molecules.
You might wonder why it chooses to use six orbitals rather than four or
eight or whatever. Six is the maximum number of water molecules it is
possible to fit around an aluminium ion (and most other metal ions). By
making the maximum number of bonds, it releases most energy and so
becomes most energetically stable.

Only one lone pair is shown on each water molecule. The other lone pair
is pointing away from the aluminium and so isn't involved in the bonding.
The resulting ion looks like this:

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co-ordinate (dative covalent) bonding

Because of the movement of electrons towards the centre of the ion, the
3+ charge is no longer located entirely on the aluminium, but is now
spread over the whole of the ion.

Note: Dotted arrows represent lone pairs coming from water


molecules behind the plane of the screen or paper. Wedge
shaped arrows represent bonds from water molecules in front
of the plane of the screen or paper.

Two more molecules

Note: Only one current A'level syllabus wants these two.


Check yours! If you haven't got a copy of your syllabus, follow
this link to find out how to get one.

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co-ordinate (dative covalent) bonding

Carbon monoxide, CO
Carbon monoxide can be thought of as having two ordinary covalent
bonds between the carbon and the oxygen plus a co-ordinate bond using
a lone pair on the oxygen atom.

Nitric acid, HNO3


In this case, one of the oxygen atoms can be thought of as attaching to
the nitrogen via a co-ordinate bond using the lone pair on the nitrogen
atom.

In fact this structure is misleading because it suggests that the two


oxygen atoms on the right-hand side of the diagram are joined to the
nitrogen in different ways. Both bonds are actually identical in length and
strength, and so the arrangement of the electrons must be identical.
There is no way of showing this using a dots-and-crosses picture. The
bonding involves delocalisation.

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co-ordinate (dative covalent) bonding

If you are interested: The bonding is rather similar to the


bonding in the ethanoate ion (although without the negative
charge). You will find thisdescribed on a page about the
acidity of organic acids.

Where would you like to go now?


To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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covalent bonding - single bonds

COVALENT BONDING - SINGLE BONDS

This page explains what covalent bonding is. It starts with a simple
picture of the single covalent bond, and then modifies it slightly for A'level
purposes. It also takes a more sophisticated view (beyond A'level) if you
are interested. You will find a link to a page on double covalent bonds at
the bottom of the page.

A simple view of covalent bonding


The importance of noble gas structures
At a simple level (like GCSE) a lot of importance is attached to the
electronic structures of noble gases like neon or argon which have eight
electrons in their outer energy levels (or two in the case of helium).
These noble gas structures are thought of as being in some way a
"desirable" thing for an atom to have.
You may well have been left with the strong impression that when other
atoms react, they try to achieve noble gas structures.
As well as achieving noble gas structures by transferring electrons from
one atom to another as in ionic bonding, it is also possible for atoms to
reach these stable structures by sharing electrons to give covalent bonds.
Some very simple covalent molecules
Chlorine
For example, two chlorine atoms could both achieve stable structures by
sharing their single unpaired electron as in the diagram.

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covalent bonding - single bonds

The fact that one chlorine has been drawn with electrons marked as
crosses and the other as dots is simply to show where all the electrons
come from. In reality there is no difference between them.
The two chlorine atoms are said to be joined by a covalent bond. The
reason that the two chlorine atoms stick together is that the shared pair
of electrons is attracted to the nucleus of both chlorine atoms.
Hydrogen

Hydrogen atoms only need two electrons in their outer level to reach the
noble gas structure of helium. Once again, the covalent bond holds the
two atoms together because the pair of electrons is attracted to both
nuclei.
Hydrogen chloride

The hydrogen has a helium structure, and the chlorine an argon structure.

Covalent bonding at A'level


Cases where there isn't any difference from the simple view
If you stick closely to modern A'level syllabuses, there is little need to
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covalent bonding - single bonds

move far from the simple (GCSE) view. The only thing which must be
changed is the over-reliance on the concept of noble gas structures.
Most of the simple molecules you draw do in fact have all their atoms
with noble gas structures.
For example:

Even with a more complicated molecule like PCl3, there's no problem. In


this case, only the outer electrons are shown for simplicity. Each atom in
this structure has inner layers of electrons of 2,8. Again, everything
present has a noble gas structure.

Cases where the simple view throws up problems


Boron trifluoride, BF3

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covalent bonding - single bonds

A boron atom only has 3 electrons in its outer level, and there is no
possibility of it reaching a noble gas structure by simple sharing of
electrons. Is this a problem? No. The boron has formed the maximum
number of bonds that it can in the circumstances, and this is a perfectly
valid structure.
Energy is released whenever a covalent bond is formed. Because energy
is being lost from the system, it becomes more stable after every
covalent bond is made. It follows, therefore, that an atom will tend to
make as many covalent bonds as possible. In the case of boron in BF3,
three bonds is the maximum possible because boron only has 3
electrons to share.

Note: You might perhaps wonder why boron doesn't form


ionic bonds with fluorine instead. Boron doesn't form ions
because the total energy needed to remove three electrons
to form a B3+ ion is simply too great to be recoverable when
attractions are set up between the boron and fluoride ions.

Phosphorus(V) chloride, PCl5


In the case of phosphorus 5 covalent bonds are possible - as in PCl5.
Phosphorus forms two chlorides - PCl3 and PCl5. When phosphorus
burns in chlorine both are formed - the majority product depending on
how much chlorine is available. We've already looked at the structure of
PCl3.
The diagram of PCl5 (like the previous diagram of PCl3) shows only the
outer electrons.

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covalent bonding - single bonds

Notice that the phosphorus now has 5 pairs of electrons in the outer level
- certainly not a noble gas structure. You would have been content to
draw PCl3 at GCSE, but PCl5 would have looked very worrying.
Why does phosphorus sometimes break away from a noble gas structure
and form five bonds? In order to answer that question, we need to
explore territory beyond the limits of current A'level syllabuses. Don't be
put off by this! It isn't particularly difficult, and is extremely useful if you
are going to understand the bonding in some important organic
compounds.

A more sophisticated view of covalent bonding


The bonding in methane, CH4

Warning! If you aren't happy with describing electron


arrangements in s and p notation, and with the shapes of s
and p orbitals, you need to read about orbitals before you go
on.
Use the BACK button on your browser to return quickly to this
point.

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covalent bonding - single bonds

What is wrong with the dots-and-crosses picture of bonding in


methane?
We are starting with methane because it is the simplest case which
illustrates the sort of processes involved. You will remember that the dotsand-crossed picture of methane looks like this.

There is a serious mis-match between this structure and the modern


electronic structure of carbon, 1s22s22px12py1. The modern structure
shows that there are only 2 unpaired electrons for hydrogens to share
with, instead of the 4 which the simple view requires.
You can see this more readily using the
electrons-in-boxes notation. Only the 2level electrons are shown. The 1s2
electrons are too deep inside the atom to
be involved in bonding. The only electrons
directly available for sharing are the 2p
electrons. Why then isn't methane CH2?
Promotion of an electron

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covalent bonding - single bonds

When bonds are formed, energy is


released and the system becomes more
stable. If carbon forms 4 bonds rather than
2, twice as much energy is released and so
the resulting molecule becomes even more
stable.
There is only a small energy gap between
the 2s and 2p orbitals, and so it pays the
carbon to provide a small amount of energy
to promote an electron from the 2s to the
empty 2p to give 4 unpaired electrons. The
extra energy released when the bonds form
more than compensates for the initial input.

Note: People sometimes worry that the promoted electron is


drawn as an up-arrow, whereas it started as a down-arrow. It
simply makes the diagram look tidier - nothing very
sophisticated is going on!

Now that we've got 4 unpaired electrons ready for bonding, another
problem arises. In methane all the carbon-hydrogen bonds are identical,
but our electrons are in two different kinds of orbitals. You aren't going to
get four identical bonds unless you start from four identical orbitals.
Hybridisation
The electrons rearrange themselves again
in a process called hybridisation. This
reorganises the electrons into four identical
hybrid orbitals called sp3 hybrids (because
they are made from one s orbital and three
p orbitals). You should read "sp3" as "s p
three" - not as "s p cubed".

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covalent bonding - single bonds

sp3 hybrid orbitals look a bit like half a p orbital,


and they arrange themselves in space so that
they are as far apart as possible. You can picture
the nucleus as being at the centre of a
tetrahedron (a triangularly based pyramid) with
the orbitals pointing to the corners. For clarity,
the nucleus is drawn far larger than it really is.

What happens when the bonds are formed?


Remember that hydrogen's electron is in a 1s orbital - a spherically
symmetric region of space surrounding the nucleus where there is some
fixed chance (say 95%) of finding the electron. When a covalent bond is
formed, the atomic orbitals (the orbitals in the individual atoms) merge to
produce a new molecular orbital which contains the electron pair which
creates the bond.

Four molecular orbitals are formed, looking rather like the original sp3
hybrids, but with a hydrogen nucleus embedded in each lobe. Each
orbital holds the 2 electrons that we've previously drawn as a dot and a
cross.
The principles involved - promotion of electrons if necessary, then
hybridisation, followed by the formation of molecular orbitals - can be
applied to any covalently-bound molecule.

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covalent bonding - single bonds

Note: You will find this bit on methane repeated in the


organic section of this site. That article on methane goes on
to look at the formation of carbon-carbon single bonds in
ethane.

The bonding in the phosphorus chlorides, PCl3 and PCl5


What's wrong with the simple view of PCl3?
This diagram only shows the outer (bonding) electrons.

Nothing is wrong with this! (Although it doesn't account for the shape of
the molecule properly.) If you were going to take a more modern look at
it, the argument would go like this:
Phosphorus has the electronic structure 1s22s22p63s23px13py13pz1. If
we look only at the outer electrons as "electrons-in-boxes":

There are 3 unpaired electrons that can be used to form bonds with 3
chlorine atoms. The four 3-level orbitals hybridise to produce 4
equivalent sp3 hybrids just like in carbon - except that one of these hybrid

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covalent bonding - single bonds

orbitals contains a lone pair of electrons.

Each of the 3 chlorines then forms a covalent bond by merging the


atomic orbital containing its unpaired electron with one of the phosphorus
unpaired electrons to make 3 molecular orbitals.
You might wonder whether all this is worth the bother! Probably not! It is
worth it with PCl5, though.
What's wrong with the simple view of PCl5?
You will remember that the dots-and-crosses picture of PCl5 looks
awkward because the phosphorus doesn't end up with a noble gas
structure. This diagram also shows only the outer electrons.

In this case, a more modern view makes things look better by


abandoning any pretence of worrying about noble gas structures.
If the phosphorus is going to form PCl5 it has first to generate 5 unpaired
electrons. It does this by promoting one of the electrons in the 3s orbital
to the next available higher energy orbital.
Which higher energy orbital? It uses one of the 3d orbitals. You might
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covalent bonding - single bonds

have expected it to use the 4s orbital because this is the orbital that fills
before the 3d when atoms are being built from scratch. Not so! Apart
from when you are building the atoms in the first place, the 3d always
counts as the lower energy orbital.

This leaves the phosphorus with this arrangement of its electrons:

The 3-level electrons now rearrange (hybridise) themselves to give 5


hybrid orbitals, all of equal energy. They would be called sp3d hybrids
because that's what they are made from.

The electrons in each of these orbitals would then share space with
electrons from five chlorines to make five new molecular orbitals - and
hence five covalent bonds.
Why does phosphorus form these extra two bonds? It puts in an amount
of energy to promote an electron, which is more than paid back when the
new bonds form. Put simply, it is energetically profitable for the
phosphorus to form the extra bonds.
The advantage of thinking of it in this way is that it completely ignores the

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covalent bonding - single bonds

question of whether you've got a noble gas structure, and so you don't
worry about it.

A non-existent compound - NCl5


Nitrogen is in the same Group of the Periodic Table as phosphorus, and
you might expect it to form a similar range of compounds. In fact, it
doesn't. For example, the compound NCl3 exists, but there is no such
thing as NCl5.
Nitrogen is 1s22s22px12py12pz1. The reason that NCl5 doesn't exist is
that in order to form five bonds, the nitrogen would have to promote one
of its 2s electrons. The problem is that there aren't any 2d orbitals to
promote an electron into - and the energy gap to the next level (the 3s) is
far too great.
In this case, then, the energy released when the extra bonds are made
isn't enough to compensate for the energy needed to promote an
electron - and so that promotion doesn't happen.
Atoms will form as many bonds as possible provided it is energetically
profitable.

Where would you like to go now?


To explore double covalent bonding . . .
To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

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covalent bonding - single bonds

Jim Clark 2000

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bonding in methane - sp3 hybridisation

BONDING IN METHANE AND ETHANE

Warning! If you aren't happy with describing electron


arrangements in s and p notation, and with the shapes of s
and p orbitals, you really should read about orbitals.
Use the BACK button on your browser to return quickly to this
point.

Methane, CH4
The simple view of the bonding in methane
You will be familiar with drawing methane
using dots and crosses diagrams, but it is
worth looking at its structure a bit more
closely.
There is a serious mis-match between this
structure and the modern electronic structure
of carbon, 1s22s22px12py1. The modern
structure shows that there are only 2 unpaired electrons for hydrogens to
share with, instead of the 4 which the simple view requires.
You can see this more readily using the
electrons-in-boxes notation. Only the 2level electrons are shown. The 1s2
electrons are too deep inside the atom to
be involved in bonding. The only electrons
directly available for sharing are the 2p
electrons. Why then isn't methane CH2?
Promotion of an electron

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bonding in methane - sp3 hybridisation

When bonds are formed, energy is


released and the system becomes more
stable. If carbon forms 4 bonds rather than
2, twice as much energy is released and so
the resulting molecule becomes even more
stable.
There is only a small energy gap between
the 2s and 2p orbitals, and so it pays the
carbon to provide a small amount of energy
to promote an electron from the 2s to the
empty 2p to give 4 unpaired electrons. The
extra energy released when the bonds form
more than compensates for the initial input.

Note: People sometimes worry that the promoted electron is


drawn as an up-arrow, whereas it started as a down-arrow. It
simply makes the diagram look tidier - nothing very
sophisticated is going on!

Now that we've got 4 unpaired electrons ready for bonding, another
problem arises. In methane all the carbon-hydrogen bonds are identical,
but our electrons are in two different kinds of orbitals. You aren't going to
get four identical bonds unless you start from four identical orbitals.
Hybridisation
The electrons rearrange themselves again
in a process called hybridisation. This
reorganises the electrons into four identical
hybrid orbitals called sp3 hybrids (because
they are made from one s orbital and three
p orbitals). You should read "sp3" as "s p
three" - not as "s p cubed".

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bonding in methane - sp3 hybridisation

sp3 hybrid orbitals look a bit like half a p orbital,


and they arrange themselves in space so that
they are as far apart as possible. You can picture
the nucleus as being at the centre of a
tetrahedron (a triangularly based pyramid) with
the orbitals pointing to the corners. For clarity,
the nucleus is drawn far larger than it really is.

What happens when the bonds are formed?


Remember that hydrogen's electron is in a 1s orbital - a spherically
symmetric region of space surrounding the nucleus where there is some
fixed chance (say 95%) of finding the electron. When a covalent bond is
formed, the atomic orbitals (the orbitals in the individual atoms) merge to
produce a new molecular orbital which contains the electron pair which
creates the bond.

Four molecular orbitals are formed, looking rather like the original sp3
hybrids, but with a hydrogen nucleus embedded in each lobe. Each
orbital holds the 2 electrons that we've previously drawn as a dot and a
cross.
The principles involved - promotion of electrons if necessary, then
hybridisation, followed by the formation of molecular orbitals - can be
applied to any covalently-bound molecule.

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bonding in methane - sp3 hybridisation

Ethane, C2H6
The formation of molecular orbitals in ethane
Ethane isn't particularly important in its own right, but is included because
it is a simple example of how a carbon-carbon single bond is formed.
Each carbon atom in the ethane promotes an electron and then forms
sp3 hybrids exactly as we've described in methane. So just before
bonding, the atoms look like this:

The hydrogens bond with the two carbons to produce molecular orbitals
just as they did with methane. The two carbon atoms bond by merging
their remaining sp3 hybrid orbitals end-to-end to make a new molecular
orbital. The bond formed by this end-to-end overlap is called a sigma
bond. The bonds between the carbons and hydrogens are also sigma
bonds.

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bonding in methane - sp3 hybridisation

In any sigma bond, the most likely place to find the pair of electrons is on
a line between the two nuclei.
Free rotation about the carbon-carbon single bond
The two ends of this molecule can spin quite freely about the sigma bond
so that there are, in a sense, an infinite number of possibilities for the
shape of an ethane molecule. Some possible shapes are:

In each case, the left hand CH3 group has been kept in a constant
position so that you can see the effect of spinning the right hand one.
Other alkanes
All other alkanes will be bonded in the same way:

The carbon atoms will each promote an electron and then


hybridise to give sp3 hybrid orbitals.
The carbon atoms will join to each other by forming sigma bonds
by the end-to-end overlap of their sp3 hybrid orbitals.
Hydrogen atoms will join on wherever they are needed by
overlapping their 1s1 orbitals with sp3 hybrid orbitals on the carbon
atoms.

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bonding in methane - sp3 hybridisation

Where would you like to go now?


To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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electronic structure and atomic orbitals

ELECTRONIC STRUCTURE AND ATOMIC


ORBITALS

A simple view
In any introductory chemistry course you will have come across the
electronic structures of hydrogen and carbon drawn as:

Note: There are many places where you could still make use
of this model of the atom at A' level. It is, however, a
simplification and can be misleading. It gives the impression
that the electrons are circling the nucleus in orbits like planets
around the sun. As you will see in a moment, it is impossible
to know exactly how they are actually moving.

The circles show energy levels - representing increasing distances from


the nucleus. You could straighten the circles out and draw the electronic
structure as a simple energy diagram.

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electronic structure and atomic orbitals

Atomic orbitals
Orbits and orbitals sound similar, but they have quite different meanings.
It is essential that you understand the difference between them.
The impossibility of drawing orbits for electrons
To plot a path for something you need to know exactly where the object
is and be able to work out exactly where it's going to be an instant later.
You can't do this for electrons.

Note: In order to plot a plane's course, it is no use knowing


its exact location in mid-Atlantic if you don't know its direction
or speed. Equally it's no use knowing that it is travelling at
500 mph due west if you have no idea whether it is near
Iceland or the Azores at that particular moment.

The Heisenberg Uncertainty Principle (not required at A'level) says loosely - that you can't know with certainty both where an electron is and
where it's going next. That makes it impossible to plot an orbit for an
electron around a nucleus. Is this a big problem? No. If something is
impossible, you have to accept it and find a way around it.
Hydrogen's electron - the 1s orbital

Note: In this diagram (and the orbital diagrams that follow),


the nucleus is shown very much larger than it really is. This is
just for clarity.

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electronic structure and atomic orbitals

Suppose you had a single hydrogen atom and at a


particular instant plotted the position of the one
electron. Soon afterwards, you do the same thing,
and find that it is in a new position. You have no
idea how it got from the first place to the second.
You keep on doing this over and over again, and
gradually build up a sort of 3D map of the places that the electron is likely
to be found.
In the hydrogen case, the electron can be found anywhere within a
spherical space surrounding the nucleus. The diagram shows a crosssection through this spherical space.
95% of the time (or any other percentage you choose), the electron will
be found within a fairly easily defined region of space quite close to the
nucleus. Such a region of space is called an orbital. You can think of an
orbital as being the region of space in which the electron lives.

Note: If you wanted to be absolutely 100% sure of where the


electron is, you would have to draw an orbital the size of the
Universe!

What is the electron doing in the orbital? We don't know, we can't know,
and so we just ignore the problem! All you can say is that if an electron is
in a particular orbital it will have a particular definable energy.
Each orbital has a name.
The orbital occupied by the hydrogen electron is called a 1s orbital. The
"1" represents the fact that the orbital is in the energy level closest to the
nucleus. The "s" tells you about the shape of the orbital. s orbitals are
spherically symmetric around the nucleus - in each case, like a hollow
ball made of rather chunky material with the nucleus at its centre.

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electronic structure and atomic orbitals

The orbital on the left is a 2s orbital. This is


similar to a 1s orbital except that the region
where there is the greatest chance of
finding the electron is further from the
nucleus - this is an orbital at the second
energy level.
If you look carefully, you will notice that
there is another region of slightly higher
electron density (where the dots are thicker)
nearer the nucleus. ("Electron density" is another way of talking about
how likely you are to find an electron at a particular place.)
2s (and 3s, 4s, etc) electrons spend some of their time closer to the
nucleus than you might expect. The effect of this is to slightly reduce the
energy of electrons in s orbitals. The nearer the nucleus the electrons
get, the lower their energy.
3s, 4s (etc) orbitals get progressively further from the nucleus.
p orbitals
Not all electrons inhabit s orbitals (in fact, very few
electrons live in s orbitals). At the first energy level,
the only orbital available to electrons is the 1s
orbital, but at the second level, as well as a 2s
orbital, there are also orbitals called 2p orbitals.
A p orbital is rather like 2 identical balloons tied
together at the nucleus. The diagram on the right is
a cross-section through that 3-dimensional region
of space. Once again, the orbital shows where
there is a 95% chance of finding a particular
electron.

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electronic structure and atomic orbitals

Beyond A'level: If you imagine a horizontal plane through


the nucleus, with one lobe of the orbital above the plane and
the other beneath it, there is a zero probability of finding the
electron on that plane. So how does the electron get from
one lobe to the other if it can never pass through the plane of
the nucleus? For A'level chemistry you just have to accept
that it does! If you want to find out more, read about the wave
nature of electrons.

Unlike an s orbital, a p orbital points in a particular direction - the one


drawn points up and down the page.
At any one energy level it is possible to have three absolutely equivalent
p orbitals pointing mutually at right angles to each other. These are
arbitrarily given the symbols px, py and pz. This is simply for
convenience - what you might think of as the x, y or z direction changes
constantly as the atom tumbles in space.
The p orbitals at the second energy level are
called 2px, 2py and 2pz. There are similar
orbitals at subsequent levels - 3px, 3py, 3pz,
4px, 4py, 4pz and so on.
All levels except for the first level have p
orbitals. At the higher levels the lobes get
more elongated, with the most likely place to
find the electron more distant from the
nucleus.

Fitting electrons into orbitals


Because for the moment we are only interested in the electronic
structures of hydrogen and carbon, we don't need to concern ourselves
with what happens beyond the second energy level.
Remember:

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electronic structure and atomic orbitals

At the first level there is only one orbital - the 1s orbital.


At the second level there are four orbitals - the 2s, 2px, 2py and
2pz orbitals.
Each orbital can hold either 1 or 2 electrons, but no more.
"Electrons-in-boxes"
Orbitals can be represented as boxes with the electrons in them shown
as arrows. Often an up-arrow and a down-arrow are used to show that
the electrons are in some way different.

Beyond A'level: The need to have all electrons in an atom


different comes out of quantum theory. If they live in different
orbitals, that's fine - but if they are both in the same orbital
there has to be some subtle distinction between them.
Quantum theory allocates them a property known as "spin" which is what the arrows are intended to suggest.

A 1s orbital holding 2 electrons would be drawn as shown


on the right, but it can be written even more quickly as 1s2.
This is read as "one s two" - not as "one s squared".
You mustn't confuse the two numbers in this notation:

The order of filling orbitals


Electrons fill low energy orbitals (closer to the nucleus) before they fill
higher energy ones. Where there is a choice between orbitals of equal
energy, they fill the orbitals singly as far as possible.
The diagram (not to scale) summarises the energies of the various
orbitals in the first and second levels.
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electronic structure and atomic orbitals

Notice that the 2s orbital has a slightly lower energy than the 2p orbitals.
That means that the 2s orbital will fill with electrons before the 2p
orbitals. All the 2p orbitals have exactly the same energy.

The electronic structure of hydrogen


Hydrogen only has one electron and that will go into the orbital with the
lowest energy - the 1s orbital.
Hydrogen has an electronic structure of 1s1. We have already described
this orbital earlier.

The electronic structure of carbon


Carbon has six electrons. Two of them will be found in the 1s orbital
close to the nucleus. The next two will go into the 2s orbital. The
remaining ones will be in two separate 2p orbitals. This is because the p
orbitals all have the same energy and the electrons prefer to be on their
own if that's the case.

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electronic structure and atomic orbitals

Note: People sometimes wonder why the electrons choose


to go into the 2px and 2py orbitals rather than the 2pz. They
don't! All of the 2p orbitals are exactly equivalent, and the
names we give them are entirely arbitrary. It just looks tidier if
we call the orbitals the electrons occupy the 2px and 2py.

The electronic structure of carbon is normally written 1s22s22px12py1.

Where would you like to go now?


To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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Organic Bonding Menu

Understanding Chemistry

ORGANIC BONDING MENU

Electronic structure and orbitals . . .


An introduction to the arrangement of electrons in atoms - leading
to the modern electronic structures of carbon and hydrogen.
Bonding in methane . . .
Covers bonding in methane and ethane, including a simple look at
hybridisation.
Bonding in ethene . . .
Covers bonding in ethene, including a simple look at hybridisation.
Bonding in benzene - the Kekul structure . . .
A description of the Kekul structure for benzene and the reasons
(including hydrogenation energies) why it isn't satisfactory.
Bonding in benzene - a modern orbital view . . .
Covers a modern view of the bonding in benzene, including a
simple look at hybridisation.
Bonding in carbonyl compounds . . .
Describes the carbon-oxygen double bond in methanal (including
a simple look at hybridisation), but applies equally to other
aldehydes and ketones like ethanal and propanone.

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Organic Bonding Menu

Electronegativity . . .
An introduction to electronegativity as it applies to organic
chemistry, including its causes. Bond polarity.

Go to menu of basic organic chemistry. . .


Go to Main Menu . . .

Jim Clark 2000

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Understanding Chemistry - Basic Organic Chemistry Menu

Understanding Chemistry

BASIC ORGANIC CHEMISTRY MENU

Bonding in organic compounds . . .


Includes basic electronic structure, bonding in methane, ethene,
benzene and carbonyl compounds, and ideas about
electronegativity and bond polarity.
Organic chemistry conventions . . .
Includes how to name and draw organic compounds, and the use
of curly arrows in reaction mechanisms.
Isomerism in organic compounds . . .
Includes structural isomerism and stereoisomerism (both
geometric and optical).
Organic acids and bases . . .
Includes the acid strengths of carboxylic acids, phenols and
alcohols, and the base strengths of primary amines.

Go to Main Menu . . .

Jim Clark 2000


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Understanding Chemistry - Basic Organic Chemistry Menu

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Organic Conventions Menu

Understanding Chemistry

ORGANIC CONVENTIONS MENU

How to draw organic molecules . . .


Explains the various conventions used in drawing organic
molecules.
An introduction to naming organic molecules . . .
A guide to understanding the names of organic compounds,
including alkanes, cycloalkanes,alkenes, simple halogen
compounds, alcohols, aldehydes and ketones.
More organic names . . .
Explains the naming of carboxylic acids and their salts, esters, acyl
chlorides, acid anhydrides, amides, nitriles, amines and amino
acids. It assumes that you have already read the introductory page.
Naming aromatic compounds . . .
Looks at the special problems involved in naming compounds
containing benzene rings. It assumes that you are familiar with the
naming of simple chain compounds.
The use of curly arrows . . .
How to use curly arrows to show the movement of electron pairs or
single electrons in reaction mechanisms.

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Organic Conventions Menu

If you are interested in testing your ability to write names for organic
compounds, you might like to explore these links to Dr Phil Brown's
website:
Multiple choice tests on organic names . . .
"Type in the name" tests on organic names . . .

Go to menu of basic organic chemistry. . .


Go to Main Menu . . .

Jim Clark 2000

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How to draw organic molecules

DRAWING ORGANIC MOLECULES

This page explains the various ways that organic molecules can be
represented on paper or on screen - including molecular formulae, and
various forms of structural formulae.

Molecular formulae
A molecular formula simply counts the numbers of each sort of atom
present in the molecule, but tells you nothing about the way they are
joined together.
For example, the molecular formula of butane is C4H10, and the
molecular formula of ethanol is C2H6O.
Molecular formulae are very rarely used in organic chemistry, because
they don't give any useful information about the bonding in the molecule.
About the only place where you might come across them is in equations
for the combustion of simple hydrocarbons, for example:

In cases like this, the bonding in the organic molecule isn't important.

Structural formulae
A structural formula shows how the various atoms are bonded. There are
various ways of drawing this and you will need to be familiar with all of
them.
Displayed formulae
A displayed formula shows all the bonds in the molecule as individual

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How to draw organic molecules

lines. You need to remember that each line represents a pair of shared
electrons.
For example, this is a model of methane together with its displayed
formula:

Notice that the way the methane is drawn bears no resemblance to the
actual shape of the molecule. Methane isn't flat with 90 bond angles.
This mismatch between what you draw and what the molecule actually
looks like can lead to problems if you aren't careful.
For example, consider the simple molecule with the molecular formula
CH2Cl2. You might think that there were two different ways of arranging
these atoms if you drew a displayed formula.

The chlorines could be opposite each other or at right angles to each


other. But these two structures are actually exactly the same. Look at
how they appear as models.

One structure is in reality a simple rotation of the other one.

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How to draw organic molecules

Note: This is all much easier to understand if you have


actually got some models to play with. If your school or
college hasn't given you the opportunity to play around with
molecular models in the early stages of your organic
chemistry course, you might consider getting hold of a cheap
set. The models made by molymod are both cheap and easy
to use. An introductory organic set is more than adequate.
Find them at www.molymod.com.
Alternatively , get hold of some coloured Plasticene and
some used matches and make your own. It's cheaper, but
distinctly messier!

Consider a slightly more complicated molecule, C2H5Cl. The displayed


formula could be written as either of these:

But, again these are exactly the same. Look at the models.

The commonest way to draw structural formulae


For anything other than the most simple molecules, drawing a fully
displayed formula is a bit of a bother - especially all the carbon-hydrogen
bonds. You can simplify the formula by writing, for example, CH3 or CH2
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How to draw organic molecules

instead of showing all these bonds.


So for example, ethanoic acid would be shown in a fully displayed form
and a simplified form as:

You could even condense it further to CH3COOH, and would probably do


this if you had to write a simple chemical equation involving ethanoic
acid. You do, however, lose something by condensing the acid group in
this way, because you can't immediately see how the bonding works.
You still have to be careful in drawing structures in this way. Remember
from above that these two structures both represent the same molecule:

The next three structures all represent butane.

All of these are just versions of four carbon atoms joined up in a line. The
only difference is that there has been some rotation about some of the
carbon-carbon bonds. You can see this in a couple of models.

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How to draw organic molecules

Not one of the structural formulae accurately represents the shape of


butane. The convention is that we draw it with all the carbon atoms in a
straight line - as in the first of the structures above.
This is even more important when you start to have branched chains of
carbon atoms. The following structures again all represent the same
molecule - 2-methylbutane.

The two structures on the left are fairly obviously the same - all we've
done is flip the molecule over. The other one isn't so obvious until you
look at the structure in detail. There are four carbons joined up in a row,
with a CH3 group attached to the next-to-end one. That's exactly the
same as the other two structures. If you had a model, the only difference
between these three diagrams is that you have rotated some of the
bonds and turned the model around a bit.
To overcome this possible confusion, the convention is that you always
look for the longest possible chain of carbon atoms, and then draw it
horizontally. Anything else is simply hung off that chain.
It doesn't matter in the least whether you draw any side groups pointing
up or down. All of the following represent exactly the same molecule.

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How to draw organic molecules

If you made a model of one of them, you could turn it into any other one
simply by rotating one or more of the carbon-carbon bonds.
How to draw structural formulae in 3-dimensions
There are occasions when it is important to be able to show the precise 3D arrangement in parts of some molecules. To do this, the bonds are
shown using conventional symbols:

For example, you might want to show the 3-D arrangement of the groups
around the carbon which has the -OH group in butan-2-ol.
Butan-2-ol has the structural formula:

Using conventional bond notation, you could draw it as, for example:

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How to draw organic molecules

The only difference between these is a slight rotation of the bond


between the centre two carbon atoms. This is shown in the two models
below. Look carefully at them - particularly at what has happened to the
lone hydrogen atom. In the left-hand model, it is tucked behind the
carbon atom. In the right-hand model, it is in the same plane. The
change is very slight.

It doesn't matter in the least which of the two arrangements you draw.
You could easily invent other ones as well. Choose one of them and get
into the habit of drawing 3-dimensional structures that way. My own habit
(used elsewhere on this site) is to draw two bonds going back into the
paper and one coming out - as in the left-hand diagram above.
Notice that no attempt was made to show the whole molecule in 3dimensions in the structural formula diagrams. The CH2CH3 group was
left in a simple form. Keep diagrams simple - trying to show too much
detail makes the whole thing amazingly difficult to understand!
Skeletal formulae
In a skeletal formula, all the hydrogen atoms are removed from carbon
chains, leaving just a carbon skeleton with functional groups attached to
it.
For example, we've just been talking about butan-2-ol. The normal
structural formula and the skeletal formula look like this:

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How to draw organic molecules

In a skeletal diagram of this sort

there is a carbon atom at each junction between bonds in a chain


and at the end of each bond (unless there is something else there
already - like the -OH group in the example);
there are enough hydrogen atoms attached to each carbon to
make the total number of bonds on that carbon up to 4.

Beware! Diagrams of this sort take practice to interpret correctly - and


may well not be acceptable to your examiners (see below).
There are, however, some very common cases where they are frequently
used. These cases involve rings of carbon atoms which are surprisingly
awkward to draw tidily in a normal structural formula.
Cyclohexane, C6H12, is a ring of carbon atoms each with two hydrogens
attached. This is what it looks like in both a structural formula and a
skeletal formula.

And this is cyclohexene, which is similar but contains a double bond:

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How to draw organic molecules

But the commonest of all is the benzene ring, C6H6, which has a special
symbol of its own.

Note: Explaining exactly what this structure means needs


more space than is available here. It is explained in full in two
pages on the structure of benzene elsewhere in this site. It
would probably be better not to follow this link unless you are
actively interested in benzene chemistry at the moment - it
will lead you off into quite deep water!

Deciding which sort of formula to use


There's no easy, all-embracing answer to this problem. It depends more
than anything else on experience - a feeling that a particular way of
writing a formula is best for the situation you are dealing with.
Don't worry about this - as you do more and more organic chemistry, you
will probably find it will come naturally. You'll get so used to writing
formulae in reaction mechanisms, or for the structures for isomers, or in
simple chemical equations, that you won't even think about it.
There are, however, a few guidelines that you should follow.
What does your syllabus say?
Different examiners will have different preferences. Check first with your
syllabus. If you've down-loaded a copy of your syllabus from your Exam
Board's web site, it is easy to check what they say they want. Use the
"find" function on your Adobe Acrobat Reader to search the organic
section(s) of the syllabus for the word "formula".
You should also check recent exam papers and (particulary) mark
schemes to find out what sort of formula the examiners really prefer in
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How to draw organic molecules

given situations. You could also look at any support material published
by your Board.

Note: If you haven't got a copy of your syllabus and recent


exam papers, follow this link to find out how to get them.

What if you still aren't sure?


Draw the most detailed formula that you can fit into the space available.
If in doubt, draw a fully displayed formula. You would never lose marks
for giving too much detail.
Apart from the most trivial cases (for example, burning hydrocarbons),
never use a molecular formula. Always show the detail around the
important part(s) of a molecule. For example, the important part of an
ethene molecule is the carbon-carbon double bond - so write (at the very
least) CH2=CH2 and not C2H4.
Where a particular way of drawing a structure is important, this will
always be pointed out where it arises elsewhere on this site.

Where would you like to go now?


To the organic conventions menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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bonding in benzene - the Kekul structure

BONDING IN BENZENE
The Kekul structure for benzene, C6H6
What is the Kekul structure?
Kekul was the first to suggest a sensible structure
for benzene. The carbons are arranged in a
hexagon, and he suggested alternating double and
single bonds between them. Each carbon atom
has a hydrogen attached to it.
This diagram is often simplified by leaving out all
the carbon and hydrogen atoms!

In diagrams of this sort, there is a carbon atom at each


corner. You have to count the bonds leaving each
carbon to work out how many hydrogens there are
attached to it.
In this case, each carbon has three bonds leaving it. Because carbon
atoms form four bonds, that means you are a bond missing - and that
must be attached to a hydrogen atom.
Problems with the Kekul structure
Although the Kekul structure was a good attempt in its time, there are
serious problems with it . . .
Problems with the chemistry
Because of the three double bonds, you might expect benzene to have
reactions like ethene - only more so!
Ethene undergoes addition reactions in which one of the two bonds
joining the carbon atoms breaks, and the electrons are used to bond with
additional atoms.

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bonding in benzene - the Kekul structure

Benzene rarely does this. Instead, it usually undergoes substitution


reactions in which one of the hydrogen atoms is replaced by something
new.

Note: Follow these links to get details about the addition


reactions of ethene, or the substitution reactions of benzene.

Problems with the shape


Benzene is a planar molecule (all the atoms lie in one plane), and that
would also be true of the Kekul structure. The problem is that C-C
single and double bonds are different lengths.
C-C
C=C

0.154 nm
0.134 nm

Note: "nm" means "nanometre", which is 10-9 metre.

That would mean that the hexagon would be irregular if it had the Kekul
structure, with alternating shorter and longer sides. In real benzene all
the bonds are exactly the same - intermediate in length between C-C and
C=C at 0.139 nm. Real benzene is a perfectly regular hexagon.
Problems with the stability of benzene
Real benzene is a lot more stable than the Kekul structure would give it
credit for. Every time you do a thermochemistry calculation based on the
Kekul structure, you get an answer which is wrong by about 150 kJ mol1. This is most easily shown using enthalpy changes of hydrogenation.

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bonding in benzene - the Kekul structure

Help! It doesn't matter whether you've done any


thermochemistry sums recently or not. This is all so simple
that you could understand it even if you had never done any!

Hydrogenation is the addition of hydrogen to something. If, for example,


you hydrogenate ethene you get ethane:
CH2=CH2 + H2

CH3CH3

In order to do a fair comparison with benzene (a ring


structure) we're going to compare it with cyclohexene.
Cyclohexene, C6H10, is a ring of six carbon atoms
containing just one C=C.

Note: If you are a bit shaky on names: cyclohexene: hex


means six carbons, cyclo means in a ring, ene means with a
C=C bond.

When hydrogen is added to this, cyclohexane, C6H12, is formed. The


"CH" groups become CH2 and the double bond is replaced by a single
one.

Note: cyclohexane: six carbons in a ring, but the ane


ending means NO C=C bond.

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bonding in benzene - the Kekul structure

The structures of cyclohexene and cyclohexane are usually simplified in


the same way that the Kekul structure for benzene is simplified - by
leaving out all the carbons and hydrogens.

In the cyclohexane case, for example, there is a carbon atom at each


corner, and enough hydrogens to make the total bonds on each carbon
atom up to four. In this case, then, each corner represents CH2.
The hydrogenation equation could be written:

The enthalpy change during this reaction is -120 kJ mol-1. In other words,
when 1 mole of cyclohexene reacts, 120 kJ of heat energy is evolved.

Help! "Enthalpy change" can be translated as "heat evolved


or absorbed". The negative sign shows that heat is evolved.

Where does this heat energy come from? When the reaction happens,
bonds are broken (C=C and H-H) and this costs energy. Other bonds
have to be made, and this releases energy.
Because the bonds made are stronger than those broken, more energy
is released than was used to break the original bonds and so there is a
net evolution of heat energy.
If the ring had two double bonds in it initially (cyclohexa-1,3-diene),
exactly twice as many bonds would have to be broken and exactly twice
as many made. In other words, you would expect the enthalpy change of
hydrogenation of cyclohexa-1,3-diene to be exactly twice that of
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bonding in benzene - the Kekul structure

cyclohexene - that is, -240 kJ mol-1.

Note: The name (cyclohexa-1,3-diene) is unimportant. Don't


worry about it unless you want to!

In fact, the enthalpy change is -232 kJ mol-1 - which isn't far off what we
are predicting.

Note: Thermochemistry sums often throw up discrepancies


of this sort of magnitude, and you couldn't be sure whether
there was any significance in it.

Applying the same argument to the Kekul structure for benzene (what
might be called cyclohexa-1,3,5-triene), you would expect an enthalpy
change of -360 kJ mol-1, because there are exactly three times as many
bonds being broken and made as in the cyclohexene case.

In fact what you get is -208 kJ mol-1 - not even within distance of the
predicted value!
This is very much easier to see on an enthalpy diagram. Notice that in
each case heat energy is released, and in each case the product is the
same (cyclohexane). That means that all the reactions "fall down" to the
same end point.

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bonding in benzene - the Kekul structure

Heavy lines, solid arrows and bold numbers represent real changes.
Predicted changes are shown by dotted lines and italics.
The most important point to notice is that real benzene is much lower
down the diagram than the Kekul form predicts. The lower down a
substance is, the more energetically stable it is.
This means that real benzene is about 150 kJ mol-1 more stable than the
Kekul structure gives it credit for. This increase in stability of benzene is
known as the delocalisation energy or resonance energy of benzene.
The first term (delocalisation energy) is the more commonly used.

Note: If you look at the diagram closely, you will see that
cyclohexa-1,3-diene is also a shade more stable than
expected. There is a tiny amount of delocalisation energy
involved here as well.

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bonding in benzene - the Kekul structure

Why is benzene so much more stable than the Kekul structure


suggests? To explain that needs a separate article! Follow the first link
below.

Where would you like to go now?


To read about the modern view of the structure of benzene. . .
To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic addition reactions menu

Understanding Chemistry

ELECTROPHILIC ADDITION MECHANISMS MENU

Addition to symmetrical alkenes


Covers addition to symmetrical alkenes like ethene and cyclohexene. A
symmetrical alkene has the same groups attached to both ends of the
carbon-carbon double bond.
What is electrophilic addition? . . .
An explanation of the terms addition and electrophile, together
with a general mechanism for these reactions.
The reaction with hydrogen halides . . .
The mechanism for the reaction between ethene (and
cyclohexene) and hydrogen halides (like hydrogen bromide).
The reaction with sulphuric acid . . .
The mechanism for the reaction between ethene (and
cyclohexene) and sulphuric acid.
The reaction with bromine . . .
The mechanism for the reaction between ethene (and
cyclohexene) and bromine.

Addition to unsymmetrical alkenes


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electrophilic addition reactions menu

Covers addition to unsymmetrical alkenes like propene. An


unsymmetrical alkene has different groups attached to each end of the
carbon-carbon double bond.

Warning! Don't even think about reading articles in this


section until you are sure you understand the corresponding
reaction(s) above!

Carbocations (carbonium ions) and their stability . . .


Essential pre-reading before you tackle anything else in this
section.
Why unsymmetric alkenes are a problem . . .
Explains the reasons behind Markovnikov's Rule, and gives a
general mechanism for these more awkward reactions. This is also
essential reading before you look at specific reactions.
The reaction with hydrogen halides . . .
The mechanism for the reaction between propene and hydrogen
halides (like hydrogen bromide).
The reaction with sulphuric acid . . .
The mechanism for the reaction between propene and sulphuric
acid.
The reaction with bromine . . .
The mechanism for the reaction between propene and bromine.

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electrophilic addition reactions menu

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of alkenes . . .
A survey of all the physical and chemical properties of alkenes
required by UK A level syllabuses.

Jim Clark 2000 (modified 2004)

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What is electrophilic addition?

ELECTROPHILIC ADDITION

Background
Electrophilic addition happens in many of the reactions of compounds
containing carbon-carbon double bonds - the alkenes.
The structure of ethene
We are going to start by looking at ethene, because it is the simplest
molecule containing a carbon-carbon double bond. What is true of C=C
in ethene will be equally true of C=C in more complicated alkenes.
Ethene, C2H4, is often modelled as shown on
the right. The double bond between the carbon
atoms is, of course, two pairs of shared
electrons. What the diagram doesn't show is
that the two pairs aren't the same as each other.
One of the pairs of electrons is held on the line between the two carbon
nuclei as you would expect, but the other is held in a molecular orbital
above and below the plane of the molecule. A molecular orbital is a
region of space within the molecule where there is a high probability of
finding a particular pair of electrons.
In this diagram, the line between the two
carbon atoms represents a normal bond - the
pair of shared electrons lies in a molecular
orbital on the line between the two nuclei
where you would expect them to be. This
sort of bond is called a sigma bond.
The other pair of electrons is found
somewhere in the shaded part above and
below the plane of the molecule. This bond is called a pi bond. The
electrons in the pi bond are free to move around anywhere in this shaded
region and can move freely from one half to the other.

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What is electrophilic addition?

Note: This diagram shows a side view of an ethene


molecule. The dotted lines to two of the hydrogens show
bonds going back into the screen or paper away from you.
The wedge shapes show bonds coming out towards you.

The pi electrons are not as fully under the control of the carbon nuclei as
the electrons in the sigma bond and, because they lie exposed above
and below the rest of the molecule, they are relatively open to attack by
other things.

Note: Check your syllabus to see if you need to know how a


pi bond is formed. Haven't got a syllabus? Find out how to
get one by following this link.
If you do need to know about the bonding in ethene in detail,
follow this link as well.

Electrophiles
An electrophile is something which is attracted to electron-rich regions in
other molecules or ions. Because it is attracted to a negative region, an
electrophile must be something which carries either a full positive charge,
or has a slight positive charge on it somewhere.

Note: The ending ". . phile" means a liking for. For example,
a francophile is someone who likes the French; an anglophile
is someone who likes the English.

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What is electrophilic addition?

Ethene and the other alkenes are attacked by


electrophiles. The electrophile is normally the
slightly positive ( +) end of a molecule like hydrogen bromide, HBr.

Note: If you aren't sure about why some bonds are polar,
read the page on electronegativity.
Use the BACK button on your browser to return to this page.

Electrophiles are strongly attracted to the exposed electrons in the pi


bond and reactions happen because of that initial attraction - as you will
see shortly.
You might wonder why fully positive ions like sodium, Na+, don't react
with ethene. Although these ions may well be attracted to the pi bond,
there is no possibility of the process going any further to form bonds
between sodium and carbon, because sodium forms ionic bonds,
whereas carbon normally forms covalent ones.
Addition reactions
In a sense, the pi bond is an unnecessary bond. The structure would
hold together perfectly well with a single bond rather than a double bond.
The pi bond often breaks and the electrons in it are used to join other
atoms (or groups of atoms) onto the ethene molecule. In other words,
ethene undergoes addition reactions.
For example, using a general molecule X-Y . . .

Summary: electrophilic addition reactions

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What is electrophilic addition?

An addition reaction is a reaction in which two molecules join together to


make a bigger one. Nothing is lost in the process. All the atoms in the
original molecules are found in the bigger one.
An electrophilic addition reaction is an addition reaction which happens
because what we think of as the "important" molecule is attacked by an
electrophile. The "important" molecule has a region of high electron
density which is attacked by something carrying some degree of positive
charge.

Note: When we talk about reactions of alkenes like ethene,


we think of the ethene as being attacked by other molecules
such as hydrogen bromide. Because ethene is the molecule
we are focusing on, we quite arbitrarily think of it as the
central molecule and hydrogen bromide as its attacker.
There's no real justification for this, of course, apart from the
fact that it helps to put things in some sort of logical pattern.
In reality, the molecules just collide and may react if they
have enough energy and if they are lined up correctly.

Understanding the electrophilic addition mechanism


The mechanism for the reaction between ethene and a molecule X-Y
It is very unlikely that any two different atoms
joined together will have the same
electronegativity. We are going to assume that
Y is more electronegative than X, so that the
pair of electrons is pulled slightly towards the Y
end of the bond. That means that the X atom carries a slight positive
charge.

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What is electrophilic addition?

Note: Once again, if you aren't sure about electronegativity


and bond polarity follow this link before you read on.
Use the BACK button on your browser to return to this page.

The slightly positive X atom is an electrophile and is attracted to the


exposed pi bond in the ethene. Now imagine what happens as they
approach each other.

You are now much more likely to find the electrons in the half of the pi
bond nearest the XY. As the process continues, the two electrons in the
pi bond move even further towards the X until a covalent bond is made.
The electrons in the X-Y bond are pushed entirely onto the Y to give a
negative Y- ion.

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What is electrophilic addition?

Help! Why does the carbon atom have a positive charge?


The pi bond was originally made using an electron from each
carbon atom, but both of these electrons have now been
used to make a bond to the X atom. This leaves the righthand carbon atom an electron short - hence positively
charged.
Note also that we are only showing one of the pairs of
electrons around the Y- ion. There will be other lone pairs as
well, but we are only actually interested in the one we've
drawn.

Important term
An ion in which the positive charge is carried on a
carbon atom is called a carbocation or a
carbonium ion (an older term).

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What is electrophilic addition?

In the final stage of the reaction the


electrons in the lone pair on the Y- ion are
strongly attracted towards the positive
carbon atom. They move towards it and
form a co-ordinate (dative covalent) bond
between the Y and the carbon.

Help! A co-ordinate (dative covalent) bond is simply a


covalent bond in which both shared electrons originate from
the same atom. The bond formed between the X and the
other carbon atom was also a co-ordinate bond. Once a coordinate bond has been formed there is no difference
whatsoever between it and any other covalent bond.

How to write this mechanism in an exam


The movements of the various electron pairs are shown using curly
arrows.

Help! If you aren't sure about the use of curly arrows in


mechanisms, you must follow this link before you go on.
Use the BACK button on your browser to return to this page.

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What is electrophilic addition?

Don't leave this page until you are sure that you understand how this
relates to the electron pair movements drawn in the previous diagrams.

Where would you like to go now?


To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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bonding in ethene - sp2 hybridisation

BONDING IN ETHENE

Important! You will find this much easier to understand if


you first read the article about the bonding in methane.
You may also find it useful to read the article on orbitals if you
aren't sure about simple orbital theory.

Ethene, C2H4
The simple view of the bonding in ethene
At a simple level, you will have drawn ethene
showing two bonds between the carbon atoms.
Each line in this diagram represents one pair of
shared electrons.
Ethene is actually much more interesting than this.
An orbital view of the bonding in ethene
Ethene is built from hydrogen atoms (1s1) and carbon atoms
(1s22s22px12py1).
The carbon atom doesn't have enough unpaired electrons to form the
required number of bonds, so it needs to promote one of the 2s2 pair into
the empty 2pz orbital. This is exactly the same as happens whenever
carbon forms bonds - whatever else it ends up joined to.

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bonding in ethene - sp2 hybridisation

Important! If this isn't really clear to you, you must go and


read the article about the bonding in methane.

Now there's a difference, because each carbon is only joining to three


other atoms rather than four - as in methane or ethane. When the carbon
atoms hybridise their outer orbitals before forming bonds, this time they
only hybridise three of the orbitals rather than all four. They use the 2s
electron and two of the 2p electrons, but leave the other 2p electron
unchanged.
The new orbitals formed are called sp2
hybrids, because they are made by an s
orbital and two p orbitals reorganising
themselves. sp2 orbitals look rather like
sp3 orbitals that you have already come
across in the bonding in methane,
except that they are shorter and fatter.
The three sp2 hybrid orbitals arrange
themselves as far apart as possible which is at 120 to each other in a plane. The remaining p orbital is at
right angles to them.
The two carbon atoms and four hydrogen atoms would look like this
before they joined together:

The various atomic orbitals which are pointing


towards each other now merge to give
molecular orbitals, each containing a bonding
pair of electrons. These are sigma bonds just like those formed by end-to-end overlap
of atomic orbitals in, say, ethane.

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bonding in ethene - sp2 hybridisation

The p orbitals on each carbon aren't pointing towards each other, and so
we'll leave those for a moment. In the diagram, the black dots represent
the nuclei of the atoms.
Notice that the p orbitals are so close that they are overlapping sideways.
This sideways overlap also creates a
molecular orbital, but of a different kind. In
this one the electrons aren't held on the line
between the two nuclei, but above and below
the plane of the molecule. A bond formed in
this way is called a pi bond.

For clarity, the sigma bonds are shown using lines - each line
representing one pair of shared electrons. The various sorts of line show
the directions the bonds point in. An ordinary line represents a bond in
the plane of the screen (or the paper if you've printed it), a broken line is
a bond going back away from you, and a wedge shows a bond coming
out towards you.

Note: The really interesting bond in ethene is the pi bond. In


almost all cases where you will draw the structure of ethene,
the sigma bonds will be shown as lines.

Be clear about what a pi bond is. It is a region of space in which you can
find the two electrons which make up the bond. Those two electrons can
live anywhere within that space. It would be quite misleading to think of
one living in the top and the other in the bottom.

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bonding in ethene - sp2 hybridisation

Beyond A'level: This is another example of the curious


behaviour of electrons. How do the electrons get from one
half of the pi bond to the other if they are never found in
between? It's an unanswerable question if you think of
electrons as particles.

Even if your syllabus doesn't expect you to know how a pi bond is


formed, it will expect you to know that it exists. The pi bond dominates
the chemistry of ethene. It is very vulnerable to attack - a very negative
region of space above and below the plane of the molecule. It is also
somewhat distant from the control of the nuclei and so is a weaker bond
than the sigma bond joining the two carbons.

Important! Check your syllabus! Find out whether you


actually need to know how a pi bond is formed. Don't forget
to look in the bonding section of your syllabus as well as
under ethene. If you don't need to know it, there's no point in
learning it! You will, however, need to know that a pi bond
exists - that the two bonds between the carbon atoms in
ethene aren't both the same.
If you haven't got a copy of your syllabus, find out how to
download one

All double bonds (whatever atoms they might be joining) will consist of a
sigma bond and a pi bond.

Where would you like to go now?


To the organic bonding menu. . .
To menu of basic organic chemistry. . .

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bonding in ethene - sp2 hybridisation

To Main Menu . . .

Jim Clark 2000

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electronegativity - polar bonds in organic compounds

ELECTRONEGATIVITY

This page deals with electronegativity in an organic chemistry context. If


you want a wider view of electronegativity, there is a link at the bottom of
the page.

What is electronegativity?
Electronegativity is a measure of the tendency of an atom to attract a
bonding pair of electrons. The Pauling scale is the most commonly used.
Fluorine (the most electronegative element) is given a value of 4.0, and
values range down to caesium and francium which are the least
electronegative at 0.7.
What happens if two atoms of equal electronegativity bond
together?
The most obvious example of this is the bond between two carbon
atoms. Both atoms will attract the bonding pair to exactly the same
extent. That means that on average the electron pair will be found half
way between the two nuclei, and you could draw a picture of the bond
like this:

It is important to realise that this is an average picture. The electrons are


actually in a sigma orbital, and are moving constantly within that orbital.

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electronegativity - polar bonds in organic compounds

Help! A sigma orbital is a molecular orbital formed by end-toend overlap between two atomic orbitals. If you aren't happy
about this, read the articles on orbitals and the bonding in
methane and ethane.

The carbon-fluorine bond


Fluorine is much more electronegative than carbon. The actual values on
the Pauling scale are
carbon
fluorine

2.5
4.0

That means that fluorine attracts the bonding pair much more strongly
than carbon does. The bond - on average - will look like this:

Why is fluorine more electronegative than carbon?


A simple dots-and-crosses diagram of a C-F bond is perfectly adequate
to explain it.

The bonding pair is in the second energy level of both carbon and
fluorine, so in the absence of any other effect, the distance of the pair
from both nuclei would be the same.
The electron pair is shielded from the full force of both nuclei by the 1s
electrons - again there is nothing to pull it closer to one atom than the

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electronegativity - polar bonds in organic compounds

other.
BUT, the fluorine nucleus has 9 protons whereas the carbon nucleus has
only 6.
Allowing for the shielding effect of the 1s electrons, the bonding pair feels
a net pull of about 4+ from the carbon, but about 7+ from the fluorine. It is
this extra nuclear charge which pulls the bonding pair (on average)
closer to the fluorine than the carbon.

Help! You have to imagine what the bonding pair "sees" if it


looks in towards the nucleus. In the carbon case, it sees 6
positive protons, and 2 negative electrons. That means that
there will be a net pull from the carbon of about 4+. The
shielding wouldn't actually be quite as high as 2-, because
the 1s electrons spend some of their time on the far side of
the carbon nucleus - and so aren't always between the
bonding pair and the nucleus.
Incidentally, thinking about electrons looking towards the
nucleus may be helpful in picturing what is going on, but
avoid using terms like this in exams.

The carbon-chlorine bond


The electronegativities are:
carbon
chlorine

2.5
3.0

The bonding pair of electrons will be dragged towards the chlorine but
not as much as in the fluorine case. Chlorine isn't as electronegative as
fluorine.
Why isn't chlorine as electronegative as fluorine?
Chlorine is a bigger atom than fluorine.

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electronegativity - polar bonds in organic compounds

fluorine: 1s22s22px22py22pz1
chlorine: 1s22s22px22py22pz23s23px23py23pz1

Help! If you aren't happy about this, read the article on


orbitals. Use the BACK button on your browser to get back to
here again.

In the chlorine case, the bonding pair will be shielded by all the 1-level
and 2-level electrons. The 17 protons on the nucleus will be shielded by
a total of 10 electrons, giving a net pull from the chlorine of about 7+.
That is the same as the pull from the fluorine, but with chlorine the
bonding pair starts off further away from the nucleus because it is in the
3-level. Since it is further away, it feels the pull from the nucleus less
strongly.

Bond polarity and inductive effects


Polar bonds
Think about the carbon-fluorine bond again. Because the bonding pair is
pulled towards the fluorine end of the bond, that end is left rather more
negative than it would otherwise be. The carbon end is left rather short of
electrons and so becomes slightly positive.

The symbols + and - mean "slightly positive" and "slightly negative".


You read + as "delta plus" or "delta positive".
We describe a bond having one end slightly positive and the other end
slightly negative as being polar.
Inductive effects
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electronegativity - polar bonds in organic compounds

An atom like fluorine which can pull the bonding pair away from the atom
it is attached to is said to have a negative inductive effect.
Most atoms that you will come across have a negative inductive effect
when they are attached to a carbon atom, because they are mostly more
electronegative than carbon.
You will come across some groups of atoms which have a slight positive
inductive effect - they "push" electrons towards the carbon they are
attached to, making it slightly negative.
Inductive effects are sometimes given symbols: -I (a negative inductive
effect) and +I (a positive inductive effect).

Note: You should be aware of terms like "negative inductive


effect", but don't get bogged down in them. Provided that you
understand what happens when electronegative atoms like
fluorine or chlorine are attached to carbon atoms in terms of
the polarity of the bonds, that's really all you need for most
purposes.

Some important examples of polar bonds


Hydrogen bromide (and other hydrogen halides)

Bromine (and the other halogens) are all more electronegative than
hydrogen, and so all the hydrogen halides have polar bonds with the
hydrogen end slightly positive and the halogen end slightly negative.

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electronegativity - polar bonds in organic compounds

Help! Halogen: a member of group VII of the Periodic Table


- fluorine, chlorine, bromine and iodine.
Halide: a compound of one of these - e.g. hydrogen chloride,
hydrogen bromide, etc.

The polarity of these molecules is important in their reactions with


alkenes.

Note: These reactions are explored in the section dealing


with the addition of hydrogen halides to alkenes.

The carbon-bromine bond in halogenoalkanes

Note: You may come across halogenoalkanes under the


names "haloalkanes" or "alkyl halides".

Bromine is more electronegative than carbon and so the bond is


polarised in the way that we have already described with C-F and C-Cl.

The polarity of the carbon-halogen bonds is important in the reactions of


the halogenoalkanes.

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electronegativity - polar bonds in organic compounds

Note: This link will take you to the nucleophilic substitution


reactions of the halogenoalkanes in which this polarity is
important.

The carbon-oxygen double bond


An orbital model of the C=O bond in methanal, HCHO, looks like this:

Note: If you aren't sure about this, read the article on


bonding in the carbonyl group (C=O).

The very electronegative oxygen atom pulls both bonding pairs towards
itself - in the sigma bond and the pi bond. That leaves the oxygen fairly
negative and the carbon fairly positive.

Note: You can read about addition reactions or additionelimination reactions of compounds containing carbonoxygen double bonds elswhere on this site.

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electronegativity - polar bonds in organic compounds

Where would you like to go now?


To look at electronegativity in a wider context. . .
To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic addition - symmetrical alkenes and hydrogen halides

THE REACTION BETWEEN SYMMETRICAL


ALKENES AND THE HYDROGEN HALIDES

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between the hydrogen halides and
alkenes like ethene and cyclohexene. Hydrogen halides include
hydrogen chloride and hydrogen bromide. If you want the mechanisms
explained to you in detail, there is a link at the bottom of the page.

Electrophilic addition reactions involving hydrogen


bromide
The facts
Alkenes react with hydrogen bromide in the cold. The double bond
breaks and a hydrogen atom ends up attached to one of the carbons and
a bromine atom to the other.
In the case of ethene, bromoethane is formed.

Note: Be careful when you write the names of the addition


products that you change the ene ending in the original
alkene (showing the C=C) into an ane ending (showing that it
has been replaced by C-C).

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electrophilic addition - symmetrical alkenes and hydrogen halides

With cyclohexene you get bromocyclohexane.

The structures of the cyclohexene and the bromocyclohexane are often


simplified:

Note: Each corner in one of these diagrams represents a


carbon atom. Each carbon atom has enough hydrogens
attached to make the total number of bonds up to 4.
In the case of the bromocyclohexane, it isn't necessary to
write the new hydrogen into the diagram, but it is helpful to
put it there to emphasise that addition has happened.

Be sure that you understand the relationship between these simplified


diagrams and the full structures.
The mechanisms
The reactions are examples of electrophilic addition.
With ethene and HBr:

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electrophilic addition - symmetrical alkenes and hydrogen halides

and with cyclohexene:

Electrophilic addition reactions involving the other


hydrogen halides
The facts
Hydrogen chloride and the other hydrogen halides add on in exactly the
same way. For example, hydrogen chloride adds to ethene to make
chloroethane:

The only difference is in how fast the reactions happen with the different
hydrogen halides. The rate of reaction increases as you go from HF to
HCl to HBr to HI.
HF slowest reaction
HCl
HBr
HI

fastest reaction

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electrophilic addition - symmetrical alkenes and hydrogen halides

The reason for this is that as the halogen atoms get bigger, the strength
of the hydrogen-halogen bond falls. Bond strengths (measured in
kilojoules per mole) are:
H-F 568
H-Cl 432
H-Br 366
H-I

298

Note: You may find slightly different values depending on


which data source you use. It doesn't matter - the differences
are minor and the pattern is always the same.

As you have seen in the HBr case, in the first step of the mechanism the
hydrogen-halogen bond gets broken. If the bond is weaker, it will break
more readily and so the reaction is more likely to happen.
The mechanisms
The reactions are still examples of electrophilic addition.
With ethene and HCl, for example:

This is exactly the same as the mechanism for the reaction between
ethene and HBr, except that we've replaced Br by Cl.
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electrophilic addition - symmetrical alkenes and hydrogen halides

All the other mechanisms for symmetrical alkenes and the hydrogen
halides would be done in the same way.

Suggestion: Find out if your syllabus mentions a particular


hydrogen halide, and learn that mechanism. You can simply
swap the halogen atom if a different hydrogen halide comes
up in an exam.
Haven't got a syllabus? Follow this link to find out how to get
one.

Where would you like to go now?


Help! Talk me through this mechanism . . .
Look at the same reactions involving unsymmetrical
alkenes . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/eladd/symhbr.html (5 of 5)30/12/2004 11:02:10

Explaining electrophilic addition involving hydrogen halides

EXPLAINING THE REACTION BETWEEN


SYMMETRICAL ALKENES AND THE HYDROGEN
HALIDES

This page guides you through the mechanism for the electrophilic
addition of hydrogen halides such as hydrogen bromide with symmetrical
alkenes like ethene or cyclohexene. Unsymmetrical alkenes are covered
separately, and you will find a link at the bottom of the page.

Electrophilic addition reactions involving hydrogen


bromide
Hydrogen bromide is chosen as a typical
hydrogen halide. Bromine is more
electronegative than hydrogen. That means
that the bonding pair of electrons is pulled
towards the bromine end of the bond, and so
the hydrogen bromide molecule is polar.

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you read on.
Use the BACK button on your browser to return to this page.

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Explaining electrophilic addition involving hydrogen halides

The reaction of ethene with hydrogen bromide


The structure of ethene is shown in the
diagram on the right. The pi bond is an
orbital above and below the plane of the rest
of the molecule, and relatively exposed to
things around it. The two electrons in this
orbital are highly attractive to anything which
is positively charged.

Note: If you aren't sure about this, it would be a good idea to


read the introductory page on electrophilic addition before
you go on.
Use the BACK button on your browser to return to this page.

The slightly positive hydrogen atom in the hydrogen bromide acts as an


electrophile, and is strongly attracted to the electrons in the pi bond.

Electrophile: A substance with a strong attraction to a


negative region in another substance. Electrophiles are either
fully positive ions, or the slightly positive end of a polar
molecule.

The electrons from the pi bond move down towards the


slightly positive hydrogen atom.
In the process, the electrons in the H-Br bond are
repelled down until they are entirely on the bromine
atom, producing a bromide ion.

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Explaining electrophilic addition involving hydrogen halides

Help! If you aren't sure about the use of curly arrows in


mechanisms, you must follow this link before you go on.
Use the BACK button on your browser to return to this page.

That leaves you with these two ions at this half-way stage of the reaction:

The ion with a positive charge on the carbon atom is called a


carbocation or carbonium ion (an older term).
Why is there a positive charge on the carbon atom? The pi bond was
originally made up of an electron from each of the carbon atoms. Both of
those electrons have been used to make a new bond to the hydrogen.
That leaves the right-hand carbon an electron short - hence positively
charged.
In the second stage of the mechanism, the lone pair of electrons on the
bromide ion is strongly attracted to the positive carbon and moves
towards it until a bond is formed.

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Explaining electrophilic addition involving hydrogen halides

Note: For clarity only one of the lone pairs around the
bromide ion is shown. That's perfectly acceptable, because
the other three lone pairs aren't involved in the process - they
are pointing in the wrong directions.

The overall mechanism is therefore

The reaction of cyclohexene with hydrogen bromide


Cyclohexene is chosen an an example of a fairly commonly used
symmetrical alkene. The fact that it is a ring structure doesn't make any
difference to the mechanism.
The full structure of cyclohexene is

but it is often abbreviated to

In this diagram, there is a carbon atom at each corner, and enough


hydrogens attached to each carbon to bring the total number of bonds
per carbon atom up to 4.

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Explaining electrophilic addition involving hydrogen halides

The double bond has an easily attacked pi bond exactly as in ethene,


and the electrons in that bond are attracted towards the slightly positive
hydrogen atom in the HBr.
Once again, the pi bond electrons swing to make a bond with the
hydrogen, and push the electrons in the H-Br bond fully onto the
bromine, making a bromide ion.

Care! Think carefully about which way the pi bond electrons


swing. In this case, think of them as being pivotted about the
top carbon atom. It is therefore that carbon atom which is
joined to the new hydrogen.

In the second stage, one of the lone pairs of electrons on the bromide ion
is attracted to the positively charged carbon atom and forms a bond with
it.

The overall mechanism is therefore:

Electrophilic addition reactions involving the other


hydrogen halides
The mechanisms
The other hydrogen halides behave in exactly the same way as hydrogen
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Explaining electrophilic addition involving hydrogen halides

bromide. For example, compare the reaction between ethene and


hydrogen bromide with the one between ethene and hydrogen chloride.

There's no need to learn both mechanisms. As long as you know one of


them, all you have to do is swap one halogen atom for another. That's
equally true for hydrogen fluoride or hydrogen iodide.
The different rates of reaction
The rate of reaction increases as you go from HF to HCl to HBr to HI.
HF slowest reaction
HCl
HBr
HI

fastest reaction

The reason for this is that as the halogen atoms get bigger, the strength
of the hydrogen-halogen bond falls. Bond strengths (measured in
kilojoules per mole) are:

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Explaining electrophilic addition involving hydrogen halides

H-F 568
H-Cl 432
H-Br 366
H-I

298

In the first step of these mechanisms, the hydrogen-halogen bond breaks


as the electron pair is forced down onto the halogen atom.
Breaking bonds needs energy, and if the bond is weaker, it will break
more easily - needing less energy. That means that the activation energy
for the reactions will fall as you go from hydrogen fluoride to hydrogen
iodide. The lower the activation energy, the faster the reaction.

Activation energy: The minimum energy needed before a


reaction will occur. In this case it is the energy needed to
break the various bonds and make the carbocation and the
halide ion.

Beware! A red herring!


People sometimes get confused because there is another tempting place
to look for the reason why the reaction rates are different between the
various hydrogen halides.
The halogens have different electronegativities - with fluorine being the
most electronegative and iodine the least. That means that the hydrogen
in HF will have the greatest positive charge and so will be attracted most
strongly to the pi bond.
It would be tempting to think that that would produce the fastest reaction

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Explaining electrophilic addition involving hydrogen halides

- but not so! Although the HF may well be attracted most strongly,
attraction alone isn't enough. If anything is to happen, bonds have to be
broken - and here HF is at a disadvantage, because the bond is very
strong.
The lesson from all this
When you are trying to find reasons for differing rates of reactions,
always look first at differences in bond strengths. Electronegativity
differences may be interesting, but rarely give you the answer you want!

Where would you like to go now?


Look at the same reactions involving unsymmetrical
alkenes . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/eladd/symhbrtt.html (8 of 8)30/12/2004 11:02:15

The use of curly arrows to show electron movements in reaction mechanisms

USING CURLY ARROWS IN REACTION


MECHANISMS

This page explains the use of curly arrows to show the movement both of
electron pairs and of single electrons during organic reaction
mechanisms.
You can jump straight to the movement of single electrons further down
this page if that is all you are interested in for the moment (for example, if
you are currently working on free radical reactions).

Using curly arrows to show the movement of electron pairs


Curly arrows (and that's exactly what they are called!) are used in
mechanisms to show the various electron pairs moving around. You
mustn't use them for any other purpose.

The arrow tail is where the electron pair starts from. That's always
fairly obvious, but you must show the electron pair either as a
bond or, if it is a lone pair, as a pair of dots. Remember that a lone
pair is a pair of electrons at the bonding level which isn't currently
being used to join on to anything else.
The arrow head is where you want the electron pair to end up.

For example, in the reaction between ethene and


hydrogen bromide, one of the two bonds between the
two carbon atoms breaks. That bond is simply a pair of
electrons.
Those electrons move to form a new bond with the
hydrogen from the HBr. At the same time the pair of electrons in the
hydrogen-bromine bond moves down on to the bromine atom.

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The use of curly arrows to show electron movements in reaction mechanisms

There's no need to draw the pairs of electrons in the


bonds as two dots. Drawing the bond as a line is
enough, but you could put two dots in as well if you
wanted to.
Notice that the arrow head points between the C and
H because that's where the electron pair ends up. Notice also that the
electron movement between the H and Br is shown as a curly arrow even
though the electron pair moves straight down. You have to show electron
pair movements as curly arrows - not as straight ones.
The second stage of this reaction nicely illustrates how you use a curly
arrow if a lone pair of electrons is involved.
The first stage leaves you with a positive charge on
the right hand carbon atom and a negative bromide
ion. You can think of the electrons shown on the
bromide ion as being the ones which originally made
up the hydrogen-bromine bond.

Note: There are another three lone pairs around the outside
of the bromide ion - making four in all. These aren't normally
shown because they don't actually do anything new and
interesting!
However, it is essential that you show the lone pair you are
interested in as a pair of dots. If you don't, you risk losing
marks in an exam.

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The use of curly arrows to show electron movements in reaction mechanisms

The lone pair on the bromide ion moves to form a new bond between the
bromine and the right hand carbon atom. That movement is again shown
by a curly arrow. Notice again, that the curly arrow points between the
carbon and the bromine because that's where the electron pair ends up.
That leaves you with the product of this reaction, bromoethane:

Note: You can read a full description of this mechanism


together with other similar reactions of ethene and the other
alkenes by following this link.

Using curly arrows to show the movement of single


electrons
The most common use of "curly arrows" is to show the movement of
pairs of electrons. You can also use similar arrows to show the
movement of single electrons - except that the heads of these arrows
only have a single line rather than two lines.
shows the movement of an electron pair

shows the movement of a single electron


The first stage of the polymerisation of ethene, for example, could be
shown as:

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The use of curly arrows to show electron movements in reaction mechanisms

You should draw the dots showing the interesting electrons. The half
arrows show where they go. This is very much a "belt-and-braces" job,
and the arrows don't add much.
Whether you choose to use these half arrows to show the movement of a
single electron should be governed by what your syllabus says. If your
syllabus encourages the use of these arrows, then it makes sense to use
them. If not - if the syllabus says that they "may" be used, or just ignores
them altogether - then they are as well avoided.
There is some danger of confusing them with the arrows showing
electron pair movements, which you will use all the time. If, by mistake,
you use an ordinary full arrow to show the movement of a single electron
you run the risk of losing marks.

Help! You must have a copy of your syllabus! If you haven't


got a copy, find out how to get a syllabus by following this link.

Where would you like to go now?


To the organic conventions menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/basicorg/conventions/curlies.html (4 of 4)30/12/2004 11:02:20

electrophilic addition - unsymmetrical alkenes and hydrogen halides

THE REACTION BETWEEN UNSYMMETRICAL


ALKENES AND THE HYDROGEN HALIDES

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between the hydrogen halides and
alkenes like propene. Hydrogen halides include hydrogen chloride and
hydrogen bromide. If you want the mechanisms explained to you in
detail, there is a link at the bottom of the page.
An unsymmetrical alkene is one like propene in which the groups or
atoms attached to either end of the carbon-carbon double bond are
different.
For example, in propene there are a hydrogen and a methyl group at one
end, but two hydrogen atoms at the other end of the double bond. But-1ene is another unsymmetrical alkene.

Electrophilic addition reactions involving hydrogen


bromide
The facts
As with all alkenes, unsymmetrical alkenes like propene react with
hydrogen bromide in the cold. The double bond breaks and a hydrogen
atom ends up attached to one of the carbons and a bromine atom to the
other.
In the case of propene, 2-bromopropane is formed.

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electrophilic addition - unsymmetrical alkenes and hydrogen halides

This would normally be written in a more condensed form as

The product is 2-bromopropane.

Note: There is another possible reaction between


unsymmetrical alkenes and hydrogen bromide (but not the
other hydrogen halides) unless the hydrogen bromide and
alkene are absolutely pure.
A different mechanism happens (a free radical chain reaction
- not on UK A' level syllabuses) which leads to the hydrogen
and bromine adding the opposite way round. For A' level
purposes, you don't need to worry about that. However, if you
are interested, you will find the free radical addition
mechanism by following this link.
Use the BACK button on your browser to return to this page
later.

This is in line with Markovnikov's Rule which says:


When a compound HX is added to an unsymmetrical alkene,
the hydrogen becomes attached to the carbon with the most
hydrogens attached to it already.
In this case, the hydrogen becomes attached to the CH2 group, because
the CH2 group has more hydrogens than the CH group.
Notice that only the hydrogens directly attached to the carbon atoms at
either end of the double bond count. The ones in the CH3 group are
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electrophilic addition - unsymmetrical alkenes and hydrogen halides

totally irrelevant.

Warning! Markovnikov's Rule is a useful guide for you to


work out which way round to add something across a double
bond, but it isn't the reason why things add that way. As a
general principle, don't quote Markovnikov's Rule in an exam
unless you are specifically asked for it.

The mechanism
This is an example of electrophilic addition.

The addition is this way around because the intermediate carbocation


(previously called a carbonium ion) formed is secondary. This is more
stable (and so is easier to form) than the primary carbocation which
would be produced if the hydrogen became attached to the centre
carbon atom and the bromine to the end one.

Electrophilic addition reactions involving the other


hydrogen halides
The facts
Hydrogen fluoride, hydrogen chloride and hydrogen iodide all add on in
exactly the same way as hydrogen bromide.
The only differences lie in the rates of reaction:

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electrophilic addition - unsymmetrical alkenes and hydrogen halides

HF slowest reaction
HCl
HBr
HI

fastest reaction

This is because the hydrogen-halogen bond gets weaker as the halogen


atom gets bigger. If the bond is weaker, it breaks more easily and so the
reaction is faster.
If the halogen is given the symbol X, the equation for the reaction with
propene is:

Notice that the product is still in line with Markovnikov's Rule.


The mechanism
These are still examples of electrophilic addition.
Again using X to stand for any halogen:

Again, the intermediate carbocation formed is secondary. This is more


stable than the primary carbocation ion which would be formed if the
hydrogen attached to the centre carbon atom and the X to the end one. If
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electrophilic addition - unsymmetrical alkenes and hydrogen halides

it is more stable it will be easier to make.

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/eladd/unsymhbr.html (5 of 5)30/12/2004 11:02:26

hydrogen bromide and alkenes - the peroxide effect

HYDROGEN BROMIDE AND ALKENES: THE


PEROXIDE EFFECT

This page gives you the facts and simple uncluttered mechanisms for the
free radical addition of hydrogen bromide to alkenes - often known as the
"peroxide effect". If you want the mechanisms explained to you in more
detail, there is a link at the bottom of the page.

Addition to symmetrical alkenes


A symmetrical alkene is one like ethene where the groups at both ends
of the carbon-carbon double bond are the same.
The facts
The reaction happens at room temperature in the presence of organic
peroxides or some oxygen from the air. Alkenes react very slowly with
oxygen to produce traces of organic peroxides - so the two possible
conditions are equivalent to each other.
The reaction is a simple addition of the hydrogen bromide. For example,
with ethene:

With a symmetrical alkene you get exactly the same product in the
absence of the organic peroxides or oxygen - but the mechanism is
different.

The mechanism
Hydrogen halides (hydrogen chloride, hydrogen bromide and the rest)
usually react with alkenes using an electrophilic addition mechanism.
However, in the presence of organic peroxides, hydrogen bromide adds
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hydrogen bromide and alkenes - the peroxide effect

by a different mechanism.

Note: If you are interested, you will find the electrophilic


addition mechanism for the addition of hydrogen bromide and
other hydrogen halides to alkenes if you follow this link. You
may need to explore several pages in this section.
Use the BACK button (or the HISTORY file or GO menu) on
your browser to return to this page.

With the organic peroxides present you get a free radical chain
reaction.
Chain initiation
The chain is initiated by free radicals produced by an oxygen-oxygen
bond in the organic peroxide breaking.

These free radicals extract a hydrogen atom from a hydrogen bromide


molecule to produce bromine radicals.

Chain propagation
A bromine radical joins to the ethene using one of the electrons in the pi
bond. That creates a new radical with the single electron on the other
carbon atom.

That radical reacts with another HBr molecule to produce bromoethane


and another bromine radical to continue the process.

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hydrogen bromide and alkenes - the peroxide effect

etc
Chain termination
Eventually two free radicals hit each other and produce a molecule of
some sort. The process stops here because no new free radicals are
formed.

Addition to unsymmetrical alkenes


An unsymmetrical alkene is one like propene where the groups at either
end of the carbon-carbon double bond are different.
The facts
The reaction happens under the same conditions as with a symmetrical
alkene, but there is a complication because the hydrogen and the
bromine can add in two different ways. Which way they add depends on
whether there are organic peroxides (or oxygen) present or not.

Normally, when a molecule HX adds to a carbon-carbon double bond,


the hydrogen becomes attached to the carbon with the more hydrogens
on already. This is known as Markovnikov's Rule.
Because the HBr adds on the "wrong way around " in the presence of
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hydrogen bromide and alkenes - the peroxide effect

organic peroxides, this is often known as the peroxide effect or antiMarkovnikov addition.
In the absence of peroxides, hydrogen bromide adds to propene via an
electrophilic addition mechanism. That gives the product predicted by
Markovnikov's Rule.

The free radical mechanism


Chain initiation
This is exactly the same as in the ethene case above.

Chain propagation
When the bromine radical joins to the propene, it attaches so that a
secondary radical is formed. This is more stable (and so easier to form)
than the primary radical which would be formed if it attached to the other
carbon atom.

That radical reacts with another HBr molecule to produce 1bromopropane and another bromine radical to continue the process.

etc
Chain termination
Eventually two free radicals hit each other and produce a molecule of
some sort. The process stops here because no new free radicals are
formed.

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hydrogen bromide and alkenes - the peroxide effect

Why don't the other hydrogen halides behave in the same way?
The reason that hydrogen bromide adds in an anti-Markovnikov fashion
in the presence of organic peroxides is simply a question of reaction
rates. The free radical mechanism is much faster than the alternative
electrophilic addition mechanism.
Both mechanisms happen, but most of the product is the one from the
free radical mechanism because that is working faster.
With the other hydrogen halides, the opposite is true.
Hydrogen fluoride
The hydrogen-fluorine bond is so strong that fluorine radicals aren't
formed in the initiation step.
Hydrogen chloride
With hydrogen chloride, the second half of the propagation stage is very
slow. If you do a bond enthalpy sum, you will find that the following
reaction is endothermic.

This is due to the relatively high hydrogen-chlorine bond strength.


Hydrogen iodide
In this case, the first step of the propagation stage turns out to be
endothermic and this slows the reaction down. Not enough energy is
released when the weak carbon-iodine bond is formed.

In the case of hydrogen bromide, both steps of the propagation stage are
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hydrogen bromide and alkenes - the peroxide effect

exothermic.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2003

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

EXPLAINING THE "PEROXIDE EFFECT" IN THE


REACTION BETWEEN HYDROGEN BROMIDE
AND ALKENES

This page guides you through the mechanism for the free radical addition
of hydrogen bromide to alkenes - often known as the "peroxide effect".

Note: If you just want the facts and mechanism with a


minimum of discussion you will find them by following this link.

Free radical addition to a carbon-carbon double bond


If you have read the introductory page (see above), you will know that
hydrogen bromide adds to the carbon-carbon double bond in alkenes via
a free radical mechanism in the presence of organic peroxides or oxygen
from the air.
Oxygen reacts slowly with alkenes to produce small amounts of organic
peroxides, so we don't need to look at that as a separate case.
We'll start by looking at the general case without worrying about what is
attached at either end of the carbon-carbon double bond.

The function of the organic peroxides - chain initiation


Organic peroxides are compounds containing an oxygen-oxygen single
bond, and are commonly given a general formula R-O-O-R.
The "R" groups can be quite complicated and aren't necessarily just
simple alkyl groups.
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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

The oxygen-oxygen bond is quite weak, and breaks easily so that each
oxygen gets a single electron. Free radicals are formed.

If these free radicals collide with a hydrogen bromide molecule, a


hydrogen atom is transferred, breaking the hydrogen-bromine bond to
produce bromine radicals.

Chain propagation
In any alkene (like ethene, for example), the two pairs of electrons which
make up the double bond aren't the same. One pair is held securely on
the line between the two carbon nuclei in a bond called a sigma bond.
The other pair is more loosely held in an orbital above and below the
plane of the molecule known as a pi bond.

Note: It would be helpful - but not essential - if you read


about the structure of ethene before you went on. If the
diagram above is unfamiliar to you, then you certainly ought
to read this background material.
Use the BACK button on your browser to return to this page.

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

Imagine what happens if a free radical approaches the pi bond in an


alkene. Once again, we'll draw it as if it is ethene - but it would apply to
any case.
The bromine radical uses one of the electrons in the pi bond to help to
form a new bond between itself and the left hand carbon atom. The other
electron returns to the right hand carbon.

Note: Don't worry that we've gone back to a simpler


diagram. It is perfectly adequate for this discussion.

The sigma bond between the carbon atoms isn't affected by any of this.
Now this new free radical reacts with a hydrogen bromide molecule. It
takes a hydrogen atom from it, leaving another bromine radical.

The bromine radical can then react with another carbon-carbon double
bond, which eventually produces a new bromine radical - and so on, and
so on . . . There is a chain reaction.

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

Chain termination
The chain will be broken when any two radicals happen to hit each other
and form a new bond using both of the single electrons. Removing a free
radical from the system without producing a new one immediately stops
that particular chain.

What happens if the alkene is unsymmetrical?


Unsymmetrical alkenes?
An unsymmetrical alkene is one like propene, CH3CH=CH2. At one end
of the double bond there is a CH3 group and a hydrogen atom. At the
other end there are two hydrogen atoms.
A question of orientation
The problem with these unsymmetrical alkenes is that you could get two
different products depending on which end of the bond the hydrogen and
the bromine add.
In fact, under free radical conditions, most of the product is 1bromopropane.

This happens because when the bromine radical attacks the pi bond, it
joins to the carbon atom at the CH2 end of the double bond rather than
the CH end.

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

Why does the bromine add this way?


You might think that there would be an equal chance of it attaching to
either end, but where it attaches is controlled by the stability of the free
radical formed. The more stable radical will be formed more quickly.
Think of this in terms of activation energy.

The activation energy will be lower for the reaction where the bromine
attaches to the end carbon because the radical produced is more
energetically stable.

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

The stability of various sorts of radicals


What matters is the number of carbon atoms attached to the carbon with
the single electron.
Looking at the simplest possibilities:

Tertiary radicals are more stable than secondary ones, and secondary
radicals are more stable than primary.
In the case of a bromine radical attacking the double bond in propene, it
forms a secondary radical rather than a primary one because it is more
stable.

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

Note: The order of stability of the various tertiary, secondary


and primary free radicals exactly reflects the order of stability
of carbocations (carbonium ions).
If you are interested in following this link, use the BACK
button on your browser to return to this page.

The rest of the reaction


Once the bromine has attached to the carbon to form the secondary
radical, there is nothing different about the rest of the reaction. The new
radical takes a hydrogen from a hydrogen bromide molecule.
This produces the 1-bromopropane and a bromine radical.

The bromine radical now goes into another cycle exactly as before to
continue the chain reaction.

Where would you like to go now?


To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2003

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explaining the peroxide effect in the addition of hydrogen bromide to alkenes

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carbocations (or carbonium ions)

CARBOCATIONS (or CARBONIUM IONS)


All carbocations (previously known as carbonium ions) carry a positive
charge on a carbon atom. The name tells you that - a cation is a positive
ion, and the "carbo" bit refers to a carbon atom. However there are
important differences in the structures of various types of carbocations.

The different kinds of carbocations


Primary carbocations
In a primary (1) carbocation, the carbon which carries the positive
charge is only attached to one other alkyl group.

Help! An alkyl group is a group such as methyl, CH3, or


ethyl, CH3CH2. These are groups containing chains of
carbon atoms which may be branched. Alkyl groups are
given the general symbol R.

Some examples of primary carbocations include:

Notice that it doesn't matter how complicated the attached alkyl group is.
All you are doing is counting the number of bonds from the positive
carbon to other carbon atoms. In all the above cases there is only one
such link.

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carbocations (or carbonium ions)

Using the symbol R for an alkyl group, a primary


carbocation would be written as in the box.

Secondary carbocations
In a secondary (2) carbocation, the carbon with the positive charge is
attached to two other alkyl groups, which may be the same or different.
Examples:

A secondary carbocation has the general formula


shown in the box. R and R' represent alkyl groups
which may be the same or different.

Tertiary carbocations
In a tertiary (3) carbocation, the positive carbon atom is attached to
three alkyl groups, which may be any combination of same or different.

A tertiary carbocation has the general formula


shown in the box. R, R' and R" are alkyl groups
and may be the same or different.

The stability of the various carbocations


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carbocations (or carbonium ions)

The "electron pushing effect" of alkyl groups


You are probably familiar with the idea that bromine is more
electronegative than hydrogen, so that in a H-Br bond the electrons are
held closer to the bromine than the hydrogen. A bromine atom attached
to a carbon atom would have precisely the same effect - the electrons
being pulled towards the bromine end of the bond. The bromine has a
negative inductive effect.

Help! If you aren't familiar with all of this, follow this link to
read about electronegativity and bond polarity before you go
any further.
Use the BACK button on your browser to return to this page.

Alkyl groups do precisely the opposite and, rather than draw electrons
towards themselves, tend to "push" electrons away.

Note: The term "electron pushing" is only to help remember


what happens. The alkyl group doesn't literally "push" the
electrons away - the other end of the bond attracts them
more strongly.

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carbocations (or carbonium ions)

This means that the alkyl group becomes slightly positive ( +) and the
carbon they are attached to becomes slightly negative ( -). The alkyl
group has a positive inductive effect.
This is sometimes shown as, for example:

The arrow shows the electrons being "pushed" away from the CH3
group. The plus sign on the left-hand end of it shows that the CH3 group
is becoming positive. The symbols + and - simply reinforce that idea.
The importance of spreading charge around in making ions stable
The general rule-of-thumb is that if a charge is very localised (all
concentrated on one atom) the ion is much less stable than if the charge
is spread out over several atoms.
Applying that to carbocations of various sorts . . .

You will see that the electron pushing effect of the CH3 group is placing
more and more negative charge on the positive carbon as you go from
primary to secondary to tertiary carbocations. The effect of this, of
course, is to cut down that positive charge.
At the same time, the region around the various CH3 groups is becoming
somewhat positive. The net effect, then, is that the positive charge is
being spread out over more and more atoms as you go from primary to
secondary to tertiary ions.
The more you can spread the charge around, the more stable the ion
becomes.

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carbocations (or carbonium ions)

Order of stability of carbocations


primary < secondary < tertiary

Note: The symbol "<" means "is less than". So what this is
saying is that primary ions are less stable than secondary
ones which in turn are less stable than tertiary ones.

The stability of the carbocations in terms of energetics


When we talk about secondary
carbocations being more stable than
primary ones, what exactly do we mean?
We are actually talking about energetic
stability - secondary carbocations are
lower down an energy "ladder" than
primary ones.
This means that it is going to take more
energy to make a primary carbocation
than a secondary one.
If there is a choice between making a
secondary ion or a primary one, it will be much easier to make the
secondary one.
Similarly, if there is a choice between making a tertiary ion or a
secondary one, it will be easier to make the tertiary one.
This has important implications in the reactions of unsymmetrical
alkenes. If you are interested in these, follow the link below to the
electrophilic addition reactions menu.

Where would you like to go now?

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carbocations (or carbonium ions)

To menu of electrophilic addition reactions. . .


To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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Understanding Chemistry - Organic Mechanisms Menu

Understanding Chemistry

ORGANIC MECHANISMS MENU


Free radical reactions . . .
Free radical substitution reactions in alkanes and alkyl groups.
Free radical addition during the polymerisation of ethene and the
reaction between HBr and alkenes in the presence of organic
peroxides.
Electrophilic addition reactions . . .
Addition reactions of alkenes such as ethene and propene.
Electrophilic substitution reactions . . .
Substitution reactions of benzene and other simple arenes.
Nucleophilic substitution reactions . . .
Substitution reactions of halogenoalkanes such as bromoethane.
Elimination reactions . . .
The formation of alkenes from halogenoalkanes such as 2bromopropane, and the dehydration of alcohols.
Nucleophilic addition reactions . . .
Addition reactions of carbonyl compounds such as ethanal and
propanone.
Nucleophilic addition / elimination reactions . . .

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Understanding Chemistry - Organic Mechanisms Menu

The reactions of acyl chlorides (acid chlorides) with water,


alcohols, ammonia and amines.

Mechanisms described elsewhere on the site


These are discussed in a section on acid catalysis in organic chemistry.
The hydration of ethene to make ethanol . . .
The esterification reaction . . .
The acid catalysed hydrolysis of esters . . .

Go to Main Menu . . .

Jim Clark 2002

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Free Radical Mechanisms Menu

Understanding Chemistry

FREE RADICAL MECHANISMS MENU

Free radical substitution


What is free radical substitution? . . .
A brief explanation of the terms free radical and substitution.
methane and chlorine . . .
Free radical substitution of hydrogen atoms in methane by chlorine
atoms. Includes multiple substitution if you need it.
methane and bromine . . .
Free radical substitution of hydrogen atoms in methane by
bromine atoms. Includes multiple substitution if you need it.
methylbenzene and chlorine . . .
Free radical substitution of hydrogen atoms in the methyl group in
methylbenzene by chlorine atoms in the presence of UV light
(sunlight). Includes multiple substitution if you need it.

Free radical addition


polymerisation of ethene . . .
The mechanism for the polymerisation of ethene under free radical
http://www.chemguide.co.uk/mechanisms/frmenu.html (1 of 3)30/12/2004 11:02:49

Free Radical Mechanisms Menu

conditions.
alkenes with hydrogen bromide . . .
The mechanism for the addition of hydrogen bromide to alkenes
under free radical conditions. This is often known as the "peroxide
effect".

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of alkanes . . .
A survey of all the physical and chemical properties of alkanes
required by UK A level syllabuses.
properties and reactions of alkenes . . .
For more about the reactions and physical properties of alkenes like
ethene and propene.
more reactions of methylbenzene (toluene) . . .
A link to the arenes (aromatic hydrocarbons) section of the site.

Jim Clark 2000 (modified 2004)


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Free Radical Mechanisms Menu

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What is free radical substitution?

FREE RADICAL SUBSTITUTION

Substitution reactions
These are reactions in which one atom in a molecule is replaced by
another atom or group of atoms. Free radical substitution for A' level
purposes involves breaking a carbon-hydrogen bond in alkanes such as
methane

CH4

ethane

CH3CH3

propane

CH3CH2CH3

A new bond is then formed to something else.


It also happens in alkyl groups like methyl, ethyl (and so on) wherever
these appear in more complicated molecules.
methyl

CH3

ethyl

CH3CH2

For example, ethanoic acid is CH3COOH and contains a methyl group.


The carbon-hydrogen bonds in the methyl group behave just like those in
methane, and can be broken and replaced by something else in the
same way.
A simple example of substitution is the reaction between methane and
chlorine in the presence of UV light (or sunlight).
CH4 + Cl2

CH3Cl + HCl

Notice that one of the hydrogen atoms in the methane has been replaced
by a chlorine atom. That's substitution.

Free radical reactions

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What is free radical substitution?

Free radicals are atoms or groups of atoms which have a single unpaired
electron. A free radical substitution reaction is one involving these
radicals.
Free radicals are formed if a bond splits evenly - each atom getting one
of the two electrons. The name given to this is homolytic fission.

Note: If a bond were to split unevenly (one atom getting both


electrons, and the other none), ions would be formed. The
atom that got both electrons would become negatively
charged, while the other one would become positive. This is
called heterolytic fission.
Warning! It is important that you get these terms the right
way round. "Fission" is obvious - it just means "splitting".
"Homo" and "hetero" are used in the sense of "same" (homo)
or "different" (hetero). This is just like their use in
"homosexual" or "heterosexual".
So, homolytic fission is splitting a bond to produce two
particles which are the same in the sense that they both have
a single unpaired electron (both are free radicals). Heterolytic
fission produces two particles which are different because
one is a positive ion and the other a negative ion.

To show that a species (either an atom or a group of atoms) is a free


radical, the symbol is written with a dot attached to show the unpaired
electron. For example:
a chlorine radical
a methyl radical

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Cl
CH3

What is free radical substitution?

Note: If you wanted to be fussy, the dot showing the electron


really ought to be written next to the carbon atom in the
methyl radical, because that's the atom with the unpaired
electron - in other words as CH3. This isn't normally done
unless the radical gets more complicated. Examples of this
will crop up when you look at the mechanisms.

Where would you like to go now?


To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/freerad/whatis.html (3 of 3)30/12/2004 11:02:52

Electrophilic Substitution Mechanisms Menu

Understanding Chemistry

ELECTROPHILIC SUBSTITUTION MECHANISMS


MENU
What is electrophilic substitution? . . .
Some background on benzene (including links to more detailed
discussions) and a general mechanism which covers several of
benzene's reactions.
The nitration of benzene . . .
The mechanism for the formation of nitrobenzene from benzene.
The Friedel-Crafts acylation of benzene . . .
The mechanism for the substitution of an acyl group such as
CH3CO into benzene.
The Friedel-Crafts alkylation of benzene . . .
The mechanism for the substitution of an alkyl group such as CH3
into benzene.
An industrial alkylation of benzene . . .
The mechanism for the substitution of an alkyl group such as
CH3CH2 into benzene, by a reaction involving an alkene such as
ethene.
The halogenation of benzene . . .
The mechanism for the substitution of atoms like chlorine and
bromine into benzene rings.
http://www.chemguide.co.uk/mechanisms/elsubmenu.html (1 of 2)30/12/2004 11:02:53

Electrophilic Substitution Mechanisms Menu

The sulphonation of benzene . . .


The mechanism for reaction between benzene and concentrated
sulphuric acid to produce benzenesulphonic acid
Some substitution reactions of methylbenzene . . .
Illustrates how to cope with the problem of substituting things into
rings which already have something else attached.

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of arenes (aromatic hydrocarbons). . .
Covers all the physical and chemical properties of arenes like
benzene and methylbenzene required by UK A level syllabuses.

Jim Clark 2000 (modified 2004)

http://www.chemguide.co.uk/mechanisms/elsubmenu.html (2 of 2)30/12/2004 11:02:53

What is electrophilic substitution?

ELECTROPHILIC SUBSTITUTION

Background
Electrophilic substitution happens in many of the reactions of compounds
containing benzene rings - the arenes. For simplicity, we'll only look for
now at benzene itself.

Note: Before you start it would be a good idea if you had a


clear idea about the structure of benzene. Check your
syllabus now to find out what you need to know, and then
read the page on the modern orbital view of benzene in the
organic bonding section of this site. Don't forget to look in the
section(s) in your syllabus on bonding as well as organic
chemistry.
Haven't got a syllabus? Follow this link to find out how to get
one.

This is what you need to understand for the purposes of the electrophilic
substitution mechanisms:

Benzene, C6H6, is a planar molecule containing a ring of six


carbon atoms each with a hydrogen atom attached.
There are delocalised electrons above and below the plane of the
ring.

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What is electrophilic substitution?

The presence of the delocalised electrons makes benzene


particularly stable.
Benzene resists addition reactions because that would involve
breaking the delocalisation and losing that stability.
Benzene is represented by this symbol, where the
circle represents the delocalised electrons, and
each corner of the hexagon has a carbon atom
with a hydrogen attached.

Electrophilic substitution reactions involving positive ions


Benzene and electrophiles
Because of the delocalised electrons exposed above and below the
plane of the rest of the molecule, benzene is obviously going to be highly
attractive to electrophiles - species which seek after electron rich areas in
other molecules.

Species: A useful word which can mean any particle you


want it to mean - an atom, a molecule, an ion or a free radical.

The electrophile will either be a positive ion, or the slightly positive end of
a polar molecule.

Help! If you aren't sure what a polar molecule is, read about
electronegativity and polar bonds before you go on.
Use the BACK button on your browser to return to this page.

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What is electrophilic substitution?

The delocalised electrons above and below the plane of the benzene
molecule are open to attack in the same way as those above and below
the plane of an ethene molecule. However, the end result will be different.

If benzene underwent addition reactions in the same way as ethene, it


would need to use some of the delocalised electrons to form bonds with
the new atoms or groups. This would break the delocalisation - and this
costs energy.

Note: You can read about electrophilic addition to ethene if


you are interested.
Use the BACK button on your browser to return to this page.

Instead, it can maintain the delocalisation if it replaces a hydrogen atom


by something else - a substitution reaction. The hydrogen atoms aren't
involved in any way with the delocalised electrons.
In most of benzene's reactions, the electrophile is a positive ion, and
these reactions all follow a general pattern.
The general mechanism
The first stage
Suppose the electrophile is a positive ion X+.
Two of the electrons in the delocalised system are attracted towards the
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What is electrophilic substitution?

X+ and form a bond with it. This has the effect of breaking the
delocalisation, although not completely.

Note: If you aren't sure about the use of curly arrows in


mechanisms, you must follow this link before you go on.
Use the BACK button on your browser to return to this page.

The ion formed in this step isn't the final product. It immediately goes on
to react with something else. It is just an intermediate.
There is still delocalisation in the intermediate formed, but
it only covers part of the ion. When you write one of these
mechanisms, draw the partial delocalisation to take in all
the carbon atoms apart from the one that the X has
become attached to.
The intermediate ion carries a positive charge because
you are joining together a neutral molecule and a positive
ion. This positive charge is spread over the delocalised part of the ring.
Simply draw the "+" in the middle of the ring.
The hydrogen at the top isn't new - it's the hydrogen that was already
attached to that carbon. We need to show that it is there for the next
stage.
The second stage

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What is electrophilic substitution?

Here we've introduced a new ion, Y-. Where did this come from? You
have to remember that it is impossible to get a positive ion on its own in a
chemical system - so Y- is simply the negative ion that was originally
associated with X+. Don't worry about this at the moment - it's much
easier to see when you've got a real example in front of you.
A lone pair of electrons on Y- forms a bond with
the hydrogen atom at the top of the ring. That
means that the pair of electrons joining the
hydrogen onto the ring aren't needed any more.
These then move down to plug the gap in the
delocalised electrons, so restoring the delocalised
ring of electrons which originally gave the benzene its special stability.
The energetics of the reaction
The complete delocalisation is temporarily broken as X replaces H on the
ring, and this costs energy. However, that energy is recovered when the
delocalisation is re-established. This initial input of energy is simply the
activation energy for the reaction. In this case, it is going to be high
(something around 150 kJ mol-1), and this means that benzene's
reactions tend to be slow.

Electrophilic substitution reactions not involving positive


ions
Halogenation and sulphonation
In these reactions, the electrophiles are polar molecules rather than fully
positive ions.
Because these mechanisms are different from what's gone before (and

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What is electrophilic substitution?

from each other), there isn't any point in dealing with them in a general
way. You will find them explained in full if you follow the link to the
electrophilic substitution menu below.

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/whatis.html (6 of 6)30/12/2004 11:02:58

bonding in benzene - sp2 hybridisation and delocalisation

BONDING IN BENZENE

Important! This article builds on knowledge about the


bonding in methane, and the bonding in ethene.
You will find the current page much easier to understand if
you read these other ones first.
You may also find it useful to read the article on orbitals if you
aren't sure about simple orbital theory.
You can also read about the evidence which leads to the
structure described in this article. That page includes the
Kekul structure for benzene and the reasons that it isn't very
satisfactory.

An orbital model for the benzene structure


Building the orbital model
Benzene is built from hydrogen atoms (1s1) and carbon atoms
(1s22s22px12py1).
Each carbon atom has to join to three other atoms (one hydrogen and
two carbons) and doesn't have enough unpaired electrons to form the
required number of bonds, so it needs to promote one of the 2s2 pair into
the empty 2pz orbital. This is exactly the same as happens whenever
carbon forms bonds - whatever else it ends up joined to.

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bonding in benzene - sp2 hybridisation and delocalisation

Important! If you have any doubts about this then you


should follow the links at the top of the page.

Because each carbon is only joining to three other atoms, when the
carbon atoms hybridise their outer orbitals before forming bonds, they
only need to hybridise three of the orbitals rather than all four. They use
the 2s electron and two of the 2p electrons, but leave the other 2p
electron unchanged.
The new orbitals formed are called sp2 hybrids, because they are made
by an s orbital and two p orbitals reorganising themselves. The three sp2
hybrid orbitals arrange themselves as far apart as possible - which is at
120 to each other in a plane. The remaining p orbital is at right angles to
them.
Each carbon atom now looks like the
diagram on the right. This is all exactly
the same as happens in ethene.
The difference in benzene is that each
carbon atom is joined to two other similar
carbon atoms instead of just one. Each
carbon atom uses the sp2 hybrids to
form sigma bonds with two other
carbons and one hydrogen atom. The next diagram shows the sigma
bonds formed, but for the moment leaves the p orbitals alone.

Remember: A sigma bond is formed by the end-to-end


overlap between atomic orbitals.

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bonding in benzene - sp2 hybridisation and delocalisation

Only a part of the ring is shown because the diagram gets extremely
cluttered if you try to draw any more.
Notice that the p electron on each carbon atom is overlapping with those
on both sides of it. This extensive sideways overlap produces a system
of pi bonds which are spread out over the whole carbon ring. Because
the electrons are no longer held between just two carbon atoms, but are
spread over the whole ring, the electrons are said to be delocalised. The
six delocalised electrons go into three molecular orbitals - two in each.

Remember: A molecular orbital is the region of space which


contains a bonding pair of electrons.
Warning! Be very careful how you phrase this in exams.
You must never talk about the p orbitals on the carbons
overlapping sideways to produce a delocalised pi bond. This
upsets examiners because a pi bond can only hold 2
electrons - whereas in benzene there are 6 delocalised
electrons. Talk instead about a "pi system" - or just about the
delocalised electrons.

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bonding in benzene - sp2 hybridisation and delocalisation

In common with the great majority of descriptions of the bonding in


benzene, we are only going to show one of these delocalised molecular
orbitals for simplicity.
In the diagram, the sigma bonds
have been shown as simple lines to
make the diagram less confusing.
The two rings above and below the
plane of the molecule represent
one molecular orbital. The two
delocalised electrons can be found
anywhere within those rings. The
other four delocalised electrons live in two similar (but not identical)
molecular orbitals.
Relating the orbital model to the properties of benzene

Note: To get the best out of this section you ought to read
the article on the Kekul structure for benzene.

The shape of benzene


This is easily explained. Benzene is a regular hexagon because all the
bonds are identical. The delocalisation of the electrons means that there
aren't alternating double and single bonds.
The energetic stability of benzene
This is accounted for by the delocalisation. As a general principle, the
more you can spread electrons around - in other words, the more they
are delocalised - the more stable the molecule becomes. The extra
stability of benzene is often referred to as "delocalisation energy".
The reluctance of benzene to undergo addition reactions
With the delocalised electrons in place, benzene is about 150 kJ mol-1
more stable than it would otherwise be. If you added other atoms to a
benzene ring you would have to use some of the delocalised electrons to
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bonding in benzene - sp2 hybridisation and delocalisation

join the new atoms to the ring. That would disrupt the delocalisation and
the system would become less stable.
Since about 150 kJ per mole of benzene would have to be supplied to
break up the delocalisation, this isn't going to be an easy thing to do.
The symbol for benzene
Although you will still come across the Kekul structure
for benzene, for most purposes we use the structure on
the right.
The hexagon shows the ring of six carbon atoms, each
of which has one hydrogen attached. (You have to know
that - counting bonds to find out how many hydrogens to add doesn't
work in this particular case.)
The circle represents the delocalised electrons. It is essential that you
include the circle. If you miss it out, you are drawing cyclohexane and not
benzene.

Where would you like to go now?


To read about the Kekul structure for benzene. . .
To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic substitution - the nitration of benzene

THE NITRATION OF BENZENE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic substitution reaction between benzene and a mixture of
concentrated nitric acid and concentrated sulphuric acid. If you want the
nitration mechanism explained to you in detail, there is a link at the
bottom of the page.

The electrophilic substitution reaction between benzene


and nitric acid
The facts
Benzene is treated with a mixture of concentrated nitric acid and
concentrated sulphuric acid at a temperature not exceeding 50C. As
temperature increases there is a greater chance of getting more than one
nitro group, -NO2, substituted onto the ring.
Nitrobenzene is formed.

or:

The concentrated sulphuric acid is acting as a catalyst.

The formation of the electrophile


The electrophile is the "nitronium ion" or the "nitryl cation", NO2+. This is
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electrophilic substitution - the nitration of benzene

formed by reaction between the nitric acid and the sulphuric acid.

The electrophilic substitution mechanism


Stage one

Stage two

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

http://www.chemguide.co.uk/mechanisms/elsub/nitration.html (2 of 3)30/12/2004 11:03:04

electrophilic substitution - the nitration of benzene

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/nitration.html (3 of 3)30/12/2004 11:03:04

Explaining the nitration of benzene - electrophilic substitution

EXPLAINING THE NITRATION OF BENZENE

This page guides you through the mechanism for the nitration of benzene
involving an electrophilic substitution reaction between benzene and
nitric acid.

Important! It would help if you first read the page What is


electrophilic substitution? before you went on.

The electrophilic substitution reaction between benzene


and nitric acid
The formation of the electrophile
If you are going to substitute an -NO2 group into the ring, then the
electrophile must be NO2+. This is called the "nitronium ion" or the "nitryl
cation", and is formed by reaction between the nitric acid and sulphuric
acid.

Note: If you don't understand why the electrophile has got to


be NO2+, then you really should look at What is electrophilic
substitution? before you go on.
If you are going to substitute X onto the ring, then the
electrophile must be X+. If you are going to insert an -NO2
group onto the ring, then the electrophile must be NO2+.

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Explaining the nitration of benzene - electrophilic substitution

The equation

Important! Check past exam papers to see whether you will


need to quote this equation in an exam. It's probable that you
will, so learn it! There are ways of building it up, but they
involve much more effort than learning it in the first place.

The hydrogensulphate ion, HSO4-, will also be involved in the


mechanism. The hydroxonium ion, H3O+, isn't involved.

Note: The hydroxonium ion (also called the hydronium ion or


oxonium ion) is simply a hydrogen ion attached to a water
molecule - what is often written more simply as H+(aq).

The electrophilic substitution mechanism


Stage one
As the NO2+ ion approaches the delocalised electrons in the benzene,
those electrons are strongly attracted towards the positive charge.
Two electrons from the delocalised system are used to form a new bond
with the NO2+ ion. Because those two electrons aren't a part of the
delocalised system any longer, the delocalisation is partly broken, and in
the process the ring gains a positive charge.

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Explaining the nitration of benzene - electrophilic substitution

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom - it's nothing new or subtle! We need to show it
there because it has to be removed in the second stage.
Stage two
The second stage involves a hydrogensulphate ion,
HSO4-, which was produced at the same time as the
NO2+ ion (refer back to the equation showing the
formation of the electrophile if you've forgotten).

Note: Only one of the lone pairs in the hydrogensulphate ion


is shown. There are lots more, but those aren't involved in the
reaction.

This removes a hydrogen from the ring to form sulphuric acid - the
catalyst has therefore been regenerated. The electrons which originally
joined the hydrogen to the ring are now used to re-establish the
delocalised system.
Stage two - a sloppy way of writing the same thing!
You will often find the second stage of this reaction simplified in many (or
even most!) books. The second stage is shown as:

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Explaining the nitration of benzene - electrophilic substitution

The hydrogen is shown as "falling off" the ring as a hydrogen ion. This is
sloppy and unsatisfactory on two counts:

Hydrogen ions never exist on their own in a chemical reaction. A


hydrogen ion is a raw proton - the most intensely positive thing you
can imagine. It will always be attached to something else.
By not showing the hydrogensulphate ion, you can't show that the
sulphuric acid catalyst has been regenerated. That's simply
unsatisfying!

Showing exactly how the hydrogen is removed from the ring isn't difficult
- do it properly!

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/nitrationtt.html (4 of 4)30/12/2004 11:03:07

electrophilic substitution - the acylation of benzene

THE FRIEDEL-CRAFTS ACYLATION OF


BENZENE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic substitution reaction between benzene and ethanoyl
chloride in the presence of an aluminium chloride catalyst. If you want
the Friedel-Crafts acylation mechanism explained to you in detail, there
is a link at the bottom of the page.

The electrophilic substitution reaction between benzene


and ethanoyl chloride
What is acylation?
An acyl group is an alkyl group attached to a carbonoxygen double bond. If "R" represents any alkyl group,
then an acyl group has the formula RCO-. Acylation
means substituting an acyl group into something - in this
case, into a benzene ring.
The most commonly used acyl group is CH3CO-. This is called the
ethanoyl group. In the example which follows we are substituting a
CH3CO- group into the ring, but you could equally well use any other
alkyl group instead of the CH3.
The facts
The most reactive substance containing an acyl group is an acyl chloride
(also known as an acid chloride). These have the general formula RCOCl.
Benzene is treated with a mixture of ethanoyl chloride, CH3COCl, and
aluminium chloride as the catalyst. A ketone called phenylethanone is
formed.

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electrophilic substitution - the acylation of benzene

Note: Ketones: A family of compounds containing a carbonoxygen double bond with a hydrocarbon group either side of
it. In this case there is a methyl group on one side and a
benzene ring on the other.
Don't worry too much about the name "phenylethanone" - all
that matters is that you can draw the structure.

or better:

The aluminium chloride isn't written into these equations because it is


acting as a catalyst. If you wanted to include it, you could write AlCl3 over
the top of the arrow.

The formation of the electrophile


The electrophile is CH3CO+. It is formed by
reaction between the ethanoyl chloride and the
aluminium chloride catalyst.

The electrophilic substitution mechanism


Stage one
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electrophilic substitution - the acylation of benzene

Stage two

The hydrogen is removed by the AlCl4- ion which was formed at the
same time as the CH3CO+ electrophile. The aluminium chloride catalyst
is re-generated in this second stage.

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/fcacyl.html (3 of 3)30/12/2004 11:03:11

Explaining the Friedel-Crafts acylation of benzene - electrophilic substitution

EXPLAINING THE FRIEDEL-CRAFTS


ACYLATION OF BENZENE

This page guides you through the mechanism for the Friedel-Crafts
acyation of benzene involving an electrophilic substitution reaction
between benzene and ethanoyl chloride in the presence of an aluminium
chloride catalyst.

Important! It would help if you first read the page What is


electrophilic substitution? before you went on.

The electrophilic substitution reaction between benzene


and ethanoyl chloride
The formation of the electrophile
If you are going to replace a hydrogen atom in a
benzene ring by CH3CO, then the electrophile
must be the ion CH3CO+. The positive charge must be on the carbon
atom, because that's what gets attached to the ring.

Note: If you don't understand why the electrophile has got to


be CH3CO+, then you really should look at What is
electrophilic substitution? before you go on.
If you are going to substitute X onto the ring, then the
electrophile must be X+. If you are going to insert an CH3CO
group onto the ring, then the electrophile must be CH3CO+.

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Explaining the Friedel-Crafts acylation of benzene - electrophilic substitution

Aluminium chloride, AlCl3, is an electron deficient molecule. It is


covalently bonded, but because the aluminium is only forming 3 bonds,
and has no lone pairs, there are only 6 electrons around the aluminium
atom rather than 8. It takes a chlorine (as a chloride ion) from the
ethanoyl chloride, and forms a co-ordinate (dative covalent) bond with it.

Help! A co-ordinate bond is a covalent bond in which both


electrons originally came from the same atom. In this case,
both the electrons in the bond come from the chlorine being
removed from the ethanoyl chloride.

The equation simplified

The electrophilic substitution mechanism


Stage one
As the CH3CO+ ion approaches the delocalised electrons in the
benzene, those electrons are strongly attracted towards the positive
charge.
Two electrons from the delocalised system are used to form a new bond
with the CH3CO+ ion. Because those two electrons aren't a part of the
delocalised system any longer, the delocalisation is partly broken, and in
the process the ring gains a positive charge.

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Explaining the Friedel-Crafts acylation of benzene - electrophilic substitution

Help! Don't be confused that we have reversed the way we


have written the CH3CO+ ion to show it as +COCH3.
This is just so that it is easier to draw the mechanism tidily in
the same way that the general mechanism was drawn on the
page What is electrophilic substitution?

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom. We need to show it there because it has to be
removed in the second stage.
Stage two
The second stage involves the AlCl4-, which was produced at the same
time as the CH3CO+ ion.

One of the aluminium-chlorine bonds breaks and both electrons from it


are used to join to the hydrogen. This removes the hydrogen from the
ring to form HCl, and re-generates the aluminium chloride catalyst in the
process. The electrons which originally joined the hydrogen to the ring
are now used to re-establish the delocalised system.

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Explaining the Friedel-Crafts acylation of benzene - electrophilic substitution

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/fcacyltt.html (4 of 4)30/12/2004 11:03:14

electrophilic substitution - the alkylation of benzene

THE FRIEDEL-CRAFTS ALKYLATION OF


BENZENE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic substitution reaction between benzene and
chloromethane in the presence of an aluminium chloride catalyst. Any
other chloroalkane would work similarly. If you want the Friedel-Crafts
alkylation mechanism explained to you in detail, there is a link at the
bottom of the page.

The electrophilic substitution reaction between benzene


and chloromethane
What is alkylation?
Alkylation means substituting an alkyl group into something - in this case
into a benzene ring. A hydrogen on the ring is replaced by a group like
methyl or ethyl and so on.
The facts
Benzene is treated with a chloroalkane (for example, chloromethane or
chloroethane) in the presence of aluminium chloride as a catalyst. On
this page, we will look at substituting a methyl group, but any other alkyl
group could be used in the same way.
Substituting a methyl group gives methylbenzene - once known as
toluene.

or better:

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electrophilic substitution - the alkylation of benzene

The aluminium chloride isn't written into these equations because it is


acting as a catalyst. If you wanted to include it, you could write AlCl3 over
the top of the arrow.

Note: The methylbenzene formed is more reactive than the


original benzene, and so the reaction doesn't stop there. You
get further methyl groups substituted around the ring.
You won't have to worry about this for A' level.

The formation of the electrophile


The electrophile is CH3+. It is formed by reaction between the
chloromethane and the aluminium chloride catalyst.

The electrophilic substitution mechanism


Stage one

Stage two

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electrophilic substitution - the alkylation of benzene

The hydrogen is removed by the AlCl4- ion which was formed at the
same time as the CH3+ electrophile. The aluminium chloride catalyst is regenerated in this second stage.

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/fcalkyl.html (3 of 3)30/12/2004 11:03:19

Explaining the Friedel-Crafts alkylation of benzene - electrophilic substitution

EXPLAINING THE FRIEDEL-CRAFTS


ALKYLATION OF BENZENE

This page guides you through the mechanism for the Friedel-Crafts
alkyation of benzene involving an electrophilic substitution reaction
between benzene and a chloroalkane like chloromethane in the presence
of an aluminium chloride catalyst.

Important! It would help if you first read the page What is


electrophilic substitution? before you went on.

The electrophilic substitution reaction between benzene


and chloromethane
The formation of the electrophile
If you are going to replace a hydrogen atom in a benzene ring by CH3,
then the electrophile must be the ion CH3+.

Note: If you don't understand why the electrophile has got to


be CH3+, then you really should look at What is electrophilic
substitution? before you go on.
If you are going to substitute X onto the ring, then the
electrophile must be X+. If you are going to insert an CH3
group onto the ring, then the electrophile must be CH3+.

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Explaining the Friedel-Crafts alkylation of benzene - electrophilic substitution

Aluminium chloride, AlCl3, is an electron deficient molecule. It is


covalently bonded, but because the aluminium is only forming 3 bonds,
and has no lone pairs, there are only 6 electrons around the aluminium
atom rather than 8. It takes a chlorine (as a chloride ion) from the
chloromethane, and forms a co-ordinate (dative covalent) bond with it.

Help! A co-ordinate bond is a covalent bond in which both


electrons originally came from the same atom. In this case,
both the electrons in the bond come from the chlorine being
removed from the chloromethane.

The equation simplified

The electrophilic substitution mechanism


Stage one
As the CH3+ ion approaches the delocalised electrons in the benzene,
those electrons are strongly attracted towards the positive charge.
Two electrons from the delocalised system are used to form a new bond
with the CH3+ ion. Because those two electrons aren't a part of the
delocalised system any longer, the delocalisation is partly broken, and in
the process the ring gains a positive charge.

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Explaining the Friedel-Crafts alkylation of benzene - electrophilic substitution

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom. We need to show it there because it has to be
removed in the second stage.
Stage two
The second stage involves the AlCl4-, which was produced at the same
time as the CH3+ ion.

One of the aluminium-chlorine bonds breaks and both electrons from it


are used to join to the hydrogen. This removes the hydrogen from the
ring to form HCl, and re-generates the aluminium chloride catalyst in the
process. The electrons which originally joined the hydrogen to the ring
are now used to re-establish the delocalised system.

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

http://www.chemguide.co.uk/mechanisms/elsub/fcalkyltt.html (3 of 4)30/12/2004 11:03:21

Explaining the Friedel-Crafts alkylation of benzene - electrophilic substitution

Jim Clark 2000

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electrophilic substitution - an industrial alkylation of benzene

AN INDUSTRIAL ALKYLATION OF BENZENE

This page gives you the facts and simple, uncluttered mechanisms for
the electrophilic substitution reaction between benzene and alkenes in
the presence of a mixture of aluminium chloride and hydrogen chloride
as the catalyst. If you want these mechanisms explained to you in detail,
there is a link at the bottom of the page.

Note: The process described below is one of several ways


of making alkylbenzenes like ethylbenzene from benzene
and alkenes, using a variety of different catalysts and
conditions.
The process to produce ethylbenzene is currently asked for
by the UK A level Exam Board AQA, and I am including it
solely to satisfy their requirements. If you don't actually need
to read this, don't!

The electrophilic substitution reaction between benzene


and ethene
The facts
Industrially, alkyl groups can be substituted into a benzene ring using a
variant on Friedel-Crafts alkylation. One possibility is that instead of
using a chloroalkane with an aluminium chloride catalyst, they use an
alkene and a mixture of aluminium chloride and hydrogen chloride as the
catalyst.
This is a cheaper method because it saves having to make the
chloroalkane first.

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electrophilic substitution - an industrial alkylation of benzene

Note: If you haven't already done so, you might like to look
at the Friedel-Crafts alkylation reaction before you go on.

To put an ethyl group on the ring (to make ethylbenzene), benzene is


treated with a mixture of ethene, HCl and aluminium chloride.

or better:

The aluminium chloride and HCl aren't written into these equations
because they are acting as catalysts. If you wanted to include them, you
could write AlCl3 and HCl over the top of the arrow.
The formation of the electrophile
The electrophile is CH3CH2+. It is formed by reaction between the ethene
and the HCl - exactly as if you were beginning to add the HCl to the
ethene.

The chloride ion is immediately picked up by the aluminium chloride to


form an AlCl4- ion. That prevents the chloride ion from reacting with the
CH3CH2+ ion to form chloroethane.

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electrophilic substitution - an industrial alkylation of benzene

Note: It wouldn't matter if it did react, because chloroethane


will react with benzene using a simple Friedel-Crafts
alkylation reaction to give the product you want anyway.

The electrophilic substitution mechanism


Stage one

Stage two

The hydrogen is removed by the AlCl4- ion which was formed at the
same time as the CH3CH2+ electrophile. The aluminium chloride and
hydrogen chloride catalysts are re-generated in this second stage.

The electrophilic substitution reaction between benzene


and propene
The facts
The problem with more complicated alkenes like propene is that you
have to be careful about the structure of the product. In each case, you
can only really be sure of that structure if you work through the
mechanism first.
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electrophilic substitution - an industrial alkylation of benzene

For example, the propyl group becomes attached to the ring via its
middle carbon atom - and not its end one.

You still need a mixture of aluminium chloride and hydrogen chloride as


catalysts.
The formation of the electrophile
When the propene reacts with the HCl, the hydrogen becomes attached
to the end carbon atom. A secondary carbocation (carbonium ion) is
formed because it is more stable than the primary one which would have
been formed if the addition was the other way round.

Because the positive charge is on the centre carbon atom, that is the one
which will become attached to the ring.
The electrophilic substitution mechanism
Stage one

Stage two
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electrophilic substitution - an industrial alkylation of benzene

Again, the hydrogen is removed by the AlCl4- ion. The aluminium


chloride and hydrogen chloride catalysts are re-generated in this second
stage.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000 (slightly modified 2004)

http://www.chemguide.co.uk/mechanisms/elsub/indalkyl.html (5 of 5)30/12/2004 11:03:27

Explaining the industrial alkylation of benzene - electrophilic substitution

EXPLAINING THE INDUSTRIAL ALKYLATION OF


BENZENE

This page guides you through the mechanisms for the electrophilic
substitution reaction between benzene and alkenes in the presence of a
mixture of aluminium chloride and hydrogen chloride as catalysts.

Important! There is some quite complicated chemistry


involved on this page. Be sure that you actually need to know
about it!
Although these mechanisms weren't actually required by the
syllabus, in the past one Exam Board (NEAB - now part of
AQA) frequently asked guided questions about them. Check
recent exam papers to see if that's the case with your current
Exam Board. If you haven't already got any, find out how to
get copies of recent past papers by accessing your Exam
Board's web site (links on the syllabuses page).

The electrophilic substitution reaction between benzene


and ethene
The formation of the electrophile
If you are going to replace a hydrogen atom in a benzene ring by
CH3CH2, then the electrophile must be the ion CH3CH2+.

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Explaining the industrial alkylation of benzene - electrophilic substitution

Note: If you don't understand why the electrophile has got to


be CH3CH2+, then you should look at What is electrophilic
substitution? before you go on.
If you are going to substitute X onto the ring, then the
electrophile must be X+. If you are going to insert an CH3CH2
group onto the ring, then the electrophile must be CH3CH2+.

The electrophile is formed by reaction between the ethene and the HCl exactly as if you were beginning to add the HCl to the ethene.

Note: If you haven't done any alkene chemistry recently, it


would be worth your while looking at the reaction of ethene
with hydrogen halides, if you aren't sure about it.

The chloride ion is immediately picked up by the aluminium chloride to


form an AlCl4- ion. That prevents the chloride ion from reacting with the
CH3CH2+ ion to form chloroethane.
Aluminium chloride is an electron deficient molecule, with only 3 pairs of
electrons around the aluminium. By forming a fourth bond with the
chloride ion, it becomes more energetically stable.

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Explaining the industrial alkylation of benzene - electrophilic substitution

Note: We are only showing one of the lone pairs around the
chloride ion. The other three aren't involved in this reaction.

The electrophilic substitution mechanism

Note: From now on the mechanism is exactly the same as


the Friedel-Crafts alkylation of benzene. You might like to
compare the two.

Stage one
As the CH3CH2+ ion approaches the delocalised electrons in the
benzene, those electrons are strongly attracted towards the positive
charge.
Two electrons from the delocalised system are used to form a new bond
with the positive carbon atom. Because those two electrons aren't a part
of the delocalised system any longer, the delocalisation is partly broken,
and in the process the ring gains a positive charge.

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom. We need to show it there because it has to be
removed in the second stage.
Stage two
The second stage involves the AlCl4-.

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Explaining the industrial alkylation of benzene - electrophilic substitution

One of the aluminium-chlorine bonds breaks and both electrons from it


are used to join to the hydrogen. Removing the hydrogen from the ring reforms the HCl and the aluminium chloride catalysts in the process. The
electrons which originally joined the hydrogen to the ring are now used to
re-establish the delocalised system.

The electrophilic substitution reaction between benzene


and propene
Important! Don't even think about reading this section until
you are sure that you understand everything on this page so
far! The next bit adds another layer of difficulty.

The problem lies in how you attach the carbon chain to the ring. You
might remember that the propene joins on via the middle carbon atom.

The formation of the electrophile


When the propene reacts with the HCl, there are two different ways that
the initial stage of the addition reaction could happen.
The pi bond could swing so that the hydrogen atom becomes attached to
the left-hand carbon. This produces a primary carbocation (carbonium
ion).

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Explaining the industrial alkylation of benzene - electrophilic substitution

Alternatively, the pi bond electrons could move the other way and form a
secondary carbocation.

Note: If you don't understand about primary and secondary


carbocations (carbonium ions) follow this link before you go
any further.
You might also find it useful to read about the addition of
hydrogen halides to unsymmetrical alkenes as well.

The secondary carbocation (with the positive charge on the centre


carbon atom) is the more stable, and so that forms more readily.
Because the electrophile has the positive charge on the centre carbon,
that will be where it attaches to the benzene ring.
The electrophilic substitution mechanism
The mechanism is now exactly the same as the one involving ethene that
we've already looked at in detail.
Stage one
Two electrons from the delocalised system are used to form a new bond
with the positive carbon atom. Because those two electrons aren't a part
of the delocalised system any longer, the delocalisation is partly broken,
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Explaining the industrial alkylation of benzene - electrophilic substitution

and in the process the ring gains a positive charge.

Stage two
In the second stage, one of the aluminium-chlorine bonds breaks and
both electrons from it are used to join to the hydrogen. Removing the
hydrogen from the ring re-forms the HCl and the aluminium chloride
catalysts in the process. The electrons which originally joined the
hydrogen to the ring are now used to re-establish the delocalised system.

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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Explaining the industrial alkylation of benzene - electrophilic substitution

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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

EXPLAINING THE REACTION BETWEEN


UNSYMMETRICAL ALKENES AND THE
HYDROGEN HALIDES

This page guides you through the mechanism for the electrophilic
addition of hydrogen halides such as hydrogen bromide to unsymmetrical
alkenes like propene.

Important! To make sense of this page, you will need to


understand about the structure and stability of carbocations
(previously called carbonium ions) and be confident about
electrophilic addition to simple alkenes like ethene.
If you aren't sure about either of these things, follow these
links first.
You would also find it easier if you first read about the
electrophilic addition reactions between hydrogen halides
and symmetrical alkenes like ethene, and addition to
unsymmetrical alkenes in general. If you have just come from
those, ignore these links!

Electrophilic addition reactions involving hydrogen


bromide
If you want the mechanism for one of the other hydrogen halides, simply
replace Br by whatever else you are interested in - F or Cl or I. There is
no difference whatsoever in the mechanisms.
You might, however, need to be aware that there is an alternative
mechanism involving hydrogen bromide and alkenes if the reaction
mixture is impure in the presence of organic peroxides or oxygen from
the air.

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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

Note: The different mechanism (a free radical chain reaction


- not on UK A' level syllabuses) leads to the hydrogen and
bromine adding the opposite way round. For A' level
purposes, you don't need to worry about that. However, if you
are interested, you will find the free radical addition
mechanism by following this link.
Use the BACK button on your browser to return to this page
later.

Hydrogen bromide as an electrophile


Hydrogen bromide is chosen as a typical
hydrogen halide. Bromine is more
electronegative than hydrogen. That means
that the bonding pair of electrons is pulled towards the bromine end of
the bond, and so the hydrogen bromide molecule is polar.

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you read on.
Use the BACK button on your browser to return to this page.

The slightly positive hydrogen atom will be attracted to negative regions


in other molecules, and is therefore an electrophile.

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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

Electrophile: A substance with a strong attraction to a


negative region in another substance. Electrophiles are either
fully positive ions, or the slightly positive end of a polar
molecule.

The reaction of propene with hydrogen bromide


The double bond in all alkenes is made up of two different parts. One
pair of electrons lies on the line between the two nuclei where you would
expect them to be. This is called a sigma bond.
The other pair lies in an orbital above and below the plane of the rest of
the molecule, and is called a pi bond. The pi bond is weaker than a
sigma bond and is very vulnerable to attack.

Note: If this isn't fairly obvious to you, you really ought to


read the page introducing electrophilic addition before you go
on.
Use the BACK button on your browser to return to this page.

As the HBr approaches the pi bond, the electrons in that bond are
attracted towards the slightly positive hydrogen atom. That repels the
electrons in the hydrogen-bromine bond down towards the bromine.

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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

The electron movements continue until a new bond is made between one
of the carbon atoms and the hydrogen. The bromine now has both
electrons from the H-Br bond, and so is negatively charged as a bromide
ion.
The problem is that there are two possible ways that the pi bond
electrons could move.
They could form a bond between the hydrogen and the left-hand carbon:

or they could form a bond with the right-hand one:

It's the second of these changes that happens more readily. In that case,
a secondary carbocation is formed - and that's more energetically stable
than the primary one formed in the first possibility.
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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

Because the secondary ion is more energetically stable, it will form more
easily and so the reaction needs less activation energy.

Important! If you don't understand about the structure and


stability of carbocations (carbonium ions) follow this link.
Activation energy: The minimum energy needed before a
reaction will occur. In this case it is the energy needed to
break the various bonds and make the carbocation and the
bromide ion.

Once the ions have been formed, the lone pair on the bromide ion is
strongly attracted towards the positive carbon atom. It moves towards it
and forms a bond.

Note: There are actually 4 lone pairs around the bromide


ion, but we are only interested in the one shown.

That leaves you with the over-all mechanism:

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Explaining electrophilic addition involving hydrogen halides and unsymmetrical alkenes

Important! If you've had problems with this page you might


find it useful to read about addition to unsymmetrical alkenes
in general, and then come back here again.

Where would you like to go now?


To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic addition to unsymmetrical alkenes

ELECTROPHILIC ADDITION TO
UNSYMMETRICAL ALKENES

Important! To make sense of this page, you will need to


understand about the structure and stability of carbocations
(previously called carbonium ions) and be confident about
electrophilic addition to simple alkenes like ethene.
If you aren't sure about either of these things, follow these
links first. Trying to build on shaky foundations risks confusing
you and undermining your confidence.

The Problem
The addition of H-X to an unsymmetrical alkene like propene
An unsymmetrical alkene is one like propene or but-1-ene in which the
groups or atoms attached to either end of the carbon-carbon double bond
are different.
For example, in propene there are a hydrogen and a methyl group at one
end, but two hydrogen atoms at the other end of the double bond.

With these unsymmetrical alkenes, it is possible to get two different


products during some addition reactions.
During the addition of a molecule HX to propene, you could in principle
get either this reaction:

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electrophilic addition to unsymmetrical alkenes

or this one:

It depends on which way around you add the HX across the double bond.
In fact, in most cases, it's mainly the second reaction which happens.
The hydrogen atom becomes attached to the right-hand carbon atom as
we've drawn it.
Markovnikov's Rule

Note: Don't worry too much about the spelling of


Markovnikov - there are nearly as many versions as there are
text books. It's an English attempt at a Russian name and
Markovnikov wouldn't actually have recognised any of them!

When a compound HX is added to an unsymmetrical alkene, the


hydrogen becomes attached to the carbon with the most hydrogens
attached to it already.
Remember that the HX has to attach itself to the carbon atoms which
were originally part of the double bond. So in this case, adding HX to
CH3CH=CH2, the hydrogen is attached to the CH2 group, because the
CH2 group has more hydrogens than the CH group.
Notice that only the hydrogens directly attached count. The ones in the
CH3 group are totally irrelevant.

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electrophilic addition to unsymmetrical alkenes

Warning! Markovnikov's Rule is a useful guide for you to


work out which way round to add something across a double
bond, but it isn't the reason why things add that way. Propene
has never even heard of Markovnikov! When the question
arises in an exam, you will need a much more fundamental
explanation which is coming up next. As a general principle,
don't quote Markovnikov's Rule in an exam unless you are
specifically asked for it.

The Mechanism
HX as an electrophile
In each of the cases we are interested in, X is
more electronegative than hydrogen. That
means that the bonding pair of electrons will be
dragged towards the X end of the bond, and so
the hydrogen becomes slightly positively
charged.
The slightly positive hydrogen is the electrophile, and is attracted to the pi
bond in the propene.
What happens next determines which way around the HX adds across
the double bond.
The two possible mechanisms
In both possibilities, the pi bond breaks and the electron pair swings
down to form a bond with the hydrogen atom. At the same time, the
electrons in the H-X bond are repelled right down on to the X to give an
X- ion.
The difference lies in which way the electron pair in the pi bond swings.
First possibility
The electron pair moves to form a bond between the hydrogen and the
left-hand carbon.
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electrophilic addition to unsymmetrical alkenes

When the second stage of the mechanism happens, and the lone pair on
X- forms a bond with the positive carbon atom, the product of this
mechanism is not the one which Markovnikov's Rule predicts.
Second possibility
The electron pair moves to form a bond between the hydrogen and the
right-hand carbon.

This time, the overall mechanism leads to the correct product.


Why does one of these work better than the other?
That's the truth of the situation! One of these mechanisms works better
than the other one. The second mechanism works much faster than the
first, and so most of the product that you get is CH3-CHX-CH3.
There will be small amounts of CH3-CH2-CH2X despite what
Markovnikov says!
The difference between the two mechanisms lies in the intermediates the things formed at the half-way stage.
In the mechanism that works best, you get a secondary carbocation
formed as one of the intermediate ions.

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electrophilic addition to unsymmetrical alkenes

In the slow mechanism which produces hardly any product, you get a
primary carbocation formed instead.

It is much easier to form the secondary carbocation because it is more


energetically stable. The activation energy for the reaction will be less,
and so most of the reaction happens via that mechanism.

Activation energy: The minimum energy needed before a


reaction will occur. In this case it is the energy needed to
break the various bonds and make the carbocation and the Xion.

How to attack this sort of question in an exam


Suppose you were asked for the mechanism for the addition of HX to
some alkene you hadn't come across before.
First, you need to decide whether the alkene is symmetrical or not. If it is
symmetrical, there's no problem - it wouldn't matter which way around
you added the HX. If it is unsymmetrical, you need to decide which way
round the HX is going to add.
For example, supposed you were asked for the mechanism for the
addition of HX to but-1-ene, CH3-CH2-CH=CH2.
First, use Markovnikov's Rule to decide which carbon to attach the
hydrogen to. In this case, the hydrogen would get attached to the CH2
end of the double bond, because that carbon has more hydrogens than
the CH end.

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electrophilic addition to unsymmetrical alkenes

Warning! Markovnikov's Rule is only to help you decide.


Don't give the examiners any hint that you are using it unless they specifically ask.

Now write the mechanism, taking care to draw the curly arrow showing
the movement of the pi bond so that the hydrogen gets attached to that
particular CH2 carbon.

If you are asked why the HX adds this way round, look at the carbocation
formed as an intermediate and decide whether it is secondary or tertiary.
Here it is a secondary ion. Then think about what sort of ion would be
formed if the HX added the other way around. In this case that would be
a primary ion.

Then say something like:


"The secondary carbocation formed in this reaction is more energetically
stable than the primary one which would be formed if the addition was
the other way round, and so less activation energy is needed."

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electrophilic addition to unsymmetrical alkenes

Important! If there were bits of this that you found you


couldn't understand, you are probably trying to do too much
too quickly.
Follow the links to carbocations (carbonium ions) and
electrophilic addition to simple alkenes, get the basics sorted
out properly, and then try again.

Where would you like to go now?


To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic substitution - the halogenation of benzene

THE HALOGENATION OF BENZENE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic substitution reaction between benzene and chlorine or
bromine in the presence of a catalyst such as aluminium chloride or iron.
If you want this mechanism explained to you in detail, there is a link at
the bottom of the page.

The electrophilic substitution reaction between benzene


and chlorine or bromine
The facts
Benzene reacts with chlorine or bromine in an electrophilic substitution
reaction, but only in the presence of a catalyst. The catalyst is either
aluminium chloride (or aluminium bromide if you are reacting benzene
with bromine) or iron.
Strictly speaking iron isn't a catalyst, because it gets permanently
changed during the reaction. It reacts with some of the chlorine or
bromine to form iron(III) chloride, FeCl3, or iron(III) bromide, FeBr3.

These compounds act as the catalyst and behave exactly like aluminium
chloride in these reactions.
The reaction with chlorine
The reaction between benzene and chlorine in the presence of either
aluminium chloride or iron gives chlorobenzene.

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electrophilic substitution - the halogenation of benzene

or:

The reaction with bromine


The reaction between benzene and bromine in the presence of either
aluminium bromide or iron gives bromobenzene. Iron is usually used
because it is cheaper and more readily available.

or:

The formation of the electrophile


We are going to explore the reaction using chlorine and aluminium
chloride. If you want one of the other combinations, all you have to do is
to replace each Cl by Br, or each Al by Fe.
As a chlorine molecule approaches the benzene ring, the delocalised
electrons in the ring repel electrons in the chlorine-chlorine bond.

It is the slightly positive end of the chlorine molecule which acts as the
electrophile. The presence of the aluminium chloride helps this
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electrophilic substitution - the halogenation of benzene

polarisation.
The electrophilic substitution mechanism
Stage one

Stage two

The hydrogen is removed by the AlCl4- ion which was formed in the first
stage. The aluminium chloride catalyst is re-generated in this second
stage.

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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electrophilic substitution - the halogenation of benzene

Jim Clark 2000

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Explaining the halogenation of benzene - electrophilic substitution

EXPLAINING THE HALOGENATION OF BENZENE

This page guides you through the mechanism for the electrophilic
substitution reaction between benzene and chlorine in the presence of an
aluminium chloride or an iron catalyst.
The reaction involving bromine is exactly the same, except that iron
would be the preferred catalyst. Aluminium bromide could be used as an
alternative.
In what follows, if you want one of the other combinations, all you have to
do is to replace each Cl by Br, or each Al by Fe.

Note: The reason that iron functions in the same way as the
aluminium compounds is explained in the "facts" section of
the introductory page on halogenation of benzene. If you've
forgotten, you might like to look back at that before you go on.

The electrophilic substitution reaction between benzene


and chlorine
The formation of the electrophile
Many of the electrophilic substitution reactions of benzene involve an
attack on the benzene by a positive ion. In the chlorine case, forming a Cl
+ ion needs too much energy.
As the chlorine molecule approaches a benzene ring, the delocalised
electrons in the ring repel the electrons in the chlorine-chlorine bond.
That induces a dipole in the chlorine.

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Explaining the halogenation of benzene - electrophilic substitution

Note: If you aren't happy about the structure of benzene,


you could follow this link.
The formation of the induced dipole is much the same as
happens in the addition of bromine to ethene. If you aren't
sure about induced dipoles, you might like to have a look at
the beginning of that page.

Also nearby is the aluminium chloride, and this encourages the


polarisation of the chlorine. The aluminium chloride is an electron
deficient molecule, with the aluminium only having 3 pairs of electrons in
its bonding level. The aluminium is strongly attracted to the slightly
negative end of the chlorine molecule, and pulls electrons even more
towards that end.
The electrophilic substitution mechanism
Stage one
Two electrons from the delocalised system are used to form a new bond
with the slightly positive chlorine atom. Because those two electrons
aren't a part of the delocalised system any longer, the delocalisation is
partly broken, and in the process the ring gains a positive charge.

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Explaining the halogenation of benzene - electrophilic substitution

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom. We need to show it there because it has to be
removed in the second stage.
Notice that the chlorine-chlorine bond breaks, transferring a chloride ion
to the AlCl3 to make an AlCl4- ion.
Stage two
The second stage involves that AlCl4-.

One of the aluminium-chlorine bonds breaks and both electrons from it


are used to join to the hydrogen. Removing the hydrogen from the ring
forms the HCl which is also produced in the reaction, and the aluminium
chloride catalyst is re-generated. The electrons which originally joined
the hydrogen to the ring are now used to re-establish the delocalised
system.

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .
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Explaining the halogenation of benzene - electrophilic substitution

Jim Clark 2000

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Explaining electrophilic addition involving bromine and symmetrical alkenes

EXPLAINING THE REACTION BETWEEN


SYMMETRICAL ALKENES AND BROMINE

This page guides you through the mechanism for the electrophilic
addition of bromine to symmetrical alkenes like ethene or cyclohexene.
Unsymmetrical alkenes are covered separately, and you will find a link at
the bottom of the page.

The electrophilic addition of bromine to ethene


The structure of ethene
The structure of ethene is shown in the
diagram on the right. The pi bond is an
orbital above and below the plane of the rest
of the molecule, and relatively exposed to
things around it.

Note: If you aren't sure about this, then you should read the
page What is electrophilic addition? before you go on.
Use the BACK button on your browser to return to this page.

Bromine as an electrophile
Since two identical bromine atoms are joined together in the bromine
molecule there is no reason why one atom should pull the bonding pair of
electrons towards itself - they must be equally electronegative and so
there won't be any separation of charge, + or -. How, then, can
bromine be an electrophile?

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Explaining electrophilic addition involving bromine and symmetrical alkenes

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you read on.
Equally, if you aren't sure about terms like electrophile, then it
really would be a good idea to read the page What is
electrophilic addition? before you go on.
Use the BACK button on your browser to return to this page.

In fact, bromine is a very polarisable molecule - in other words, the


electrons in the bond are very easily pushed to one end or the other. As
the bromine molecule approaches the ethene, the electrons in the pi
bond tend to repel the electrons in the bromine-bromine bond, leaving
the nearer bromine slightly positive and the further one slightly negative.

The bromine molecule therefore acquires an induced dipole which is


automatically lined up the right way round for a successful attack on the
ethene.

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Explaining electrophilic addition involving bromine and symmetrical alkenes

Help! What is an "induced dipole"? A dipole is simply a


separation of charge between + at one end and - at the
other. "Induced" means that it has been created by some
external influence (in this case the approach of the pi bond),
and didn't already exist.
Where it does already exist - as, for example, in HBr - it is
called a permanent dipole.

The simplified version of the mechanism

Note: Use this version unless your examiners insist on the


more accurate one.
If you've come into this web site from a search engine directly
to this page, read the notes on the introductory page to this
reaction before you go any further.

The electrons from the pi bond move down towards the slightly positive
bromine atom.

In the process, the electrons in the Br-Br bond are repelled down until
they are entirely on the bottom bromine atom, producing a bromide ion.

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Explaining electrophilic addition involving bromine and symmetrical alkenes

Help! If you aren't sure about the use of curly arrows in


mechanisms, you must follow this link before you go on.
Use the BACK button on your browser to return to this page.

The ion with a positive charge on the carbon atom is called a


carbocation or carbonium ion.
Why is there a positive charge on the carbon atom? The pi bond was
originally made up of an electron from each of the carbon atoms. Both of
those electrons have been used to make a new bond to the bromine.
That leaves the right-hand carbon an electron short - hence positively
charged.
In the second stage of the mechanism, the lone pair of electrons on the
bromide ion is strongly attracted to the positive carbon and moves
towards it until a bond is formed.

The overall mechanism is therefore

The more accurate version of the mechanism

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Explaining electrophilic addition involving bromine and symmetrical alkenes

Note: Don't learn this unless you have to. There is a real risk
of getting confused. If your examiners are happy to accept
the simple version, there's no point in making life difficult for
yourself.

The reaction starts off just the same as in the simplified version, with the
pi bond electrons moving down towards the slightly positive bromine
atom.
But this time, the top bromine atom becomes attached to both carbon
atoms, with the positive charge being found on the bromine rather than
on one of the carbons. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction. It can't be attacked by its original bromide
ion because the bromonium ion is completely cluttered up with a positive
bromine on that side.

It doesn't matter which of the carbon atoms the bromide ion attacks - the
end result would be just the same.

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Explaining electrophilic addition involving bromine and symmetrical alkenes

Note: You can't really draw this mechanism tidily in one line
because the bromide ion has to be in a different place at the
beginning of the second stage than it was at the end of the
first stage.

The electrophilic addition of bromine to cyclohexene


The simplified version of the mechanism

Note: Use this version unless your examiners insist on the


more accurate one.

The electrons from the pi bond move towards the slightly positive
bromine atom.

In the process, the electrons in the bromine-bromine bond are repelled


until they are entirely on the right-hand bromine atom, producing a
bromide ion.
Exactly as with ethene, a carbocation is formed. The bottom carbon atom
lost one of its electrons when the pi bond swung towards the bromine.
In the second stage of the mechanism, the lone pair of electrons on the
bromide ion is strongly attracted to the positive carbon and moves
towards it until a bond is formed.

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Explaining electrophilic addition involving bromine and symmetrical alkenes

The overall mechanism is therefore

The alternative version of the mechanism

Note: Don't learn this unless your examiners insist on it.


Keep life simple!

The reaction starts off just the same as in the simplified version, with the
pi bond electrons moving towards the slightly positive bromine atom.
But this time, the left-hand bromine atom becomes attached to both
carbon atoms, with the positive charge being found on the bromine rather
than on one of the carbons. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction. It can't be attacked by its original bromide
ion because approach from that side is hindered by the positive bromine
atom.

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Explaining electrophilic addition involving bromine and symmetrical alkenes

It doesn't matter which of the carbon atoms on either end of the original
double bond the bromide ion attacks - the end result would be just the
same.

Note: Once again, you can't really draw this mechanism


tidily in one line because of the need to move the bromide ion.

Where would you like to go now?


Look at the same reactions involving unsymmetrical
alkenes . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic addition - symmetrical alkenes and bromine

THE REACTION BETWEEN SYMMETRICAL


ALKENES AND BROMINE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between bromine (and the other
halogens) and alkenes like ethene and cyclohexene. If you want the
mechanisms explained to you in detail, there is a link at the bottom of the
page.

The electrophilic addition of bromine to ethene


The facts
Alkenes react in the cold with pure liquid bromine, or with a solution of
bromine in an organic solvent like tetrachloromethane. The double bond
breaks, and a bromine atom becomes attached to each carbon. The
bromine loses its original red-brown colour to give a colourless liquid. In
the case of the reaction with ethene, 1,2-dibromoethane is formed.

This decolourisation of bromine is often used as a test for a carboncarbon double bond. If an aqueous solution of bromine is used ("bromine
water"), you get a mixture of products. The presence of the water
complicates the mechanism beyond what is required by current A'level
syllabuses.
The other halogens, apart from fluorine, behave similarly. (Fluorine
reacts explosively with all hydrocarbons - including alkenes - to give
carbon and hydrogen fluoride.)
If you are interested in the reaction with, say, chlorine, all you have to do
is to replace Br by Cl in all the equations on this page.

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electrophilic addition - symmetrical alkenes and bromine

The mechanism for the reaction between ethene and bromine


The reaction is an example of electrophilic addition.

Warning! There are two versions of the ethene / bromine


mechanism in common use, and you must know which your
examiners will accept.
One version is simplified to bring it into line with the other
alkene electrophilic addition mechanisms. You will probably
find that your examiners will accept this one, but you must
find out to be sure.
You almost certainly won't be able to tell this from your
syllabus. You need to refer to recent mark schemes, or to
any support material that your Exam Board provides. If you
still aren't sure, contact your Exam Board direct. You can find
out how to do this by using the link to your Board's web site
on the syllabuses page.
The person you need to contact will probably have the title
Subject Officer for Chemistry or something similar. Ask
whether they want the mechanism for the reaction between
bromine and alkenes which proceeds via a carbocation or via
a bromonium ion intermediate.

Bromine as an electrophile
The bromine is a very "polarisable" molecule and the approaching pi
bond in the ethene induces a dipole in the bromine molecule. If you draw
this mechanism in an exam, write the words "induced dipole" next to the
bromine molecule - to show that you understand what's going on.
The simplified version of the mechanism

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electrophilic addition - symmetrical alkenes and bromine

Note: Use this version unless your examiners insist on the


more accurate one.

The more accurate version of the mechanism

Note: Don't learn this unless you have to. There is a real risk
of getting confused. If your examiners are happy to accept
the simple version, there's no point in making life difficult for
yourself.

In the first stage of the reaction, one of the bromine atoms becomes
attached to both carbon atoms, with the positive charge being found on
the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction.

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electrophilic addition - symmetrical alkenes and bromine

The electrophilic addition of bromine to cyclohexene


The facts
Cyclohexene reacts with bromine in the same way and under the same
conditions as any other alkene. 1,2-dibromocyclohexane is formed.

The mechanism for the reaction between cyclohexene and bromine


The reaction is an example of electrophilic addition.

Warning! Again, there are two versions of this mechanism in


common use, and you must know which your examiners will
accept.

Bromine as an electrophile
Again, the bromine is polarised by the approaching pi bond in the
cyclohexene. Don't forget to write the words "induced dipole" next to the
bromine molecule.
The simplified version of the mechanism

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electrophilic addition - symmetrical alkenes and bromine

Note: Use this version unless your examiners insist on the


more accurate one.

The alternative version of the mechanism

Note: Don't learn this unless you have to. If your examiners
are happy to accept the simple version, there's no point in
making life difficult for yourself.

In the first stage of the reaction, one of the bromine atoms becomes
attached to both carbon atoms, with the positive charge being found on
the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction.

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electrophilic addition - symmetrical alkenes and bromine

Where would you like to go now?


Help! Talk me through these mechanisms . . .
Look at the same reactions involving unsymmetrical
alkenes . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic addition - unsymmetrical alkenes and bromine

THE REACTION BETWEEN UNSYMMETRICAL


ALKENES AND BROMINE

Important! This page assumes that you have already read


the page on the addition of bromine to symmetrical alkenes. If
you haven't, you must read it before you go on. It contains
important advice that you will need to make best use of this
page.

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between bromine and alkenes like
propene. If you want the mechanism explained to you in detail, there is a
link at the bottom of the page.
An unsymmetrical alkene is one like propene in which the groups or
atoms attached to either end of the carbon-carbon double bond are
different.
For example, in propene there are a hydrogen and a methyl group at one
end, but two hydrogen atoms at the other end of the double bond. But-1ene is another unsymmetrical alkene.

The electrophilic addition of bromine to propene


The facts
In common with all other alkenes, propene reacts in the cold with pure
liquid bromine, or with a solution of bromine in an organic solvent like
tetrachloromethane. The double bond breaks, and a bromine atom
becomes attached to each carbon. The bromine loses its original redhttp://www.chemguide.co.uk/mechanisms/eladd/unsymbr2.html (1 of 4)30/12/2004 11:04:08

electrophilic addition - unsymmetrical alkenes and bromine

brown colour to give a colourless liquid. In the case of the reaction with
propene, 1,2-dibromopropane is formed.

The other halogens, apart from fluorine, behave similarly. (Fluorine


reacts explosively with all hydrocarbons - including alkenes - to give
carbon and hydrogen fluoride.)
If you are interested in the reaction with, say, chlorine, all you have to do
is to replace Br by Cl in all the equations on this page.
The mechanism for the reaction between propene and bromine
The reaction is an example of electrophilic addition.

Warning! Just as with symmetrical alkenes, there are two


versions of the propene / bromine mechanism in common
use, and you must know which your examiners will accept.
How you can find out which one your examiners expect is
explained on the page on the addition of bromine to
symmetrical alkenes.

Bromine as an electrophile
The bromine is a very "polarisable" molecule and the approaching pi
bond in the propene induces a dipole in the bromine molecule. If you
draw this mechanism in an exam, write the words "induced dipole" next
to the bromine molecule.
The simplified version of the mechanism

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electrophilic addition - unsymmetrical alkenes and bromine

Note: Use this version unless your examiners insist on the


more accurate one.

The more accurate version of the mechanism

Note: Don't learn this unless your examiners insist on it.


There's no point in making life difficult for yourself.

In the first stage of the reaction, one of the bromine atoms becomes
attached to both carbon atoms, with the positive charge being found on
the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction.

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electrophilic addition - unsymmetrical alkenes and bromine

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/eladd/unsymbr2.html (4 of 4)30/12/2004 11:04:08

Explaining electrophilic addition involving bromine and unsymmetrical alkenes

EXPLAINING THE REACTION BETWEEN


UNSYMMETRICAL ALKENES AND BROMINE

This page guides you through the mechanism for the electrophilic
addition of bromine to unsymmetrical alkenes like propene.

Important! You will find it easier to make sense of this page


if you first read about the electrophilic addition reactions
between bromine and symmetrical alkenes like ethene, and
addition to unsymmetrical alkenes in general. You may want
to follow other links from those pages as well before you
come back here again.

The electrophilic addition of bromine to propene


The attraction between the propene and the bromine
The double bond in all alkenes is made up of two different parts. One pair
of electrons lies on the line between the two nuclei where you would
expect them to be. This is called a sigma bond.
The other pair lies in an orbital above and below the plane of the rest of
the molecule, and is called a pi bond. The pi bond is weaker than a
sigma bond and is very vulnerable to attack.

Note: If this isn't fairly obvious to you, you really should


follow the links at the top of the page before you go on - and
perhaps explore other simpler reactions from the electrophilic
addition menu as well.

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Explaining electrophilic addition involving bromine and unsymmetrical alkenes

As the bromine molecule approaches the pi bond, the electrons in that


bond repel the electrons in the bromine-bromine bond down towards the
bottom bromine. That produces an induced dipole in the bromine
molecule.

Help! What is an "induced dipole"? A dipole is simply a


separation of charge between + at one end and - at the
other. "Induced" means that it has been created by some
external influence (in this case the approach of the pi bond),
and didn't already exist.
Where it does already exist - as, for example, in HBr - it is
called a permanent dipole.

The simplified version of the mechanism

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Explaining electrophilic addition involving bromine and unsymmetrical alkenes

Note: Use this version unless your examiners insist on the


more accurate one.
If you've come into this web site from a search engine directly
to this page, read the notes on the addition of bromine to
ethene before you go any further.
Use the BACK button on your browser to return to this page.

The electrons from the pi bond move down towards the slightly positive
bromine atom.

In the process, the electrons in the Br-Br bond are repelled down until
they are entirely on the bottom bromine atom, producing a bromide ion.
Notice the way that the pi bond electrons have moved. By swinging so
that the bromine is attached to the right-hand carbon, a secondary
carbocation has been formed. That is more stable than the primary one
which would have been formed if the pi electrons had swung the other
way.

Note: If this doesn't make sense to you, read about


carbocations (previously called carbonium ions) and addition
to unsymmetrical alkenes in general.

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Explaining electrophilic addition involving bromine and unsymmetrical alkenes

In the second stage of the mechanism, the lone pair of electrons on the
bromide ion is strongly attracted to the positive carbon and moves
towards it until a bond is formed.

The overall mechanism is therefore

The more accurate version of the mechanism

Note: Don't learn this unless you have to. There is a real risk
of getting confused. If your examiners are happy to accept
the simple version, there's no point in making life difficult for
yourself.

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Explaining electrophilic addition involving bromine and unsymmetrical alkenes

The reaction starts off just the same as in the simplified version, with the
pi bond electrons moving down towards the slightly positive bromine
atom.
But this time, the top bromine atom becomes attached to both carbon
atoms, with the positive charge being found on the bromine rather than
on one of the carbons. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion
formed in a nearby reaction. It can't be attacked by its original bromide
ion because the bromonium ion is completely cluttered up with a positive
bromine on that side.

It doesn't matter which of the carbon atoms which were originally part of
the double bond the bromide ion attacks - the end result would be just
the same.

Note: You can't really draw this mechanism tidily in one line
because the bromide ion has to be in a different place at the
beginning of the second stage than it was at the end of the
first stage.

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Explaining electrophilic addition involving bromine and unsymmetrical alkenes

Where would you like to go now?


To menu of electrophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/eladd/unsymbr2tt.html (6 of 6)30/12/2004 11:04:10

electrophilic substitution - the sulphonation of benzene

THE SULPHONATION OF BENZENE

This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic substitution reaction between benzene and sulphuric
acid (or sulphur trioxide). If you want this mechanism explained to you in
detail, there is a link at the bottom of the page.

The electrophilic substitution reaction between benzene


and sulphuric acid
The facts
There are two equivalent ways of sulphonating benzene:

Heat benzene under reflux with concentrated sulphuric acid for


several hours.
Warm benzene under reflux at 40C with fuming sulphuric acid for
20 to 30 minutes.

Or:

The product is benzenesulphonic acid.


The electrophile is actually sulphur trioxide, SO3, and you may find the
equation for the sulphonation reaction written:

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electrophilic substitution - the sulphonation of benzene

Note: Which version of this equation you use will depend on


what question you are being asked. If the question refers to
the reaction with sulphuric acid, then you must use that one.
If the question refers to SO3 as the electrophile, then you
could use this one.

The formation of the electrophile


The sulphur trioxide electrophile arises in one of two ways depending on
which sort of acid you are using.
Concentrated sulphuric acid contains traces of SO3 due to slight
dissociation of the acid.

Fuming sulphuric acid, H2S2O7, can be thought of as a solution of SO3 in


sulphuric acid - and so is a much richer source of the SO3.
Sulphur trioxide is an electrophile because it is a highly polar molecule
with a fair amount of positive charge on the sulphur atom. It is this which
is attracted to the ring electrons.
The electrophilic substitution mechanism
Stage one

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electrophilic substitution - the sulphonation of benzene

Stage two

The second stage of the reaction involves a transfer of the hydrogen


from the ring to the negative oxygen.

Where would you like to go now?


Help! Talk me through this mechanism . . .
To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000 (updated 2004)

http://www.chemguide.co.uk/mechanisms/elsub/sulphonation.html (3 of 3)30/12/2004 11:04:21

Explaining the sulphonation of benzene - electrophilic substitution

EXPLAINING THE SULPHONATION OF BENZENE

This page guides you through the mechanism for the electrophilic
substitution reaction between benzene and sulphuric acid (or sulphur
trioxide)

The electrophilic substitution reaction between benzene


and sulphuric acid
The formation of the electrophile
The electrophile is sulphur trioxide, and this arises in one of two ways
depending on which sort of acid you are using.
Concentrated sulphuric acid contains traces of SO3 due to slight
dissociation of the acid.

Dissociation: This is a reversible splitting up of a


compound. In this case, the sulphuric acid splits into water
and SO3, and at the same time these combine back together
again to make sulphuric acid. The overall effect is that
concentrated sulphuric acid contains small amounts of SO3.

Fuming sulphuric acid, H2S2O7, can be thought of as a solution of SO3


in sulphuric acid - and so is a much richer source of the SO3.

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Explaining the sulphonation of benzene - electrophilic substitution

Note: You could think of the formula as being essentially


H2SO4.SO3.

Although sulphur trioxide isn't ionic, it is highly polar.


The three oxygens are more electronegative than
the sulphur and so draw electrons towards
themselves. That leaves the sulphur atom fairly
positively charged. It is this + sulphur atom which
attacks the benzene ring.

Note: If you aren't sure about electronegativity and polar


bonds you might like to follow this link.
Use the BACK button on your browser to return to this page.

The electrophilic substitution mechanism


Stage one
Two electrons from the delocalised system are used to form a new bond
with the slightly positive sulphur atom. Because those two electrons
aren't a part of the delocalised system any longer, the delocalisation is
partly broken, and in the process the ring gains a positive charge.
To make room for the new bond between the ring and the sulphur, two of
the electrons joining the sulphur to one of the oxygens are forced right
out on to the oxygen atom, giving it a negative charge.

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Explaining the sulphonation of benzene - electrophilic substitution

The hydrogen shown on the ring is the one which was already attached
to that top carbon atom. We need to show it there because it has to be
removed in the second stage.

Note: If you aren't sure about the use of curly arrows follow
this link before you go on.
Use the BACK button on your browser to return to this page.

Stage two
This second step is different from all the other benzene electrophilic
substitution reactions you might have already looked at on this site.
This time there isn't a separate negative ion to remove the hydrogen
atom from the ring. Instead it is removed by a lone pair on the negative
oxygen atom.

The lone pair forms a bond with the hydrogen atom, releasing the
electrons in the hydrogen-to-ring bond so that they can re-establish the
delocalisation.
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Explaining the sulphonation of benzene - electrophilic substitution

This particular mechanism needs to be drawn with rather more thought


than the other electrophilic substitution mechanisms. In particular, you
have to make sure that you put the negative charge on the right oxygen
in the intermediate ion. It must be the one which is closest to the
hydrogen you intend to take off the ring, otherwise there is no way of
drawing sensible curly arrows in the second stage!

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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electrophilic substitution in methylbenzene and nitrobenzene

ELECTROPHILIC SUBSTITUTION INTO


ALREADY SUBSTITUTED BENZENE RINGS

This page discusses the problems which arise if you try to write the
mechanism for an electrophilic substitution reaction into a benzene ring
which already has something else attached to it.
There are two problems you might come across:

Whereabouts in the ring does the substitution happen? Does this


make a difference to how you draw the mechanisms?
Can the group already attached to the ring get involved in any
way?

Important! This page assumes that you can already write


the mechanisms for substitution into a simple benzene ring. If
you can't, go back to the electrophilic substitution menu and
read about the reactions you are interested in before you
tackle this page.

Electrophilic substitution in methylbenzene


The nitration of methylbenzene
If you substitute a nitro group, -NO2, into the benzene ring in
methylbenzene, you could possibly get any of the following products:

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electrophilic substitution in methylbenzene and nitrobenzene

The carbon with the methyl group attached is thought of as the number 1
carbon, and the ring is then numbered around from 1 to 6. You number in
a direction (in this case, clockwise) which produces the smaller number
in the name - hence 2-nitromethylbenzene rather than 6nitromethylbenzene.
In the case of methylbenzene, whatever you attach to the ring, you
always get a mixture consisting mainly of the 2- and 4- isomers. The
methyl group is said to be 2,4-directing, in the sense that it seems to
"push" incoming groups into those positions.

Isomers: Molecules which have the same molecular formula


(i.e. contain exactly the same number and type of atoms), but
with a different spatial arrangement of those atoms.

Some other groups which might already be on the ring (for example, the NO2 group in nitrobenzene) "push" incoming groups into the 3- position.
We'll have a quick look at this later on this page.
What to expect in exams
At A' level, you will not be expected to explain why different groups have
different directing effects.
It is possible, however, that you may be expected to remember the
directing effect of one or two groups. It is very difficult to tell this from the
syllabuses, most of which don't specifically exclude the possibility - but
that could simply be an oversight. Your best option is to check past exam
papers, or any support material published by your Exam Board. If in
doubt, contact them and find out exactly what they expect.
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electrophilic substitution in methylbenzene and nitrobenzene

Note: You will find links to help you to contact your Exam
Board on the syllabuses page.

In an exam, then, you may have to remember the directing effect of a


particular group, or more likely you will be told it. Your problem may then
be to write the mechanism.
How to write the mechanism for the nitration of methylbenzene

Important! This assumes that you are already familiar with


the nitration of benzene. If you aren't, read about it before
you go any further.

Reacting methylbenzene with a mixture of concentrated nitric and


sulphuric acids gives both 2-nitromethylbenzene and 4nitromethylbenzene. The mechanism is exactly the same as the nitration
of benzene. You just have to be careful about the way that you draw the
structure of the intermediate ion.
Making 2-nitromethylbenzene (the first step)

This just shows the first step of the electrophilic substitution reaction.
Notice that the partial delocalisation in the intermediate ion covers all the
carbon atoms in the ring except for the one that the -NO2 group gets
attached to.
That is the only point of interest in this example - everything else is just
the same as with the nitration of benzene. The hydrogen atom is then

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electrophilic substitution in methylbenzene and nitrobenzene

removed by an HSO4- ion - exactly as in the benzene case.


Making 4-nitromethylbenzene (the first step)

Once again, the only point of interest is in the way the partial
delocalisation in the intermediate ion is drawn - again, it covers all the
carbon atoms in the ring apart from the one with the -NO2 group attached.
The electrophilic substitution reaction between methylbenzene and
chlorine
This is a good example of a case where what is already attached to the
ring can also get involved in the reaction.
It is possible to get two quite different substitution reactions between
methylbenzene and chlorine depending on the conditions used. The
chlorine can substitute into the ring or into the methyl group.
Here we are only interested in substitution into the ring. This happens in
the presence of aluminium chloride or iron, and in the absence of UV
light.

Note: If you are also interested in substitution into the methyl


group (in the presence of UV light - and with no catalyst
present), you will find this explained in the page on the free
radical reaction between methylbenzene and chlorine.

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electrophilic substitution in methylbenzene and nitrobenzene

Substituting into the ring gives a mixture of 2-chloromethylbenzene and 4chloromethylbenzene.

The mechanisms are exactly the same as the substitution of chlorine into
benzene - although you would have to be careful about the way you draw
the intermediate ion.

Important! This assumes that you are already familiar with


the chlorination of benzene. If you aren't, read about it before
you go any further.

For example, the complete mechanism for substitution into the 4position is:
Stage one

Stage two

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electrophilic substitution in methylbenzene and nitrobenzene

Electrophilic substitution in nitrobenzene


Substitution into the 3- position (the first step)
Methyl groups direct new groups into the 2- and 4- positions, but a nitro
group, -NO2, already on the ring directs incoming groups into the 3position.
For example, if the temperature is raised above 50C, the nitation of
benzene doesn't just produce nitrobenzene - it also produces some 1,3dinitrobenzene. A second nitro group is substituted into the ring in the 3position.

The mechanism is exactly the same as the nitration of benzene or of


methylbenzene - you just have to be careful in drawing the intermediate
ion. Draw the partial delocalisation to include all the carbons except for
the one the new -NO2 group gets attached to.

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electrophilic substitution in methylbenzene and nitrobenzene

In the second stage, the hydrogen atom is then removed by an HSO4ion - exactly as in the benzene case. This isn't shown because there's
nothing new.

Where would you like to go now?


To menu of electrophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elsub/toluene.html (7 of 7)30/12/2004 11:04:30

free radical substitution in the methylbenzene and chlorine reaction

THE REACTION BETWEEN METHYLBENZENE


AND CHLORINE

A Free Radical Substitution Reaction


This page gives you the facts and a simple, uncluttered
mechanism for the free radical substitution reaction
between methylbenzene (previously known as toluene)
and chlorine. If you want the mechanism explained to you
in detail, there is a link at the bottom of the page.
Methylbenzene has a methyl group attached to a benzene ring. The
hexagon with the circle inside is the standard symbol for this ring. There
is a carbon atom at each corner of the hexagon, and a hydrogen atom on
each carbon apart from the one with the methyl group attached.

Note: There is no need to worry about the bonding in the


benzene ring at this point. If you are interested, you can
follow the link - but it isn't important for now.

The facts
The reaction we are going to explore happens between methylbenzene
and chlorine in the presence of ultraviolet light - typically sunlight. This is
a good example of a photochemical reaction - a reaction brought about
by light.

Note: These reactions are sometimes described as


examples of photocatalysis - reactions catalysed by light. It
is better to use the term "photochemical" and keep the keep
the word "catalysis" for reactions speeded up by actual
substances rather than light.

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free radical substitution in the methylbenzene and chlorine reaction

The organic product is (chloromethyl)benzene. The brackets in the name


emphasise that the chlorine is part of the attached methyl group, and isn't
on the ring.
One of the hydrogen atoms in the methyl group has been replaced by a
chlorine atom, so this is a substitution reaction. However, the reaction
doesn't stop there, and all three hydrogens in the methyl group can in
turn be replaced by chlorine atoms. Multiple substitution is dealt with on a
separate page, and you will find a link to that at the bottom of this page.

Important! There is another reaction which happens


between methylbenzene and chlorine in the absence of light
and in the presence of a number of possible catalysts. In that
one, substitution happens in the benzene ring instead of in
the methyl group. You will find this reaction discussed under
electrophilic substitution reactions.

The mechanism
The mechanism involves a chain reaction. During a chain reaction, for
every reactive species you start off with, a new one is generated at the
end - and this keeps the process going.

Species: a useful word which is used in chemistry to mean


any sort of particle you want it to mean. It covers molecules,
ions, atoms, or (in this case) free radicals.

The over-all process is known as free radical substitution, or as a free


radical chain reaction.

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free radical substitution in the methylbenzene and chlorine reaction

Note: If you aren't sure about the words free radical or


substitution, read the page What is free radical substitution?
Use the BACK button on your browser to return quickly to this
page.

Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2

2Cl

Chain propagation reactions


These are the reactions which keep the chain going.

Chain termination reactions


These are reactions which remove free radicals from the system without
replacing them by new ones. If any two free radicals collide, they will join
together without producing any new radicals.
The simplest example of this is a collision between two chlorine radicals.
2Cl

Cl2

Where would you like to go now?

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free radical substitution in the methylbenzene and chlorine reaction

Help! Talk me through this mechanism . . .


Look at multiple substitution in this reaction . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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Explaining the methylbenzene - chlorine free radical substitution mechanism

EXPLAINING THE REACTION BETWEEN


METHYLBENZENE AND CHLORINE

A Free Radical Substitution Reaction


This page guides you through the mechanism for the substitution of one
of the hydrogen atoms in methylbenzene by one chlorine atom. Multiple
substitution is covered separately, and you will find a link at the bottom of
the page.
We are going to talk through this mechanism in a very detailed way so
that you get a feel for what is going on. You couldn't possibly do the
same thing in an exam. At the bottom of the page, you will find the
condensed down version corresponding to the sort of answer you would
produce in an exam.
The role of the UV light
The ultraviolet light is simply a source of energy, and is being used to
break bonds. In fact, the energies in UV are exactly right to break the
bonds in chlorine molecules to produce chlorine atoms.

Note: Only the outer electrons of the chlorine are shown.


Notice also that it is quite acceptable to use a simple view of
atomic structure. There is no point in using a complicated
model of the atom if a simple one will do the job.

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Explaining the methylbenzene - chlorine free radical substitution mechanism

Because we want to stress the fact that the chlorine atoms have single
unpaired electrons, then we call them chlorine free radicals - or more
usually just chlorine radicals.
To show that a species (either an atom or a group of atoms) is a free
radical, the symbol is written with a dot attached to show the unpaired
electron. The splitting of the chlorine molecule would be shown as:
Cl2

2Cl

Free radicals are formed if a bond splits evenly - each atom getting one
of the two electrons. The name given to this is homolytic fission.
What happens to the chlorine radicals?
Reactions happen because things hit each other. In this case, you need
to think about what the chlorine radicals are likely to hit, and what could
happen as a result of that collision.
At the moment the mixture contains

lots of methylbenzene molecules


lots of chlorine molecules (only a few will have been fractured by
the UV light)
a few chlorine radicals

Let's start with the unproductive collisions.


The least likely collision is between two chlorine radicals. There aren't
very many of them in the mixture and so the chances of them hitting
each other are relatively small. If they do collide, they will combine to
form a chlorine molecule. That's worse than useless because it removes
the active free radicals from the system.
2Cl

Cl2

A chlorine radical could also hit a chlorine molecule. If this happens there
could possibly be an exchange of chlorine atoms, but nothing new would
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Explaining the methylbenzene - chlorine free radical substitution mechanism

be formed. It is just a wasted collision.


Cl + Cl-Cl
Cl

Cl-Cl +

Note: There is no difference between the chlorine atoms


shown in bold type or ordinary type. They are shown
differently so that the exchange is made clear.

The productive collision happens if a chlorine radical hits a


methylbenzene molecule.

The chlorine radical removes a hydrogen atom from the methyl group.
That hydrogen atom only needs to bring one electron with it to form a
new bond to the chlorine, and so one electron is left behind on the
carbon atom. A new free radical is formed - called a phenylmethyl radical.

Note: Don't worry about the name of this new radical. All that
matters is that you can draw its structure.

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Explaining the methylbenzene - chlorine free radical substitution mechanism

What happens to the phenylmethyl radicals?


It depends what they collide with. There are three interesting collisions
which need to be explored. Two of these involve a set-back to the
reaction, and only one is useful.
Luckily, the two unhelpful collisions don't happen very often, because
they involve collisions between two free radicals - and there won't be
many of these present in the mixture at any one time.

A phenylmethyl radical hits a chlorine radical. These will combine


to make what you want - (chloromethyl)benzene - but the reaction
removes the active free radicals from the system. That stops any
further reactions happening.

Even worse, two phenylmethyl radicals could hit each other. Not
only does this remove radicals from the system, but produces an
unwanted side reaction.

So what is the useful collision? If a phenylmethyl radical hits a chlorine


molecule (something that's quite likely to occur), the following change
can happen:

The phenylmethyl radical takes one of the chlorine atoms to form


(chloromethyl)benzene (which is what we want to make), but in the
process generates another chlorine radical. This new chlorine radical can
now go through the whole sequence again, and at the end will produce
yet another chlorine radical - and so on and so on.
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Explaining the methylbenzene - chlorine free radical substitution mechanism

The process is described as a free radical chain reaction. The chain


continues because for every chlorine radical that goes in at the
beginning, a new one is generated at the end.
Chain termination
Does this mean that one tiny burst of UV light, splitting one chlorine
molecule into two free radicals, is enough to convert a whole reactionsworth of methylbenzene and chlorine into (chloromethyl)benzene and
HCl?
Sadly, no! As we've seen, there are collisions which result in the removal
of free radicals without producing any new ones. These radicals can only
be replaced by starting the process all over again with a new burst of
light energy. In practice, then, the chains propagate many thousands of
times, but eventually any chain will be brought to an end by one of these
chain termination processes.

Simplifying all this for exam purposes:


The over-all process is known as free radical substitution, or as a free
radical chain reaction.
Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2

2Cl

Chain propagation reactions


These are the reactions which keep the chain going.

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Explaining the methylbenzene - chlorine free radical substitution mechanism

Chain termination reactions


These are reactions which remove free radicals from the system without
replacing them by new ones. If any two free radicals collide, they will join
together without producing any new radicals.
2Cl

Cl2

Important! If you have found this mechanism difficult


because of the names and structures involved it would be
worth looking at the methane and chlorine reaction. The two
mechanisms are identical as far as the substitution is
concerned, but the methane / chlorine one looks easier!

Where would you like to go now?


Look at multiple substitution in this reaction . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .
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Explaining the methylbenzene - chlorine free radical substitution mechanism

Jim Clark 2000

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free radical substitution in the methane and chlorine reaction

THE REACTION BETWEEN METHANE AND


CHLORINE

A Free Radical Substitution Reaction


This page gives you the facts and a simple, uncluttered mechanism for
the free radical substitution reaction between methane and chlorine. If
you want the mechanism explained to you in detail, there is a link at the
bottom of the page.
The facts
If a mixture of methane and chlorine is exposed to a flame, it explodes producing carbon and hydrogen chloride. This isn't a very useful reaction!
The reaction we are going to explore is a more gentle one between
methane and chlorine in the presence of ultraviolet light - typically
sunlight. This is a good example of a photochemical reaction - a
reaction brought about by light.

Note: These reactions are sometimes described as


examples of photocatalysis - reactions catalysed by light. It
is better to use the term "photochemical" and keep the keep
the word "catalysis" for reactions speeded up by actual
substances rather than light.

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free radical substitution in the methane and chlorine reaction

CH4 + Cl2

CH3Cl + HCl

The organic product is chloromethane.


One of the hydrogen atoms in the methane has been replaced by a
chlorine atom, so this is a substitution reaction. However, the reaction
doesn't stop there, and all the hydrogens in the methane can in turn be
replaced by chlorine atoms. Multiple substitution is dealt with on a
separate page, and you will find a link to that at the bottom of this page.
The mechanism
The mechanism involves a chain reaction. During a chain reaction, for
every reactive species you start off with, a new one is generated at the
end - and this keeps the process going.

Species: a useful word which is used in chemistry to mean


any sort of particle you want it to mean. It covers molecules,
ions, atoms, or (in this case) free radicals.

The over-all process is known as free radical substitution, or as a free


radical chain reaction.

Note: If you aren't sure about the words free radical or


substitution, read the page What is free radical substitution?
Use the BACK button on your browser to return quickly to this
page.

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free radical substitution in the methane and chlorine reaction

Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2

2Cl

Chain propagation reactions


These are the reactions which keep the chain going.
CH4 + Cl
CH3

CH3

+ Cl2

+ HCl

CH3Cl + Cl

Chain termination reactions


These are reactions which remove free radicals from the system without
replacing them by new ones.
2Cl
CH3
Cl

Cl2
+

CH3 +
CH3

CH3Cl
CH3CH3

Where would you like to go now?


Help! Talk me through this mechanism . . .
Look at multiple substitution in this reaction . . .
Look at why side reactions happen in this reaction . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .

http://www.chemguide.co.uk/mechanisms/freerad/ch4andcl2.html (3 of 4)30/12/2004 11:04:40

free radical substitution in the methane and chlorine reaction

To Main Menu . . .

Jim Clark 2000

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Explaining the methane - chlorine free radical substitution mechanism

EXPLAINING THE REACTION BETWEEN


METHANE AND CHLORINE

A Free Radical Substitution Reaction


This page guides you through the mechanism for the substitution of one
of the hydrogen atoms in methane by one chlorine atom. Multiple
substitution is covered separately, and you will find a link at the bottom of
the page.
We are going to talk through this mechanism in a very detailed way so
that you get a feel for what is going on. You couldn't possibly do the
same thing in an exam. At the bottom of the page, you will find the
condensed down version corresponding to the sort of answer you would
produce in an exam.
The role of the UV light
The ultraviolet light is simply a source of energy, and is being used to
break bonds. In fact, the energies in UV are exactly right to break the
bonds in chlorine molecules to produce chlorine atoms.

Note: Only the outer electrons of the chlorine are shown.


Notice also that it is quite acceptable to use a simple view of
atomic structure. There is no point in using a complicated
model of the atom if a simple one will do the job.

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Explaining the methane - chlorine free radical substitution mechanism

Because we want to stress the fact that the chlorine atoms have single
unpaired electrons, then we call them chlorine free radicals - or more
usually just chlorine radicals.
To show that a species (either an atom or a group of atoms) is a free
radical, the symbol is written with a dot attached to show the unpaired
electron. The splitting of the chlorine molecule would be shown as:
Cl2

2Cl

Free radicals are formed if a bond splits evenly - each atom getting one
of the two electrons. The name given to this is homolytic fission.
What happens to the chlorine radicals?
There's nothing magic about reaction mechanisms. Reactions happen
because things hit each other. If the conditions are right something useful
might happen. In this case, you need to think about what the chlorine
radicals are likely to hit, and what could happen as a result of that
collision.
At the moment the mixture contains

lots of methane molecules


lots of chlorine molecules (only a few will have been fractured by
the UV light)
a few chlorine radicals

Let's start with the unproductive collisions.


The least likely collision is between two chlorine radicals. There aren't
very many of them in the mixture and so the chances of them hitting
each other are relatively small. If they do collide, they will combine to
form a chlorine molecule. That's worse than useless because it removes
the active free radicals from the system.
2Cl

Cl2

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Explaining the methane - chlorine free radical substitution mechanism

A chlorine radical could also hit a chlorine molecule. If this happens there
could possibly be an exchange of chlorine atoms, but nothing new would
be formed. It is just a wasted collision.
Cl + Cl-Cl
Cl

Cl-Cl +

Note: There is no difference between the chlorine atoms


shown in bold type or ordinary type. They are shown
differently so that the exchange is made clear.

The productive collision happens if a chlorine radical hits a methane


molecule.

The chlorine radical removes a hydrogen atom from the methane. That
hydrogen atom only needs to bring one electron with it to form a new
bond to the chlorine, and so one electron is left behind on the carbon
atom. A new free radical is formed - this time a methyl radical, CH3 .
CH4 + Cl

CH3

+ HCl

What happens to the methyl radicals?


It depends what they collide with. There are three interesting collisions
which need to be explored. Two of these involve a set-back to the
reaction, and only one is useful.
Luckily, the two unhelpful collisions don't happen very often, because
they involve collisions between two free radicals - and there won't be
many of these present in the mixture at any one time.

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Explaining the methane - chlorine free radical substitution mechanism

CH3
Cl

+
CH3Cl

CH3 +
CH3

CH3CH3

Even though the first reaction seems to produce what you want, the
problem with both of these reactions is that they use up the free radicals
in the system - we'll come back to that problem shortly. The second
reaction, of course, also introduces an impurity into the mixture.
So what is the useful collision? If a methyl radical hits a chlorine
molecule (something that's quite likely to occur), the following change
can happen:
CH3

+ Cl2

CH3Cl + Cl

The methyl radical takes one of the chlorine atoms to form


chloromethane (which is what we want to make), but in the process
generates another chlorine radical. This new chlorine radical can now go
through the whole sequence again, and at the end will produce yet
another chlorine radical - and so on and so on.
The process is described as a free radical chain reaction. The chain
continues because for every chlorine radical that goes in at the
beginning, a new one is generated at the end.
Chain termination
Does this mean that one tiny burst of UV light, splitting one chlorine
molecule into two free radicals, is enough to convert a whole reactionsworth of methane and chlorine into chloromethane and HCl?
Sadly, no! As we've seen, there are collisions which result in the removal
of free radicals without producing any new ones. These radicals can only
be replaced by starting the process all over again with a new burst of
light energy. In practice, then, the chains propagate many thousands of
times, but eventually any chain will be brought to an end by one of these
chain termination processes.

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Explaining the methane - chlorine free radical substitution mechanism

Simplifying all this for exam purposes:


The over-all process is known as free radical substitution, or as a free
radical chain reaction.
Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2

2Cl

Chain propagation reactions


These are the reactions which keep the chain going.
CH4 + Cl
CH3

CH3

+ Cl2

+ HCl

CH3Cl + Cl

Chain termination reactions


These are reactions which remove free radicals from the system without
replacing them by new ones.
2Cl
CH3
Cl

Cl2
+

CH3 +
CH3

CH3Cl
CH3CH3

Where would you like to go now?


Look at multiple substitution in this reaction . . .
Look at why side reactions happen in this reaction . . .
To menu of free radical reactions. . .

http://www.chemguide.co.uk/mechanisms/freerad/ch4andcl2tt.html (5 of 6)30/12/2004 11:04:44

Explaining the methane - chlorine free radical substitution mechanism

To menu of other types of mechanism. . .


To Main Menu . . .

Jim Clark 2000

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Multiple substitution in the methane and chlorine reaction

MULTIPLE SUBSTITUTION IN THE METHANE


AND CHLORINE REACTION

Warning! We are just about to muddy the water quite


considerably! Don't go on until you are sure that you
understand the mechanism for the production of
chloromethane - and are confident that you could write it in
an exam. If you aren't sure about it, go back to that reaction
and look at it again.
It would be worth checking your syllabus and past exam
papers to see if you need to know about these further
substitution reactions.

The facts
When a mixture of methane and chlorine is exposed to ultraviolet light typically sunlight - a substitution reaction occurs and the organic product
is chloromethane.
CH4 + Cl2

CH3Cl + HCl

However, the reaction doesn't stop there, and all the hydrogens in the
methane can in turn be replaced by chlorine atoms. That means that you
could get any of chloromethane, dichloromethane, trichloromethane or
tetrachloromethane.
CH4 + Cl2

CH3Cl + HCl

CH3Cl + Cl2

CH2Cl2 + HCl

CH2Cl2 + Cl2

CHCl3 + HCl

CHCl3 + Cl2

CCl4 + HCl

You might think that you could control which product you got by the
proportions of methane and chlorine you used, but it isn't as simple as
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Multiple substitution in the methane and chlorine reaction

that. If you use enough chlorine you will eventually get CCl4, but any
other proportions will always lead to a mixture of products.

The mechanisms
The formation of multiple substitution products like di-, tri- and
tetrachloromethane can be explained in just the same sort of way as the
formation of the original chloromethane. You just have to look at the
likely collisions as the reaction progresses.
Making dichloromethane
You will remember that the over-all equation for the first stage of the
reaction is
CH4 + Cl2

CH3Cl + HCl

As the reaction proceeds, the methane is getting used up and


chloromethane is taking its place. That means that the argument about
what a chlorine radical is likely to hit changes during the course of the
reaction. As time goes by there is an increasing chance of it hitting a
chloromethane molecule rather than a methane molecule.
When that happens, the chlorine radical can take a hydrogen from the
chloromethane just as well as it could from a methane. In this new case:
CH3Cl + Cl

CH2Cl + HCl

Notice: The dot representing the electron has been moved


against the carbon which is the atom with the unpaired
electron. It would be potentially confusing to leave it next to
the chlorine.

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Multiple substitution in the methane and chlorine reaction

The chloromethyl radical formed can then interact with a chlorine


molecule in a new propagation step . . .
CH2Cl + Cl2

CH2Cl2 + Cl

. . . and so dichloromethane is formed and a chlorine radical regenerated.


These propagation steps continue until the chain is terminated by any
two radicals colliding and combining together.
Making tri- and tetrachloromethane
Obviously, as time goes on, there is an increasing chance of the
dichloromethane being hit by a chlorine radical - producing these
propagation steps giving trichloromethane:
CH2Cl2 + Cl
CHCl2 + Cl2

CHCl2 + HCl
CHCl3 + Cl

Care! Don't just skip lightly over these equations. Look


carefully at each one so that you understand what is
happening, and can relate it to what has gone before. Talk
through the equations with yourself.
For example: "A chlorine radical hits the dichloromethane
molecule and steals a hydrogen. That leaves a new radical (I
don't know what it's called, but that doesn't really matter, as
long as I can work out its formula if I have to!), which then
bumps into a chlorine molecule - etc, etc."
Doing this helps you to focus properly on the equations. If
you just read them quickly, you'll have forgotten all about
them again in 15 seconds!

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Multiple substitution in the methane and chlorine reaction

As the amount of trichloromethane builds up, then you will get these
steps giving tetrachloromethane:
CHCl3 + Cl
CCl3 + Cl2

CCl3 + HCl
CCl4 + Cl

This is why you will always get a mixture of products whatever the
reaction proportions of methane and chlorine you use. The whole
process is simply governed by chance. Having produced some
chloromethane there is no way that you can prevent it from being hit by
chlorine radicals, and similarly for dichloromethane and trichloromethane.
Trying to produce mainly one product
If you wanted tetrachloromethane, you could of course get it by using a
large excess of chlorine, so that eventually all the hydrogens would be
replaced.
If you wanted mainly chloromethane, you could favour this by using a
huge excess of methane so that the chances were always greater of a
chlorine radical hitting a methane rather than anything else - but even so,
you would still get some mixture of products.
There is no obvious way of getting mainly dichloromethane or
trichloromethane.

Where would you like to go now?


Look at single substitution again . . .
Look at why side reactions happen in this reaction . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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Multiple substitution in the methane and chlorine reaction

Jim Clark 2000

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Side reactions in the methane and chlorine reaction

SIDE REACTIONS IN THE METHANE AND


CHLORINE REACTION

You may remember that one of the chain termination steps produces
ethane, CH3CH3.
CH3 +
CH3

CH3CH3

If chlorine radicals hit that, you are going to get chloroethane and
dichloroethane and so on - and in the course of those reactions you will
get ethyl radicals which could themselves become involved in chain
termination steps leading to propane (from methyl radical hitting ethyl
radical) or butane (from two ethyl radicals combining), which could then
start to undergo substitution - and on and on!
To be honest, all of these side products are going to be present in very
small amounts because the reaction producing ethane won't, by chance,
happen very often, but it nicely illustrates a typical organic chemistry
problem - when you do a reaction in the lab to produce an organic
chemical, a high proportion of your time is spent in purifying the product
from all the side reactions that have gone on!

Where would you like to go now?


To basic facts and mechanism for this reaction . . .
Look at multiple substitution in this reaction . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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Side reactions in the methane and chlorine reaction

Jim Clark 2000

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Multiple substitution in the methylbenzene and chlorine reaction

MULTIPLE SUBSTITUTION IN THE


METHYLBENZENE AND CHLORINE REACTION

Warning! Don't go on until you are sure that you understand


the mechanism for the production of (chloromethyl)benzene and are confident that you could write it in an exam. If you
aren't sure about it, go back to that reaction and look at it
again.
It would be worth checking your syllabus and past exam
papers to see if you need to know about these further
substitution reactions.

The facts
When a mixture of methylbenzene and chlorine is exposed to ultraviolet
light - typically sunlight - a substitution reaction occurs in the methyl
group and the organic product is (chloromethyl)benzene.

However, the reaction doesn't stop there, and all the hydrogens in the
methyl group can in turn be replaced by chlorine atoms. That means that
you could get any of (chloromethyl)benzene, (dichloromethyl)benzene, or
(trichloromethyl)benzene.

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Multiple substitution in the methylbenzene and chlorine reaction

Care! Look at these equations carefully so that you are sure


that you understand what's going on.
All that's happening is that the three hydrogens in the methyl
group are being replaced by chlorine atoms one at a time.

If you use enough chlorine you will eventually get (trichloromethyl)


benzene, but any other proportions will always lead to a mixture of
products.

The mechanisms
Making (dichloromethyl)benzene
You will remember that the over-all equation for the first stage of the
reaction is

As the reaction proceeds, the methylbenzene is getting used up and


(chloromethyl)benzene is taking its place. Remember that these
reactions happen because chlorine radicals bump into things. As time
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Multiple substitution in the methylbenzene and chlorine reaction

goes by there is an increasing chance of a chlorine radical hitting a


(chloromethyl)benzene molecule rather than a methylbenzene molecule.
When that happens, the chlorine radical can take a hydrogen from the
(chloromethyl)benzene just as well as it could from a methylbenzene
molecule. In this new case:

The new radical formed can then interact with a chlorine molecule in a
new propagation step . . .

. . . and so (dichloromethyl)benzene is formed and a chlorine radical


regenerated.
These propagation steps continue until the chain is terminated by any
two radicals colliding and combining together.
Making (trichloromethyl)benzene
Obviously, as time goes on, there is an increasing chance of the
(dichloromethyl)benzene being hit by a chlorine radical - producing these
propagation steps giving (trichloromethyl)benzene:

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Multiple substitution in the methylbenzene and chlorine reaction

Care! Nothing new is hapening here, but don't just glance


briefly at these equations and then move on. Talk them
through with yourself.
"A chlorine radical takes a hydrogen away from the first
molecule (I can't remember what it's called, but that doesn't
matter much, because I know how to draw it!) and forms a
new radical. That bumps into a chlorine molecule, and gives
the product and a new chlorine radical - which can go
through the process all over again. So it's a chain reaction."

You will always get a mixture of products whatever the reaction


proportions of methylbenzene and chlorine you use. The whole process
is simply governed by chance. Having produced some (chloromethyl)
benzene there is no way that you can prevent it from being hit by chlorine
radicals, and similarly for (dichloromethyl)benzene.

Where would you like to go now?


Look at single substitution again . . .
To menu of free radical reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/freerad/multisubtol.html (4 of 4)30/12/2004 11:04:53

Arenes (aromatic hydrocarbons) Menu

Understanding Chemistry

ARENES MENU

Arenes are aromatic hydrocarbons (compounds based on benzene rings)


such as benzene and methylbenzene.

Background . . .
An introduction to the arenes and their physical properties.
Manufacture . . .
The manufacture of arenes from petroleum by reforming.
Nitration . . .
The nitration of benzene and methylbenzene.
Halogenation . . .
The reactions of benzene and methylbenzene with chlorine and
bromine.
Friedel-Crafts reactions . . .
The alkylation and acylation of benzene and methylbenzene.
Other reactions of benzene and methylbenzene . . .
Combustion, hydrogenation, sulphonation, and the oxidation of

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Arenes (aromatic hydrocarbons) Menu

side chains on benzene rings.

Go to menu of other organic compounds . . .


Go to Main Menu . . .

Jim Clark 2004

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an introduction to arenes (aromatic hydrocarbons)

INTRODUCING ARENES (AROMATIC


HYDROCARBONS)

This page looks at the structures and physical properties of the simplest
arenes (benzene and methylbenzene), together with a very brief
introduction to their reactivity. Much of this is covered in detail elsewhere
on the site - in sections on bonding and mechanisms, for example. You
will find links to all of these pages.

What are arenes?


Arenes are aromatic hydrocarbons. The term "aromatic" originally
referred to their pleasant smells, but now implies a particular sort of
delocalised bonding (see below).
The arenes are based on benzene rings. The simplest of them is
benzene itself, C6H6. The next simplest is methylbenzene (old name:
toluene) which has one of the hydrogen atoms attached to the ring
replaced by a methyl group - C6H5CH3.

The structure of benzene


The structure of benzene is covered in detail in two pages in the organic
bonding section of this site. It is important to understand these thoroughly
to make sense of benzene and methylbenzene chemistry. Unless you
have read these pages recently, you should spend some time on them
now before you go any further on this page.

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an introduction to arenes (aromatic hydrocarbons)

Note: You will find two pages dealing with the bonding in
benzene. One deals with the Kelul structure, and the other
with the modern delocalised structure.
You should read both of these pages starting with the one
about the Kelul structure. You will find a link to the second
page at the bottom of the first one.
This is likely to take you some time because you will probably
have to follow up other links as well in order to fully
understand the second page. Don't try to short-cut this.
Use the BACK button (or more likely, the HISTORY file or
GO menu) on your browser to return to this page later.

What you need to understand about benzene is:

Benzene, C6H6, is a planar molecule containing a ring of six


carbon atoms each with a hydrogen atom attached.
The six carbon atoms form a perfectly regular hexagon. All the
carbon-carbon bonds have exactly the same lengths - somewhere
between single and double bonds.

There are delocalised electrons above and below the plane of the
ring.

This diagram shows one of the molecular orbitals containing two of


the delocalised electrons, which may be found anywhere within the
two "doughnuts". The other molecular orbitals are almost never
drawn.
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an introduction to arenes (aromatic hydrocarbons)

The presence of the delocalised electrons makes benzene


particularly stable.
Benzene resists addition reactions because that would involve
breaking the delocalisation and losing that stability.
Benzene is represented by this symbol, where the
circle represents the delocalised electrons, and
each corner of the hexagon has a carbon atom
with a hydrogen attached.

The structure of methylbenzene (toluene)


Methylbenzene just has a methyl group attached to the benzene ring replacing one of the hydrogen atoms.

Attached groups are often drawn at the top of the ring, but you may
occasionally find them drawn in other places with the ring rotated.

Note: If you have to count up the hydrogens in a diagram of


this kind, don't forget that there isn't a hydrogen atom at any
corner of the hexagon where there is something else
attached. The molecular formula of methylbenzene, for
example, is C7H8. Check that you get that answer from this
diagram!

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an introduction to arenes (aromatic hydrocarbons)

Physical properties
Boiling points
In benzene, the only attractions between neighbouring molecules are van
der Waals dispersion forces. There is no permanent dipole on the
molecule.
Benzene boils at 80C - rather higher than other hydrocarbons of similar
molecular size (pentane and hexane, for example). This is presumably
due to the ease with which temporary dipoles can be set up involving the
delocalised electrons.

Note: If you aren't happy about van der Waals dispersion


forces then you should follow this link before you go on.
Use the BACK button on your browser to return to this page.

Methylbenzene boils at 111C. It is a bigger molecule and so the van der


Waals dispersion forces will be bigger.
Methylbenzene also has a small permanent dipole, so there will be
dipole-dipole attractions as well as dispersion forces. The dipole is due to
the CH3 group's tendency to "push" electrons away from itself. This also
affects the reactivity of methylbenzene (see below).

Melting points
You might have expected that methylbenzene's melting point would be
higher than benzene's as well, but it isn't - it is much lower! Benzene
melts at 5.5C; methylbenzene at -95C.

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an introduction to arenes (aromatic hydrocarbons)

Molecules must pack efficiently in the solid if they are to make best use
of their intermolecular forces. Benzene is a tidy, symmetrical molecule
and packs very efficiently. The methyl group sticking out in
methylbenzene tends to disrupt the closeness of the packing. If the
molecules aren't as closely packed, the intermolecular forces don't work
as well and so the melting point falls.

Solubility in water
The arenes are insoluble in water.
Benzene is quite large compared with a water molecule. In order for
benzene to dissolve it would have to break lots of existing hydrogen
bonds between water molecules. You also have to break the quite strong
van der Waals dispersion forces between benzene molecules. Both of
these cost energy.
The only new forces between the benzene and the water would be van
der Waals dispersion forces. These aren't as strong as hydrogen bonds
(or the original dispersion forces in the benzene), and so you wouldn't get
much energy released when they form.
It simply isn't energetically profitable for benzene to dissolve in water. It
would, of course, be even worse for larger arene molecules.

Reactivity
Benzene
It has already been pointed out above that benzene is resistant to
addition reactions. Adding something new to the ring would need you to
use some of the delocalised electrons to form bonds with whatever you
are adding. That results in a major loss of stability as the delocalisation is
broken.
Instead, benzene mainly undergoes substitution reactions - replacing one
or more of the hydrogen atoms by something new. That leaves the
delocalised electrons as they were.
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an introduction to arenes (aromatic hydrocarbons)

Note: The delocalisation is, in fact, broken during a


substitution reaction, but reforms at the end. If you are
interested in the mechanisms for benzene's substitution
reactions you could follow this link.
Should you want to come back to this page later, it would
probably be best to use the HISTORY file or GO menu on
your browser.

Methylbenzene
You have to consider the reactivity of something like methylbenzene in
two distinct bits:

For example, if you explore other pages in this section, you will find that
alkyl groups attached to a benzene ring are oxidised by alkaline
potassium manganate(VII) solution. This doesn't happen in the absence
of the benzene ring.
The tendency of the CH3 group to "push" electrons away from itself also
has an effect on the ring, making methylbenzene react more quickly than
benzene itself. You will find this explored in other pages in this section as
well.

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an introduction to arenes (aromatic hydrocarbons)

Where would you like to go now?


To the arenes menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2004

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intermolecular bonding - van der Waals forces

INTERMOLECULAR BONDING - VAN DER


WAALS FORCES

This page explains the origin of the two weaker forms of intermolecular
attractions - van der Waals dispersion forces and dipole-dipole
attractions. If you are also interested in hydrogen bonding there is a link
at the bottom of the page.

What are intermolecular attractions?


Intermolecular versus intramolecular bonds
Intermolecular attractions are attractions between one molecule and a
neighbouring molecule. The forces of attraction which hold an individual
molecule together (for example, the covalent bonds) are known as
intramolecular attractions. These two words are so confusingly similar
that it is safer to abandon one of them and never use it. The term
"intramolecular" won't be used again on this site.
All molecules experience intermolecular attractions, although in some
cases those attractions are very weak. Even in a gas like hydrogen, H2, if
you slow the molecules down by cooling the gas, the attractions are large
enough for the molecules to stick together eventually to form a liquid and
then a solid.
In hydrogen's case the attractions are so weak that the molecules have
to be cooled to 21 K (-252C) before the attractions are enough to
condense the hydrogen as a liquid. Helium's intermolecular attractions
are even weaker - the molecules won't stick together to form a liquid until
the temperature drops to 4 K (-269C).

van der Waals forces: dispersion forces


Dispersion forces (one of the two types of van der Waals force we are
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intermolecular bonding - van der Waals forces

dealing with on this page) are also known as "London forces" (named
after Fritz London who first suggested how they might arise).
The origin of van der Waals dispersion forces
Temporary fluctuating dipoles
Attractions are electrical in nature. In a symmetrical molecule like
hydrogen, however, there doesn't seem to be any electrical distortion to
produce positive or negative parts. But that's only true on average.

The lozenge-shaped diagram represents a small symmetrical molecule H2, perhaps, or Br2. The even shading shows that on average there is no
electrical distortion.
But the electrons are mobile, and at any one instant they might find
themselves towards one end of the molecule, making that end -. The
other end will be temporarily short of electrons and so becomes +.

Note: (read as "delta") means "slightly" - so + means


"slightly positive".

An instant later the electrons may well have moved up to the other end,
reversing the polarity of the molecule.

This constant "sloshing around" of the electrons in the molecule causes


rapidly fluctuating dipoles even in the most symmetrical molecule. It even
happens in monatomic molecules - molecules of noble gases, like
helium, which consist of a single atom.
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intermolecular bonding - van der Waals forces

If both the helium electrons happen to be on one side of the atom at the
same time, the nucleus is no longer properly covered by electrons for
that instant.

How temporary dipoles give rise to intermolecular attractions


Imagine a molecule which has a temporary polarity being approached by
one which happens to be entirely non-polar just at that moment. (A pretty
unlikely event, but it makes the diagrams much easier to draw! In reality,
one of the molecules is likely to have a greater polarity than the other at
that time - and so will be the dominant one.)

As the right hand molecule approaches, its electrons will tend to be


attracted by the slightly positive end of the left hand one.
This sets up an induced dipole in the approaching molecule, which is
orientated in such a way that the + end of one is attracted to the - end
of the other.

An instant later the electrons in the left hand molecule may well have
moved up the other end. In doing so, they will repel the electrons in the
right hand one.

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intermolecular bonding - van der Waals forces

The polarity of both molecules reverses, but you still have + attracting
-. As long as the molecules stay close to each other the polarities will
continue to fluctuate in synchronisation so that the attraction is always
maintained.

There is no reason why this has to be restricted to two molecules. As


long as the molecules are close together this synchronised movement of
the electrons can occur over huge numbers of molecules.

This diagram shows how a whole lattice of molecules could be held


together in a solid using van der Waals dispersion forces. An instant
later, of course, you would have to draw a quite different arrangement of
the distribution of the electrons as they shifted around - but always in
synchronisation.

The strength of dispersion forces


Dispersion forces between molecules are much weaker than the covalent
bonds within molecules. It isn't possible to give any exact value, because
the size of the attraction varies considerably with the size of the molecule
and its shape.
How molecular size affects the strength of the dispersion forces
The boiling points of the noble gases are
helium

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-269C

intermolecular bonding - van der Waals forces

neon
argon
krypton
xenon
radon

-246C
-186C
-152C
-108C
-62C

All of these elements have monatomic molecules.


The reason that the boiling points increase as you go down the group is
that the number of electrons increases, and so also does the radius of
the atom. The more electrons you have, and the more distance over
which they can move, the bigger the possible temporary dipoles and
therefore the bigger the dispersion forces.

Because of the greater temporary dipoles, xenon molecules are "stickier"


than neon molecules. Neon molecules will break away from each other at
much lower temperatures than xenon molecules - hence neon has the
lower boiling point.
This is the reason that (all other things being equal) bigger molecules
have higher boiling points than small ones. Bigger molecules have more
electrons and more distance over which temporary dipoles can develop and so the bigger molecules are "stickier".

How molecular shape affects the strength of the dispersion forces


The shapes of the molecules also matter. Long thin molecules can
develop bigger temporary dipoles due to electron movement than short
fat ones containing the same numbers of electrons.
Long thin molecules can also lie closer together - these attractions are at
their most effective if the molecules are really close.

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intermolecular bonding - van der Waals forces

For example, the hydrocarbon molecules butane and 2-methylpropane


both have a molecular formula C4H10, but the atoms are arranged
differently. In butane the carbon atoms are arranged in a single chain,
but 2-methylpropane is a shorter chain with a branch.

Butane has a higher boiling point because the dispersion forces are
greater. The molecules are longer (and so set up bigger temporary
dipoles) and can lie closer together than the shorter, fatter 2methylpropane molecules.

van der Waals forces: dipole-dipole interactions

Warning! There's a bit of a problem here with modern


A'level syllabuses. The majority of the syllabuses talk as if
dipole-dipole interactions were quite distinct from van der
Waals forces. Such a syllabus will talk about van der Waals
forces (meaning dispersion forces) and, separately, dipoledipole interactions.
All intermolecular attractions are known collectively as van
der Waals forces. The various different types were first
explained by different people at different times. Dispersion
forces, for example, were described by London in 1930;
dipole-dipole interactions by Keesom in 1912.
This oddity in the syllabuses doesn't matter in the least as far
as understanding is concerned - but you obviously must
know what your particular examiners mean by the terms they
use in the questions. Check your syllabus.
If you don't have a copy of your syllabus follow this link to find
out how to get one.

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intermolecular bonding - van der Waals forces

A molecule like HCl has a permanent dipole because chlorine is more


electronegative than hydrogen. These permanent, in-built dipoles will
cause the molecules to attract each other rather more than they
otherwise would if they had to rely only on dispersion forces.

Note: If you aren't happy about electronegativity and polar


molecules, follow this link before you go on.

It's important to realise that all molecules experience dispersion forces.


Dipole-dipole interactions are not an alternative to dispersion forces they occur in addition to them. Molecules which have permanent dipoles
will therefore have boiling points rather higher than molecules which only
have temporary fluctuating dipoles.
Surprisingly dipole-dipole attractions are fairly minor compared with
dispersion forces, and their effect can only really be seen if you compare
two molecules with the same number of electrons and the same size. For
example, the boiling points of ethane, CH3CH3, and fluoromethane,
CH3F, are

Why choose these two molecules to compare? Both have identical


numbers of electrons, and if you made models you would find that the
sizes were similar - as you can see in the diagrams. That means that the
dispersion forces in both molecules should be much the same.

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intermolecular bonding - van der Waals forces

The higher boiling point of fluoromethane is due to the large permanent


dipole on the molecule because of the high electronegativity of fluorine.
However, even given the large permanent polarity of the molecule, the
boiling point has only been increased by some 10.

Here is another example showing the


dominance of the dispersion forces.
Trichloromethane, CHCl3, is a highly polar
molecule because of the electronegativity of
the three chlorines. There will be quite strong
dipole-dipole attractions between one molecule
and its neighbours.

On the other hand, tetrachloromethane, CCl4,


is non-polar. The outside of the molecule is
uniformly - in all directions. CCl4 has to rely
only on dispersion forces.

So which has the highest boiling point? CCl4 does, because it is a bigger
molecule with more electrons. The increase in the dispersion forces more
than compensates for the loss of dipole-dipole interactions.
The boiling points are:
CHCl3

61.2C

CCl4

76.8C

Where would you like to go now?


To look at hydrogen bonding . . .

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intermolecular bonding - van der Waals forces

To the bonding menu . . .


To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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electronegativity

ELECTRONEGATIVITY

This page explains what electronegativity is, and how and why it varies
around the Periodic Table. It looks at the way that electronegativity
differences affect bond type and explains what is meant by polar bonds
and polar molecules.
If you are interested in electronegativity in an organic chemistry context,
you will find a link at the bottom of this page.

What is electronegativity
Definition
Electronegativity is a measure of the tendency of an atom to attract a
bonding pair of electrons.
The Pauling scale is the most commonly used. Fluorine (the most
electronegative element) is assigned a value of 4.0, and values range
down to caesium and francium which are the least electronegative at 0.7.

What happens if two atoms of equal electronegativity bond


together?
Consider a bond between two atoms, A and B. Each atom may be
forming other bonds as well as the one shown - but these are irrelevant
to the argument.

If the atoms are equally electronegative, both have the same tendency to
attract the bonding pair of electrons, and so it will be found on average
half way between the two atoms. To get a bond like this, A and B would
usually have to be the same atom. You will find this sort of bond in, for
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electronegativity

example, H2 or Cl2 molecules.

Note: It's important to realise that this is an average picture.


The electrons are actually in a molecular orbital, and are
moving around all the time within that orbital.

This sort of bond could be thought of as being a "pure" covalent bond where the electrons are shared evenly between the two atoms.

What happens if B is slightly more electronegative than A?


B will attract the electron pair rather more than A does.

That means that the B end of the bond has more than its fair share of
electron density and so becomes slightly negative. At the same time, the
A end (rather short of electrons) becomes slightly positive. In the
diagram, " " (read as "delta") means "slightly" - so + means "slightly
positive".
Defining polar bonds
This is described as a polar bond. A polar bond is a covalent bond in
which there is a separation of charge between one end and the other - in
other words in which one end is slightly positive and the other slightly
negative. Examples include most covalent bonds. The hydrogen-chlorine
bond in HCl or the hydrogen-oxygen bonds in water are typical.

What happens if B is a lot more electronegative than A?


In this case, the electron pair is dragged right over to B's end of the bond.
To all intents and purposes, A has lost control of its electron, and B has
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electronegativity

complete control over both electrons. Ions have been formed.

A "spectrum" of bonds
The implication of all this is that there is no clear-cut division between
covalent and ionic bonds. In a pure covalent bond, the electrons are held
on average exactly half way between the atoms. In a polar bond, the
electrons have been dragged slightly towards one end.
How far does this dragging have to go before the bond counts as ionic?
There is no real answer to that. You normally think of sodium chloride as
being a typically ionic solid, but even here the sodium hasn't completely
lost control of its electron. Because of the properties of sodium chloride,
however, we tend to count it as if it were purely ionic.

Note: Don't worry too much about the exact cut-off point
between polar covalent bonds and ionic bonds. At A'level,
examples will tend to avoid the grey areas - they will be
obviously covalent or obviously ionic. You will, however, be
expected to realise that those grey areas exist.

Lithium iodide, on the other hand, would be described as being "ionic


with some covalent character". In this case, the pair of electrons hasn't
moved entirely over to the iodine end of the bond. Lithium iodide, for
example, dissolves in organic solvents like ethanol - not something which
ionic substances normally do.

Summary

No electronegativity difference between two atoms leads to a pure


non-polar covalent bond.

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electronegativity

A small electronegativity difference leads to a polar covalent bond.

A large electronegativity difference leads to an ionic bond.

Polar bonds and polar molecules


In a simple molecule like HCl, if the bond is polar, so also is the whole
molecule. What about more complicated molecules?
In CCl4, each bond is polar.

Note: Ordinary lines represent bonds in the plane of the


screen or paper. Dotted lines represent bonds going away
from you into the screen or paper. Wedged lines represent
bonds coming out of the screen or paper towards you.

The molecule as a whole, however, isn't polar - in the sense that it


doesn't have an end (or a side) which is slightly negative and one which
is slightly positive. The whole of the outside of the molecule is somewhat
negative, but there is no overall separation of charge from top to bottom,
or from left to right.
By contrast, CHCl3 is polar.

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electronegativity

The hydrogen at the top of the molecule is less electronegative than


carbon and so is slightly positive. This means that the molecule now has
a slightly positive "top" and a slightly negative "bottom", and so is overall
a polar molecule.
A polar molecule will need to be "lop-sided" in some way.

Patterns of electronegativity in the Periodic Table


The most electronegative element is fluorine. If you remember that fact,
everything becomes easy, because electronegativity must always
increase towards fluorine in the Periodic Table.

Note: This simplification ignores the noble gases.


Historically this is because they were believed not to form
bonds - and if they don't form bonds, they can't have an
electronegativity value. Even now that we know that some of
them do form bonds, data sources still don't quote
electronegativity values for them.

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electronegativity

Trends in electronegativity across a period


As you go across a period the electronegativity increases. The chart
shows electronegativities from sodium to chlorine - you have to ignore
argon. It doesn't have an electronegativity, because it doesn't form bonds.

Trends in electronegativity down a group


As you go down a group, electronegativity decreases. (If it increases up
to fluorine, it must decrease as you go down.) The chart shows the
patterns of electronegativity in Groups 1 and 7.

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electronegativity

Explaining the patterns in electronegativity


The attraction that a bonding pair of electrons feels for a particular
nucleus depends on:

the number of protons in the nucleus;

the distance from the nucleus;

the amount of screening by inner electrons.

Note: If you aren't happy about the concept of screening or


shielding, it would pay you to read the page on ionisation
energies before you go on. The factors influencing ionisation
energies are just the same as those influencing
electronegativities.
Use the BACK button on your browser to return to this page.

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electronegativity

Why does electronegativity increase across a period?


Consider sodium at the beginning of period 3 and chlorine at the end
(ignoring the noble gas, argon). Think of sodium chloride as if it were
covalently bonded.

Both sodium and chlorine have their bonding electrons in the 3-level. The
electron pair is screened from both nuclei by the 1s, 2s and 2p electrons,
but the chlorine nucleus has 6 more protons in it. It is no wonder the
electron pair gets dragged so far towards the chlorine that ions are
formed.
Electronegativity increases across a period because the number of
charges on the nucleus increases. That attracts the bonding pair of
electrons more strongly.
Why does electronegativity fall as you go down a group?
Think of hydrogen fluoride and hydrogen chloride.

The bonding pair is shielded from the fluorine's nucleus only by the 1s2
electrons. In the chlorine case it is shielded by all the 1s22s22p6
electrons.
In each case there is a net pull from the centre of the fluorine or chlorine
of +7. But fluorine has the bonding pair in the 2-level rather than the 3level as it is in chlorine. If it is closer to the nucleus, the attraction is
greater.
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electronegativity

As you go down a group, electronegativity decreases because the


bonding pair of electrons is increasingly distant from the attraction of the
nucleus.

The polarising ability of positive ions


What do we mean by "polarising ability"?
In the discussion so far, we've thought of ions as arising from highly
distorted covalent bonds. You can also think of it the other way round.
Solid aluminium chloride is covalent. Imagine instead that it was ionic. It
would contain Al3+ and Cl- ions.
The aluminium ion is very small and is packed with three positive
charges - the "charge density" is therefore very high. That will have a
considerable effect on any nearby electrons.

In the case of aluminium chloride, the electron pairs are dragged back
towards the aluminium to such an extent that the bonds becomes
covalent.

Factors affecting polarising ability


Positive ions can have the effect of polarising (electrically distorting)
nearby negative ions. The polarising ability depends on the charge
density in the positive ion.

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electronegativity

Polarising ability increases as the positive ion gets smaller and the
number of charges gets larger.
As a negative ion gets bigger, it becomes easier to polarise. For
example, in an iodide ion, I-, the outer electrons are in the 5-level relatively distant from the nucleus.
A positive ion would be more effective in attracting a pair of electrons
from an iodide ion than the corresponding electrons in, say, a fluoride ion
where they are much closer to the nucleus.
Aluminium iodide is covalent because the electron pair is easily dragged
away from the iodide ion. On the other hand, aluminium fluoride is ionic
because the aluminium ion can't polarise the small fluoride ion sufficiently
to form a covalent bond.

Where would you like to go now?


To look at electronegativity in an organic chemistry
context . . .
To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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intermolecular bonding - hydrogen bonds

INTERMOLECULAR BONDING - HYDROGEN


BONDS

This page explains the origin of hydrogen bonding - a relatively strong


form of intermolecular attraction. If you are also interested in the weaker
intermolecular forces (van der Waals dispersion forces and dipole-dipole
interactions), there is a link at the bottom of the page.

The evidence for hydrogen bonding


Many elements form compounds with hydrogen - referred to as
"hydrides". If you plot the boiling points of the hydrides of the Group 4
elements, you find that the boiling points increase as you go down the
group.

The increase in boiling point happens because the molecules are getting
larger with more electrons, and so van der Waals dispersion forces
become greater.

Note: If you aren't sure about van der Waals dispersion


forces, it would pay you to follow this link before you go on.

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intermolecular bonding - hydrogen bonds

If you repeat this exercise with the hydrides of elements in Groups 5, 6


and 7, something odd happens.

Although for the most part the trend is exactly the same as in group 4 (for
exactly the same reasons), the boiling point of the hydride of the first
element in each group is abnormally high.
In the cases of NH3, H2O and HF there must be some additional
intermolecular forces of attraction, requiring significantly more heat
energy to break. These relatively powerful intermolecular forces are
described as hydrogen bonds.

The origin of hydrogen bonding


The molecules which have this extra bonding are:

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intermolecular bonding - hydrogen bonds

Note: The solid line represents a bond in the plane of the


screen or paper. Dotted bonds are going back into the screen
or paper away from you, and wedge-shaped ones are coming
out towards you.

Notice that in each of these molecules:

The hydrogen is attached directly to one of the most


electronegative elements, causing the hydrogen to acquire a
significant amount of positive charge.
Each of the elements to which the hydrogen is attached is not only
significantly negative, but also has at least one "active" lone pair.
Lone pairs at the 2-level have the electrons contained in a
relatively small volume of space which therefore has a high density
of negative charge. Lone pairs at higher levels are more diffuse
and not so attractive to positive things.

Note: If you aren't happy about electronegativity, you should


follow this link before you go on.

Consider two water molecules coming close together.

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intermolecular bonding - hydrogen bonds

The + hydrogen is so strongly attracted to the lone pair that it is almost


as if you were beginning to form a co-ordinate (dative covalent) bond. It
doesn't go that far, but the attraction is significantly stronger than an
ordinary dipole-dipole interaction.
Hydrogen bonds have about a tenth of the strength of an average
covalent bond, and are being constantly broken and reformed in liquid
water. If you liken the covalent bond between the oxygen and hydrogen
to a stable marriage, the hydrogen bond has "just good friends" status.
On the same scale, van der Waals attractions represent mere passing
acquaintances!
Water as a "perfect" example of hydrogen bonding
Notice that each water molecule can potentially form four hydrogen
bonds with surrounding water molecules. There are exactly the right
numbers of + hydrogens and lone pairs so that every one of them can
be involved in hydrogen bonding.
This is why the boiling point of water is higher than that of ammonia or
hydrogen fluoride. In the case of ammonia, the amount of hydrogen
bonding is limited by the fact that each nitrogen only has one lone pair. In
a group of ammonia molecules, there aren't enough lone pairs to go
around to satisfy all the hydrogens.
In hydrogen fluoride, the problem is a shortage of hydrogens. In water,
there are exactly the right number of each. Water could be considered as
the "perfect" hydrogen bonded system.

Note: You will find more discussion on the effect of


hydrogen bonding on the properties of water in the page on
molecular structures.

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intermolecular bonding - hydrogen bonds

More complex examples of hydrogen bonding


The hydration of negative ions
When an ionic substance dissolves in water, water molecules cluster
around the separated ions. This process is called hydration.
Water frequently attaches to positive ions by co-ordinate (dative
covalent) bonds. It bonds to negative ions using hydrogen bonds.

Note: If you are interested in the bonding in hydrated


positive ions, you could follow this link to co-ordinate (dative
covalent) bonding.

The diagram shows the potential hydrogen bonds formed to a chloride


ion, Cl-. Although the lone pairs in the chloride ion are at the 3-level and
wouldn't normally be active enough to form hydrogen bonds, in this case
they are made more attractive by the full negative charge on the chlorine.

However complicated the negative ion, there will always be lone pairs
that the hydrogen atoms from the water molecules can hydrogen bond to.

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intermolecular bonding - hydrogen bonds

Hydrogen bonding in alcohols


An alcohol is an organic molecule containing an -O-H group.
Any molecule which has a hydrogen atom attached directly to an oxygen
or a nitrogen is capable of hydrogen bonding. Such molecules will always
have higher boiling points than similarly sized molecules which don't
have an -O-H or an -N-H group. The hydrogen bonding makes the
molecules "stickier", and more heat is necessary to separate them.
Ethanol, CH3CH2-O-H, and methoxymethane, CH3-O-CH3, both have
the same molecular formula, C2H6O.

Note: If you haven't done any organic chemistry yet, don't


worry about the names.

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intermolecular bonding - hydrogen bonds

They have the same number of electrons, and a similar length to the
molecule. The van der Waals attractions (both dispersion forces and
dipole-dipole attractions) in each will be much the same.
However, ethanol has a hydrogen atom attached directly to an oxygen and that oxygen still has exactly the same two lone pairs as in a water
molecule. Hydrogen bonding can occur between ethanol molecules,
although not as effectively as in water. The hydrogen bonding is limited
by the fact that there is only one hydrogen in each ethanol molecule with
sufficient + charge.
In methoxymethane, the lone pairs on the oxygen are still there, but the
hydrogens aren't sufficiently + for hydrogen bonds to form. Except in
some rather unusual cases, the hydrogen atom has to be attached
directly to the very electronegative element for hydrogen bonding to
occur.
The boiling points of ethanol and methoxymethane show the dramatic
effect that the hydrogen bonding has on the stickiness of the ethanol
molecules:
ethanol (with hydrogen bonding)
methoxymethane (without hydrogen bonding)

78.5C
-24.8C

The hydrogen bonding in the ethanol has lifted its boiling point about 100
C.

It is important to realise that hydrogen bonding exists in addition to van


der Waals attractions. For example, all the following molecules contain
the same number of electrons, and the first two are much the same
length. The higher boiling point of the butan-1-ol is due to the additional
hydrogen bonding.

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intermolecular bonding - hydrogen bonds

Comparing the two alcohols (containing -OH groups), both boiling points
are high because of the additional hydrogen bonding due to the
hydrogen attached directly to the oxygen - but they aren't the same.
The boiling point of the 2-methylpropan-1-ol isn't as high as the butan-1ol because the branching in the molecule makes the van der Waals
attractions less effective than in the longer butan-1-ol.

Hydrogen bonding in organic molecules containing nitrogen


Hydrogen bonding also occurs in organic molecules containing N-H
groups - in the same sort of way that it occurs in ammonia. Examples
range from simple molecules like CH3NH2 (methylamine) to large
molecules like proteins and DNA. The two strands of the famous alphahelix in DNA are held together by hydrogen bonds involving N-H groups.

Where would you like to go now?


To look at van der Waals forces . . .
To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

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intermolecular bonding - hydrogen bonds

Jim Clark 2000

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physical properties of molecular substances

MOLECULAR STRUCTURES

This page describes how the physical properties of substances having


molecular structures varies with the type of intermolecular attractions hydrogen bonding or van der Waals forces.

Important! There's not much point in reading this page


unless you are reasonably happy about the origin of
hydrogen bonding and van der Waals forces. Follow these
links first if you aren't sure about these.

The physical properties of molecular substances


Molecules are made of fixed numbers of atoms joined together by
covalent bonds, and can range from the very small (even down to single
atoms, as in the noble gases) to the very large (as in polymers, proteins
or even DNA).
The covalent bonds holding the molecules together are very strong, but
these are largely irrelevant to the physical properties of the substance.
Physical properties are governed by the intermolecular forces - forces
attracting one molecule to its neighbours - van der Waals attractions or
hydrogen bonds.
Melting and boiling points
Molecular substances tend to be gases, liquids or low melting point
solids, because the intermolecular forces of attraction are comparatively
weak. You don't have to break any covalent bonds in order to melt or boil
a molecular substance.

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physical properties of molecular substances

Note: This is really important! You can make yourself look


extremely stupid if you imply in an exam that boiling water,
for example, splits it into hydrogen and oxygen by breaking
covalent bonds. Exactly the same water molecules are
present in ice, water and steam.

The size of the melting or boiling point will depend on the strength of the
intermolecular forces. The presence of hydrogen bonding will lift the
melting and boiling points. The larger the molecule the more van der
Waals attractions are possible - and those will also need more energy to
break.

Solubility in water
Most molecular substances are insoluble (or only very sparingly soluble)
in water. Those which do dissolve often react with the water, or else are
capable of forming hydrogen bonds with the water.
Why doesn't methane, CH4, dissolve in water?
The methane itself isn't the problem. Methane is a gas, and so its
molecules are already separate - the water doesn't need to pull them
apart from one another.
The problem is the hydrogen bonds between the water molecules. If
methane were to dissolve, it would have to force its way between water
molecules and so break hydrogen bonds. That costs a reasonable
amount of energy.
The only attractions possible between methane and water molecules are
the much weaker van der Waals forces - and not much energy is
released when these are set up. It simply isn't energetically profitable for
the methane and water to mix.
Why does ammonia, NH3, dissolve in water?
Ammonia has the ability to form hydrogen bonds. When the hydrogen
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physical properties of molecular substances

bonds between water molecules are broken, they can be replaced by


equivalent bonds between water and ammonia molecules.
Some of the ammonia also reacts with the water to produce ammonium
ions and hydroxide ions.

The reversible arrows show that the reaction doesn't go to completion. At


any one time only about 1% of the ammonia has actually reacted to form
ammonium ions. The solubility of ammonia is mainly due to the hydrogen
bonding and not the reaction.
Other common substances which are freely soluble in water because
they can hydrogen bond with water molecules include ethanol (alcohol)
and sucrose (sugar).

Solubility in organic solvents


Molecular substances are often soluble in organic solvents - which are
themselves molecular. Both the solute (the substance which is
dissolving) and the solvent are likely to have molecules attracted to each
other by van der Waals forces. Although these attractions will be
disrupted when they mix, they are replaced by similar ones between the
two different sorts of molecules.

Electrical conductivity
Molecular substances won't conduct electricity. Even in cases where
electrons may be delocalised within a particular molecule, there isn't
sufficient contact between the molecules to allow the electrons to move
through the whole solid or liquid.

Some individual examples

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physical properties of molecular substances

Iodine, I2
Iodine is a dark grey crystalline solid with a purple vapour. M.Pt: 114C.
B.Pt: 184C. It is very, very slightly soluble in water, but dissolves freely
in organic solvents.
Iodine is therefore a low melting point solid. The crystallinity suggests a
regular packing of the molecules.

The structure is described as face centred cubic - it is a cube of iodine


molecules with another molecule at the centre of each face.
The orientation of the iodine molecules within this structure is quite
difficult to draw (let alone remember!). If your syllabus and past exam
papers suggests that you need to remember it, look carefully at the next
sequence of diagrams showing the layers.

Note: If you haven't got a copy of your syllabus or copies of


recent past papers, follow this link to find out how to get them.

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physical properties of molecular substances

Notice that as you look down on the cube, all the molecules on the left
and right hand sides are aligned the same way. The ones in the middle
are aligned in the opposite way.
All these diagrams show an "exploded" view of the crystal. The iodine
molecules are, of course, touching each other. Measurements of the
distances between the centres of the atoms in the crystal show two
different values:

The iodine atoms within each molecule are pulled closely together by the
covalent bond. The van der Waals attraction between the molecules is
much weaker, and you can think of the atoms in two separate molecules
as just loosely touching each other.

Ice
Ice is a good example of a hydrogen bonded solid.
There are lots of different ways that the water molecules can be arranged
in ice. This is one of them, but NOT the common one - I can't draw that in
any way that makes sense! The one below is known as "cubic ice", or
"ice Ic". It is based on the water molecules arranged in a diamond
structure.

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physical properties of molecular substances

This is just a small part of a structure which extends over huge numbers
of molecules in three dimensions. In the diagram, the lines represent
hydrogen bonds. The lone pairs that the hydrogen atoms are attracted to
are left out for clarity.
Cubic ice is only stable at temperatures below -80C. The ice you are
familiar with has a different, hexagonal structure. It is called "ice Ih".

Note: Don't worry about this problem. If asked to draw ice in


a UK A level exam, don't try to be too clever. It is probably
best not to go beyond the top five molecules in the above
diagram. This will show the essential features of the bonding
in the structure without getting bogged down in stuff which is
far beyond this level.
If you are interested in following this up, try a Google search
(at the bottom of the Main Menu - link below) using the
search term ice structure hexagonal cubic (or something
similar). This will throw up lots of information together with an
assortment of fairly dreadful diagrams which I for one don't
have the visual imagination to unscramble!

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physical properties of molecular substances

The unusual density behaviour of water


The hydrogen bonding forces a rather open structure on the ice - if you
made a model of it, you would find a significant amount of wasted space.
When ice melts, the structure breaks down and the molecules tend to fill
up this wasted space.
This means that the water formed takes up less space than the original
ice. Ice is a very unusual solid in this respect - most solids show an
increase in volume on melting.
When water freezes, the opposite happens - there is an expansion as the
hydrogen bonded structure establishes. Most liquids contract on freezing.
Remnants of the rigid hydrogen bonded structure are still present in very
cold liquid water, and don't finally disappear until 4C. The density of
water increases from 0C to 4C as the molecules free themselves from
the open structure and take up less space. After 4C, the thermal motion
of the molecules causes them to move apart and the density falls. That's
the normal behaviour with liquids on heating.

Note: You can find more about water (particularly its


abnormally high boiling point) in the page on hydrogen
bonding.

Polymers
Bonding in polymers
Polymers like poly(ethene) - commonly called polythene - consist of very
long molecules. Poly(ethene) molecules are made by joining up lots of
ethene molecules into chains of covalently bound carbon atoms with
hydrogens attached. There may be short branches along the main chain,
also consisting of carbon chains with attached hydrogens. The molecules
are attracted to each other in the solid by van der Waals dispersion
forces.
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physical properties of molecular substances

By controlling the conditions under which ethene is polymerised, it is


possible to control the amount of branching to give two distinct types of
polythene.
High density polythene
High density polythene has virtually unbranched chains. The lack of
branching allows molecules to lie close together in a regular way which is
almost crystalline.
Because the molecules lie close together, dispersion forces are more
effective, and so the plastic is relatively strong and has a somewhat
higher melting point than low density polythene.
High density polythene is used for containers for household chemicals
like washing-up liquid, for example, or for bowls or buckets.
Low density polythene
Low density polythene has lots of short branches along the chain. These
branches prevent the chains from lying close together in a tidy
arrangement. As a result dispersion forces are less and the plastic is
weaker and has a lower melting point. Its density is lower, of course,
because of the wasted space within the unevenly packed structure.
Low density polythene is used for things like plastic bags.

Where would you like to go now?


To the structures menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

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physical properties of molecular substances

Jim Clark 2000

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Structures menu

Understanding Chemistry

STRUCTURES MENU

Ionic structures . . .
Takes NaCl as a typical example to show the relationship between
the physical properties of an ionic compound and its structure.
Giant covalent structures . . .
Looks at diamond, graphite and silicon dioxide and the way their
physical properties are affected by their structures.
Metallic structures . . .
Looks at the relationship between the physical properties of metals
and their structures.
Molecular structures . . .
Looks in detail at the structures of ice, iodine and poly(ethene) as
well as dealing in general with the sort of physical properties you
might expect of molecular substances.
How to decide . . .
Explains how you can decide which sort of structure a substance
has by looking at its physical properties.
Physical properties of Period 3 elements . . .
Explains how the structures of the elements from Na to Ar in the
Periodic Table affect their simple physical properties.
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Structures menu

Go to atomic structure and bonding menu . . .


Go to Main Menu . . .

Jim Clark 2000

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covalent bonding - double bonds

COVALENT BONDING - DOUBLE BONDS

This page explains how double covalent bonds arise. It starts with a
simple picture of double covalent bonding, and then takes a more
sophisticated view of the bonding in ethene.

Warning! This page assumes that you have already read


the page on single covalent bonds. If you have come straight
to this page via a search engine follow this link before you go
on.

A simple view of double covalent bonds


A double covalent bond is where two pairs of electrons are shared
between the atoms rather than just one pair.
Some simple molecules containing double bonds
Oxygen, O2
Two oxygen atoms can both achieve stable structures by sharing two
pairs of electrons as in the diagram.

The double bond is shown conventionally by two lines joining the atoms.
Each line represents one pair of shared electrons.
Carbon dioxide, CO2

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covalent bonding - double bonds

Ethene, C2H4
Ethene has a double bond between the two carbon atoms.

A more sophisticated view of the bonding in ethene


It is important to explore the bonding in ethene in more detail because it
has a direct impact on its chemistry. Unless you have some
understanding of the true nature of the double bond, you can't really
understand the way that ethene behaves.
An orbital view of the bonding in ethene
Ethene is built from hydrogen atoms (1s1) and carbon atoms
(1s22s22px12py1).
The carbon atom doesn't have enough unpaired electrons to form the
required number of bonds, so it needs to promote one of the 2s2 pair into
the empty 2pz orbital. This is exactly the same as happens whenever
carbon forms bonds - whatever else it ends up joined to.

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covalent bonding - double bonds

Now there's a difference, because each carbon is only joining to three


other atoms (another carbon and two hydrogens) rather than four - as,
for example, in methane.
The carbon re-organises the s orbital and two of the p orbitals to give
three new orbitals with exactly the same energy. This process is called
hybridisation. The other p orbital is left unchanged.

Note: You might wonder why it chooses to hybridise these


three orbitals rather than just use the three p orbitals which
already have the same energy. It's because it uses the
orbitals with the lowest energy first.

The new orbitals formed are called sp2


hybrids, because they are made by an s
orbital and two p orbitals reorganising
themselves. sp2 orbitals look rather like
sp3 orbitals that we discussed in the
bonding in methane in the page on
single bonds, except that they are
shorter and fatter. The three sp2 hybrid
orbitals arrange themselves as far apart as possible - which is at 120 to
each other in a plane. The remaining p orbital is at right angles to them.
The two carbon atoms and four hydrogen atoms would look like this
before they joined together:

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covalent bonding - double bonds

The various atomic orbitals which are pointing


towards each other now merge to give
molecular orbitals, each containing a bonding
pair of electrons. Molecular orbitals made by
end-to-end overlap of atomic orbitals are
called sigma bonds.

The p orbitals on each carbon aren't pointing towards each other, and so
we'll leave those for a moment. In the diagram, the black dots represent
the nuclei of the atoms.
Notice that the p orbitals are so close that they are overlapping sideways.
This sideways overlap also creates a
molecular orbital, but of a different kind. In
this one the electrons aren't held on the line
between the two nuclei, but above and below
the plane of the molecule. A bond formed in
this way is called a pi bond.

For clarity, the sigma bonds are shown using lines - each line
representing one pair of shared electrons. The various sorts of line show
the directions the bonds point in. An ordinary line represents a bond in
the plane of the screen (or the paper if you've printed it), a broken line is
a bond going back away from you, and a wedge shows a bond coming
out towards you.

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covalent bonding - double bonds

Note: The really interesting bond in ethene is the pi bond. In


almost all cases where you will draw the structure of ethene,
the sigma bonds will be shown as lines.

Be clear about what a pi bond is. It is a region of space in which you can
find the two electrons which make up the bond. Those two electrons can
live anywhere within that space. It would be quite misleading to think of
one living in the top and the other in the bottom.

Beyond A'level: This is a good example of the curious


behaviour of electrons. How do the electrons get from one
half of the pi bond to the other if they are never found in
between? It's an unanswerable question if you think of
electrons as particles. If you want to follow this up, you will
have to read some fairly high-powered stuff on the wave
nature of electrons.

Even if your syllabus doesn't expect you to know how a pi bond is


formed, it will expect you to know that it exists. The pi bond dominates
the chemistry of ethene. It is very vulnerable to attack - a very negative
region of space above and below the plane of the molecule. It is also
somewhat distant from the control of the nuclei and so is a weaker bond
than the sigma bond joining the two carbons.

Important! Check your syllabus! Find out whether you


actually need to know how a pi bond is formed. Don't forget
to look under ethene as well as in the bonding section of your
syllabus. If you don't need to know it, there's no point in
learning it! You will, however, need to know that a pi bond
exists - that the two bonds between the carbon atoms in
ethene aren't both the same.
If you haven't got a copy of your syllabus, find out how to
download one.

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covalent bonding - double bonds

All double bonds (whatever atoms they might be joining) will consist of a
sigma bond and a pi bond.
This orbital view of the double bond is only really important at A'level with
regard to organic compounds. If you want to read more about this, follow
the first link below which leads you to the menu for a section specifically
on organic bonding. You will find the description of ethene repeated, but
will also find information about the bonding in benzene and in the carbonoxygen double bond.

Where would you like to go now?


To explore more organic bonding . . .
To the bonding menu . . .
To the atomic structure and bonding menu . . .
To Main Menu . . .

Jim Clark 2000

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Explaining the acidity of organic acids

THE ACIDITY OF ORGANIC ACIDS

This page explains the acidity of simple organic acids and looks at the
factors which affect their relative strengths.

Why are organic acids acidic?


Organic acids as weak acids
For the purposes of this topic, we are going to take the definition of an
acid as "a substance which donates hydrogen ions (protons) to other
things". We are going to get a measure of this by looking at how easily the
acids release hydrogen ions to water molecules when they are in solution
in water.
An acid in solution sets up this equilibrium:

Note: We are writing the acid as AH rather than HA, because,


in all the cases we shall be looking at, the hydrogen we are
interested in is at the right-hand end of a molecule.

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Explaining the acidity of organic acids

A hydroxonium ion is formed together with the anion (negative ion) from
the acid.
This equilibrium is sometimes simplified by leaving out the water to
emphasise the ionisation of the acid.

If you write it like this, you must include the state symbols - "(aq)". Writing
H+(aq) implies that the hydrogen ion is attached to a water molecule as
H3O+. Hydrogen ions are always attached to something during chemical
reactions.
The organic acids are weak in the sense that this ionisation is very
incomplete. At any one time, most of the acid will be present in the
solution as un-ionised molecules. For example, in the case of dilute
ethanoic acid, the solution contains about 99% of ethanoic acid molecules
- at any instant, only about 1% have actually ionised. The position of
equilibrium therefore lies well to the left.
Comparing the strengths of weak acids
The strengths of weak acids are measured on the pKa scale. The smaller
the number on this scale, the stronger the acid is.
Three of the compounds we shall be looking at, together with their pKa
values are:

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Explaining the acidity of organic acids

Remember - the smaller the number the stronger the acid. Comparing the
other two to ethanoic acid, you will see that phenol is very much weaker
with a pKa of 10.00, and ethanol is so weak with a pKa of about 16 that it
hardly counts as acidic at all!

Why are these acids acidic?


In each case, the same bond gets broken - the bond between the
hydrogen and oxygen in an -OH group. Writing the rest of the molecule as
"X":

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Explaining the acidity of organic acids

Note: If you aren't sure about coordinate covalent (dative


covalent) bonding, you might like to follow this link. It isn't,
however, particularly important to the rest of the current page.
Use the BACK button on your browser to return to this page
later.

So . . . if the same bond is being broken in each case, why do these three
compounds have such widely different acid strengths?

Differences in acid strengths between carboxylic acids,


phenols and alcohols
The factors to consider
Two of the factors which influence the ionisation of an acid are:

the strength of the bond being broken,

the stability of the ions being formed.

In these cases, you seem to be breaking the same oxygen-hydrogen bond


each time, and so you might expect the strengths to be similar.

Note: You've got to be a bit careful about this. The bonds


won't be identically strong, because what's around them in the
molecule isn't the same in each case.

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Explaining the acidity of organic acids

The most important factor in determining the relative acid strengths of


these molecules is the nature of the ions formed. You always get a
hydroxonium ion - so that's constant - but the nature of the anion (the
negative ion) varies markedly from case to case.

Ethanoic acid
Ethanoic acid has the structure:

The acidic hydrogen is the one attached to the oxygen. When ethanoic
acid ionises it forms the ethanoate ion, CH3COO-.
You might reasonably suppose that the structure of the ethanoate ion was
as below, but measurements of bond lengths show that the two carbonoxygen bonds are identical and somewhere in length between a single
and a double bond.

To understand why this is, you have to look in some detail at the bonding
in the ethanoate ion.

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Explaining the acidity of organic acids

Warning! If you don't already understand about the bonding


in the carbon-oxygen double bond, you would be well advised
to skip this next bit - all the way down to the simplified
structure of the ethanoate ion towards the end of it. It goes
beyond anything that you are likely to want for UK A level
purposes.
If you do choose to follow this link, it will probably take you to
several other pages before you are ready to come back here
again. Use the BACK button (or HISTORY file or GO menu) on
your browser to return to this page.

Like any other double bond, a carbon-oxygen double bond is made up of


two different parts. One electron pair is found on the line between the two
nuclei - this is known as a sigma bond. The other electron pair is found
above and below the plane of the molecule in a pi bond.
Pi bonds are made by sideways overlap between p orbitals on the carbon
and the oxygen.
In an ethanoate ion, one of the lone pairs on the negative oxygen ends up
almost parallel to these p orbitals, and overlaps with them.

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Explaining the acidity of organic acids

This leads to a delocalised pi system over the whole of the -COO- group,
rather like that in benzene.

All the oxygen lone pairs have been left out of this diagram to avoid
confusion.
Because the oxygens are more electronegative than the carbon, the
delocalised system is heavily distorted so that the electrons spend much
more time in the region of the oxygen atoms.
So where is the negative charge in all this? It has been spread around
over the whole of the -COO- group, but with the greatest chance of finding
it in the region of the two oxygen atoms.
Ethanoate ions can be drawn simply as:

The dotted line represents the delocalisation. The negative charge is


written centrally on that end of the molecule to show that it isn't localised
on one of the oxygen atoms.
The more you can spread charge around, the more stable an ion
becomes. In this case, if you delocalise the negative charge over several
atoms, it is going to be much less attractive to hydrogen ions - and so you
are less likely to re-form the ethanoic acid.

Phenol
Phenols have an -OH group attached directly to a benzene ring. Phenol
itself is the simplest of these with nothing else attached to the ring apart
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Explaining the acidity of organic acids

from the -OH group.

When the hydrogen-oxygen bond in phenol breaks, you get a phenoxide


ion, C6H5O-.

Warning! You need to understand about the bonding in


benzene in order to make sense of this next bit.
If your syllabus says that you need to know about the acidity of
phenol, then you will have to understand the next few
paragraphs - which in turn means that you will have to
understand about benzene. If it doesn't mention phenol, skip it!
If you follow this link, you may have to explore several other
pages before you are ready to come back here again. Use the
BACK button (or HISTORY file or GO menu) on your browser
to return to this page.

Delocalisation also occurs in this ion. This time, one of the lone pairs on
the oxygen atom overlaps with the delocalised electrons on the benzene
ring.

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Explaining the acidity of organic acids

This overlap leads to a delocalisation which extends from the ring out over
the oxygen atom. As a result, the negative charge is no longer entirely
localised on the oxygen, but is spread out around the whole ion.

Why then is phenol a much weaker acid than ethanoic acid?


In the ethanoate ion, the delocalised system was distorted towards the
two oxygen atoms, therefore essentially sharing the negative charge
between them.
Since each oxygen atom only has about half the charge it would have if
there wasn't any delocalisation, neither oxygen is going to be as attractive
towards hydrogen ions as it would otherwise be.
That means that the ethanoate ion won't take up a hydrogen ion as easily
as it might otherwise. If it stays ionised, the formation of the hydrogen ions
means that it is acidic.
In the phenoxide ion, the single oxygen atom is still the most
electronegative thing present, and the delocalised system will be heavily
distorted towards it. That still leaves the oxygen atom with most of its
negative charge.
What delocalisation there is makes the phenoxide ion more stable than it
would otherwise be, and so phenol is acidic to an extent.
However, the delocalisation hasn't shared the charge around very
effectively. There is still lots of negative charge around the oxygen to
which hydrogen ions will be attracted - and so the phenol will readily re-

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Explaining the acidity of organic acids

form. Phenol is therefore only very weakly acidic.

Ethanol
Ethanol, CH3CH2OH, is so weakly acidic that you would hardly count it as
acidic at all. If the hydrogen-oxygen bond breaks to release a hydrogen
ion, an ethoxide ion is formed:

This has nothing at all going for it. There is no way of delocalising the
negative charge, which remains firmly on the oxygen atom. That intense
negative charge will be highly attractive towards hydrogen ions, and so
the ethanol will instantly re-form.
Since ethanol is very poor at losing hydrogen ions, it is hardly acidic at all.

Variations in acid strengths between different carboxylic


acids
You might think that all carboxylic acids would have the same strength
because each depends on the delocalisation of the negative charge
around the -COO- group to make the anion more stable, and so more
reluctant to re-combine with a hydrogen ion.
In fact, the carboxylic acids have widely different acidities. One obvious
difference is between methanoic acid, HCOOH, and the other simple
carboxylic acids:
pKa
HCOOH

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3.75

Explaining the acidity of organic acids

CH3COOH

4.76

CH3CH2COOH

4.87

CH3CH2CH2COOH

4.82

Remember that the higher the value for pKa, the weaker the acid is.
Why is ethanoic acid weaker than methanoic acid? It again depends on
the stability of the anions formed - on how much it is possible to delocalise
the negative charge. The less the charge is delocalised, the less stable
the ion, and the weaker the acid.
The methanoate ion (from methanoic acid) is:

The only difference between this and the ethanoate ion is the presence of
the CH3 group in the ethanoate.
But that's important! Alkyl groups have a tendency to "push" electrons
away from themselves. That means that there will be a small amount of
extra negative charge built up on the -COO- group. Any build-up of charge
will make the ion less stable, and more attractive to hydrogen ions.
Ethanoic acid is therefore weaker than methanoic acid, because it will reform more easily from its ions.

The other alkyl groups have "electron-pushing" effects very similar to the
methyl group, and so the strengths of propanoic acid and butanoic acid

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Explaining the acidity of organic acids

are very similar to ethanoic acid.

Note: If you want more information about the inductive effect


of alkyl groups, you could read about carbocations (carbonium
ions) in the mechanism section of this site.
Use the BACK button on your browser to return to this page if
you choose to follow this link.

The acids can be strengthened by pulling charge away from the -COOend. You can do this by attaching electronegative atoms like chlorine to
the chain.

As the next table shows, the more chlorines you can attach the better:
pKa
CH3COOH

4.76

CH2ClCOOH

2.86

CHCl2COOH

1.29

CCl3COOH

0.65

Trichloroethanoic acid is quite a strong acid.


Attaching different halogens also makes a difference. Fluorine is the most
electronegative and so you would expect it to be most successful at

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Explaining the acidity of organic acids

pulling charge away from the -COO- end and so strengthening the acid.
pKa
CH2FCOOH

2.66

CH2ClCOOH

2.86

CH2BrCOOH

2.90

CH2ICOOH

3.17

The effect is there, but isn't as great as you might expect.


Finally, notice that the effect falls off quite quickly as the attached halogen
gets further away from the -COO- end. Here is what happens if you move
a chlorine atom along the chain in butanoic acid.
pKa
CH3CH2CH2COOH

4.82

CH3CH2CHClCOOH

2.84

CH3CHClCH2COOH

4.06

CH2ClCH2CH2COOH

4.52

The chlorine is effective at withdrawing charge when it is next-door to the COO- group, and much less so as it gets even one carbon further away.

Where would you like to go now?


To the acids and bases menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .
http://www.chemguide.co.uk/basicorg/acidbase/acids.html (13 of 14)30/12/2004 11:06:05

Explaining the acidity of organic acids

You might also be interested in:


The properties and reactions of:
carboxylic acids . . .
amino acids . . .
phenol . . .
alcohols . . .

Jim Clark 2000

http://www.chemguide.co.uk/basicorg/acidbase/acids.html (14 of 14)30/12/2004 11:06:05

bonding in carbonyl compounds - the carbon oxygen double bond

BONDING IN CARBONYL COMPOUNDS

Important! Don't try to read this unless you are sure that
you fully understand the orbital view of the bonding in
methane and the bonding in ethene.
You may also find it useful to read the article on orbitals if you
aren't sure about simple orbital theory.

The carbonyl group


The simple view of the bonding in carbon - oxygen double bonds
Where the carbon-oxygen double bond, C=O, occurs in
organic compounds it is called a carbonyl group. The
simplest compound containing this group is methanal.
We are going to look at the bonding in methanal, but it
would equally apply to any other compound containing
C=O. The interesting thing is the nature of the carbon-oxygen double
bond - not what it's attached to.

Note: Methanal is normally written as HCHO. If you wrote it


as HCOH, it looks as if it contains an -O-H group - and it
doesn't. Methanal is an aldehyde. All aldehydes contain the
CHO group.
Naming: methanal: meth counts 1 carbon atom, an means
no C=C, al says that it is an aldehyde and so contains CHO.

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bonding in carbonyl compounds - the carbon oxygen double bond

An orbital view of the bonding in carbon - oxygen double bonds


The carbon atom
Just as in ethene or benzene, the carbon atom is joined to three other
atoms. The carbon's electrons rearrange themselves, and promotion and
hybridisation give sp2 hybrid orbitals.
Promotion gives:

Hybridisation of the 2s orbital and two of


the 2p orbitals means that the carbon
atom now looks like the diagram on the
right.
Three sp2 hybrid orbitals are formed and
these arrange themselves as far apart in
space as they can - at 120 to each
other. The remaining p orbital is at right
angles to them.
This is exactly the same as in ethene or in benzene.

Important! If this isn't really clear to you, you must go and


read the article about the bonding in ethene.

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bonding in carbonyl compounds - the carbon oxygen double bond

The oxygen atom


Oxygen's electronic structure is 1s22s22px22py12pz1.
The 1s electrons are too deep inside the atom to be concerned with the
bonding and so we'll ignore them from now on. Hybridisation occurs in
the oxygen as well. It is easier to see this using "electrons-in-boxes".

This time two of the sp2 hybrid orbitals contain lone pairs of electrons.

Help! A "lone pair" of electrons is a pair of electrons at the


bonding level which isn't being used to bond on to another
atom.

The carbon atom and oxygen atom then bond in much the same way as
the two carbons do in ethene. In the next diagram, we are assuming that
the carbon will also bond to two hydrogens to make methanal - but it
could equally well bond to anything else.

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bonding in carbonyl compounds - the carbon oxygen double bond

End-to-end overlap between the atomic orbitals that are pointing towards
each other produce sigma bonds.
Notice that the p orbitals are overlapping sideways.

This sideways overlap produces a pi bond. So just like C=C, C=O is


made up of a sigma bond and a pi bond.
Does that mean that the bonding is exactly the same as in ethene? No!
The distribution of electrons in the pi bond is heavily distorted towards
the oxygen end of the bond, because oxygen is much more
electronegative than carbon.

Help! You can read about the origins of electronegativity and


its effects in organic compounds in a separate article.

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bonding in carbonyl compounds - the carbon oxygen double bond

This distortion in the pi bond causes major differences in the reactions of


compounds containing carbon-oxygen double bonds like methanal
compared with compounds containing carbon-carbon double bonds like
ethene.

Note: You can read about addition reactions or additionelimination reactions of carbonyl compounds elswhere on this
site.

Where would you like to go now?


To the organic bonding menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/basicorg/bonding/carbonyl.html (5 of 5)30/12/2004 11:06:17

Nucleophilic Addition Mechanisms Menu

Understanding Chemistry

NUCLEOPHILIC ADDITION MECHANISMS MENU

The addition of hydrogen cyanide to aldehydes and ketones . . .


Facts and mechanism for the nucleophilic addition of hydrogen
cyanide, HCN, to aldehydes and ketones.
The reduction of aldehydes and ketones . . .
Facts and a simplified mechanism for the reduction of aldehydes
and ketones using sodium tetrahydridoborate, NaBH4.

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of aldehydes and ketones . . .
Covers all the physical and chemical properties of aldehydes and
ketones required by UK A level syllabuses.

http://www.chemguide.co.uk/mechanisms/nucaddmenu.html (1 of 2)30/12/2004 11:06:18

Nucleophilic Addition Mechanisms Menu

Jim Clark 2000 (modified 2004)

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

THE NUCLEOPHILIC ADDITION OF HYDROGEN


CYANIDE TO ALDEHYDES AND KETONES

This page gives you the facts and simple, uncluttered mechanisms for
the nucleophilic addition reactions between carbonyl compounds
(specifically aldehydes and ketones) and hydrogen cyanide, HCN. If you
want the mechanisms explained to you in detail, there is a link at the
bottom of the page.
Aldehydes and ketones behave identically in their reaction with hydrogen
cyanide, and so will be considered together - although equations and
mechanisms will be given for both types of compounds for the sake of
completeness.

The reaction of aldehydes and ketones with hydrogen


cyanide
The facts
Hydrogen cyanide adds across the carbon-oxygen double bond in
aldehydes and ketones to produce compounds known as hydroxynitriles.
For example, with ethanal (an aldehyde) you get 2-hydroxypropanenitrile:

With propanone (a ketone) you get 2-hydroxy-2-methylpropanenitrile:

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

Note: When you are naming these compounds, don't forget


that the longest carbon chain has to include the carbon in the
-CN group. In both of the above examples, the longest
carbon chain is 3 carbons - hence the "prop" in both names.
The carbon with the nitrogen attached is always counted as
the number 1 carbon in the chain.

The reaction isn't normally done using hydrogen cyanide itself, because
this is an extremely poisonous gas. Instead, the aldehyde or ketone is
mixed with a solution of sodium or potassium cyanide in water to which a
little sulphuric acid has been added. The pH of the solution is adjusted to
about 4 - 5, because this gives the fastest reaction.
The solution will contain hydrogen cyanide (from the reaction between
the sodium or potassium cyanide and the sulphuric acid), but still
contains some free cyanide ions. This is important for the mechanism.

Note: If the reaction is done using hydrogen cyanide itself, a


little sodium hydroxide solution is added to produce some
cyanide ions from the weakly acidic HCN. Again the pH of the
solution is adjusted to around pH 5 - in other words, the
sodium hydroxide is not added to excess. The rate of the
reaction falls if the pH is any higher.
Whichever set of reagents you use, the reaction contains the
same mixture of hydrogen cyanide and cyanide ions.

The mechanisms
These are examples of nucleophilic addition.
The carbon-oxygen double bond is highly polar, and
the slightly positive carbon atom is attacked by the
cyanide ion acting as a nucleophile.

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

Nucleophile: A species (molecule or ion) which attacks a


positive site in something else. Nucleophiles are either fully
negative ions or contain a fairly negative region somewhere
in a molecule. All nucleophiles have at least one active lone
pair of electrons. When you write mechanisms for reactions
involving nucleophiles, you must show that lone pair.

The mechanism for the addition of HCN to propanone


In the first stage, there is a nucleophilic attack by the cyanide ion on the
slightly positive carbon atom.

The negative ion formed then picks up a hydrogen ion from somewhere for example, from a hydrogen cyanide molecule.

The hydrogen ion could also come from the water or the H3O+ ions
present in the slightly acidic solution. You don't need to remember all of
these. One equation is perfectly adequate.

Note: The product molecule here has been drawn differently


from the one in the equation further up this page. It has been
rotated through 90. There is no reason why you can't do that
if it makes the appearance of the mechanism easier to follow.

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

The mechanism for the addition of HCN to ethanal


As before, the reaction starts with a nucleophilic attack by the cyanide
ion on the slightly positive carbon atom.

It is completed by the addition of a hydrogen ion from, for example, a


hydrogen cyanide molecule.

Note: Again, the product molecule looks different from the


one in the equation further up this page. The central carbon
atom still has the same four groups attached, but to make the
mechanism easier to follow, they are simply arranged
differently. That's not a problem - we're still talking about the
same substance.

Optical isomerism in 2-hydroxypropanenitrile


When 2-hydroxypropanenitrile is made in this last mechanism, it occurs
as a racemic mixture - a 50/50 mixture of two optical isomers. It is
possible that you might be exected to explain how this arises.

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

Note: You almost certainly won't be able to tell whether or


not you need to know this from the syllabus. You need to
refer to recent exam papers and mark schemes. If you
haven't already got these, you can obtain them from your
Exam Board via links on the syllabuses page.

Optical isomerism occurs in compounds which have four different groups


attached to a single carbon atom. In this case, the product molecule
contains a CH3, a CN, an H and an OH all attached to the central carbon
atom.
The reason for the formation of equal amounts of
two isomers lies in the way the ethanal gets
attacked.
Ethanal is a planar molecule, and attack by a
cyanide ion will either be from above the plane of the molecule, or from
below. There is an equal chance of either happening.

Attack from one side will lead to one of the two isomers, and attack from
the other side will lead to the other.

Note: This is probably as much as you need to know for


exam purposes, but a full explanation of this is given on the
"talk through" page. Follow the link below.

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nucleophilic addition - carbonyl compounds and hydrogen cyanide

All aldehydes will form a racemic mixture in this way. Unsymmetrical


ketones will as well. (A ketone can be unsymmetrical in the sense that
there is a different alkyl group either side of the carbonyl group.) What
matters is that the product molecule must have four different groups
attached to the carbon which was originally part of the carbon-oxygen
double bond.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of nucleophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

EXPLAINING THE NUCLEOPHILIC ADDITION OF


HYDROGEN CYANIDE TO ALDEHYDES AND
KETONES
This page explains the mechanism for the nucleophilic addition reaction
between carbonyl compounds (specifically aldehydes and ketones) and
hydrogen cyanide. It also looks in some detail at why a racemic mixture
is formed when hydrogen cyanide reacts with an aldehyde like ethanal.

Background
Bonding in the carbonyl group: the carbon-oxygen double bond
Oxygen is far more electronegative than carbon and
so has a strong tendency to pull electrons in a
carbon-oxygen bond towards itself. One of the two
pairs of electrons that make up a carbon-oxygen
double bond is even more easily pulled towards the oxygen. That makes
the carbon-oxygen double bond very highly polar.

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you go on.
If you are interested in really understanding the bonding in
the carbon-oxygen double bond you could explore it in detail
by following this link. You don't need to know about this to
understand the rest of this page. You might find that following
this link will take you some time, because you will probably
have to explore several pages of background material as well.

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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

The cyanide ion as a nucleophile


A nucleophile is a species (either a negatively charged ion or a negative
region in a polar molecule) which is attracted to a positive site in another
substance. All nucleophiles contain an active lone pair of electrons.
The cyanide ion comes from hydrogen cyanide, which is a covalent
molecule. Hydrogen cyanide is very weakly acidic, which means that it
can lose a hydrogen ion - although not very easily.

Notice that when the hydrogen is lost, it leaves its electron behind on the
carbon. That leaves a lone pair of electrons on that carbon, together with
a negative charge. It's essential to realise that in the cyanide ion the
active lone pair and the charge are on the carbon atom and not the
nitrogen.

Note: There is also a lone pair on the nitrogen atom (not


shown to avoid confusion), but that isn't important because
that's not where the negative charge is.

Explaining the conditions for the reaction


Remember that the reaction is done by reacting the aldehyde or ketone
with a solution of sodium or potassium cyanide to which enough dilute
sulphuric acid is added to give a pH of around 4 - 5.
Hydrogen cyanide as a very weak acid
The initial attack on the carbonyl group is by a cyanide ion. Although the
reaction overall adds hydrogen cyanide across the double bond, using
hydrogen cyanide as the reagent isn't successful because hydrogen
cyanide is such a weak acid. It produces very, very few hydrogen ions
and cyanide ions in solution. The number of cyanide ions available to
attack the slightly positive carbon is extremely small and so the reaction
would be very slow.
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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

Why is the potassium cyanide acidified slightly?


The presence of an acid in solution helps to strengthen the polarity of the
carbon-oxygen double bond. The electrons in that bond are strongly
attracted towards the hydrogen ions in the solution.

Why isn't a lot more acid added to give a really low pH?
You might think that the more acid you added, the more you could
increase the polarity of the carbon-oxygen double bond. Unfortunately,
there is a competing effect.
The more acid you add, the more the cyanide ions get converted into
hydrogen cyanide. Since cyanide ions are what actually attacks the
slightly positive carbon, removing them isn't helpful!
A pH of 4 - 5 is found experimentally to give you the best rate of reaction.
It increases the polarity of the double bond by a useful amount, but
without removing too many of the cyanide ions as HCN.

The mechanisms
Mechanisms for the addition of hydrogen cyanide to aldehydes and
ketones are given separately for completeness, but there is no absolutely
no difference between them. They are examples of nucleophilic
addition.
The mechanism for the addition of HCN to propanone
As the cyanide ion approaches the slightly positive carbon atom, the lone

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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

pair of electrons is attracted towards the carbon and forms a bond with it.
At the same time the two electrons in one of the bonds joining the carbon
to the oxygen are repelled until they end up entirely on the oxygen giving it a negative charge.

Note: If you aren't happy about the use of curly arrows in


mechanisms, follow this link before you go on. Use the BACK
button on your browser to return to this page.

The negative ion formed then picks up a hydrogen ion from somewhere for example, from a hydrogen cyanide molecule.

The hydrogen ion could also come from the water or the H3O+ ions (often
written as H+(aq)) present in the slightly acidic solution. You don't need to
remember all of these. One equation is perfectly adequate. In fact, most
sources show this final stage as a reaction with just H+.

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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

Note: Although most people (including examiners) probably


take this short cut, it doesn't mean that it's right. It is sloppy
because it suggests the possibility of free hydrogen ions in a
chemical reaction - hydrogen ions are simply protons, and
are always attached to something else. It also denies you the
satisfaction of writing an equation which shows the
production of a new cyanide ion which can go on to react with
another molecule of the carbonyl compound.
If you can't be bothered to do it properly, then do at least
write the hydrogen ion as H+(aq) - not just as H+.

The mechanism for the addition of HCN to ethanal


Exactly as before, as the cyanide ion approaches the slightly positive
carbon atom, the lone pair of electrons is attracted towards the carbon
and forms a bond with it. At the same time the two electrons in one of the
bonds joining the carbon to the oxygen are repelled until they end up
entirely on the oxygen - giving it a negative charge.

The negative ion formed then picks up a hydrogen ion from somewhere for example, from a hydrogen cyanide molecule.

Once again, most sources show this final stage as a reaction with just H
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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

+.

If you must do it that way, then write the hydrogen ion as H+(aq) - not

just as H+.

Optical isomerism in 2-hydroxypropanenitrile


2-hydroxypropanenitrile is the name of the product when ethanal reacts
with hydrogen cyanide. It is formed in this reaction as an exactly equal
mixture of two optical isomers, known as a racemic mixture.

Note: For a full discussion of optical isomerism follow this


link. Use the BACK button on your browser to return to this
page.

Optical isomerism occurs in compounds which have four different groups


attached to a single carbon atom. In this case, the product molecule
contains a CH3, a CN, an H and an OH all attached to the central carbon
atom.
The reason for the formation of equal amounts of
two isomers lies in the way the ethanal gets
attacked.
Ethanal is a planar molecule, and attack by a
cyanide ion will either be from above the plane of the molecule, or from
below. There is an equal chance of either happening.

Attack from above will lead to one of the two isomers, and attack from
below will lead to the other.
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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

The next diagram shows what happens if attack is from above the plane
of the molecule. Notice that the existing groups get forced down away
from the approaching cyanide ion. The diagram shows the final product
after it has gained a hydrogen ion.

Attack from below forces the existing groups upwards.

Why are these two product molecules different from each other?
Everything seems to be attached in the same way, but look what
happens if you rotate the second molecule in space so that the cyanide
group is at the top.

Now compare that with the molecule formed by attack from above.

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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

They aren't the same! Although the CN and H are lined up the same way,
the CH3 and OH are reversed. There is no way that you can rotate one
molecule in space to make it look the same as the other one. These are
therefore isomers.
The relationship between them is that they are mirror images of each
other. If one isomer were to look in a mirror, what it would see would be
the other one. Optical isomers are described as "non-superimposable
mirror images".
Because there is an equal chance of the attack coming from above or
below the plane of the molecule, then you will get equal amounts of the
two isomers formed - a racemic mixture.
This argument applies to all aldehydes, and to ketones as long as they
are unsymmetric - with a different alkyl group either side of the carbonyl
group.
A symmetric ketone like propanone, CH3COCH3, will only produce a
single product - not a mixture of isomers. The product doesn't have four
different groups around the central carbon atom, and so won't have
optical isomers. If you followed the above argument through with
propanone, you would find that you ended up with two molecules which
could be rotated in space so that they were identical. Convince yourself
by trying it!

Where would you like to go now?


To menu of nucleophilic addition reactions. . .
To menu of other types of mechanism. . .
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Explaining the nucleophilic addition of hydrogen cyanide to carbonyl compounds

To Main Menu . . .

Jim Clark 2000

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optical isomerism

STEREOISOMERISM - OPTICAL ISOMERISM

Optical isomerism is a form of stereoisomerism. This page explains what


stereoisomers are and how you recognise the possibility of optical
isomers in a molecule.

What is stereoisomerism?
What are isomers?
Isomers are molecules that have the same molecular formula, but have a
different arrangement of the atoms in space. That excludes any different
arrangements which are simply due to the molecule rotating as a whole,
or rotating about particular bonds.
Where the atoms making up the various isomers are joined up in a
different order, this is known as structural isomerism. Structural
isomerism is not a form of stereoisomerism, and is dealt with on a
separate page.

Note: If you aren't sure about structural isomerism, it might


be worth reading about it before you go on with this page.

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optical isomerism

What are stereoisomers?


In stereoisomerism, the atoms making up the isomers are joined up in
the same order, but still manage to have a different spatial arrangement.
Optical isomerism is one form of stereoisomerism.

Optical isomerism
Why optical isomers?
Optical isomers are named like this because of their effect on plane
polarised light.

Help! If you don't understand about plane polarised light,


follow this link before you go on with this page.

Simple substances which show optical isomerism exist as two isomers


known as enantiomers.

A solution of one enantiomer rotates the plane of polarisation in a


clockwise direction. This enantiomer is known as the (+) form.
For example, one of the optical isomers (enantiomers) of the
amino acid alanine is known as (+)alanine.

A solution of the other enantiomer rotates the plane of polarisation


in an anti-clockwise direction. This enantiomer is known as the (-)
form. So the other enantiomer of alanine is known as or (-)alanine.
If the solutions are equally concentrated the amount of rotation
caused by the two isomers is exactly the same - but in opposite
directions.
When optically active substances are made in the lab, they often
occur as a 50/50 mixture of the two enantiomers. This is known as

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optical isomerism

a racemic mixture or racemate. It has no effect on plane


polarised light.

Note: One of the worrying things about optical isomerism is


the number of obscure words that suddenly get thrown at
you. Bear with it - things are soon going to get more visual!
There is an alternative way of describing the (+) and (-) forms
which is potentially very confusing. This involves the use of
the lowercase letters d- and l-, standing for dextrorotatory
and laevorotatory respectively. Unfortunately, there is
another different use of the capital letters D- and L- in this
topic. This is totally confusing! Stick with (+) and (-).

How optical isomers arise


The examples of organic optical isomers required at A' level all contain a
carbon atom joined to four different groups. These two models each have
the same groups joined to the central carbon atom, but still manage to be
different:

Obviously as they are drawn, the orange and blue groups aren't aligned
the same way. Could you get them to align by rotating one of the
molecules? The next diagram shows what happens if you rotate
molecule B.

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optical isomerism

They still aren't the same - and there is no way that you can rotate them
so that they look exactly the same. These are isomers of each other.
They are described as being non-superimposable in the sense that (if
you imagine molecule B being turned into a ghostly version of itself) you
couldn't slide one molecule exactly over the other one. Something would
always be pointing in the wrong direction.

Note: Unless your visual imagination is reasonably good,


this is much easier to understand if you have actually got
some models to play with. If your school or college hasn't
given you the opportunity to play around with molecular
models, you might consider getting hold of a cheap set. The
models made by molymod are both cheap and easy to use.
An introductory organic set is more than adequate. Find them
at www.molymod.com.
Alternatively , get hold of some coloured Plasticene and
some used matches and make your own.

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optical isomerism

What happens if two of the groups attached to the central carbon atom
are the same? The next diagram shows this possibility.

The two models are aligned exactly as before, but the orange group has
been replaced by another pink one.
Rotating molecule B this time shows that it is exactly the same as
molecule A. You only get optical isomers if all four groups attached to the
central carbon are different.

Chiral and achiral molecules


The essential difference between the two examples we've looked at lies
in the symmetry of the molecules.
If there are two groups the same attached to the central carbon atom, the
molecule has a plane of symmetry. If you imagine slicing through the
molecule, the left-hand side is an exact reflection of the right-hand side.
Where there are four groups attached, there is no symmetry anywhere in
the molecule.

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optical isomerism

A molecule which has no plane of symmetry is described as chiral. The


carbon atom with the four different groups attached which causes this
lack of symmetry is described as a chiral centre or as an asymmetric
carbon atom.
The molecule on the left above (with a plane of symmetry) is described
as achiral.
Only chiral molecules have optical isomers.

The relationship between the enantiomers


One of the enantiomers is simply a non-superimposable mirror image
of the other one.
In other words, if one isomer looked in a mirror, what it would see is the
other one. The two isomers (the original one and its mirror image) have a
different spatial arrangement, and so can't be superimposed on each
other.

If an achiral molecule (one with a plane of symmetry) looked in a mirror,


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optical isomerism

you would always find that by rotating the image in space, you could
make the two look identical. It would be possible to superimpose the
original molecule and its mirror image.

Some real examples of optical isomers


Butan-2-ol
The asymmetric carbon atom in a compound (the one with four different
groups attached) is often shown by a star.

It's extremely important to draw the isomers correctly. Draw one of them
using standard bond notation to show the 3-dimensional arrangement
around the asymmetric carbon atom. Then draw the mirror to show the
examiner that you know what you are doing, and then the mirror image.

Help! If you don't understand this bond notation, follow this


link to drawing organic molecules before you go on with this
page.

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optical isomerism

Notice that you don't literally draw the mirror images of all the letters and
numbers! It is, however, quite useful to reverse large groups - look, for
example, at the ethyl group at the top of the diagram.
It doesn't matter in the least in what order you draw the four groups
around the central carbon. As long as your mirror image is drawn
accurately, you will automatically have drawn the two isomers.
So which of these two isomers is (+)butan-2-ol and which is (-)butan-2ol? There is no simple way of telling that. For A'level purposes, you can
just ignore that problem - all you need to be able to do is to draw the two
isomers correctly.
2-hydroxypropanoic acid (lactic acid)
Once again the chiral centre is shown by a star.

The two enantiomers are:

It is important this time to draw the COOH group backwards in the mirror
image. If you don't there is a good chance of you joining it on to the
central carbon wrongly.

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optical isomerism

If you draw it like this in an exam, you won't get the mark for that isomer
even if you have drawn everything else perfectly.
2-aminopropanoic acid (alanine)
This is typical of naturally-occurring amino acids. Structurally, it is just
like the last example, except that the -OH group is replaced by -NH2

The two enantiomers are:

Only one of these isomers occurs naturally: the (+) form. You can't tell
just by looking at the structures which this is.
It has, however, been possible to work out which of these structures is
which. Naturally occurring alanine is the right-hand structure, and the
way the groups are arranged around the central carbon atom is known
as an L- configuration. Notice the use of the capital L. The other
configuration is known as D-.
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optical isomerism

So you may well find alanine described as L-(+)alanine.


That means that it has this particular structure and rotates the plane of
polarisation clockwise.
Even if you know that a different compound has an arrangement of
groups similar to alanine, you still can't say which way it will rotate the
plane of polarisation.
The other amino acids, for example, have the same arrangement of
groups as alanine does (all that changes is the CH3 group), but some are
(+) forms and others are (-) forms.
It's quite common for natural systems to only work with one of the
enantiomers of an optically active substance. It isn't too difficult to see
why that might be. Because the molecules have different spatial
arrangements of their various groups, only one of them is likely to fit
properly into the active sites on the enzymes they work with.
In the lab, it is quite common to produce equal amounts of both forms of
a compound when it is synthesised. This happens just by chance, and
you tend to get racemic mixtures.

Note: For a detailed discussion of this, you could have a


look at the page on the addition of HCN to aldehydes

Where would you like to go now?


To the isomerism menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

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optical isomerism

Jim Clark 2000 (modified 2004)

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structural isomerism

STRUCTURAL ISOMERISM

This page explains what structural isomerism is, and looks at some of the
various ways that structural isomers can arise.

What is structural isomerism?


What are isomers?
Isomers are molecules that have the same molecular formula, but have a
different arrangement of the atoms in space. That excludes any different
arrangements which are simply due to the molecule rotating as a whole,
or rotating about particular bonds.
For example, both of the following are the same molecule. They are not
isomers. Both are butane.

There are also endless other possible ways that this molecule could twist
itself. There is completely free rotation around all the carbon-carbon
single bonds.

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structural isomerism

Note: Isomerism is much easier to understand if you have


actually got some models to play with. If your school or
college hasn't given you the opportunity to play around with
molecular models in the early stages of your organic
chemistry course, you might consider getting hold of a cheap
set. The models made by molymod are both cheap and easy
to use. An introductory organic set is more than adequate.
Find them at www.molymod.com.
Alternatively , get hold of some coloured Plasticene and
some used matches and make your own.

If you had a model of a molecule in front of you, you would have to take it
to pieces and rebuild it if you wanted to make an isomer of that molecule.
If you can make an apparently different molecule just by rotating single
bonds, it's not different - it's still the same molecule.

Note: It's really important that you understand this. If you


aren't sure, then you must get hold of (or make) some
models.

What are structural isomers?


In structural isomerism, the atoms are arranged in a completely different
order. This is easier to see with specific examples.
What follows looks at some of the ways that structural isomers can arise.
The names of the various forms of structural isomerism probably don't
matter all that much, but you must be aware of the different possibilities
when you come to draw isomers.

Types of structural isomerism

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structural isomerism

Chain isomerism
These isomers arise because of the possibility of branching in carbon
chains. For example, there are two isomers of butane, C4H10. In one of
them, the carbon atoms lie in a "straight chain" whereas in the other the
chain is branched.

Note: Although the chain is drawn as straight, in reality it's


anything but straight. If you aren't happy about the ways of
drawing organic molecules, follow this link.
Use the BACK button on your browser to return to this page.

Be careful not to draw "false" isomers which are just


twisted versions of the original molecule. For example,
this structure is just the straight chain version of butane rotated about the
central carbon-carbon bond.
You could easily see this with a model. This is the example we've already
used at the top of this page.

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structural isomerism

Pentane, C5H12, has three chain isomers. If you think you can find any
others, they are simply twisted versions of the ones below. If in doubt
make some models.

Position isomerism
In position isomerism, the basic carbon skeleton remains unchanged, but
important groups are moved around on that skeleton.
For example, there are two structural isomers with the molecular formula
C3H7Br. In one of them the bromine atom is on the end of the chain,
whereas in the other it's attached in the middle.

If you made a model, there is no way that you could twist one molecule
to turn it into the other one. You would have to break the bromine off the
end and re-attach it in the middle. At the same time, you would have to
move a hydrogen from the middle to the end.
Another similar example occurs in alcohols such as C4H9OH

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structural isomerism

These are the only two possibilities provided you keep to a four carbon
chain, but there is no reason why you should do that. You can easily
have a mixture of chain isomerism and position isomerism - you aren't
restricted to one or the other.
So two other isomers of butanol are:

Note: It's essential if you are asked to draw isomers in an


exam not to restrict yourself to chain isomers or position
isomers. You must be aware of all the possibilities.

You can also get position isomers on benzene rings. Consider the
molecular formula C7H8Cl. There are four different isomers you could
make depending on the position of the chlorine atom. In one case it is
attached to the side-group carbon atom, and then there are three other
possible positions it could have around the ring - next to the CH3 group,
next-but-one to the CH3 group, or opposite the CH3 group.

Functional group isomerism


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structural isomerism

In this variety of structural isomerism, the isomers contain different


functional groups - that is, they belong to different families of compounds
(different homologous series).
For example, a molecular formula C3H6O could be either propanal (an
aldehyde) or propanone (a ketone).

There are other possibilities as well for this same molecular formula - for
example, you could have a carbon-carbon double bond (an alkene) and
an -OH group (an alcohol) in the same molecule.

Another common example is illustrated by the molecular formula


C3H6O2. Amongst the several structural isomers of this are propanoic
acid (a carboxylic acid) and methyl ethanoate (an ester).

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structural isomerism

Note: To repeat the warning given earlier: If you are asked


to draw the structural isomers from a given molecular
formula, don't forget to think about all the possibilities. Can
you branch the carbon chain? Can you move a group around
on that chain? Is it possible to make more than one type of
compound?
Be careful though! If you are asked to draw the structures of
esters with the molecular formula C3H6O2, you aren't going to
get a lot of credit for drawing propanoic acid, even if it is a
valid isomer.

Where would you like to go now?


To the isomerism menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/basicorg/isomerism/structural.html (7 of 7)30/12/2004 11:06:49

Isomerism Menu

Understanding Chemistry

ISOMERISM MENU

Structural isomerism . . .
Explains what structural isomerism is, together with examples of
the various ways that these isomers can arise.
Geometric isomerism . . .
Explains how geometric (cis/trans) isomerism arises in simple
organic compounds containing carbon-carbon double bonds.
Optical isomerism . . .
Explains how to recognise optical isomerism in simple cases, and
how to draw the isomers.

Go to menu of basic organic chemistry. . .


Go to Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/basicorg/isomermenu.html30/12/2004 11:06:51

geometric (cis / trans) isomerism

STEREOISOMERISM - GEOMETRIC ISOMERISM

Geometric isomerism (also known as cis / trans isomerism) is a form of


stereoisomerism. This page explains what stereoisomers are and how
you recognise the possibility of geometric isomers in a molecule.

What is stereoisomerism?
What are isomers?
Isomers are molecules that have the same molecular formula, but have a
different arrangement of the atoms in space. That excludes any different
arrangements which are simply due to the molecule rotating as a whole,
or rotating about particular bonds.
Where the atoms making up the various isomers are joined up in a
different order, this is known as structural isomerism. Structural
isomerism is not a form of stereoisomerism, and is dealt with on a
separate page.

Note: If you aren't sure about structural isomerism, it might


be worth reading about it before you go on with this page.

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geometric (cis / trans) isomerism

What are stereoisomers?


In stereoisomerism, the atoms making up the isomers are joined up in
the same order, but still manage to have a different spatial arrangement.
Geometric isomerism is one form of stereoisomerism.

Geometric (cis / trans) isomerism


How geometric isomers arise
These isomers occur where you have restricted rotation somewhere in a
molecule. The only examples of this required at A' level involve the
carbon-carbon double bond.
Think about what happens in molecules where there is unrestricted
rotation about carbon bonds - in other words where the carbon-carbon
bonds are all single. The next diagram shows two possible configurations
of 1,2-dichloroethane.

These two models represent exactly the same molecule. You can get
from one to the other just by twisting around the carbon-carbon single
bond. These molecules are not isomers.
If you draw a structural formula instead of using models, you have to
bear in mind the possibility of this free rotation about single bonds. You
must accept that these two structures represent the same molecule:

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geometric (cis / trans) isomerism

But what happens if you have a carbon-carbon double bond - as in 1,2dichloroethene?

These two molecules aren't the same. The carbon-carbon double bond
won't rotate and so you would have to take the models to pieces in order
to convert one structure into the other one. That is a simple test for
isomers. If you have to take a model to pieces to convert it into another
one, then you've got isomers. If you merely have to twist it a bit, then you
haven't!

Note: In the model, the reason that you can't rotate a carboncarbon double bond is that there are two links joining the
carbons together. In reality, the reason is that you would
have to break the pi bond. Pi bonds are formed by the
sideways overlap between p orbitals. If you tried to rotate the
carbon-carbon bond, the p orbitals won't line up any more
and so the pi bond is disrupted. This costs energy and only
happens if the compound is heated strongly.
If you are interested in the bonding in carbon-carbon double
bonds, follow this link. Be warned, though, that you might
have to read several pages of background material and it
could all take a long time. It isn't necessary for understanding
the rest of this page.

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geometric (cis / trans) isomerism

Drawing structural formulae for the last pair of models gives two possible
isomers.
In one, the two chlorine atoms are locked on opposite sides of the double
bond. This is known as the trans isomer. (trans : from latin meaning
"across" - as in transatlantic).
In the other, the two chlorine atoms are locked on the same side of the
double bond. This is know as the cis isomer. (cis : from latin meaning "on
this side")

The most likely example of geometric isomerism you will meet at A' level
is but-2-ene. In one case, the CH3 groups are on opposite sides of the
double bond, and in the other case they are on the same side.

The importance of drawing geometric isomers properly


It's very easy to miss geometric isomers in exams if you take short-cuts
in drawing the structural formulae. For example, it is very tempting to
draw but-2-ene as
CH3CH=CHCH3

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geometric (cis / trans) isomerism

If you write it like this, you will almost certainly miss the fact that there are
geometric isomers. If there is even the slightest hint in a question that
isomers might be involved, always draw compounds containing carboncarbon double bonds showing the correct bond angles (120 ) around the
carbon atoms at the ends of the bond. In other words, use the format
shown in the last diagrams above.

How to recognise the possibility of geometric isomerism


You obviously need to have restricted rotation somewhere in the
molecule. For A' level purposes, that means a carbon-carbon double
bond. If you have a carbon-carbon double bond, then think carefully
about the possibility of geometric isomers.
What needs to be attached to the carbon-carbon double bond?

Note: This is much easier to understand if you have actually


got some models to play with. If your school or college hasn't
given you the opportunity to play around with molecular
models in the early stages of your organic chemistry course,
you might consider getting hold of a cheap set. The models
made by molymod are both cheap and easy to use. An
introductory organic set is more than adequate. Find them at
www.molymod.com.
Alternatively , get hold of some coloured Plasticene and
some used matches and make your own.

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geometric (cis / trans) isomerism

Think about this case:

Although we've swapped the right-hand groups around, these are still the
same molecule. To get from one to the other, all you would have to do is
to turn the whole model over.
You won't have geometric isomers if there are two groups the same on
one end of the bond - in this case, the two pink groups on the left-hand
end.
So . . . there must be two different groups on the left-hand carbon and
two different groups on the right-hand one. The cases we've been
exploring earlier are like this:

But you could make things even more different and still have geometric
isomers:

Here, the blue and green groups are either on the same side of the bond
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geometric (cis / trans) isomerism

or the opposite side.


Or you could go the whole hog and make everything different. You still
get geometric isomers, but this time the words cis and trans are
meaningless. Don't worry about this - you would never have to name a
complex case like this in an exam.

Summary
To get geometric isomers you must have:

restricted rotation (involving a carbon-carbon double bond for A'


level purposes);
two different groups on the left-hand end of the bond and two
different groups on the right-hand end. It doesn't matter whether
the left-hand groups are the same as the right-hand ones or not.

Note: You might not need this next bit if you are meeting
geometric isomerism for the first time. Don't get too bogged
down in it if you don't have to!

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geometric (cis / trans) isomerism

The effect of geometric isomerism on physical properties


The table shows the melting point and boiling point of the cis and trans
isomers of 1,2-dichloroethene.

isomer

melting point (C)

boiling point (C)

cis

-80

60

trans

-50

48

In each case, the higher melting or boiling point is shown in red.


You will notice that:

the trans isomer has the higher melting point;

the cis isomer has the higher boiling point.

This is common. You can see the same effect with the cis and trans
isomers of but-2-ene:

isomer

melting point (C)

boiling point (C)

cis-but-2-ene

-139

trans-but-2-ene

-106

Why is the boiling point of the cis isomers higher?


There must be stronger intermolecular forces between the molecules of
the cis isomers than between trans isomers.
Taking 1,2-dichloroethene as an example:
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geometric (cis / trans) isomerism

Both of the isomers have exactly the same atoms joined up in exactly the
same order. That means that the van der Waals dispersion forces
between the molecules will be identical in both cases.
The difference between the two is that the cis isomer is a polar molecule
whereas the trans isomer is non-polar.

Note: If you aren't sure about intermolecular forces (and also


about bond polarity), it is essential that you follow this link
before you go on. You need to know about van der Waals
dispersion forces and dipole-dipole interactions, and to follow
the link on that page to another about bond polarity if you
need to.
Use the BACK button on your browser to return to this page.

Both molecules contain polar chlorine-carbon bonds, but in the cis


isomer they are both on the same side of the molecule. That means that
one side of the molecule will have a slight negative charge while the
other is slightly positive. The molecule is therefore polar.

Because of this, there will be dipole-dipole interactions as well as


dispersion forces - needing extra energy to break. That will raise the
boiling point.
A similar thing happens where there are CH3 groups attached to the
carbon-carbon double bond, as in cis-but-2-ene.
Alkyl groups like methyl groups tend to "push" electrons away from
themselves. You again get a polar molecule, although with a reversed
polarity from the first example.
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geometric (cis / trans) isomerism

Note: The term "electron pushing" is only to help remember


what happens. The alkyl group doesn't literally "push" the
electrons away - the other end of the bond attracts them
more strongly. The arrows with the cross on (representing the
more positive end of the bond) are a conventional way of
showing this electron pushing effect.

By contrast, although there will still be polar bonds in the trans isomers,
overall the molecules are non-polar.

The slight charge on the top of the molecule (as drawn) is exactly
balanced by an equivalent charge on the bottom. The slight charge on
the left of the molecule is exactly balanced by the same charge on the
right.
This lack of overall polarity means that the only intermolecular attractions
these molecules experience are van der Waals dispersion forces. Less
energy is needed to separate them, and so their boiling points are lower.

Why is the melting point of the cis isomers lower?


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geometric (cis / trans) isomerism

You might have thought that the same argument would lead to a higher
melting point for cis isomers as well, but there is another important factor
operating.
In order for the intermolecular forces to work well, the molecules must be
able to pack together efficiently in the solid.
Trans isomers pack better than cis isomers. The "U" shape of the cis
isomer doesn't pack as well as the straighter shape of the trans isomer.
The poorer packing in the cis isomers means that the intermolecular
forces aren't as effective as they should be and so less energy is needed
to melt the molecule - a lower melting point.

Where would you like to go now?


To the isomerism menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000 (modified 2004)

http://www.chemguide.co.uk/basicorg/isomerism/geometric.html (11 of 11)30/12/2004 11:06:57

plane polarised light

PLANE POLARISED LIGHT

This page gives a simple explanation of what plane polarised light is and
the way it is affected by optically active compounds.

A simple analogy - "plane polarised string"


Imagine tying a piece of thick string to a hook in a wall, and then shaking
the string vigorously. The string will be vibrating in all possible directions
- up-and-down, side-to-side, and all the directions in-between - giving it a
really complex overall motion.

Now, suppose you passed the string through a vertical slit. The string is a
really snug fit in the slit. The only vibrations still happening the other side
of the slit will be vertical ones. All the others will have been prevented by
the slit.

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plane polarised light

What emerges from the slit could be described as "plane polarised


string", because the vibrations are only in a single (vertical) plane.
Now look at the possibility of putting a second slit on the string. If it is
aligned the same way as the first one, the vibrations will still get through.

But if the second slit is at 90 to the first one, the string will stop vibrating
entirely to the right of the second slit. The second slit will only let through
horizontal vibrations - and there aren't any.

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plane polarised light

The real thing - plane polarised light


Light is also made up of vibrations - this time, electromagnetic ones.
Some materials have the ability to screen out all the vibrations apart from
those in one plane and so produce plane polarised light.
The most familiar example of this is the material that Polaroid sunglasses
are made of. If you wear one pair of Polaroid sunglasses and hold
another pair up in front of them so that the glasses are held vertically
rather than horizontally, you'll find that no light gets through - you will just
see darkness. This is equivalent to the two slits at right angles in the
string analogy. The polaroids are described as being "crossed".

Care! It is important not to take the analogy too far. The


polaroid material doesn't consist of "slits" in any sense of the
word. The way it actually polarises the light is quite different
(and irrelevant to us here!).

Optically active substances


An optically active substance is one which can rotate the plane of
polarisation of plane polarised light. if you shine a beam of polarised
monochromatic light (light of only a single frequency - in other words a
single colour) through a solution of an optically active substance, when
the light emerges, its plane of polarisation is found to have rotated.
The rotation may be either clockwise or anti-clockwise. Assuming the
original plane of polarisation was vertical, you might get either of these
results.

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plane polarised light

How can you tell that the plane of polarisation has been rotated?
You use a polarimeter.

The polariser and analyser are both made of polaroid material.


The polarimeter is originally set up with water in the tube. Water isn't
optically active - it has no effect on the plane of polarisation. The
analyser is rotated until you can't see any light coming through the
instrument. The polaroids are then "crossed".

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plane polarised light

Now you put a solution of an optically active substance into the tube. It
rotates the plane of polarisation of the light, and so the analyser won't be
at right-angles to it any longer and some light will get through. You would
have to rotate the analyser in order to cut the light off again.

You can easily tell whether the plane of polarisation has been rotated
clockwise or anti-clockwise, and by how much.

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plane polarised light

Note: It is very unlikely that you will need to learn much of


this. You won't be able to tell from your syllabus whether any
of this is required. Look instead at past exam papers. If you
haven't already got these, you can get them from your Exam
Board by following the appropriate link on the syllabuses
page.
Probably all you need to be able to do is to understand the
expression "rotates the plane of polarisation of plane
polarised light" so that you can use it sensibly.

Where would you like to go now?


Back to optical isomerism. . .
To the isomerism menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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reduction of carbonyl compounds using sodium tetrahydridoborate

THE REDUCTION OF ALDEHYDES AND KETONES

This page gives you the facts and mechanisms for the reduction of
carbonyl compounds (specifically aldehydes and ketones) using sodium
tetrahydridoborate (sodium borohydride) as the reducing agent.
Only one UK A level Exam Board (AQA) is likely to ask for these
mechanisms, and they are happy with a simplified version of what is quite
a complex mechanism. Because of that simplification, these reactions are
dealt with entirely on this page - without the "talk through" page that you
will find for other mechanisms on this site.

The reduction of aldehydes and ketones by sodium


tetrahydridoborate
The facts
Sodium tetrahydridoborate (previously known as sodium borohydride) has
the formula NaBH4, and contains the BH4- ion. That ion acts as the
reducing agent.
There are several quite different ways of carrying out this reaction. Two
possible variants (there are several others!) are:

The reaction is carried out in solution in water to which some


sodium hydroxide has been added to make it alkaline. The reaction
produces an intermediate which is converted into the final product
by addition of a dilute acid like sulphuric acid.
The reaction is carried out in solution in an alcohol like methanol,
ethanol or propan-2-ol. This produces an intermediate which can be
converted into the final product by boiling it with water.

In each case, reduction essentially involves the addition of a hydrogen


atom to each end of the carbon-oxygen double bond to form an alcohol.
Reduction of aldehydes and ketones lead to two different sorts of alcohol.
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reduction of carbonyl compounds using sodium tetrahydridoborate

The reduction of an aldehyde


For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to


examiners. The H in square brackets means "hydrogen from a reducing
agent".
In general terms, reduction of an aldehyde leads to a primary alcohol. A
primary alcohol is one which only has one alkyl group attached to the
carbon with the -OH group on it. They all contain the grouping -CH2OH.

Note: There is one exception to this. Methanol CH3OH is also


a primary alcohol. Think of this as H-CH2OH.

The reduction of a ketone


For example, with propanone you get propan-2-ol:

Reduction of a ketone leads to a secondary alcohol. A secondary


alcohol is one which has two alkyl groups attached to the carbon with the OH group on it. They all contain the grouping -CHOH.

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reduction of carbonyl compounds using sodium tetrahydridoborate

Beware! The following mechanisms are simplified for UK A


level purposes to the point that they are wrong! If you are
working outside the UK A level system, please don't read any
further!

The simplified mechanisms


The BH4- ion is essentially a source of hydride ions, H-. The simplification
used is to write H- instead of BH4-.
Doing this not only makes the initial attack easier to write, but avoids you
getting involved with some quite complicated boron compounds that are
formed as intermediates.
The reduction is an example of nucleophilic
addition.
The carbon-oxygen double bond is highly polar, and
the slightly positive carbon atom is attacked by the
hydride ion acting as a nucleophile. A hydride ion is a hydrogen atom with
an extra electron - hence the lone pair.

Nucleophile: A species (molecule or ion) which attacks a


positive site in something else. Nucleophiles are either fully
negative ions or contain a fairly negative region somewhere in
a molecule. All nucleophiles have at least one active lone pair
of electrons. When you write mechanisms for reactions
involving nucleophiles, you must show that lone pair.

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reduction of carbonyl compounds using sodium tetrahydridoborate

The mechanism for the reduction of ethanal


In the first stage, there is a nucleophilic attack by the hydride ion on the
slightly positive carbon atom. The lone pair of electrons on the hydride ion
forms a bond with the carbon, and the electrons in one of the carbonoxygen bonds are repelled entirely onto the oxygen, giving it a negative
charge.

What happens now depends on whether you add an acid or water to


complete the reaction.
Adding an acid:
When the acid is added, the negative ion formed picks up a hydrogen ion
to give an alcohol.

Note: You may find that other sources write the hydrogen ion
simply as H+. That's not good practice, because it suggests a
free hydrogen ion. The hydrogen ion is actually attached to a
water molecule as H3O+. Writing that makes the equation look
more complicated. H+(aq) is a happy compromise.

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Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.

The mechanism for the reduction of propanone


As before, the reaction starts with a nucleophilic attack by the hydride ion
on the slightly positive carbon atom.

Again, what happens next depends on whether you add an acid or water
to complete the reaction.
Adding an acid:
The negative ion reacts with a hydrogen ion from the acid added in the
second stage of the reaction.

Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.

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reduction of carbonyl compounds using sodium tetrahydridoborate

Important!
Remember that the equations and mechanisms given on this page are not
the truth - they are merely simplifications to suit the demands of a
particular A' level syllabus.

Where would you like to go now?


To menu of nucleophilic addition reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000 (modified 2004)

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Aldehydes and Ketones Menu

Understanding Chemistry

ALDEHYDES AND KETONES MENU

Background . . .
An introduction to aldehydes and ketones, their reactivity and their
physical properties.
Preparation of aldehydes and ketones . . .
Their preparation by the oxidation of primary or secondary
alcohols.
Simple addition reactions . . .
The addition of hydrogen cyanide and of sodium hydrogensulphite
(sodium bisulphite) to aldehydes and ketones.
Reduction of aldehydes and ketones . . .
The reduction of aldehydes and ketones using sodium
tetrahydridoborate(III) or lithium tetrahydridoaluminate(III) (sodium
borohydride or lithium aluminium hydride).
Reactions with Grignard reagents . . .
The reactions of aldehydes and ketones with Grignard reagents as
a way of making complicated alcohols.
Oxidation of aldehydes and ketones . . .
Covers the main ways of distinguishing between aldehydes and
ketones using, for example, Tollens' reagent, Fehling's solution or
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Aldehydes and Ketones Menu

Benedict's solution.
Addition-elimination reactions . . .
Looks at the test for aldehydes and ketones using 2,4dinitrophenylhydrazine (Brady's reagent), plus a quick look at
some similar reactions.
The triiodomethane (iodoform) reaction . . .
The use of this reaction to detect the presence of the CH3CO
group in aldehydes and ketones.

Go to menu of other organic compounds . . .


Go to Main Menu . . .

Jim Clark 2004

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an introduction to aldehydes and ketones

INTRODUCING ALDEHYDES AND KETONES

This page explains what aldehydes and ketones are, and looks at the
way their bonding affects their reactivity. It also considers their simple
physical properties such as solubility and boiling points. Details of the
chemical reactions of aldehydes and ketones are described on separate
pages.

What are aldehydes and ketones?


Aldehydes and ketones as carbonyl compounds
Aldehydes and ketones are simple compounds which contain a carbonyl
group - a carbon-oxygen double bond. They are simple in the sense that
they don't have other reactive groups like -OH or -Cl attached directly to
the carbon atom in the carbonyl group - as you might find, for example, in
carboxylic acids containing -COOH.
Examples of aldehydes
In aldehydes, the carbonyl group has a hydrogen atom attached to it
together with either

a second hydrogen atom


or, more commonly, a hydrocarbon group which might be an alkyl
group or one containing a benzene ring.

For the purposes of this section, we shall ignore those containing


benzene rings.

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an introduction to aldehydes and ketones

Note: There is no very significant reason for this. It is just


that if you are fairly new to organic chemistry you might not
have come across any compounds with benzene rings in
them yet. I'm just trying to avoid adding to your confusion!

Notice that these all have exactly the same end to the molecule. All that
differs is the complexity of the other group attached.
When you are writing formulae for these, the aldehyde group (the
carbonyl group with the hydrogen atom attached) is always written as CHO - never as COH. That could easily be confused with an alcohol.
Ethanal, for example, is written as CH3CHO; methanal as HCHO.
The name counts the total number of carbon atoms in the longest chain including the one in the carbonyl group. If you have side groups attached
to the chain, notice that you always count from the carbon atom in the
carbonyl group as being number 1.
Note: If you aren't confident about naming organic
compounds, then you really ought to follow this link before
you go on.
Use the BACK button on your browser to return to this page.

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an introduction to aldehydes and ketones

Examples of ketones
In ketones, the carbonyl group has two hydrocarbon groups
attached. Again, these can be either alkyl groups or ones containing
benzene rings. Again, we'll concentrated on those containing alkyl
groups just to keep things simple.
Notice that ketones never have a hydrogen atom attached to the
carbonyl group.

Propanone is normally written CH3COCH3. Notice the need for


numbering in the longer ketones. In pentanone, the carbonyl group could
be in the middle of the chain or next to the end - giving either pentan-3one or pentan-2-one.

Bonding and reactivity


Bonding in the carbonyl group
Oxygen is far more electronegative than carbon and
so has a strong tendency to pull electrons in a
carbon-oxygen bond towards itself. One of the two
pairs of electrons that make up a carbon-oxygen
double bond is even more easily pulled towards the oxygen. That makes
the carbon-oxygen double bond very highly polar.

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an introduction to aldehydes and ketones

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you go on.
If you are interested in really understanding the bonding in
the carbon-oxygen double bond you could explore it in detail
by following this link. You might find that following this link will
take you some time, because you will probably have to
explore several pages of background material as well.
Use the BACK button (or HISTORY file or GO menu) on your
browser to return to this page.

Important reactions of the carbonyl group


The slightly positive carbon atom in the carbonyl group can be attacked
by nucleophiles. A nucleophile is a negatively charged ion (for example,
a cyanide ion, CN-), or a slightly negatively charged part of a molecule
(for example, the lone pair on a nitrogen atom in ammonia, NH3).
During the reaction, the carbon-oxygen double bond gets broken. The
net effect of all this is that the carbonyl group undergoes addition
reactions, often followed by the loss of a water molecule. This gives a
reaction known as addition-elimination or condensation. You will find
examples of simple addition reactions and addition-elimination if you
explore the aldehydes and ketones menu (link at the bottom of the page).
Both aldehydes and ketones contain a carbonyl group. That means that
their reactions are very similar in this respect.
Where aldehydes and ketones differ
An aldehyde differs from a ketone by having a hydrogen atom attached
to the carbonyl group. This makes the aldehydes very easy to oxidise.
For example, ethanal, CH3CHO, is very easily oxidised to either ethanoic
acid, CH3COOH, or ethanoate ions, CH3COO-.

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an introduction to aldehydes and ketones

Ketones don't have that hydrogen atom and are resistant to oxidation.
They are only oxidised by powerful oxidising agents which have the
ability to break carbon-carbon bonds.
You will find the oxidation of aldehydes and ketones discussed if you
follow a link from the aldehydes and ketones menu (see the bottom of
this page).

Physical properties
Boiling points
Methanal is a gas (boiling point -21C), and ethanal has a boiling point of
+21C. That means that ethanal boils at close to room temperature.
The other aldehydes and the ketones are liquids, with boiling points
rising as the molecules get bigger.
The size of the boiling point is governed by the strengths of the
intermolecular forces.
van der Waals dispersion forces
These attractions get stronger as the molecules get longer and have
more electrons. That increases the sizes of the temporary dipoles that
are set up. This is why the boiling points increase as the number of
carbon atoms in the chains increases - irrespective of whether you are
talking about aldehydes or ketones.

Note: If you aren't happy about intermolecular forces


(particularly van der Waals dispersion forces and dipoledipole interactions) then you really ought to follow this link
before you go on.
Use the BACK button on your browser to return to this page.

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an introduction to aldehydes and ketones

van der Waals dipole-dipole attractions


Both aldehydes and ketones are polar molecules because of the
presence of the carbon-oxygen double bond. As well as the dispersion
forces, there will also be attractions between the permanent dipoles on
nearby molecules.
That means that the boiling points will be higher than those of similarly
sized hydrocarbons - which only have dispersion forces.
It is interesting to compare three similarly sized molecules. They have
similar lengths, and similar (although not identical) numbers of electrons.

molecule

type

boiling point (C)

CH3CH2CH3

alkane

-42

CH3CHO

aldehyde

+21

CH3CH2OH

alcohol

+78

Notice that the aldehyde (with dipole-dipole attractions as well as


dispersion forces) has a boiling point higher than the similarly sized
alkane which only has dispersion forces.
However, the aldehyde's boiling point isn't as high as the alcohol's. In the
alcohol, there is hydrogen bonding as well as the other two kinds of
intermolecular attraction.
Although the aldehydes and ketones are highly polar molecules, they
don't have any hydrogen atoms attached directly to the oxygen, and so
they can't hydrogen bond with each other.

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an introduction to aldehydes and ketones

Note: If you aren't sure about hydrogen bonding then it


would be a good idea to follow this link before you go on.
Use the BACK button on your browser to return to this page.

Solubility in water
The small aldehydes and ketones are freely soluble in water but solubility
falls with chain length. For example, methanal, ethanal and propanone the common small aldehydes and ketones - are miscible with water in all
proportions.
The reason for the solubility is that although aldehydes and ketones can't
hydrogen bond with themselves, they can hydrogen bond with water
molecules.
One of the slightly positive hydrogen atoms in a water molecule can be
sufficiently attracted to one of the lone pairs on the oxygen atom of an
aldehyde or ketone for a hydrogen bond to be formed.

There will also, of course, be dispersion forces and dipole-dipole


attractions between the aldehyde or ketone and the water molecules.
Forming these attractions releases energy which helps to supply the
energy needed to separate the water molecules and aldehyde or ketone
molecules from each other before they can mix together.
As chain lengths increase, the hydrocarbon "tails" of the molecules (all
the hydrocarbon bits apart from the carbonyl group) start to get in the
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an introduction to aldehydes and ketones

way.
By forcing themselves between water molecules, they break the
relatively strong hydrogen bonds between water molecules without
replacing them by anything as good. This makes the process
energetically less profitable, and so solubility decreases.

Where would you like to go now?


To the aldehydes and ketones menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2003

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Understanding the names of organic compounds

THE NAMES OF ORGANIC COMPOUNDS

This page explains how to write the formula for an organic compound
given its name - and vice versa. It covers alkanes, cycloalkanes, alkenes,
simple compounds containing halogens, alcohols, aldehydes and
ketones. At the bottom of the page, you will find links to other types of
compound.

Background
How this page is going to tackle the problem
There are two skills you have to develop in this area:

You need to be able to translate the name of an organic


compound into its structural formula.
You need to be able to name a compound from its given formula.

The first of these is more important (and also easier!) than the second. In
an exam, if you can't write a formula for a given compound, you aren't
going to know what the examiner is talking about and could lose lots of
marks. However, you might only be asked to write a name for a given
formula once in a whole exam - in which case you only risk 1 mark.
So, we're going to look mainly at how you decode names and turn them
into formulae. In the process you will also pick up tips about how to
produce names yourself.
In the early stages of an organic chemistry course people frequently get
confused and daunted by the names because they try to do too much at
once. Don't try to read all these pages in one go. Just go as far as the
compounds you are interested in at the moment and ignore the rest.
Come back to them as they arise during the natural flow of your course.
Cracking the code

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Understanding the names of organic compounds

A modern organic name is simply a code. Each part of the name gives
you some useful information about the compound.
For example, to understand the name 2-methylpropan-1-ol you need to
take the name to pieces.
The prop in the middle tells you how many carbon atoms there are in the
longest chain (in this case, 3). The an which follows the "prop" tells you
that there aren't any carbon-carbon double bonds.
The other two parts of the name tell you about interesting things which
are happening on the first and second carbon atom in the chain. Any
name you are likely to come across can be broken up in this same way.
Counting the carbon atoms
You will need to remember the codes for the number of carbon atoms in
a chain up to 6 carbons. There is no easy way around this - you have got
to learn them. If you don't do this properly, you won't be able to name
anything!
code

no of carbons

meth

eth

prop

but

pent

hex

Types of carbon-carbon bonds


Whether or not the compound contains a carbon-carbon double bond is
shown by the two letters immediately after the code for the chain length.
code

means

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Understanding the names of organic compounds

an

only carbon-carbon single bonds

en

contains a carbon-carbon double


bond

For example, butane means four carbons in a chain with no double bond.
Propene means three carbons in a chain with a double bond between
two of the carbons.
Alkyl groups
Compounds like methane, CH4, and ethane, CH3CH3, are members of a
family of compounds called alkanes. If you remove a hydrogen atom
from one of these you get an alkyl group.
For example:

A methyl group is CH3.

An ethyl group is CH3CH2.

These groups must, of course, always be attached to something else.

Types of compounds
The alkanes
Example 1: Write the structural formula for 2-methylpentane.
Start decoding the name from the bit that counts the number of carbon
atoms in the longest chain - pent counts 5 carbons.
Are there any carbon-carbon double bonds? No - an tells you there aren't
any.
Now draw this carbon skeleton:
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Understanding the names of organic compounds

Put a methyl group on the number 2 carbon atom:

Does it matter which end you start counting from? No - if you counted
from the other end, you would draw the next structure. That's exactly the
same as the first one, except that it has been flipped over.

Finally, all you have to do is to put in the correct number of hydrogen


atoms on each carbon so that each carbon is forming four bonds.

If you had to name this yourself:

Count the longest chain of carbons that you can find. Don't
assume that you have necessarily drawn that chain horizontally. 5
carbons means pent.
Are there any carbon-carbon double bonds? No - therefore
pentane.
There's a methyl group on the number 2 carbon - therefore 2methylpentane. Why the number 2 as opposed to the number 4
carbon? In other words, why do we choose to number from this
particluar end? The convention is that you number from the end
which produces the lowest numbers in the name - hence 2- rather
than 4-.

Example 2: Write the structural formula for 2,3-dimethylbutane.

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Understanding the names of organic compounds

Start with the carbon backbone. There are 4 carbons in the longest chain
(but) with no carbon-carbon double bonds (an).

This time there are two methyl groups (di) on the number 2 and number
3 carbon atoms.

Completing the formula by filling in the hydrogen atoms gives:

Note: Does it matter whether you draw the two methyl


groups one up and one down, or both up, or both down? Not
in the least! If you aren't sure about drawing organic
molecules, follow this link before you go on. Use the BACK
button on your browser to return to this page.

Example 3: Write the structural formula for 2,2-dimethylbutane.


This is exactly like the last example, except that both methyl groups are
on the same carbon atom. Notice that the name shows this by using 2,2as well as di. The structure is worked out as before:

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Understanding the names of organic compounds

Example 4: Write the structural formula for 3-ethyl-2-methylhexane.


hexan shows a 6 carbon chain with no carbon-carbon double bonds.

This time there are two different alkyl groups attached - an ethyl group on
the number 3 carbon atom and a methyl group on number 2.

Filling in the hydrogen atoms gives:

Note: Once again it doesn't matter whether the ethyl and


methyl groups point up or down. You might also have chosen
to start numbering from the right-hand end of the chain.
These would all be perfectly valid structures. All you would
have done is to rotate the whole molecule in space, or rotate
it around particular bonds.
If you aren't sure about this, then you must read about
drawing organic molecules before you go on.

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Understanding the names of organic compounds

If you had to name this yourself:


How do you know what order to write the different alkyl groups at the
beginning of the name? The convention is that you write them in
alphabetical order - hence ethyl comes before methyl which in turn
comes before propyl.

The cycloalkanes
In a cycloalkane the carbon atoms are joined up in a ring - hence cyclo.
Example: Write the structural formula for cyclohexane.
hexan shows 6 carbons with no carbon-carbon double bonds. cyclo
shows that they are in a ring. Drawing the ring and putting in the correct
number of hydrogens to satisfy the bonding requirements of the carbons
gives:

The alkenes
Example 1: Write the structural formula for propene.
prop counts 3 carbon atoms in the longest chain. en tells you that there
is a carbon-carbon double bond. That means that the carbon skeleton
looks like this:

Putting in the hydrogens gives you:

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Understanding the names of organic compounds

Example 2: Write the structural formula for but-1-ene.


but counts 4 carbon atoms in the longest chain and en tells you that
there is a carbon-carbon double bond. The number in the name tells you
where the double bond starts.
No number was necessary in the propene example above because the
double bond has to start on one of the end carbon atoms. In the case of
butene, though, the double bond could either be at the end of the chain
or in the middle - and so the name has to code for the its position.
The carbon skeleton is:

And the full structure is:

Incidentally, you might equally well have decided that the right-hand
carbon was the number 1 carbon, and drawn the structure as:

Example 3: Write the structural formula for 3-methylhex-2-ene.


The longest chain has got 6 carbon atoms (hex) with a double bond
starting on the second one (-2-en).
But this time there is a methyl group attached to the chain on the number
3 carbon atom, giving you the underlying structure:

Adding the hydrogens gives the final structure:

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Understanding the names of organic compounds

Be very careful to count the bonds around each carbon atom when you
put the hydrogens in. It would be very easy this time to make the mistake
of writing an H after the third carbon - but that would give that carbon a
total of 5 bonds.

Compounds containing halogens


Example 1: Write the structural formula for 1,1,1-trichloroethane.
This is a two carbon chain (eth) with no double bonds (an). There are
three chlorine atoms all on the first carbon atom.

Example 2: Write the structural formula for 2-bromo-2-methylpropane.


First sort out the carbon skeleton. It's a three carbon chain with no
double bonds and a methyl group on the second carbon atom.

Draw the bromine atom which is also on the second carbon.

And finally put the hydrogen atoms in.

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Understanding the names of organic compounds

If you had to name this yourself:


Notice that the whole of the hydrocarbon part of the name is written
together - as methylpropane - before you start adding anything else on to
the name.
Example 2: Write the structural formula for 1-iodo-3-methylpent-2-ene.
This time the longest chain has 5 carbons (pent), but has a double bond
starting on the number 2 carbon. There is also a methyl group on the
number 3 carbon.

Now draw the iodine on the number 1 carbon.

Giving a final structure:

Note: You could equally well draw this molecule the other
way round, but normally where you have, say, 1-bromosomething, you tend to write the bromine (or other halogen)
on the right-hand end of the structure.

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Understanding the names of organic compounds

Alcohols
All alcohols contain an -OH group. This is shown in a name by the
ending ol.
Example 1: Write the structural formula for methanol.
This is a one carbon chain with no carbon-carbon double bond
(obviously!). The ol ending shows it's an alcohol and so contains an -OH
group.

Example 2: Write the structural formula for 2-methylpropan-1-ol.


The carbon skeleton is a 3 carbon chain with no carbon-carbon double
bonds, but a methyl group on the number 2 carbon.

The -OH group is attached to the number 1 carbon.

The structure is therefore:

Example 3: Write the structural formula for ethane-1,2-diol.


This is a two carbon chain with no double bond. The diol shows 2 -OH
groups, one on each carbon atom.

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Understanding the names of organic compounds

Note: There's no particular significance in the fact that this


formula has the carbon chain drawn vertically. If you draw it
horizontally, unless you stretch the carbon-carbon bond a lot,
the -OH groups look very squashed together. Drawing it
vertically makes it look tidier!

Aldehydes
All aldehydes contain the group:

If you are going to write this in a condensed form, you write it as -CHO never as -COH, because that looks like an alcohol.
The names of aldehydes end in al.
Example 1: Write the structural formula for propanal.
This is a 3 carbon chain with no carbon-carbon double bonds. The al
ending shows the presence of the -CHO group. The carbon in that group
counts as one of the chain.

Example 2: Write the structural formula for 2-methylpentanal.


This time there are 5 carbons in the longest chain, including the one in
the -CHO group. There aren't any carbon-carbon double bonds. A methyl
group is attached to the number 2 carbon. Notice that in aldehydes, the
carbon in the -CHO group is always counted as the number 1 carbon.

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Understanding the names of organic compounds

Ketones
Ketones contain a carbon-oxygen double bond just like aldehydes, but
this time it's in the middle of a carbon chain. There isn't a hydrogen atom
attached to the group as there is in aldehydes.
Ketones are shown by the ending one.
Example 1: Write the structural formula for propanone.
This is a 3 carbon chain with no carbon-carbon double bond. The carbonoxygen double bond has to be in the middle of the chain and so must be
on the number 2 carbon.

Ketones are often written in this way to emphasise the carbon-oxygen


double bond.
Example 2: Write the structural formula for pentan-3-one.
This time the position of the carbon-oxygen double bond has to be stated
because there is more than one possibility. It's on the third carbon of a 5
carbon chain with no carbon-carbon double bonds. If it was on the
second carbon, it would be pentan-2-one.

This could equally well be written:

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Understanding the names of organic compounds

Where would you like to go now?


Continue naming more chain compounds. . .
Naming aromatic compounds. . .
To the organic conventions menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

Jim Clark 2000

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Understanding the names of organic compounds

THE NAMES OF MORE ORGANIC COMPOUNDS

This page continues looking at the names of organic compounds


containing chains of carbon atoms. It assumes that you have already
looked at the introductory page covering compounds from alkanes to
ketones.

Note: If you haven't already looked at that page, it would be


a good idea to do so before you go on. The names on this
second page aren't explained in quite as much detail as
those on the introductory page - it assumes that you have
already understood the main principles. If in doubt, follow this
link first.

More types of organic compound


Carboxylic acids
Carboxylic acids contain the -COOH group, which is better written out in
full as:

Carboxylic acids are shown by the ending oic acid. When you count the
carbon chain, you have to remember to include the carbon in the -COOH
group. That carbon is always thought of as number 1 in the chain.
Example 1: Write the structural formula for 3-methylbutanoic acid.
This is a four carbon acid with no carbon-carbon double bonds. There is
a methyl group on the third carbon (counting the -COOH carbon as
number 1).

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Understanding the names of organic compounds

Example 2: Write the structural formula for 2-hydroxypropanoic acid.


The hydroxy part of the name shows the presence of an -OH group.
Normally, you would show that by the ending ol, but this time you can't
because you've already got another ending. You are forced into this
alternative way of describing it.

The old name for 2-hydroxypropanoic acid is lactic acid. That name
sounds more friendly, but is utterly useless when it comes to writing a
formula for it. In the old days, you would have had to learn the formula
rather than just working it out should you need it.
Example 3: Write the structural formula for 2-chlorobut-3-enoic acid.
This time, not only is there a chlorine attached to the chain, but the chain
also contains a carbon-carbon double bond (en) starting on the number 3
carbon (counting the -COOH carbon as number 1).

Salts of carboxylic acids


Example: Write the structural formula for sodium propanoate.
This is the sodium salt of propanoic acid - so start from that. Propanoic
acid is a three carbon acid with no carbon-carbon double bonds.

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Understanding the names of organic compounds

When the carboxylic acids form salts, the hydrogen in the -COOH group
is replaced by a metal. Sodium propanoate is therefore:

Notice that there is an ionic bond between the sodium and the
propanoate group. Whatever you do, don't draw a line between the
sodium and the oxygen. That would represent a covalent bond. It's
wrong, and makes you look very incompetent in an exam!
In a shortened version, sodium propanoate would be written
CH3CH2COONa or, if you wanted to emphasise the ionic nature, as
CH3CH2COO- Na+.

Note: The confusing thing about these salts (and even more
so for the esters that are coming up next) is that they are
named the wrong way round. In the formula, the sodium is at
the end, but appears first in the name. Why?
Salts are always named with the metal first - think of sodium
chloride or potassium iodide. So for consistency you would
need to reverse the formula of sodium propanoate NaOOCCH2CH3. But if you reverse the formula, you can't
see immediately that it is related to propanoic acid. So you
learn to live with the inconsistency.

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Understanding the names of organic compounds

Esters
Esters are one of a number of compounds known collectively as acid
derivatives. In these the acid group is modified in some way. In an ester,
the hydrogen in the -COOH group is replaced by an alkyl group (or
possibly some more complex hydrocarbon group).
Example 1: Write the structural formula for methyl propanoate.
An ester name has two parts - the part that comes from the acid
(propanoate) and the part that shows the alkyl group (methyl).
Start by thinking about propanoic acid - a 3 carbon acid with no carboncarbon double bonds.

The hydrogen in the -COOH group is replaced by an alkyl group - in this


case, a methyl group.

Ester names are confusing because the name is written backwards from
the way the structure is drawn. There's no way round this - you just have
to get used to it!
In the shortened version, this formula would be written CH3CH2COOCH3.
Example 2: Write the structural formula for ethyl ethanoate.
This is probably the most commonly used example of an ester. It is
based on ethanoic acid ( hence, ethanoate) - a 2 carbon acid. The
hydrogen in the -COOH group is replaced by an ethyl group.

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Understanding the names of organic compounds

Make sure that you draw the ethyl group the right way round. A fairly
common mistake is to try to join the CH3 group to the oxygen. If you
count the bonds if you do that, you will find that both the CH3 carbon and
the CH2 carbon have the wrong number of bonds.

Acyl chlorides (acid chlorides)


An acyl chloride is another acid derivative. In this case, the -OH group of
the acid is replaced by -Cl. All acyl chlorides contain the -COCl group:

Example: Write the structural formula for ethanoyl chloride.


Acyl chlorides are shown by the ending oyl chloride. So ethanoyl
chloride is based on a 2 carbon chain with no carbon-carbon double
bonds and a -COCl group. The carbon in that group counts as part of the
chain. In a longer chain, with side groups attached, the -COCl carbon is
given the number 1 position.

Acid anhydrides
Another acid derivative! An acid anhydride is what you get if you
dehydrate an acid - that is, remove water from it.

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Understanding the names of organic compounds

Example: Write the structural formula for propanoic anhydride.


These are most easily worked out by writing it down on a scrap of paper
in the following way:

Draw two molecules of acid arranged so that the -OH groups are next to
each other. Tweak out a molecule of water - and then join up what's left.
In this case, because you want propanoic anhydride, you draw two
molecules of propanoic acid.

Amides
Yet another acid derivative! Amides contain the group -CONH2 where the
-OH of an acid is replaced by -NH2.
Example: Write the structural formula for propanamide.
This is based on a 3 carbon chain with no carbon-carbon double bonds.
At the end of the chain is a -CONH2 group. The carbon in that group
counts as part of the chain.

Nitriles
Nitriles contain a -CN group, and used to be called cyanides.
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Understanding the names of organic compounds

Example 1: Write the structural formula for ethanenitrile.


The name shows a 2 carbon chain with no carbon-carbon double bond.
nitrile shows a -CN group at the end of the chain. As with the previous
examples involving acids and acid derivatives, don't forget that the
carbon in the -CN group counts as part of the chain.

The old name for this would have been methyl cyanide. You might think
that that's easier, but as soon as the chain gets more complicated, it
doesn't work - as the next example shows.
Example 2: Write the structural formula for 2-hydroxypropanenitrile.
Here we've got a 3 carbon chain, no carbon-carbon double bonds, and a CN group on the end of the chain. The carbon in the -CN group counts
as the number 1 carbon. On the number 2 carbon there is an -OH group
(hydroxy). Notice that you can't use the ol ending because you've
already got a nitrile ending.

Primary amines
A primary amine contains the group -NH2 attached to a hydrocarbon
chain or ring. You can think of amines in general as being derived from
ammonia, NH3. In a primary amine, one of the hydrogens has been
replaced by a hydrocarbon group.
Example 1: Write the structural formula for ethylamine.
In this case, an ethyl group is attached to the -NH2 group.

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Understanding the names of organic compounds

This name (ethylamine) is fine as long as you've only got a short chain
where there isn't any ambiguity about where the -NH2 group is found. But
suppose you had a 3 carbon chain - in this case, the -NH2 group could
be on an end carbon or on the middle carbon. How you get around that
problem is illustrated in the next example.
Example 2: Write the structural formula for 2-aminopropane.
The name shows a 3 carbon chain with an amino group attached to the
second carbon. amino shows the -NH2 group.

Ethylamine (example 1 above) could equally well have been called


aminoethane.

Secondary and tertiary amines


You are only likely to come across simple examples of these. In a
secondary amine, two of the hydrogen atoms in an ammonia molecule
have been replaced by hydrocarbon groups. In a tertiary amine, all three
hydrogens have been replaced.
Example 1: Write the structural formula for dimethylamine.
In this case, two of the hydrogens in ammonia have been replaced by
methyl groups.

Example 2: Write the structural formula for trimethylamine.


Here, all three hydrogens in ammonia have been replaced by methyl
groups.
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Understanding the names of organic compounds

Amino acids
An amino acid contains both an amino group, -NH2, and a carboxylic
acid group, -COOH, in the same molecule. As with all acids the carbon
chain is numbered so that the carbon in the -COOH group is counted as
number 1.
Example: Write the structural formula for 2-aminopropanoic acid.
This has a 3 carbon chain with no carbon-carbon double bonds. On the
second carbon (counting the -COOH carbon as number 1) there is an
amino group, -NH2.

Where would you like to go now?


Naming aromatic compounds. . .
To the organic conventions menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

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Understanding the names of organic compounds

Jim Clark 2000

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Naming aromatic compounds

THE NAMES OF AROMATIC COMPOUNDS

This page looks at the names of some simple aromatic compounds. An


aromatic compound is one which contains a benzene ring. It assumes
that you are reasonably confident about naming compounds containing
chains of carbon atoms (aliphatic compounds).

Note: If you aren't sure about naming aliphatic compounds


follow this link before you go on.

Naming aromatic compounds isn't quite so straightforward as naming


chain compounds. Often, more than one name is acceptable and it's not
uncommon to find the old names still in use as well.

Background
The benzene ring
All aromatic compounds are based on benzene, C6H6, which has a ring
of six carbon atoms and has the symbol:

Each corner of the hexagon has a carbon atom with a hydrogen attached.

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Naming aromatic compounds

Note: If you don't understand this structure, it is explained in


full in two pages on the structure of benzene elsewhere in
this site. Following this link could well take you some time!

The phenyl group


Remember that you get a methyl group, CH3, by removing a hydrogen
from methane, CH4.
You get a phenyl group, C6H5, by removing a hydrogen from a benzene
ring, C6H6. Like a methyl or an ethyl group, a phenyl group is always
attached to something else.

Aromatic compounds with only one group attached to the


benzene ring
Cases where the name is based on benzene
chlorobenzene
This is a simple example of a halogen attached to the benzene ring. The
name is self-obvious.

The simplified formula for this is C6H5Cl. You could therefore (although
you never do!) call it phenyl chloride. Whenever you draw a benzene ring
with one other thing attached to it, you are in fact drawing a phenyl
group. In order to attach something else, you have to remove one of the
existing hydrogen atoms, and so automatically make a phenyl group.
nitrobenzene
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Naming aromatic compounds

The nitro group, NO2, is attached to a benzene ring.

The simplified formula for this is C6H5NO2.


methylbenzene
Another obvious name - the benzene ring has a methyl group attached.
Other alkyl side-chains would be named similarly - for example,
ethylbenzene. The old name for methylbenzene is toluene, and you may
still meet that.

The simplified formula for this is C6H5CH3.


(chloromethyl)benzene
A variant on this which you may need to know about is where one of the
hydrogens on the CH3 group is replaced by a chlorine atom. Notice the
brackets around the (chloromethyl) in the name. This is so that you are
sure that the chlorine is part of the methyl group and not somewhere else
on the ring.

If more than one of the hydrogens had been replaced by chlorine, the
names would be (dichloromethyl)benzene or (trichloromethyl)benzene.
Again, notice the importance of the brackets in showing that the chlorines
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Naming aromatic compounds

are part of the side group and not directly attached to the ring.
benzoic acid (benzenecarboxylic acid)
Benzoic acid is the older name, but is still in common use - it's a lot
easier to say and write than the modern alternative! Whatever you call it,
it has a carboxylic acid group, -COOH, attached to the benzene ring.

Cases where the name is based on phenyl


Remember that the phenyl group is a benzene ring minus a hydrogen
atom - C6H5. If you draw a benzene ring with one group attached, you
have drawn a phenyl group.
phenylamine
Phenylamine is a primary amine and contains the -NH2 group attached to
a benzene ring.

The old name for phenylamine is aniline, and you could also reasonably
call it aminobenzene. Phenylamine is what it is most commonly called at
A'level.

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Naming aromatic compounds

Note: In all cases where there is some possibility of


alternative names, you need to know what your examiners
are likely to call a particular compound. Refer to your syllabus
and recent exam papers. If you haven't got these, follow this
link to find out how to get hold of them.

phenylethene
This is an ethene molecule with a phenyl group attached. Ethene is a two
carbon chain with a carbon-carbon double bond. Phenylethene is
therefore:

The old name for phenylethene is styrene - the monomer from which
polystyrene is made.
phenylethanone
This is a slightly awkward name - take it to pieces. It consists of a two
carbon chain with no carbon-carbon double bond. The one ending shows
that it is a ketone, and so has a C=O group somewhere in the middle.
Attached to the carbon chain is a phenyl group. Putting that together
gives:

phenyl ethanoate
This is an ester based on ethanoic acid. The hydrogen atom in the COOH group has been replaced by a phenyl group.
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Naming aromatic compounds

Note: If you aren't happy about naming esters, follow this


link before you go on.

phenol
Phenol has an -OH group attached to a benzene ring and so has a
formula C6H5OH.

Aromatic compounds with more than one group attached


to the benzene ring
Numbering the ring
Any group already attached to the ring is given the number 1 position.
Where you draw it on the ring (at the top or in any other position) doesn't
matter - that's just a question of rotating the molecule a bit. It's much
easier, though, to get in the habit of drawing your main group at the top.
The other ring positions are then numbered from 2 to 6. You can number
them either clockwise or anti-clockwise. As with chain compounds, you
number the ring so that the name you end up with has the smallest
possible numbers in it. Examples will make this clear.
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Naming aromatic compounds

Some simple examples


Substituting chlorine atoms on the ring
Look at these compounds:

All of these are based on methylbenzene and so the methyl group is


given the number 1 position on the ring.
Why is it 2-chloromethylbenzene rather than 6-chloromethylbenzene?
The ring is numbered clockwise in this case because that produces a 2in the name rather than a 6-. 2 is smaller than 6.

Warning! You will find all sorts of variations on this


depending on the age of the book you look it up in, and
where it was published. What I have described above isn't in
strict accordance with the most modern interpretation of the
IUPAC recommendations for naming organic compounds.
The names should actually be 1-chloro-2-methylbenzene, 1chloro-3-methylbenzene, and so on. The substituted groups
are named in alphabetical order, and the "1" position is
assigned to the first of these - rather than to the more logical
methyl group.
This produces some silly inconsistencies. For example, if you
had the exactly equivalent compounds containing nitro
groups in place of the chlorines, the names would change
completely, to 1-methyl-2-nitrobenzene, 1-methyl-3nitrobenzene, etc. In this case, the normal practice of naming
the hydrocarbon first, and then attaching other things to it has
been completely wrecked.
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Naming aromatic compounds

Do you need to worry about this? NO! It is extremely unlikely


that you would ever be asked to name these in an exam, and
it is always easy to write a structure from one of these names
- however illogical it may be! There is a simple rule for exam
purposes. Unless you are specifically asked for the name of
anything remotely complicated, don't give it. As long as you
have got the structure right, that's all that matters.

2-hydroxybenzoic acid
This might also be called 2-hydroxybenzenecarboxylic acid. There is a COOH group attached to the ring and, because the name is based on
benzoic acid, that group is assigned the number 1 position. Next door to
it in the 2 position is a hydroxy group, -OH.

benzene-1,4-dicarboxylic acid
The di shows that there are two carboxylic acid groups, -COOH, one of
them in the 1 position and the other opposite it in the 4 position.

2,4,6-trichlorophenol
This is based on phenol - with an -OH group attached in the number 1
position on the ring. There are 3 chlorine atoms substituted onto the ring
in the 2, 4 and 6 positions.

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Naming aromatic compounds

2,4,6-trichlorophenol is the familiar antiseptic TCP.


methyl 3-nitrobenzoate
This is a name you might come across as a part of a practical exercise in
nitrating benzene rings. It's included partly for that reason, and partly
because it is a relatively complicated name to finish with!
The structure of the name shows that it is an ester. You can tell that from
the oate ending, and the methyl group floating separately from the rest of
the name at the beginning.
The ester is based on the acid, 3-nitrobenzoic acid - so start with that.
There will be a benzene ring with a -COOH group in the number 1
position and a nitro group, NO2, in the 3 position. The -COOH group is
modified to make an ester by replacing the hydrogen of the -COOH
group by a methyl group.
Methyl 3-nitrobenzoate is therefore:

Where would you like to go now?


To the organic conventions menu. . .
To menu of basic organic chemistry. . .
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Naming aromatic compounds

To Main Menu . . .

Jim Clark 2000

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properties of organic compounds menu

Understanding Chemistry

PROPERTIES OF ORGANIC COMPOUNDS MENU

You can find details of the physical and chemical properties for each of
these types of compound:

Aliphatic compounds
These are compounds where the functional group is not attached directly
to a benzene ring.
alkanes . . .
alkenes . . .
halogenoalkanes (haloalkanes or alkyl halides) . . .
alcohols . . .
aldehydes and ketones . . .
carboxylic acids . . .
acyl chlorides (acid chlorides) . . .
acid anhydrides . . .
esters . . .
amides . . .
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properties of organic compounds menu

nitriles . . .
amines . . .
amino acids and proteins . . .

Aromatic compounds
These are compounds based on benzene rings. This isn't a complete list,
but shows only those compounds where there are important differences
between them and their aliphatic equivalents.
arenes (benzene and methylbenzene) . . .
aryl halides (e.g. chlorobenzene) . . .
phenol . . .
phenylamine (aniline) and diazonium compounds . . .

Go to Main Menu . . .

Jim Clark 2004

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Alkanes Menu

Understanding Chemistry

ALKANES MENU

Background . . .
An introduction to the alkanes (including cycloalkanes) and their
physical properties.
Burning alkanes . . .
The combustion of alkanes, including incomplete combustion.
Halogenation . . .
The reaction between alkanes and chlorine or bromine.
Cracking . . .
A brief look at cracking alkanes in the oil industry.

Go to menu of other organic compounds . . .


Go to Main Menu . . .

Jim Clark 2003

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Alkanes Menu

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an introduction to alkanes and cycloalkanes

INTRODUCING ALKANES AND CYCLOALKANES

This is an introductory page about alkanes such as methane, ethane,


propane, butane and the rest. It deals with their formulae and isomerism,
their physical properties, and an introduction to their chemical reactivity.

What are alkanes and cycloalkanes?


Alkanes
Formulae
Alkanes are the simplest family of hydrocarbons - compounds containing
carbon and hydrogen only. They only contain carbon-hydrogen bonds
and carbon-carbon single bonds. The first six are:
methane

CH4

ethane

C2H6

propane

C3H8

butane

C4H10

pentane

C5H12

hexane

C6H14

You can work out the formula of any of them using: CnH2n+2
Isomerism
All the alkanes with 4 or more carbon atoms in them show structural
isomerism. This means that there are two or more different structural
formulae that you can draw for each molecular formula.

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an introduction to alkanes and cycloalkanes

For example, C4H10 could be either of these two different molecules:

These are called respectively butane and 2-methylpropane.

Note: If you aren't confident about naming organic


compounds, the various ways of drawing organic
compounds, or structural isomerism, then you really ought to
follow these links before you go on.
You should read the whole of the page about drawing organic
molecules, but there is no need to read the other two beyond
where they talk about alkanes.
Use the BACK button on your browser to return to this page.

Cycloalkanes
Cycloalkanes again only contain carbon-hydrogen bonds and carboncarbon single bonds, but this time the carbon atoms are joined up in a
ring. The smallest cycloalkane is cyclopropane.

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an introduction to alkanes and cycloalkanes

If you count the carbons and hydrogens, you will see that they no longer
fit the general formula CnH2n+2. By joining the carbon atoms in a ring,
you have had to lose two hydrogen atoms.
You are unlikely to ever need it, but the general formula for a cycloalkane
is CnH2n.
Don't imagine that these are all flat molecules. All the cycloalkanes from
cyclopentane upwards exist as "puckered rings".
Cyclohexane, for example, has a ring structure which looks like this:

This is known as the "chair" form of cyclohexane - from its shape which
vaguely resembles a chair.

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an introduction to alkanes and cycloalkanes

Note: This molecule is constantly changing, with the atom


on the left which is currently pointing down flipping up, and
the one on the right flipping down. During the process,
another (slightly less stable) form of cyclohexane is formed
known as the "boat" form. In this arrangement, both of these
atoms are either pointing up or down at the same time.

Physical Properties
Boiling Points
The facts

The boiling points shown are all for the "straight chain" isomers where
there are more than one.
Notice that the first four alkanes are gases at room temperature. Solids
don't start to appear until about C17H36.
You can't be more precise than that because each isomer has a different
melting and boiling point. By the time you get 17 carbons into an alkane,
there are unbelievable numbers of isomers!

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an introduction to alkanes and cycloalkanes

Cycloalkanes have boiling points which are about 10 - 20 K higher than


the corresponding straight chain alkane.
Explanations
There isn't much electronegativity difference between carbon and
hydrogen, so there is hardly any bond polarity. The molecules
themselves also have very little polarity. A totally symmetrical molecule
like methane is completely non-polar.

Note: If you aren't sure about electronegativity and polarity,


then you really ought to follow this link before you go on.
Use the BACK button on your browser to return to this page.

This means that the only attractions between one molecule and its
neighbours will be Van der Waals dispersion forces. These will be very
small for a molecule like methane, but will increase as the molecules get
bigger. That's why the boiling points of the alkanes increase with
molecular size.

Note: If you aren't sure about Van der Waals forces, then
you should follow this link before you go on.
Use the BACK button on your browser to return to this page.

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an introduction to alkanes and cycloalkanes

Where you have isomers, the more branched the chain, the lower the
boiling point tends to be. Van der Waals dispersion forces are smaller for
shorter molecules, and only operate over very short distances between
one molecule and its neighbours. It is more difficult for short fat
molecules (with lots of branching) to lie as close together as long thin
ones.
For example, the boiling points of the three isomers of C5H12 are:
boiling point (K)
pentane

309.2

2-methylbutane

301.0

2,2-dimethylpropane

282.6

The slightly higher boiling points for the cycloalkanes are presumably
because the molecules can get closer together because the ring
structure makes them tidier and less "wriggly"!

Solubility
The facts
What follows applies equally to alkanes and cycloalkanes.
Alkanes are virtually insoluble in water, but dissolve in organic solvents.
The liquid alkanes are good solvents for many other covalent compounds.
Explanations
Solubility in water
When a molecular substance dissolves in water, you have to

break the intermolecular forces within the substance. In the case


of the alkanes, these are Van der Waals dispersion forces.

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break the intermolecular forces in the water so that the substance


can fit between the water molecules. In water the main
intermolecular attractions are hydrogen bonds.

Note: If you aren't sure about hydrogen bonds, then you


should follow this link before you go on.
Use the BACK button on your browser to return to this page.

Breaking either of these attractions costs energy, although the amount of


energy to break the Van der Waals dispersion forces in something like
methane is pretty negligible. That isn't true of the hydrogen bonds in
water, though.
As something of a simplification, a substance will dissolve if there is
enough energy released when new bonds are made between the
substance and the water to make up for what is used in breaking the
original attractions.
The only new attractions between the alkane and water molecules are
Van der Waals. These don't release anything like enough energy to
compensate for what you need to break the hydrogen bonds in water.
The alkane doesn't dissolve.

Note: The reason that this is a simplification is that you also


have to consider entropy changes when things dissolve. If
you don't yet know about entropy, don't worry about it!

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Solubility in organic solvents


In most organic solvents, the main forces of attraction between the
solvent molecules are Van der Waals - either dispersion forces or dipoledipole attractions.
That means that when an alkane dissolves in an organic solvent, you are
breaking Van der Waals forces and replacing them by new Van der
Waals forces. The two processes more or less cancel each other out
energetically - so there isn't any barrier to solubility.

Chemical Reactivity
Alkanes
Alkanes contain strong carbon-carbon single bonds and strong carbonhydrogen bonds. The carbon-hydrogen bonds are only very slightly polar
and so there aren't any bits of the molecules which carry any significant
amount of positive or negative charge which other things might be
attracted to.
The net effect is that alkanes have a fairly restricted set of reactions.
You can

burn them - destroying the whole molecule;


react them with some of the halogens, breaking carbon-hydrogen
bonds;
crack them, breaking carbon-carbon bonds.

These reactions are all covered on separate pages if you go to the


alkanes menu (see below).
Cycloalkanes
Cycloalkanes are very similar to the alkanes in reactivity, except for the

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very small ones - especially cyclopropane. Cyclopropane is much more


reactive than you would expect.
The reason has to do with the bond angles in the ring. Normally, when
carbon forms four single bonds, the bond angles are about 109.5. In
cyclopropane, they are 60.

With the electron pairs this close together, there is a lot of repulsion
between the bonding pairs joining the carbon atoms. That makes the
bonds easier to break.
The effect of this is explored on the page about reactions of these
compounds with halogens which you can access from the alkanes menu
below.

Where would you like to go now?


To the alkanes menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2003

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Alkenes Menu

Understanding Chemistry

ALKENES MENU

Background . . .
An introduction to the alkenes, their reactivity and their physical
properties.
Making alkenes . . .
Making alkenes in the lab from alcohols.
Hydrogenation . . .
The reaction between alkenes and hydrogen.
Reactions with halogens . . .
The reactions with chlorine and bromine, including the test using
bromine water.
Reactions with hydrogen halides . . .
The reactions with compounds such as hydrogen chloride and
hydrogen bromide.
Reaction with sulphuric acid . . .
The reaction between alkenes and concentrated sulphuric acid
(including further reaction to give alcohols).
Reaction with potassium manganate(VII) . . .

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Alkenes Menu

The reaction between alkenes and potassium manganate(VII)


(potassium permanganate) solution.
Hydration . . .
The industrial hydration of alkenes (their reaction with water) to
give alcohols.
Polymerisation . . .
The polymerisation of alkenes, including some uses of the
polymers formed.
Making epoxyethane . . .
The manufacture of epoxyethane (old name: ethylene oxide) from
ethene, including its uses.

Go to menu of other organic compounds . . .


Go to Main Menu . . .

Jim Clark 2003

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an introduction to alkenes

INTRODUCING ALKENES

This is an introductory page about alkenes such as ethene, propene and


the rest. It deals with their formulae and isomerism, their physical
properties, and an introduction to their chemical reactivity.

What are alkenes?


Formulae
Alkenes are a family of hydrocarbons (compounds containing carbon and
hydrogen only) containing a carbon-carbon double bond. The first two
are:
ethene

C2H4

propene

C3H6

You can work out the formula of any of them using: CnH2n
The table is limited to the first two, because after that there are isomers
which affect the names.

Isomerism in the alkenes


Structural isomerism
All the alkenes with 4 or more carbon atoms in them show structural
isomerism. This means that there are two or more different structural
formulae that you can draw for each molecular formula.
For example, with C4H8, it isn't too difficult to come up with these three
structural isomers:
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an introduction to alkenes

Note: If you aren't confident about naming organic


compounds, the various ways of drawing organic
compounds, or structural isomerism, then you really ought to
follow these links before you go on.
Use the BACK button on your browser to return to this page.

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an introduction to alkenes

There is, however, another isomer. But-2-ene also exhibits geometric


isomerism.
Geometric (cis-trans) isomerism
The carbon-carbon double bond doesn't allow any rotation about it. That
means that it is possible to have the CH3 groups on either end of the
molecule locked either on one side of the molecule or opposite each
other.
These are called cis-but-2-ene (where the groups are on the same side)
or trans-but-2-ene (where they are on opposite sides).

Note: If you aren't confident about geometric isomerism,


then it is essential that you follow this link before you go on.
Use the BACK button on your browser to return to this page.

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an introduction to alkenes

Physical properties of the alkenes


Boiling Points
The boiling point of each alkene is very similar to that of the alkane with
the same number of carbon atoms. Ethene, propene and the various
butenes are gases at room temperature. All the rest that you are likely to
come across are liquids.
In each case, the alkene has a boiling point which is a small number of
degrees lower than the corresponding alkane. The only attractions
involved are Van der Waals dispersion forces, and these depend on the
shape of the molecule and the number of electrons it contains. Each
alkene has 2 fewer electrons than the alkane with the same number of
carbons.

Note: If you aren't sure about Van der Waals forces, then
you should follow this link before you go on.
You will find the boiling points of the alkanes explained in
some detail on the introductory alkanes page. Everything
said there applies equally to the alkenes.
You will find the way geometric isomerism affects melting and
boiling points explained towards the bottom of the page you
get to by following this link.
Use the BACK button on your browser to return to this page.

Solubility
Alkenes are virtually insoluble in water, but dissolve in organic solvents.

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an introduction to alkenes

Note: The reasons for this are exactly the same as for the
alkanes. You will find a detailed explanation on the
introductory alkanes page.
Use the BACK button on your browser to return to this page.

Chemical Reactivity
Bonding in the alkenes
We just need to look at ethene, because what is true of C=C in ethene
will be equally true of C=C in more complicated alkenes.
Ethene is often modelled like this:

The double bond between the carbon atoms is, of course, two pairs of
shared electrons. What the diagram doesn't show is that the two pairs
aren't the same as each other.
One of the pairs of electrons is held on the line between the two carbon
nuclei as you would expect, but the other is held in a molecular orbital
above and below the plane of the molecule. A molecular orbital is a
region of space within the molecule where there is a high probability of
finding a particular pair of electrons.

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In this diagram, the line between the two carbon atoms represents a
normal bond - the pair of shared electrons lies in a molecular orbital on
the line between the two nuclei where you would expect them to be. This
sort of bond is called a sigma bond.
The other pair of electrons is found somewhere in the shaded part above
and below the plane of the molecule. This bond is called a pi bond. The
electrons in the pi bond are free to move around anywhere in this shaded
region and can move freely from one half to the other.

Note: This diagram shows a side view of an ethene


molecule. The dotted lines to two of the hydrogens show
bonds going back into the screen or paper away from you.
The wedge shapes show bonds coming out towards you.

The pi electrons are not as fully under the control of the carbon nuclei as
the electrons in the sigma bond and, because they lie exposed above
and below the rest of the molecule, they are relatively open to attack by
other things.

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Note: Check your syllabus to see if you need to know how a


pi bond is formed. If you are a UK A level student and haven't
got a syllabus, find out how to get one by following this link.
If you do need to know about the bonding in ethene in detail,
follow this link as well.
Use the BACK button on your browser to return to this page.

The reactions of alkenes


Like any other hydrocarbons, alkenes burn in air or oxygen, but these
reactions are unimportant. Alkenes are too valuable to waste in this way.
The important reactions all centre around the double bond. Typically, the
pi bond breaks and the electrons from it are used to join the two carbon
atoms to other things. Alkenes undergo addition reactions.
For example, using a general molecule X-Y . . .

The rather exposed electrons in the pi bond are particularly open to


attack by things which carry some degree of positive charge. These are
called electrophiles. If you explore the rest of the alkene menu, you will
find lots of examples of this kind.

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Note: If you need to know about organic reaction


mechanisms, it would be a good idea to read the page
explaining the background to electrophilic addition before you
start looking at individual cases from the alkenes menu.
In fact, if you are only really interested in mechanisms, then
look at that page and then explore the rest of the electrophilic
addition menu in the mechanisms section of this site.

Where would you like to go now?


To the alkenes menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2003

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making alkenes in the lab

MAKING ALKENES IN THE LAB

This page looks at ways of preparing alkenes in the lab by the


dehydration of alcohols.

Dehydration of alcohols using aluminium oxide as catalyst


The dehydration of ethanol to give ethene
This is a simple way of making gaseous alkenes like ethene. If ethanol
vapour is passed over heated aluminium oxide powder, the ethanol is
essentially cracked to give ethene and water vapour.

To make a few test tubes of ethene, you can use this apparatus:

It wouldn't be too difficult to imagine scaling this up by boiling some


ethanol in a flask and passing the vapour over aluminium oxide heated in
a long tube.

Dehydration of alcohols using an acid catalyst


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The acid catalysts normally used are either concentrated sulphuric acid
or concentrated phosphoric(V) acid, H3PO4.
Concentrated sulphuric acid produces messy results. Not only is it an
acid, but it is also a strong oxidising agent. It oxidises some of the
alcohol to carbon dioxide and at the same time is reduced itself to
sulphur dioxide. Both of these gases have to be removed from the alkene.
It also reacts with the alcohol to produce a mass of carbon. There are
other side reactions as well, but these aren't required by any current UK
A level syllabus.

The dehydration of ethanol to give ethene


Ethanol is heated with an excess of concentrated sulphuric acid at a
temperature of 170C. The gases produced are passed through sodium
hydroxide solution to remove the carbon dioxide and sulphur dioxide
produced from side reactions.
The ethene is collected over water.

WARNING! This is potentially an extremely dangerous


preparation because of the close proximity of the very hot
concentrated sulphuric acid and the sodium hydroxide
solution. I knew of one chemistry teacher who put several
students into hospital by getting it wrong! That was many
years ago before safety was taken quite so seriously as it is
now.

The concentrated sulphuric acid is a catalyst. Write it over the arrow


rather than in the equation.

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Note: You will find the mechanism for the dehydration of


alcohols in the mechanism section of this site. You will also
find a discussion of how to cope with questions about the
dehydration of more complicated alcohols if you follow a link
at the bottom of that page.
Use the BACK button (or the HISTORY file or GO menu) on
your browser if you want to return to this page.

The dehydration of cyclohexanol to give cyclohexene


This is a preparation commonly used at this level to illustrate the
formation and purification of a liquid product. The fact that the carbon
atoms happen to be joined in a ring makes no difference whatever to the
chemistry of the reaction.
Cyclohexanol is heated with concentrated phosphoric(V) acid and the
liquid cyclohexene distils off and can be collected and purified.
Phosphoric(V) acid tends to be used in place of sulphuric acid because it
is safer and produces a less messy reaction.

Where would you like to go now?


To the alkenes menu . . .

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making alkenes in the lab

To the menu of other organic compounds . . .


To Main Menu . . .

Jim Clark 2003

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dehydration of ethanol to give ethene

THE DEHYDRATION OF ALCOHOLS

This page gives you the facts and a simple, uncluttered mechanism for
the acid catalysed dehydration of a simple alcohol like ethanol to give an
alkene like ethene. If you want the mechanism explained to you in detail,
there is a link at the bottom of the page.
You will also find a link to a page on the dehydration of more complicated
alcohols where more than one product may be formed.

The dehydration of ethanol


The facts
Ethanol can be dehydrated to give ethene by heating it with an excess of
concentrated sulphuric acid at about 170C. Concentrated phosphoric(V)
acid, H3PO4, can be used instead.

The acids aren't written into the equation because they serve as
catalysts. If you like, you could write, for example, "conc H2SO4" over the
top of the arrow.

Note: There are many side reactions which go on at the


same time. These aren't required by any current A' level
syllabus.

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dehydration of ethanol to give ethene

The mechanism - the full version


We are going to discuss the mechanism using sulphuric acid. Afterwards,
we'll describe how you can use a simplified version which will work for
any acid, including phosphoric(V) acid.
In the first stage, one of the lone pairs of electrons on the oxygen picks
up a hydrogen ion from the sulphuric acid. The alcohol is said to be
protonated.

The protonated ethanol loses a water molecule to give a carbocation (a


carbonium ion).

Finally, a hydrogensulphate ion (from the sulphuric acid) pulls off a


hydrogen ion from the carbocation.

The mechanism - a simplified version

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People normally quote a simplified version of this mechanism. The only


Exam Board to want the mechanism for the dehydration of alcohols
(AQA) is happy to accept this version.
Instead of showing the full structure of the sulphuric acid, you write it as if
it were simply a hydrogen ion, H+. That leaves the full mechanism:

An advantage of this (apart from the fact that it doesn't require you to
draw the structure of sulphuric acid) is that it can be used for any acid
catalyst without changing it at all. For example, if you use this version,
you wouldn't need to worry about the structure of phosphoric(V) acid.

Note: Although most people probably write the mechanism


in this form, it is actually quite misleading because it suggests
the possibility of a free hydrogen ion in a chemical system. A
free hydrogen ion is a raw proton and this is always attached
to something else during a chemical reaction.
Personally, I find this simplification sloppy - but if your
examiners are happy to accept it, who am I to argue! Go for
the simple life!

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Where would you like to go now?


Help! Talk me through these mechanisms . . .
How to deal with more complicated cases . . .
To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

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Explaining the dehydration of ethanol to give ethene

EXPLAINING THE DEHYDRATION OF ALCOHOLS

This page guides you through the mechanism for the acid catalysed
dehydration of a simple alcohol like ethanol to give an alkene like ethene.
Dehydration of more complicated alcohols is dealt with on a separate
page. This is an essential part of this topic, and you should follow the link
at the bottom of this page if you haven't already done so.

The dehydration of ethanol


The full version of the mechanism
This full version covers the mechanism using sulphuric acid. Afterwards,
we'll look at the simplified version which will work for any acid, including
phosphoric(V) acid.
The oxygen atom in the ethanol has two active lone pairs of electrons,
and one of these picks up a hydrogen ion from the sulphuric acid. The
alcohol is said to be protonated.

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Explaining the dehydration of ethanol to give ethene

Note: Only one of the lone pairs on the oxygen is being


shown because only one is used in the reaction. Similarly, all
the multitude of lone pairs in the sulphuric acid are omitted
because they aren't relevant to the mechanism.
If you aren't happy about the use of curly arrows in
mechanisms, follow this link before you go on. Use the BACK
button on your browser to return to this page.

The negative ion produced is the hydrogensulphate ion, HSO4-.


Notice that the oxygen atom in the alcohol has gained a positive charge.
That charge has to be there for two reasons:

On the left hand side of the equation you start with two overall
neutral molecules. Assuming you forgot about the positive charge,
you would end up with a neutral species and a negative ion on the
right. Charges must balance in equations, so something is wrong.
The oxygen looks wrong! The oxygen atom is joined to 3 things
rather than its usual 2. Oxygen can only join to 3 things if it carries
a positive charge.

Note: Oxygen with a positive charge has the same


arrangement of electrons as a nitrogen atom - which normally
forms 3 bonds.

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Explaining the dehydration of ethanol to give ethene

In the second stage of the reaction the protonated ethanol loses a water
molecule to leave a carbocation (previously known as a carbonium ion) an ion with a positive charge on a carbon atom. The carbon atom is
positive because it has lost the electron that it originally contributed to the
carbon-oxygen bond. Both of the electrons in that bond have moved onto
the oxygen atom, neutralising the oxygen's charge.

One of the several things that can now happen to this carbocation is for it
to lose a hydrogen ion from the CH3 group. This hydrogen ion is pulled
off by a hydrogensulphate ion to regenerate the sulphuric acid catalyst.

Note: The other things that might happen to the carbocation


lead to products like ethoxyethane and ethyl
hydrogensulphate. The mechanisms for these aren't required
by any current A' level syllabus.

The simplified version of the mechanism


Instead of showing the full structure of the sulphuric acid, it is commonly
written as if it were simply a hydrogen ion, H+.
An advantage of this (apart from the fact that it doesn't require you to
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Explaining the dehydration of ethanol to give ethene

draw the structure of sulphuric acid) is that it can be used for any acid
catalyst without changing it at all. For example, if you use this version,
you wouldn't need to worry about the structure of phosphoric(V) acid.
AQA (the only Exam Board to demand the dehydration mechanism at the
moment) is happy to accept this version.

In the first stage, the ethanol gets protonated exactly as before - the only
difference is that you are writing H+ instead of the full structure of the
sulphuric acid.
The second stage is identical to the one in the full version of the
mechanism.
The final stage shows a hydrogen ion "falling off" the carbocation - rather
than being pulled off. This is seriously misleading, but it's what the
examiners want!

Where would you like to go now?


How to deal with more complicated cases . . .
To menu of elimination reactions. . .

http://www.chemguide.co.uk/mechanisms/elim/dhethanoltt.html (4 of 5)30/12/2004 11:08:43

Explaining the dehydration of ethanol to give ethene

To menu of other types of mechanism. . .


To Main Menu . . .

Jim Clark 2000

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dehydration of more complicated alcohols

DEHYDRATION OF MORE COMPLICATED


ALCOHOLS

This page builds on your understanding of the acid catalysed dehydration


of alcohols.
You have to be wary with more complicated alcohols in case there is the
possibility of more than one alkene being formed. Butan-2-ol is a good
example of this, with no less than three different alkenes being formed
when it is dehydrated.
Butan-2-ol is just an example to illustrate the problems. It is important
that you understand it so that you can work out what will happen in
similar cases. It would be quite impossible for you to learn what happens
with every single alcohol you might be presented with.
The basic facts and mechanisms for these reactions are exactly the
same as with a simple alcohol like ethanol. This page only deals with the
extra problems created by the possibility of more than one dehydration
product.

Important! What follow assumes that you are familiar with


the mechanism for the dehydration of ethanol. If you aren't, it
is essential that you follow this link before you go on.

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dehydration of more complicated alcohols

Background
To make the diagrams less cluttered, we'll use the simplified version of
the mechanism showing gain and loss of H+.
Remember that the mechanism takes place in three stages:

The alcohol is protonated by the acid catalyst.


The protonated alcohol loses a water molecule to give a
carbocation (carbonium ion).
The carbocation formed loses a hydrogen ion and forms a double
bond.

So, in the case of the dehydration of a simple alcohol like ethanol:

The dehydration of butan-2-ol


The first two stages
There is nothing new at all in these stages.

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dehydration of more complicated alcohols

In the first stage, the alcohol is protonated by picking up a hydrogen ion


from the sulphuric acid.

In the second stage, the positive ion then sheds a water molecule and
produces a carbocation.

The complication arises in the next step. When the carbocation loses a
hydrogen ion, where is it going to come from?
Where does the hydrogen get removed from?
So that a double bond can form, it will have to come from one of the
carbons next door to the one with the positive charge.
If a hydrogen ion is lost from the CH3 group

But-1-ene is formed.
If a hydrogen ion is lost from the CH2 group

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dehydration of more complicated alcohols

This time the product is but-2-ene, CH3CH=CHCH3.


In fact the situation is even more complicated than it looks, because but2-ene exhibits geometric isomerism. You get a mixture of two isomers
formed - cis-but-2-ene and trans-but-2-ene.

Which isomer gets formed is just a matter of chance.

Geometric isomerism: Isomerism is where you can draw


more than one arrangement of the atoms for a given
molecular formula. Geometric isomerism is a special case of
this involving molecules which have restricted rotation around
one of the bonds - in this case, a carbon-carbon double bond.
The C=C bond could only rotate if enough energy is put in to
break the pi bond. Effectively, except at high temperatures,
the C=C bond is "locked".
In the case of but-2-ene, the two CH3 groups will either both
be locked on one side of the C=C (to give the cis isomer), or
on opposite sides (to give the trans one).
For a full discussion of geometric isomerism follow this link.
Use the BACK button on your browser to return to this page.
Beware! It is easy to miss geometric isomers in an exam.
Always draw alkenes with the correct 120 bond angles
around the C=C bond as shown in the diagrams for the cis
and trans isomers above. If you take a short cut and write but2-ene as CH3CH=CHCH3, you will almost certainly miss the
fact that cis and trans forms are possible.
This is a rich source of questions in an exam. You could
easily throw away marks if you miss these possibilities.

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dehydration of more complicated alcohols

The overall result


Dehydration of butan-2-ol leads to a mixture containing:

but-1-ene

cis-but-2-ene

trans-but-2-ene

Where would you like to go now?


To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elim/dhcomplex.html (5 of 5)30/12/2004 11:08:46

Elimination Mechanisms Menu

Understanding Chemistry

ELIMINATION MECHANISMS MENU

Elimination reactions involving halogenoalkanes


Elimination from 2-bromopropane . . .
The formation of an alkene (propene) from 2-bromopropane.
Elimination from unsymmetrical halogenoalkanes . . .
Explains how to cope with cases where more than one elimination
product can be formed from a single halogenoalkane.
Elimination v. substitution . . .
Discusses how the reaction between a halogenoalkane and
hydroxide ions can lead to either an elimination reaction or
nucleophilic substitution.

The dehydration of alcohols


The dehydration of ethanol . . .
Facts and mechanism for the dehydration of ethanol using an acid
catalyst to give ethene.
The dehydration of more complicated alcohols . . .
Explains how to cope with cases where more than dehydration
http://www.chemguide.co.uk/mechanisms/elimmenu.html (1 of 2)30/12/2004 11:08:48

Elimination Mechanisms Menu

product is possible.

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of halogenoalkanes . . .
Covers all the physical and chemical properties of halogenoalkanes
(haloalkanes or alkyl halides) required by UK A level syllabuses.
properties and reactions of alcohols . . .
Covers all the physical and chemical properties of alcohols required
by UK A level syllabuses.

Jim Clark 2000 (modified 2004)

http://www.chemguide.co.uk/mechanisms/elimmenu.html (2 of 2)30/12/2004 11:08:48

elimination from 2-bromopropane to give propene

THE ELIMINATION REACTIONS PRODUCING


ALKENES FROM SIMPLE HALOGENOALKANES

This page gives you the facts and a simple, uncluttered mechanism for
the elimination reaction between a simple halogenoalkane like 2bromopropane and hydroxide ions (from, for example, sodium hydroxide)
to give an alkene like propene. If you want the mechanism explained to
you in detail, there is a link at the bottom of the page.
You will also find a link to a page on elimination from more complicated
halogenoalkanes where more than one product may be formed.
Exam questions on this topic frequently ask about another possibility in
the reactions between halogenoalkanes and hydroxide ions - nucleophilic
substitution. There is also a link to a page discussing this.

Note: The competition between substitution and elimination


(including the conditions needed and the mechanisms for
both) is a rich source of exam questions if your syllabus
includes it. You will probably find that the questions centre
around secondary halogenoalkanes like 2-bromopropane,
because these can easily be persuaded to do either reaction.
That's why this page deals exclusively with 2-bromopropane.

The elimination reaction involving 2-bromopropane and


hydroxide ions
The facts
2-bromopropane is heated under reflux with a concentrated solution of
sodium or potassium hydroxide in ethanol. Heating under reflux involves
heating with a condenser placed vertically in the flask to avoid loss of
volatile liquids. Propene is formed and, because this is a gas, it passes
through the condenser and can be collected.

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elimination from 2-bromopropane to give propene

Everything else present (including anything formed in the alternative


substitution reaction) will be trapped in the flask.
The mechanism
In elimination reactions, the hydroxide ion acts as a base - removing a
hydrogen as a hydrogen ion from the carbon atom next door to the one
holding the bromine.
The resulting re-arrangement of the electrons expels the bromine as a
bromide ion and produces propene.

Where would you like to go now?


Help! Talk me through this mechanism . . .
How to deal with more complicated cases . . .
The competition between elimination and substitution . . .
To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

http://www.chemguide.co.uk/mechanisms/elim/elim.html (2 of 3)30/12/2004 11:08:51

elimination from 2-bromopropane to give propene

Jim Clark 2000

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Explaining the elimination reaction producing propene from 2-bromopropane

EXPLAINING THE ELIMINATION REACTIONS


PRODUCING ALKENES FROM SIMPLE
HALOGENOALKANES

This page guides you through the elimination mechanism for the reaction
between simple halogenoalkanes like 2-bromopropane and hydroxide
ions from, for example, sodium hydroxide.
Elimination involving more complicated halogenoalkanes and the
competition between elimination and substitution in these reactions are
dealt with on separate pages. These are essential parts of this topic, and
you should follow the links at the bottom of this page if you haven't
already done so.

The elimination reaction involving 2-bromopropane and


hydroxide ions
The role of the OH- ion in an elimination reaction
Hydroxide ions have a very strong tendency to
combine with hydrogen ions to make water - in
other words, the OH- ion is a very strong base.
In an elimination reaction, the hydroxide ion hits
one of the hydrogen atoms in the CH3 group and
pulls it off. This leads to a cascade of electron pair movements resulting
in the formation of a carbon-carbon double bond, and the loss of the
bromine as Br-.

Note: If you aren't happy about the use of curly arrows in


mechanisms, follow this link before you go on. Use the BACK
button on your browser to return to this page.

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Explaining the elimination reaction producing propene from 2-bromopropane

The complete elimination mechanism

The OH- ion takes one of the hydrogens from the CH3 group, but it
only needs the hydrogen nucleus (a hydrogen ion). That means
that the two electrons which originally joined the hydrogen to the
carbon aren't being used any more.
Those two electrons move to form a double bond between the two
carbon atoms.
The approach of those electrons repels the electrons in the carbonbromine bond right out onto the bromine, throwing the bromine off
as a negative ion.

The attack could equally well have been on any of the other hydrogens
on the left-hand carbon, or on any on the right-hand one - it simply
depends on what the OH- ion hit.

Beyond A' level: The mechanism being described here is


known as an E2 mechanism. The E stands for elimination,
and the 2 is because the initial slow part of the reaction
involves 2 species. This mechanism is used by primary and
secondary halogenoalkanes.
There is also an E1 mechanism which would apply to tertiary
halogenoalkanes. (Secondary ones will also do it to some
extent.) No current A' level syllabus is likely to ask you about
that.

http://www.chemguide.co.uk/mechanisms/elim/elimtt.html (2 of 3)30/12/2004 11:08:54

Explaining the elimination reaction producing propene from 2-bromopropane

Where would you like to go now?


How to deal with more complicated cases . . .
The competition between elimination and substitution . . .
To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elim/elimtt.html (3 of 3)30/12/2004 11:08:54

elimination from unsymmetric halogenoalkanes

ELIMINATION FROM UNSYMMETRIC


HALOGENOALKANES

This page looks at elimination from


unsymmetric halogenoalkanes such as 2bromobutane.

2-bromobutane is an unsymmetric halogenoalkane in the sense that it


has a CH3 group one side of the C-Br bond and a CH2CH3 group the
other.
You have to be careful with compounds like this because of the
possibility of more than one elimination product depending on where the
hydrogen is removed from.
The basic facts and mechanisms for these reactions are exactly the
same as with simple halogenoalkanes like 2-bromopropane. This page
only deals with the extra problems created by the possibility of more than
one elimination product.

Important! What follow assumes that you are familiar with


the mechanism for elimination from 2-bromopropane. If you
aren't, it is essential that you follow this link before you go on.

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elimination from unsymmetric halogenoalkanes

Background to the mechanism


You will remember that elimination happens when a hydroxide ion (from,
for example, sodium hydroxide) acts as a base and removes a hydrogen
as a hydrogen ion from the halogenoalkane.
For example, in the simple case of elimination from 2-bromopropane:

The hydroxide ion removes a hydrogen from one of the carbon atoms
next door to the carbon-bromine bond, and the various electron shifts
then lead to the formation of the alkene - in this case, propene.
With an unsymmetric halogenoalkane like 2-bromobutane, there are
several hydrogens which might possibly get removed. You need to think
about each of these possibilities.
Where does the hydrogen get removed from?
The hydrogen has to be removed from a carbon atom adjacent to the
carbon-bromine bond. If an OH- ion hit one of the hydrogens on the righthand CH3 group in the 2-bromobutane (as we've drawn it), there's
nowhere for the reaction to go.

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elimination from unsymmetric halogenoalkanes

To make room for the electron pair to form a double bond between the
carbons, you would have to expel a hydrogen from the CH2 group as a
hydride ion, H-. That is energetically much too difficult, and so this
reaction doesn't happen.
That still leaves the possibility of removing a hydrogen either from the lefthand CH3 or from the CH2 group.
If it was removed from the CH3 group:

The product is but-1-ene, CH2=CHCH2CH3.


If it was removed from the CH2 group:

This time the product is but-2-ene, CH3CH=CHCH3.


In fact the situation is even more complicated than it looks, because but2-ene exhibits geometric isomerism. You get a mixture of two isomers
formed - cis-but-2-ene and trans-but-2-ene.

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elimination from unsymmetric halogenoalkanes

Which isomer gets formed is just a matter of chance.

Geometric isomerism: Isomerism is where you can draw


more than one arrangement of the atoms for a given
molecular formula. Geometric isomerism is a special case of
this involving molecules which have restricted rotation around
one of the bonds - in this case, a carbon-carbon double bond.
The C=C bond could only rotate if enough energy is put in to
break the pi bond. Effectively, except at high temperatures,
the C=C bond is "locked".
In the case of but-2-ene, the two CH3 groups will either both
be locked on one side of the C=C (to give the cis isomer), or
on opposite sides (to give the trans one).
For a full discussion of geometric isomerism follow this link.
Use the BACK button on your browser to return to this page.
Beware! It is easy to miss geometric isomers in an exam.
Always draw alkenes with the correct 120 bond angles
around the C=C bond as shown in the diagrams for the cis
and trans isomers above. If you take a short cut and write but2-ene as CH3CH=CHCH3, you will almost certainly miss the
fact that cis and trans forms are possible.
This is a rich source of questions in an exam. You could
easily throw away marks if you miss these possibilities.

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elimination from unsymmetric halogenoalkanes

The overall result


Elimination from 2-bromobutane leads to a mixture containing:

but-1-ene

cis-but-2-ene

trans-but-2-ene

Where would you like to go now?


To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elim/elimunsym.html (5 of 5)30/12/2004 11:08:57

elimination v nucleophilic substitution in halogenoalkanes

ELIMINATION VERSUS SUBSTITUTION IN


HALOGENOALKANES

This page discusses the factors that decide whether halogenoalkanes


undergo elimination reactions or nucleophilic substitution when they react
with hydroxide ions from, say, sodium hydroxide or potassium hydroxide.
Details for each of these types of reaction are given elsewhere, and you
will find links to them from this page.

The reactions
Both reactions involve heating the halogenoalkane under reflux with
sodium or potassium hydroxide solution.
Nucleophilic substitution
The hydroxide ions present are good nucleophiles, and one possibility is
a replacement of the halogen atom by an -OH group to give an alcohol
via a nucleophilic substitution reaction.

In the example, 2-bromopropane is converted into propan-2-ol.

Note: If you want to read about nucleophilic substitution in


this reaction in detail, follow this link.

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elimination v nucleophilic substitution in halogenoalkanes

Elimination
Halogenoalkanes also undergo elimination reactions in the presence of
sodium or potassium hydroxide.

The 2-bromopropane has reacted to give an alkene - propene.


Notice that a hydrogen atom has been removed from one of the end
carbon atoms together with the bromine from the centre one. In all simple
elimination reactions the things being removed are on adjacent carbon
atoms, and a double bond is set up between those carbons.

Note: If you want to read about elimination in this reaction in


detail, follow this link.

What decides whether you get substitution or elimination?


The reagents you are using are the same for both substitution or
elimination - the halogenoalkane and either sodium or potassium
hydroxide solution. In all cases, you will get a mixture of both reactions
happening - some substitution and some elimination. What you get most
of depends on a number of factors.
The type of halogenoalkane
This is the most important factor.
type of halogenoalkane

substitution or elimination?

primary

mainly substitution

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elimination v nucleophilic substitution in halogenoalkanes

secondary

both substitution and elimination

tertiary

mainly elimination

Important! If you aren't clear about the various types of


halogenoalkanes, it is essential that you follow this link
before you read on.
Use the BACK button on your browser to return to this page.

For example, whatever you do with tertiary halogenoalkanes, you will


tend to get mainly the elimination reaction, whereas with primary ones
you will tend to get mainly substitution. However, you can influence
things to some extent by changing the conditions.
The solvent
The proportion of water to ethanol in the solvent matters.

Water encourages substitution.

Ethanol encourages elimination.

The temperature
Higher temperatures encourage elimination.
Concentration of the sodium or potassium hydroxide solution
Higher concentrations favour elimination.
In summary
For a given halogenoalkane, to favour elimination rather than
substitution, use:

heat

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elimination v nucleophilic substitution in halogenoalkanes

a concentrated solution of sodium or potassium hydroxide

pure ethanol as the solvent

Note: The explanations for these effects are well beyond the
demands of UK A level syllabuses. Some things you just
have to know!

The role of the hydroxide ions


The role of the hydroxide ion in a substitution reaction
In the substitution reaction between a
halogenoalkane and OH- ions, the hydroxide ions
are acting as nucleophiles. For example, one of the
lone pairs on the oxygen can attack the slightly
positive carbon. This leads on to the loss of the
bromine as a bromide ion, and the -OH group
becoming attached in its place.

The role of the hydroxide ion in an elimination reaction


Hydroxide ions have a very strong tendency to
combine with hydrogen ions to make water - in
other words, the OH- ion is a very strong base. In
an elimination reaction, the hydroxide ion hits one
of the hydrogen atoms in the CH3 group and pulls
it off. This leads to a cascade of electron pair
movements resulting in the formation of a carboncarbon double bond, and the loss of the bromine as Br-.

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elimination v nucleophilic substitution in halogenoalkanes

Note: The competition between substitution and elimination


(including the conditions needed and the mechanisms for
both) is a rich source of exam questions if your syllabus
includes it. You will probably find that the questions centre
around secondary halogenoalkanes like 2-bromopropane,
because these can easily be persuaded to do either reaction.
Important: If the elimination mechanism is on your syllabus,
you are quite likely to be asked questions in which the
substitution reaction crops up as well. If you need to revise
this in detail, now is a good time to do it.

Where would you like to go now?


To menu of elimination reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/elim/elimvsubst.html (5 of 5)30/12/2004 11:09:00

nucleophilic substitution - halogenoalkanes and hydroxide ions

THE NUCLEOPHILIC SUBSTITUTION


REACTIONS BETWEEN HALOGENOALKANES
AND HYDROXIDE IONS

This page gives you the facts and simple, uncluttered mechanisms for
the nucleophilic substitution reactions between halogenoalkanes and
hydroxide ions (from, for example, sodium hydroxide). If you want the
mechanisms explained to you in detail, there is a link at the bottom of the
page.

The reaction of primary halogenoalkanes with hydroxide


ions
Important! If you aren't sure about the difference between
primary, secondary and tertiary halogenoalkanes, it is
essential that you follow this link before you go on.
Use the BACK button on your browser to return to this page.

The facts
If a halogenoalkane is heated under reflux with a solution of sodium or
potassium hydroxide, the halogen is replaced by -OH and an alcohol is
produced. Heating under reflux means heating with a condenser placed
vertically in the flask to prevent loss of volatile substances from the
mixture.
The solvent is usually a 50/50 mixture of ethanol and water, because
everything will dissolve in that. The halogenoalkane is insoluble in water.
If you used water alone as the solvent, the halogenoalkane and the
sodium hydroxide solution wouldn't mix and the reaction could only
happen where the two layers met.

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nucleophilic substitution - halogenoalkanes and hydroxide ions

For example, using 1-bromopropane as a typical primary halogenoalkane:

You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:

The bromine (or other halogen) in the halogenoalkane is simply replaced


by an -OH group - hence a substitution reaction. In this example, propan1-ol is formed.
The mechanism
Here is the mechanism for the reaction involving bromoethane:

This is an example ofnucleophilic substitution.


Because the mechanism involves collision between two species in the
slow step (in this case, the only step) of the reaction, it is known as an
SN2 reaction.

Note: Unless your syllabus specifically mentions SN2 by


name, you can just call it nucleophilic substitution.

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nucleophilic substitution - halogenoalkanes and hydroxide ions

If your examiners want you to show the transition state, draw the
mechanism like this:

The reaction of tertiary halogenoalkanes with hydroxide


ions
The facts
The facts of the reaction are exactly the same as with primary
halogenoalkanes. If the halogenoalkane is heated under reflux with a
solution of sodium or potassium hydroxide in a mixture of ethanol and
water, the halogen is replaced by -OH, and an alcohol is produced.
For example:

Or if you want the full equation rather than the ionic one:

The mechanism
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nucleophilic substitution - halogenoalkanes and hydroxide ions

This mechanism involves an initial ionisation of the halogenoalkane:

followed by a very rapid attack by the hydroxide ion on the carbocation


(carbonium ion) formed:

This is again an example ofnucleophilic substitution.


This time the slow step of the reaction only involves one species - the
halogenoalkane. It is known as an SN1 reaction.

The reaction of secondary halogenoalkanes with


hydroxide ions
The facts
The facts of the reaction are exactly the same as with primary or tertiary
halogenoalkanes. The halogenoalkane is heated under reflux with a
solution of sodium or potassium hydroxide in a mixture of ethanol and
water.
For example:

The mechanism

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nucleophilic substitution - halogenoalkanes and hydroxide ions

Secondary halogenoalkanes use both SN2 and SN1 mechanisms. For


example, the SN2 mechanism is:

Should you need it, the two stages of the SN1 mechanism are:

Note: There is another reaction between halogenoalkanes


and hydroxide ions involving an elimination reaction. If you
want to explore that as an alternative, follow this link.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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nucleophilic substitution - halogenoalkanes and hydroxide ions

Jim Clark 2000 (modified 2004)

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Types of halogenoalkanes

HALOGENOALKANES
Halogenoalkanes are also called haloalkanes or alkyl halides.
All halogenoalkanes contain a halogen atom - fluorine, chlorine, bromine
or iodine - attached to an alkyl group.

Note: An alkyl group is a group such as methyl, CH3, or


ethyl, CH3CH2. These are groups containing chains of
carbon atoms which may be branched. Alkyl groups are
given the general symbol R.

The different kinds of halogenoalkanes


Primary halogenoalkanes
In a primary (1) halogenoalkane, the carbon which carries the halogen
atom is only attached to one other alkyl group.
Some examples of primary halogenoalkanes include:

Notice that it doesn't matter how complicated the attached alkyl group is.
In each case there is only one linkage from the CH2 group holding the
halogen to an alkyl group.
There is an exception to this. CH3Br and the other methyl halides are
often counted as primary halogenoalkanes even though there are no
alkyl groups attached to the carbon with the halogen on it.
Secondary halogenoalkanes
In a secondary (2) halogenoalkane, the carbon with the halogen
attached is joined directly to two other alkyl groups, which may be the
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Types of halogenoalkanes

same or different.
Examples:

Tertiary halogenoalkanes
In a tertiary (3) halogenoalkane, the carbon atom holding the halogen is
attached directly to three alkyl groups, which may be any combination of
same or different.
Examples:

Where would you like to go now?


To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/nucsub/types.html (2 of 2)30/12/2004 11:09:10

Nucleophilic Substitution Mechanisms Menu

Understanding Chemistry

NUCLEOPHILIC SUBSTITUTION MECHANISMS


MENU
Types of halogenoalkanes . . .
Desribes what is meant by primary, secondary and tertiary
halogenoalkanes. Essential knowledge if you are to make sense of
everything else in this section.
What is nucleophilic substitution? . . .
Includes background material on the bonding in halogenoalkanes,
and general mechanisms for their nucleophilic substitution
reactions.
Substitution reactions involving hydroxide ions . . .
The mechanisms for the formation of alcohols from
halogenoalkanes by reaction with hydroxide ions.
Substitution reactions involving water . . .
The mechanisms for the formation of alcohols from
halogenoalkanes by reaction with water.
Substitution reactions involving cyanide ions . . .
The mechanisms for the formation of nitriles from halogenoalkanes
by reaction with cyanide ions.
Substitution reactions involving ammonia . . .
The mechanisms for the formation of various sorts of amines from

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Nucleophilic Substitution Mechanisms Menu

halogenoalkanes by reaction with ammonia. Also includes the


reactions between halogenoalkanes and amines.

Go to menu of other types of mechanism. . .


Go to Main Menu . . .

You might also be interested in:


properties and reactions of halogenoalkanes . . .
Covers all the physical and chemical properties of halogenoalkanes
(haloalkanes or alkyl halides) required by UK A level syllabuses.

Jim Clark 2000 (modified 2004)

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What is nucleophilic substitution?

NUCLEOPHILIC SUBSTITUTION

Background
Bonding in the halogenoalkanes
Halogenoalkanes (also known as haloalkanes or alkyl halides) are
compounds containing a halogen atom (fluorine, chlorine, bromine or
iodine) joined to one or more carbon atoms in a chain.
The interesting thing about these compounds is the carbon-halogen
bond, and all the nucleophilic substitution reactions of the
halogenoalkanes involve breaking that bond.
The polarity of the carbon-halogen bonds
With the exception of iodine, all of the halogens are more electronegative
than carbon.
Electronegativity values (Pauling scale)
C

2.5

F
Cl
Br
I

4.0
3.0
2.8
2.5

Note: If you aren't sure about electronegativity and bond


polarity follow this link before you read on.
Use the BACK button on your browser to return to this page.

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What is nucleophilic substitution?

That means that the electron pair in the carbon-halogen bond will be
dragged towards the halogen end, leaving the halogen slightly negative
( -) and the carbon slightly positive ( +) - except in the carbon-iodine
case.
Although the carbon-iodine bond doesn't have a permanent dipole, the
bond is very easily polarised by anything approaching it. Imagine a
negative ion approaching the bond from the far side of the carbon atom:

The fairly small polarity of the carbon-bromine bond will be increased by


the same effect.
The strengths of the carbon-halogen bonds

Note: If you haven't done any work on bond strengths, or are


a bit rusty, it doesn't matter. Just realise that the bigger the
number, the stronger the bond. And don't worry if you have
found slightly different numbers in a different data source there is a lot of variability in the quoted values, but the overall
pattern is still the same.

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What is nucleophilic substitution?

Look at the strengths of various bonds (all values in kJ mol-1).


C-H

413

C-F
C-Cl
C-Br
C-I

467
346
290
228

In all of these nucleophilic substitution reactions, the carbon-halogen


bond has to be broken at some point during the reaction. The harder it is
to break, the slower the reaction will be.
The carbon-fluorine bond is very strong (stronger than C-H) and isn't
easily broken. It doesn't matter that the carbon-fluorine bond has the
greatest polarity - the strength of the bond is much more important in
determining its reactivity. You might therefore expect fluoroalkanes to be
very unreactive - and they are! We shall simply ignore them from now on.
In the other halogenoalkanes, the bonds get weaker as you go from
chlorine to bromine to iodine.
That means that chloroalkanes react most slowly, bromoalkanes react
faster, and iodoalkanes react faster still.
Rates of reaction: RCl < RBr < RI
Where "<" is read as "is less than" - or, in this instance, "is slower than",
and R represents any alkyl group.

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What is nucleophilic substitution?

Warning! Before you read on it is essential that you know


exactly what your syllabus says about these reactions so that
you can extract the right amount of detail from what follows.
The problem is that there are two different mechanisms
depending on the type of halogenoalkane you are using
(whether primary, secondary or tertiary). Some syllabuses try
to make things simpler by restricting you to just one of the
two mechanisms. Where the syllabus is vague, look at recent
exam papers and mark schemes, or any support material
published by the Exam Board.
Haven't got a syllabus or recent exam papers? Follow this
link to find out how to get them. You must know what your
examiners expect in this topic.

Nucleophilic substitution in primary halogenoalkanes


You will need to know about this if your syllabus talks about "primary
halogenoalkanes" or about SN2 reactions. If the syllabus is vague, check
recent exam papers and mark schemes, and compare them against what
follows.
Nucleophiles
A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly charge somewhere on a molecule. The common nucleophiles for A' level
purposes are hydroxide ions, cyanide ions, water and ammonia.

Notice that each of these contains at least one lone pair of electrons,
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What is nucleophilic substitution?

either on an atom carrying a full negative charge, or on a very


electronegative atom carrying a substantial - charge.
The nucleophilic substitution reaction - an SN2 reaction
We'll talk this mechanism through using an ion as a nucleophile, because
it's slightly easier. The water and ammonia mechanisms involve an extra
step which you can read about on the pages describing those particular
mechanisms.
We'll take bromoethane as a typical primary
halogenoalkane. The bromoethane has a polar bond
between the carbon and the bromine.
We'll look at its reaction with a general purpose
nucleophilic ion which we'll call Nu-. This will have at least one lone pair
of electrons. Nu- could, for example, be OH- or CN-.

The lone pair on the Nu- ion will be strongly attracted to the + carbon,
and will move towards it, beginning to make a co-ordinate (dative
covalent) bond. In the process the electrons in the C-Br bond will be
pushed even closer towards the bromine, making it increasingly negative.

Note: A co-ordinate bond is a covalent bond in which both


electrons come from one of the atoms.

The movement goes on until the -Nu is firmly attached to the carbon, and
the bromine has been expelled as a Br- ion.

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What is nucleophilic substitution?

Note: We haven't shown all the lone pairs on the bromine.


These other lone pairs aren't involved in the reaction, and
including them simply clutters the diagram to no purpose.

Things to notice
The Nu- ion approaches the + carbon from the side away from the
bromine atom. The large bromine atom hinders attack from its side and,
being -, would repel the incoming Nu- anyway. This attack from the
back is important if you need to understand why tertiary halogenoalkanes
have a different mechanism. We'll discuss this later on this page.
There is obviously a point in which the Nu- is half attached to the carbon,
and the C-Br bond is half way to being broken. This is called a transition
state. It isn't an intermediate. You can't isolate it - even for a very short
time. It's just the mid-point of a smooth attack by one group and the
departure of another.
How to write the mechanism
The simplest way is:

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What is nucleophilic substitution?

Note: In exam you must show the lone pair of electrons on


the nucleophile (in this case, the Nu- ion). It probably doesn't
matter whether you show them on the departing Br- ion or not.
If you aren't happy about the use of curly arrows in
mechanisms, follow this link before you go on. Use the BACK
button on your browser to return to this page.

Technically, this is known as an SN2 reaction. S stands for substitution, N


for nucleophilic, and the 2 is because the initial stage of the reaction
involves two species - the bromoethane and the Nu- ion. If your syllabus
doesn't refer to SN2 reactions by name, you can just call it nucleophilic
substitution.

Some examiners like you to show the transition state in the mechanism,
in which case you need to write it in a bit more detail - showing how
everything is arranged in space.

Be very careful when you draw the transition state to make a clear

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What is nucleophilic substitution?

difference between the dotted lines showing the half-made and halfbroken bonds, and those showing the bonds going back into the paper.
Notice that the molecule has been inverted during the reaction - rather
like an umbrella being blown inside-out.

Note: If you aren't happy about the various ways of drawing


bonds, it is important to follow this link to find out exactly what
the various symbols mean.
It is also important to know which of these ways of drawing
the mechanism your particular examiners want you to use. If
you haven't already checked your syllabus, recent exam
papers and mark schemes, you must do so! At the time of
writing, Edexcel, for example, wanted the transition state
included, and that isn't obvious from their syllabus. You have
to check mark schemes and examiners reports.
Use the BACK button on your browser to return to this page.

Nucleophilic substitution in tertiary halogenoalkanes

Warning! Check your syllabus, past papers and any support


material published by your Exam Board to find out whether
you need this. If there's no mention of tertiary
halogenoalkanes or SN1 reactions, then you probably don't
need it.

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What is nucleophilic substitution?

Remember that a tertiary halogenoalkane has three


alkyl groups attached to the carbon with the halogen
on it. These alkyl groups can be the same or
different, but in this section, we shall just consider a simple one, (CH3)
3CBr - 2-bromo-2-methylpropane.
The nucleophilic substitution reaction - an SN1 reaction
Once again, we'll talk this mechanism through using an ion as a
nucleophile, because it's slightly easier, and again we'll look at the
reaction of a general purpose nucleophilic ion which we'll call Nu-. This
will have at least one lone pair of electrons.
Why is a different mechanism necessary?
You will remember that when a nucleophile attacks a primary
halogenoalkane, it approaches the + carbon atom from the side away
from the halogen atom.
With a tertiary halogenoalkane, this is impossible. The back of the
molecule is completely cluttered with CH3 groups.

Since any other approach is prevented by the bromine atom, the reaction
has to go by an alternative mechanism.
The alternative mechanism

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What is nucleophilic substitution?

Important! To understand this section, you need to know


what a carbocation (carbonium ion) is, and about the relative
stabilities of primary, secondary and tertiary carbocations.
If you follow this link, use the BACK button on your browser
to return to this page.

The reaction happens in two stages. In the first, a small proportion of the
halogenoalkane ionises to give a carbocation and a bromide ion.

This reaction is possible because tertiary carbocations are relatively


stable compared with secondary or primary ones. Even so, the reaction
is slow.
Once the carbocation is formed, however, it would react immediately it
came into contact with a nucleophile like Nu-. The lone pair on the
nucleophile is strongly attracted towards the positive carbon, and moves
towards it to create a new bond.

How fast the reaction happens is going to be governed by how fast the
halogenoalkane ionises. Because this initial slow step only involves one
species, the mechanism is described as SN1 - substitution, nucleophilic,
one species taking part in the initial slow step.
Why don't primary halogenoalkanes use the SN1 mechanism?
If a primary halogenoalkane did use this mechanism, the first step would
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What is nucleophilic substitution?

be, for example:

A primary carbocation would be formed, and this is much more


energetically unstable than the tertiary one formed from tertiary
halogenoalkanes - and therefore much more difficult to produce.
This instability means that there will be a very high activation energy for
the reaction involving a primary halogenoalkane. The activation energy is
much less if it undergoes an SN2 reaction - and so that's what it does
instead.

Nucleophilic substitution in secondary halogenoalkanes


There isn't anything new in this. Secondary
halogenoalkanes will use both mechanisms - some
molecules will react using the SN2 mechanism and
others the SN1.

The SN2 mechanism is possible because the back of the molecule isn't
completely cluttered by alkyl groups and so the approaching nucleophile
can still get at the + carbon atom.
The SN1 mechanism is possible because the secondary carbocation
formed in the slow step is more stable than a primary one. It isn't as
stable as a tertiary one though, and so the SN1 route isn't as effective as
it is with tertiary halogenoalkanes.

Where would you like to go now?


To menu of nucleophilic substitution reactions. . .

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What is nucleophilic substitution?

To menu of other types of mechanism. . .


To Main Menu . . .

Jim Clark 2000 (modified 2004)

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

EXPLAINING THE NUCLEOPHILIC


SUBSTITUTION REACTIONS BETWEEN
HALOGENOALKANES AND HYDROXIDE IONS

This page guides you through the nucleophilic substitution mechanisms


for the reactions between halogenoalkanes and hydroxide ions from, for
example, sodium hydroxide.

Important! It would help if you first read the page What is


nucleophilic substitution? before you go on.
You must also be clear about the differences between
primary, secondary and tertiary halogenoalkanes.

The reactions between primary or secondary


halogenoalkanes and hydroxide ions - the SN2 mechanism
Hydroxide ions as nucleophiles
A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly charge somewhere on a molecule.
In the case of the hydroxide ion, there is a full negative
charge on the oxygen, as well as three lone pairs of
electrons.
The nucleophilic substitution reaction - an SN2 reaction

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

We'll talk this reaction through with a primary


halogenoalkane to start with, taking bromoethane as
typical. The bromoethane has a polar bond between
the carbon and the bromine.

Note: In an exam you must show the lone pair of electrons


on the nucleophile (in this case, the OH- ion). It probably
doesn't matter whether you show them on the departing Brion or not.

One of the lone pairs on the OH- ion will be strongly attracted to the +
carbon, and will move towards it, beginning to form a bond with it. The
approaching negative ion will repel the electrons in the carbon-bromine
bond closer and closer to the bromine.
At some point during this, the -OH group and the bromine will both be
half-attached to the carbon. This is called the transition state for the
reaction. It isn't an intermediate - you can't isolate it and it doesn't have
any independent existence. It's just the half-way stage of a smooth
movement of atoms and electrons.
The movement goes on until the -OH is firmly attached to the carbon,
and the bromine has been expelled as a Br- ion.
You may need to show the formation of the intermediate in the
mechanism (depending on what your examiners want). It simply needs
you to draw the mechanism showing some more detail about how the
various groups are arranged in space.

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

Be very careful when you draw the transition state to make a clear
difference between the dotted lines showing the half-made and halfbroken bonds, and those showing the bonds going back into the paper.
Notice that the molecule has been inverted during the reaction - rather
like an umbrella being blown inside-out.

Note: If you aren't happy about the various ways of drawing


bonds, it is important to follow this link to find out exactly what
the various symbols mean.
It is also important to know which of these ways of drawing
the mechanism your particular examiners want you to use. If
you haven't already checked your syllabus, recent exam
papers and mark schemes, you must do so! At the time of
writing, Edexcel, for example, wanted the transition state
included, and that isn't obvious from their syllabus. You have
to check mark schemes and examiners reports.
Use the BACK button on your browser to return to this page.

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

Technically, this is known as an SN2 reaction. S stands for substitution, N


for nucleophilic, and the 2 is because the initial stage of the reaction
involves two species - the bromoethane and the OH- ion. If your syllabus
doesn't refer to SN2 reactions by name, you can just call it nucleophilic
substitution.
The SN2 reaction in secondary halogenoalkanes
The reaction can happen in exactly the same way with a secondary
halogenoalkane, although they also have the potential for reacting via a
different mechanism (which we'll deal with shortly).

Again, a lone pair on the approaching hydroxide ion forms a bond with
the + carbon and, in the process, the electrons in the carbon-bromine
bond are forced entirely onto the bromine to create a bromide ion.

The reactions between secondary or tertiary


halogenoalkanes and hydroxide ions - the SN1 mechanism
Note: Are you sure your syllabus wants this? Several
syllabuses restrict you to primary halogenoalkanes.
Haven't got a syllabus? Follow this link to find out how to get
one.

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

To start with, we'll talk this mechanism through with a


simple tertiary halogenoalkane like the one on the
right (2-bromo-2-methylpropane).
Why do tertiary halogenoalkanes need a different mechanism?
When a nucleophile attacks a primary halogenoalkane, it approaches the
+ carbon atom from the side away from the halogen atom. Any other
approach is prevented by the halogen atom, which is both bulky and
slightly negatively charged. The charge repels the incoming nucleophile.
With a tertiary halogenoalkane, this approach from the back is
impossible. The back of the molecule is completely cluttered with CH3
groups.
The SN1 mechanism
The reaction happens in two stages. In the first, a small proportion of the
halogenoalkane ionises to give a carbocation (carbonium ion) and a
bromide ion.

This reaction is possible because tertiary carbocations are relatively


stable compared with secondary or primary ones. Even so, the reaction
is slow.

Note: Not sure about the stability of carbocations


(carbonium ions)? Follow this link if you need to find out.

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

Once the carbocation is formed, however, it would react immediately it


came into contact with an OH- ion. The lone pair on the nucleophile is
strongly attracted towards the positive carbon, and moves towards it to
create a new bond.

How fast the reaction happens is going to be governed by how fast the
halogenoalkane ionises - because that's a slow process. Because this
initial slow step only involves one species, the mechanism is described
as SN1 - substitution, nucleophilic, one species taking part in the initial
slow step.
The SN1 mechanism in secondary halogenoalkanes
Secondary halogenoalkanes (like 2-bromopropane) can use either the
SN1 or the SN2 mechanism. The back of the molecule is rather more
cluttered than in a primary halogenoalkane, but there is still room for the
lone pair on the nucleophile to approach and form a bond. We've already
dealt with that reaction.
It is also possible to get some slight ionisation of the halogenoalkane to
give an SN1 mechanism, but this reaction is much less successful than
with tertiary halogenoalkanes, because the secondary carbocation
formed isn't as stable as a tertiary one.

Once the carbocation has been formed, it will react immediately with a
hydroxide ion. A lone pair on the hydroxide ion is strongly attracted to the
positive carbon, moves towards it, and forms a bond.

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Explaining nucleophilic substitution between halogenoalkanes and hydroxide ions

Where would you like to go now?


To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000 (modified 2004)

http://www.chemguide.co.uk/mechanisms/nucsub/hydroxidett.html (7 of 7)30/12/2004 11:09:26

nucleophilic substitution - halogenoalkanes and water

THE NUCLEOPHILIC SUBSTITUTION


REACTIONS BETWEEN HALOGENOALKANES
AND WATER

This page gives you the facts and simple, uncluttered mechanisms for
the nucleophilic substitution reactions between halogenoalkanes and
water. If you want the mechanisms explained to you in detail, there is a
link at the bottom of the page.

The reaction of primary halogenoalkanes with water


Important! If you aren't sure about the difference between
primary, secondary and tertiary halogenoalkanes, it is
essential that you follow this link before you go on.
Use the BACK button on your browser to return to this page.

The facts
There is only a slow reaction between a primary halogenoalkane and
water even if they are heated. The halogen atom is replaced by -OH.
For example, using 1-bromoethane as a typical primary halogenoalkane:

An alcohol is produced together with hydrobromic acid. Be careful not to


call this hydrogen bromide. Hydrogen bromide is a gas. When it is
dissolved it in water (as it will be here), it's called hydrobromic acid.
The mechanism

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nucleophilic substitution - halogenoalkanes and water

The mechanism involves two steps. The first is a simple nucleophilic


substitution reaction:

Because the mechanism involves collision between two species in this


slow step of the reaction, it is known as an SN2 reaction.

Note: Unless your syllabus specifically mentions SN2 by


name, you can just call it nucleophilic substitution.

The nucleophilic substitution is very slow because water isn't a very good
nucleophile. It lacks the full negative charge of, say, a hydroxide ion.
The second step of the reaction simply tidies up the product. A water
molecule removes one of the hydrogens attached to the oxygen to give
an alcohol and a hydroxonium ion (also known as a hydronium ion or an
oxonium ion).

The hydroxonium ion and the bromide ion (from the nucleophilic
substitution stage of the reaction) make up the hydrobromic acid which is
formed as well as the alcohol.

The reaction of tertiary halogenoalkanes with water


The facts
If the halogenoalkane is heated under reflux with water, the halogen is
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nucleophilic substitution - halogenoalkanes and water

replaced by -OH to give an alcohol. Heating under reflux means heating


with a condenser placed vertically in the flask to prevent loss of volatile
substances from the mixture. The reaction happens much faster than the
corresponding one involving a primary halogenoalkane.
For example:

The mechanism
This mechanism involves an initial ionisation of the halogenoalkane:

followed by a very rapid attack by the water on the carbocation


(carbonium ion) formed:

This is again an example ofnucleophilic substitution.


This time the slow step of the reaction only involves one species - the
halogenoalkane. It is known as an SN1 reaction.
Now there is a final stage in which the product is tidied up. A water
molecule removes one of the hydrogens attached to the oxygen to give
an alcohol and a hydroxonium ion - exactly as happens with primary
halogenoalkanes.

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nucleophilic substitution - halogenoalkanes and water

The rate of the overall reaction is governed entirely by how fast the
halogenoalkane ionises. The fact that water isn't as good a nucleophile
as, say, OH- doesn't make any difference. The water isn't involved in the
slow step of the reaction.

The reaction of secondary halogenoalkanes with water


No current A' level syllabus is likely to ask you about this. In the
extremely unlikely event that you will ever need it, secondary
halogenoalkanes use both an SN2 mechanism and an SN1.
Make sure you understand what happens with primary and tertiary
halogenoalkanes, and then adapt it for secondary ones should ever need
to.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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nucleophilic substitution - halogenoalkanes and water

Jim Clark 2000

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Explaining nucleophilic substitution between halogenoalkanes and water

EXPLAINING THE NUCLEOPHILIC


SUBSTITUTION REACTIONS BETWEEN
HALOGENOALKANES AND WATER

This page guides you through the nucleophilic substitution mechanisms


for the reactions between halogenoalkanes and water. It deals only with
primary and tertiary halogenoalkanes. No current A' level syllabus is
likely to ask about the reaction between secondary halogenoalkanes and
water. (It's not difficult - it's just not there!)

Important! It would help if you first read the page What is


nucleophilic substitution? before you go on.
You must also be clear about the differences between
primary, secondary and tertiary halogenoalkanes.

The reaction between primary halogenoalkanes and water


- the SN2 mechanism
Water as a nucleophile
A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly charge somewhere on a molecule.
Water obviously doesn't carry a negative charge.
However, oxygen is much more electronegative than
hydrogen, and so the oxygen atom has a fairly
substantial - charge to back up its two lone pairs.

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Explaining nucleophilic substitution between halogenoalkanes and water

Note: If you aren't sure about electronegativity follow this link


before you read on.
Use the BACK button on your browser to return to this page.

The attack on the halogenoalkane is therefore by one of the lone pairs on


the oxygen. Because there isn't a full negative charge, water isn't going
to be as good a nucleophile as a negative ion like OH-, and so the
reaction is slower.
The nucleophilic substitution reaction - an SN2 reaction
We'll talk this reaction through with bromoethane as a
typical primary halogenoalkane. The bromoethane has
a polar bond between the carbon and the bromine.

One of the lone pairs on the water will be strongly attracted to the +
carbon, and will move towards it, beginning to form a bond with it. The
approaching lone pair will repel the electrons in the carbon-bromine bond
closer and closer to the bromine.
The movement goes on until the water is firmly attached to the carbon,
and the bromine has been expelled as a Br- ion.
Notice that the oxygen in the product ion carries a positive charge
(highlighted in red to draw attention to it). That charge has to be there for
two reasons:

On the left hand side of the equation you start with two overall
neutral molecules. Assuming you forgot about the positive charge,

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Explaining nucleophilic substitution between halogenoalkanes and water

you would end up with a neutral species and a negative ion on the
right. Charges must balance in equations, so something is wrong.

The oxygen looks wrong! The oxygen atom is joined to 3 things


rather than its usual 2. Oxygen can only join to 3 things if it carries
a positive charge.

Note: Oxygen with a positive charge has the same


arrangement of electrons as a nitrogen atom - which normally
forms 3 bonds.

Technically, this is known as an SN2 reaction. S stands for substitution, N


for nucleophilic, and the 2 is because the initial stage of the reaction
involves two species - the bromoethane and the water. If your syllabus
doesn't refer to SN2 reactions by name, you can just call it nucleophilic
substitution.
Finally a hydrogen ion is pulled off the product ion by another water
molecule from the solution. A lone pair on the new water molecule forms
a bond with a hydrogen atom, forcing the bonding pair of electrons back
on to the positive oxygen. That cancels the positive charge.

The organic product is ethanol. The formula is distorted in this diagram


so that you can clearly see the relationship between the atoms on both
sides of the equation.
The other product is a hydroxonium ion (also known as a hydronium ion
or an oxonium ion). This is just a hydrogen ion attached to a water
molecule - what is often written as H+(aq).

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Explaining nucleophilic substitution between halogenoalkanes and water

the SN1 mechanism


We'll talk this mechanism through with a simple
tertiary halogenoalkane like the one on the right (2bromo-2-methylpropane).
Why do tertiary halogenoalkanes need a different mechanism?
When a nucleophile attacks a primary halogenoalkane, it approaches the
+ carbon atom from the side away from the halogen atom. Any other
approach is prevented by the halogen atom, which is both bulky and
slightly negatively charged. The charge repels the incoming nucleophile.
With a tertiary halogenoalkane, this approach from the back is
impossible. The back of the molecule is completely cluttered with CH3
groups.
The SN1 mechanism
In the first stage, a small proportion of the halogenoalkane ionises to give
a carbocation (carbonium ion) and a bromide ion.

This reaction is possible because tertiary carbocations are relatively


stable compared with secondary or primary ones. Even so, the reaction
is slow.

Note: Not sure about the stability of carbocations


(carbonium ions)? Follow this link if you need to find out.

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Explaining nucleophilic substitution between halogenoalkanes and water

Once the carbocation is formed, however, it would react immediately it


came into contact with a water molecule. One of the lone pairs on the
water is strongly attracted towards the positive carbon, and moves
towards it to create a new bond.

How fast the reaction happens overall is going to be governed by how


fast the halogenoalkane ionises - because that's a slow process.
Because this initial slow step only involves one species, the mechanism
is described as SN1 - substitution, nucleophilic, one species taking part in
the initial slow step.
The water takes part in the fast step of the reaction, and so the fact that a
weakish nucleophile like water is involved doesn't significantly slow the
overall reaction down. The rate is determined by the slow ionisation of
the halogenoalkane.
As with primary halogenalkanes, there is a final stage to this reaction in
which a hydrogen ion is transferred from the organic ion to a water
molecule in the solution. What happens is exactly the same as with the
primary halogenoalkanes described above.

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Explaining nucleophilic substitution between halogenoalkanes and water

To menu of other types of mechanism. . .


To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/nucsub/watertt.html (6 of 6)30/12/2004 11:09:36

nucleophilic substitution - halogenoalkanes and cyanide ions

THE NUCLEOPHILIC SUBSTITUTION


REACTIONS BETWEEN HALOGENOALKANES
AND CYANIDE IONS

This page gives you the facts and simple, uncluttered mechanisms for
the nucleophilic substitution reactions between halogenoalkanes and
cyanide ions (from, for example, potassium cyanide). If you want the
mechanisms explained to you in detail, there is a link at the bottom of the
page.

The reaction of primary halogenoalkanes with cyanide ions


Important! If you aren't sure about the difference between
primary, secondary and tertiary halogenoalkanes, it is
essential that you follow this link before you go on.
Use the BACK button on your browser to return to this page.

The facts
If a halogenoalkane is heated under reflux with a solution of sodium or
potassium cyanide in ethanol, the halogen is replaced by a -CN group
and a nitrile is produced. Heating under reflux means heating with a
condenser placed vertically in the flask to prevent loss of volatile
substances from the mixture.
The solvent is important. If water is present you tend to get substitution
by -OH instead of -CN.

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nucleophilic substitution - halogenoalkanes and cyanide ions

Note: A solution of potassium cyanide in water is quite


alkaline, and contains significant amounts of hydroxide ions.
These react with the halogenoalkane.

For example, using 1-bromopropane as a typical primary halogenoalkane:

You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:

The bromine (or other halogen) in the halogenoalkane is simply replaced


by a -CN group - hence a substitution reaction. In this example,
butanenitrile is formed.

Note: When you are naming nitriles, you have to remember


to include the carbon in the -CN group when you count the
longest chain. In this example, there are 4 carbons in the
longest chain - hence butanenitrile.

The mechanism
Here is the mechanism for the reaction involving bromoethane:

This is an example ofnucleophilic substitution.


Because the mechanism involves collision between two species in the

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nucleophilic substitution - halogenoalkanes and cyanide ions

slow step (in this case, the only step) of the reaction, it is known as an
SN2 reaction.

Note: Unless your syllabus specifically mentions SN2 by


name, you can just call it nucleophilic substitution.

If your examiners want you to show the transition state, draw the
mechanism like this:

The reaction of tertiary halogenoalkanes with cyanide ions


The facts
The facts of the reaction are exactly the same as with primary
halogenoalkanes. If the halogenoalkane is heated under reflux with a
solution of sodium or potassium cyanide in ethanol, the halogen is
replaced by -CN, and a nitrile is produced.
For example:

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nucleophilic substitution - halogenoalkanes and cyanide ions

Or if you want the full equation rather than the ionic one:

The mechanism
This mechanism involves an initial ionisation of the halogenoalkane:

followed by a very rapid attack by the cyanide ion on the carbocation


(carbonium ion) formed:

This is again an example ofnucleophilic substitution.


This time the slow step of the reaction only involves one species - the
halogenoalkane. It is known as an SN1 reaction.

The reaction of secondary halogenoalkanes with cyanide


ions
The facts
The facts of the reaction are exactly the same as with primary or tertiary
halogenoalkanes. The halogenoalkane is heated under reflux with a
solution of sodium or potassium cyanide in ethanol.
For example:
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nucleophilic substitution - halogenoalkanes and cyanide ions

The mechanism
Secondary halogenoalkanes use both SN2 and SN1 mechanisms. For
example, the SN2 mechanism is:

Should you need it, the two stages of the SN1 mechanism are:

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
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http://www.chemguide.co.uk/mechanisms/nucsub/cyanide.html (5 of 6)30/12/2004 11:09:44

nucleophilic substitution - halogenoalkanes and cyanide ions

Jim Clark 2000 (modified 2004)

http://www.chemguide.co.uk/mechanisms/nucsub/cyanide.html (6 of 6)30/12/2004 11:09:44

Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

EXPLAINING THE NUCLEOPHILIC


SUBSTITUTION REACTIONS BETWEEN
HALOGENOALKANES AND CYANIDE IONS

This page guides you through the nucleophilic substitution mechanisms


for the reactions between halogenoalkanes and cyanide ions from, for
example, potassium cyanide.

Important! It would help if you first read the page What is


nucleophilic substitution? before you go on.
You must also be clear about the differences between
primary, secondary and tertiary halogenoalkanes.

The reactions between primary or secondary


halogenoalkanes and cyanide ions - the SN2 mechanism
Cyanide ions as nucleophiles
A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly charge somewhere on a molecule.
In the case of the cyanide ion, there is a full negative
charge on the carbon, as well as a lone pair of electrons.

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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

Note: There is a lone pair on the nitrogen atom as well, but


this isn't shown to avoid confusion. The one on the carbon is
more important in this instance because that's where the
negative charge is. The combination of the lone pair and the
negative charge makes the carbon end of the ion the
nucleophile.

The nucleophilic substitution reaction - an SN2 reaction


We'll talk this reaction through with a primary
halogenoalkane to start with, taking bromoethane as
typical. The bromoethane has a polar bond between
the carbon and the bromine.

Note: In an exam you must show the lone pair of electrons


on the nucleophile (in this case, the CN- ion). It probably
doesn't matter whether you show them on the departing Brion or not.

The lone pair on the carbon of the cyanide ion will be strongly attracted
to the + carbon, and will move towards it, beginning to form a bond with
it. The approaching negative ion will repel the electrons in the carbonbromine bond closer and closer to the bromine.
At some point during this, the -CN group and the bromine will both be
half-attached to the carbon. This is called the transition state for the
reaction. It isn't an intermediate - you can't isolate it and it doesn't have
any independent existence. It's just the half-way stage of a smooth
movement of atoms and electrons.
The movement goes on until the -CN is firmly attached to the carbon,
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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

and the bromine has been expelled as a Br- ion.


You may need to show the formation of the intermediate in the
mechanism (depending on what your examiners want). It simply needs
you to draw the mechanism showing some more detail about how the
various groups are arranged in space.

Be very careful when you draw the transition state to make a clear
difference between the dotted lines showing the half-made and halfbroken bonds, and those showing the bonds going back into the paper.
Notice that the molecule has been inverted during the reaction - rather
like an umbrella being blown inside-out.

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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

Note: If you aren't happy about the various ways of drawing


bonds, it is important to follow this link to find out exactly what
the various symbols mean.
It is also important to know which of these ways of drawing
the mechanism your particular examiners want you to use. If
you haven't already checked your syllabus, recent exam
papers and mark schemes, you must do so! At the time of
writing, Edexcel, for example, wanted the transition state
included, and that isn't obvious from their syllabus. You have
to check mark schemes and examiners reports.
Use the BACK button on your browser to return to this page.

Technically, this is known as an SN2 reaction. S stands for substitution, N


for nucleophilic, and the 2 is because the initial stage of the reaction
involves two species - the bromoethane and the CN- ion. If your syllabus
doesn't refer to SN2 reactions by name, you can just call it nucleophilic
substitution.
The SN2 reaction in secondary halogenoalkanes
The reaction can happen in exactly the same way with a secondary
halogenoalkane, although they also have the potential for reacting via a
different mechanism (which we'll deal with shortly).

Again, the lone pair on the approaching cyanide ion forms a bond with
the + carbon and, in the process, the electrons in the carbon-bromine
bond are forced entirely onto the bromine to create a bromide ion.

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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

The reactions between secondary or tertiary


halogenoalkanes and cyanide ions - the SN1 mechanism
Note: Are you sure your syllabus wants this? Several
syllabuses restrict you to primary halogenoalkanes.
Haven't got a syllabus? Follow this link to find out how to get
one.

To start with, we'll talk this mechanism through with a


simple tertiary halogenoalkane like the one on the
right (2-bromo-2-methylpropane).
Why do tertiary halogenoalkanes need a different mechanism?
When a nucleophile attacks a primary halogenoalkane, it approaches the
+ carbon atom from the side away from the halogen atom. Any other
approach is prevented by the halogen atom, which is both bulky and
slightly negatively charged. The charge repels the incoming nucleophile.
With a tertiary halogenoalkane, this approach from the back is
impossible. The back of the molecule is completely cluttered with CH3
groups.
The SN1 mechanism
The reaction happens in two stages. In the first, a small proportion of the
halogenoalkane ionises to give a carbocation (carbonium ion) and a
bromide ion.

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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

This reaction is possible because tertiary carbocations are relatively


stable compared with secondary or primary ones. Even so, the reaction
is slow.

Note: Not sure about the stability of carbocations


(carbonium ions)? Follow this link if you need to find out.

Once the carbocation is formed, however, it would react immediately it


came into contact with a CN- ion. The lone pair on the nucleophile is
strongly attracted towards the positive carbon, and moves towards it to
create a new bond.

How fast the reaction happens is going to be governed by how fast the
halogenoalkane ionises - because that's a slow process. Because this
initial slow step only involves one species, the mechanism is described
as SN1 - substitution, nucleophilic, one species taking part in the initial
slow step.
The SN1 mechanism in secondary halogenoalkanes
Secondary halogenoalkanes (like 2-bromopropane) can use either the
SN1 or the SN2 mechanism. The back of the molecule is rather more
cluttered than in a primary halogenoalkane, but there is still room for the
lone pair on the nucleophile to approach and form a bond. We've already
dealt with that reaction.
It is also possible to get some slight ionisation of the halogenoalkane to
give an SN1 mechanism, but this reaction is much less successful than
with tertiary halogenoalkanes, because the secondary carbocation
formed isn't as stable as a tertiary one.

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Explaining nucleophilic substitution between halogenoalkanes and cyanide ions

Once the carbocation has been formed, it will react immediately with a
cyanide ion. The lone pair on the cyanide ion is strongly attracted to the
positive carbon, moves towards it, and forms a bond.

Where would you like to go now?


To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000 (modified 2004)

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nucleophilic substitution - halogenoalkanes and ammonia

THE NUCLEOPHILIC SUBSTITUTION REACTIONS


BETWEEN HALOGENOALKANES AND AMMONIA

This page gives you the facts and simple, uncluttered mechanisms for the
nucleophilic substitution reactions between halogenoalkanes and
ammonia to produce primary amines. If you want the mechanisms
explained to you in detail, there is a link at the bottom of the page. If you
are interested in further substitution reactions, you will also find a link to a
separate page dealing with these.

The reaction of primary halogenoalkanes with ammonia


Important! If you aren't sure about the difference between
primary, secondary and tertiary halogenoalkanes, it is
essential that you follow this link before you go on.
Use the BACK button on your browser to return to this page.

The facts
The halogenoalkane is heated with a concentrated solution of ammonia in
ethanol. The reaction is carried out in a sealed tube. You couldn't heat this
mixture under reflux, because the ammonia would simply escape up the
condenser as a gas.
We'll talk about the reaction using 1-bromoethane as a typical primary
halogenoalkane.
The reaction happens in two stages. In the first stage, a salt is formed - in
this case, ethylammonium bromide. This is just like ammonium bromide,
except that one of the hydrogens in the ammonium ion is replaced by an
ethyl group.

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nucleophilic substitution - halogenoalkanes and ammonia

There is then the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the ethylammonium ion to


leave a primary amine - ethylamine.
The more ammonia there is in the mixture, the more the forward reaction
is favoured.

Note: You will find considerable disagreement in textbooks


and other sources about the exact nature of the products in
this reaction. Some of the information you'll come across is
simply wrong!
You can read the arguments about the products of this
reaction by following this link.

The mechanism
The mechanism involves two steps. The first is a simple nucleophilic
substitution reaction:

Because the mechanism involves collision between two species in this


slow step of the reaction, it is known as an SN2 reaction.

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nucleophilic substitution - halogenoalkanes and ammonia

Note: Unless your syllabus specifically mentions SN2 by


name, you can just call it nucleophilic substitution.

In the second step of the reaction an ammonia molecule may remove one
of the hydrogens on the -NH3+. An ammonium ion is formed, together with
a primary amine - in this case, ethylamine.

This reaction is, however, reversible. Your product will therefore contain a
mixture of ethylammonium ions, ammonia, ethylamine and ammonium
ions. Your major product will only be ethylamine if the ammonia is present
in very large excess.
Unfortunately the reaction doesn't stop here. Ethylamine is a good
nucleophile, and goes on to attack unused bromoethane. This gets so
complicated that it is dealt with on a separate page. You will find a link at
the bottom of this page.

The reaction of tertiary halogenoalkanes with ammonia


The facts
The facts of the reactions are exactly the same as with primary
halogenoalkanes. The halogenoalkane is heated in a sealed tube with a
solution of ammonia in ethanol.
For example:

Followed by:
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nucleophilic substitution - halogenoalkanes and ammonia

The mechanism
This mechanism involves an initial ionisation of the halogenoalkane:

followed by a very rapid attack by the ammonia on the carbocation


(carbonium ion) formed:

This is again an example ofnucleophilic substitution.


This time the slow step of the reaction only involves one species - the
halogenoalkane. It is known as an SN1 reaction.
There is a second stage exactly as with primary halogenoalkanes. An
ammonia molecule removes a hydrogen ion from the -NH3+ group in a
reversible reaction. An ammonium ion is formed, together with an amine.

The reaction of secondary halogenoalkanes with ammonia


No current A' level syllabus is likely to ask you about this. In the extremely
unlikely event that you will ever need it, secondary halogenoalkanes use

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nucleophilic substitution - halogenoalkanes and ammonia

both an SN2 mechanism and an SN1.


Make sure you understand what happens with primary and tertiary
halogenoalkanes, and then adapt it for secondary ones should ever need
to.

Where would you like to go now?


Help! Talk me through these mechanisms . . .
To look at further substitution in these reactions . . .
To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/nucsub/ammonia.html (5 of 5)30/12/2004 11:10:08

products of the ammonia - bromoethane reaction

THE PRODUCTS OF THE REACTION BETWEEN


AMMONIA AND BROMOETHANE

This page looks at the problems in writing an equation for the reaction
between ammonia and a halogenoalkane like bromoethane. Although the
discussion involves a primary halogenoalkane, it would apply just as well
to any other kind - secondary or tertiary.

Various incorrect solutions


The problem comes in trying to write a single overall equation for the
reaction. Unfortunately it can't be done without throwing up all sorts of
inconsistencies. If you refer to textbooks or to A' level mark schemes, you
will find three different attempts, all of them slightly unsatisfactory - or
worse!
The first possibility
This comes directly out of the mechanism. The problem is that it produces
the salt of the amine, and not the primary amine itself. Some primary
amine has to be formed to account for further substitution reactions
leading to secondary (etc) amines.
For example, with bromoethane and ammonia, ethylammonium bromide is
formed.

Ethylammonium bromide is a salt of a primary amine and the acid, HBr. A


primary amine has the formula R-NH2. It is primary in the sense that there
is only one alkyl group attached to the nitrogen atom. Primary amines are
weak bases very similar to ammonia and so form salts with acids. For
example, ammonia reacts with HBr to give ammonium bromide, NH4+ Br-.
The salt in the equation above is the one formed from ethylamine,
CH3CH2NH2, and HBr.
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products of the ammonia - bromoethane reaction

The second possibility


If a very large excess of ammonia is used, you could get these reactions:

A second ammonia molecule removes a hydrogen ion from the


ethylammonium bromide which is formed to start with, so that you end up
with ethylamine and ammonium bromide. The overall equation, which is
what is normally quoted, is:

The problem with this is that the ethylamine is a stronger base than
ammonia, and so will tend to hang on to the hydrogen ion. It won't easily
give it up to the weaker base, ammonia.
The best you could hope for is an equilibrium mixture containing some of
everything - ammonia, ethylamine and the two salts. You would only get
the above equation as the major reaction if you had a huge excess of
ammonia.
The third possibility

Unless the reaction is done at extremely high temperatures, and never


allowed to cool, this is quite simply wrong! You cannot produce a mixture
containing a base and an acid. They will react together to form a salt.
Surprisingly, some otherwise very reliable sources quote this piece of
chemical nonsense!

Help! What do I need to learn?

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products of the ammonia - bromoethane reaction

There is no simple answer to this - it depends entirely on what line your


examiners are currently taking. You need to look at recent mark schemes,
so that you can see what they are accepting. You could also look at any
support material your Exam Board publishes. Once you've found out what
they want, use that equation and forget everything else.

Important! If you haven't got a syllabus and recent exam


papers and mark schemes, it is essential that you get hold of
them. Follow this link to find out how to do that.
Use the BACK button on your browser to return to this page.

The solution used on this site


The best solution - and this is the line you'll find taken in the other pages
on this topic - is a slight modification of the second possibility above.
You simply have to abandon any attempt to simplify this into one equation,
and instead write two equations:

The first equation shows the formation of the salt exactly as before. The
second equation emphasises that the next step is reversible. These
equations are entirely consistent with the mechanism. It is only when you
try to combine them into one equation that the problems start.
If this isn't in line with what your examiners want, learn their version - even
if it's wrong! This only affects the overall equation(s) for the reaction. It
doesn't affect in any way what you write down for the mechanisms.

Where would you like to go now?

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products of the ammonia - bromoethane reaction

Return to main page on ammonia and halogenoalkanes . . .


To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

Jim Clark 2000

http://www.chemguide.co.uk/mechanisms/nucsub/ammoniaeq.html (4 of 4)30/12/2004 11:10:14

Explaining nucleophilic substitution between halogenoalkanes and ammonia

EXPLAINING THE NUCLEOPHILIC


SUBSTITUTION REACTIONS BETWEEN
HALOGENOALKANES AND AMMONIA

This page guides you through the nucleophilic substitution mechanisms


for the reactions between halogenoalkanes and ammonia to produce
primary amines. It deals only with primary and tertiary halogenoalkanes.
No current A' level syllabus is likely to ask about the reaction between
secondary halogenoalkanes and ammonia. (It's not difficult - it's just not
there!)
If you are interested in further substitution reactions, at the bottom of this
page you will find a link to a separate page dealing with these.

Important! It would help if you first read the page What is


nucleophilic substitution? before you go on.
You must also be clear about the differences between
primary, secondary and tertiary halogenoalkanes.

The reaction between primary halogenoalkanes and


ammonia - the SN2 mechanism
Ammonia as a nucleophile
A nucleophile is a species (an ion or a molecule) which is strongly
attracted to a region of positive charge in something else.
Nucleophiles are either fully negative ions, or else have a strongly charge somewhere on a molecule.

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Explaining nucleophilic substitution between halogenoalkanes and ammonia

Ammonia obviously doesn't carry a negative


charge. However, nitrogen is more electronegative
than hydrogen, and so the nitrogen atom carries
some degree of negative charge. It also has an
active lone pair of electrons. The attack on the +
carbon atom in the halogenoalkane is by this lone pair on the nitrogen
atom.

Note: If you aren't sure about electronegativity follow this link


before you read on.
Use the BACK button on your browser to return to this page.

The nucleophilic substitution reaction - an SN2 reaction


We'll talk this reaction through with bromoethane as a
typical primary halogenoalkane. The bromoethane has
a polar bond between the carbon and the bromine.
The lone pair on the nitrogen will be strongly attracted
to the + carbon, and will move towards it, beginning to form a bond with
it. The approaching lone pair will repel the electrons in the carbonbromine bond closer and closer to the bromine.
The movement goes on until the ammonia is firmly attached to the
carbon, and the bromine has been expelled as a Br- ion.

Notice that the nitrogen in the product ion carries a positive charge
(highlighted in red to draw attention to it). That charge has to be there for
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Explaining nucleophilic substitution between halogenoalkanes and ammonia

two reasons:

On the left hand side of the equation you start with two overall
neutral molecules. Assuming you forgot about the positive charge,
you would end up with a neutral species and a negative ion on the
right. Charges must balance in equations, so something is wrong.
The nitrogen looks wrong! The nitrogen atom is joined to 4 things
rather than its usual 3. Nitrogen can only join to 4 things if it carries
a positive charge.

Note: Nitrogen with a positive charge has the same


arrangement of electrons as a carbon atom - which normally
forms 4 bonds.

Technically, this is known as an SN2 reaction. S stands for substitution, N


for nucleophilic, and the 2 is because the initial stage of the reaction
involves two species - the bromoethane and the ammonia. If your
syllabus doesn't refer to SN2 reactions by name, you can just call it
nucleophilic substitution.
The product of this reaction is a salt called ethylammonium bromide.
Ethylammonium bromide is a salt of a primary amine and the acid, HBr.
A primary amine has the formula R-NH2. It is primary in the sense that
there is only one alkyl group attached to the nitrogen atom. Primary
amines are weak bases very similar to ammonia and so form salts with
acids. For example, ammonia reacts with HBr to give ammonium
bromide, NH4+ Br-. The salt in the equation above is the one formed from
ethylamine, CH3CH2NH2, and HBr.
At this point you need to know whether your examiners are happy for you
to stop there, or want you to go a stage further to form the free primary
amine.

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Explaining nucleophilic substitution between halogenoalkanes and ammonia

Note: You need to check the mark schemes for recent exam
papers, or any support material published by your Exam
Board. You won't be able to tell this by looking at your
syllabus, or at the exam papers themselves.
You can find out how to get hold of this material by visiting
your Exam Board's web site. You can find a link to this on the
syllabuses page.

If they want the second step, an ammonia molecule now removes a


hydrogen ion from the nitrogen.

The organic product is ethylamine, CH3CH2NH2.


Notice that this change is reversible. The curly arrows for the reverse
change haven't been shown to avoid confusion, but you can easily
picture the lone pair on the nitrogen reclaiming its hydrogen from the NH4
+

ion. What you will end up with is a mixture of all four of the species in
this last equation - together, of course, with the bromide ions formed in
the first stage. The higher the proportion of ammonia in the original
reaction mixture, the greater the chance of the free ethylamine being
formed.

The reaction between tertiary halogenoalkanes and


ammonia - the SN1 mechanism
We'll talk this mechanism through with a simple
tertiary halogenoalkane like the one on the right (2bromo-2-methylpropane).

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Explaining nucleophilic substitution between halogenoalkanes and ammonia

Why do tertiary halogenoalkanes need a different mechanism?


When a nucleophile attacks a primary halogenoalkane, it approaches the
+ carbon atom from the side away from the halogen atom. Any other
approach is prevented by the halogen atom, which is both bulky and
slightly negatively charged. The charge repels the incoming nucleophile.
With a tertiary halogenoalkane, this approach from the back is
impossible. The back of the molecule is completely cluttered with CH3
groups.
The SN1 mechanism
In the first stage, a small proportion of the halogenoalkane ionises to give
a carbocation (carbonium ion) and a bromide ion.

This reaction is possible because tertiary carbocations are relatively


stable compared with secondary or primary ones. Even so, the reaction
is slow.

Note: Not sure about the stability of carbocations (carbonium


ions)? Follow this link if you need to find out.

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Explaining nucleophilic substitution between halogenoalkanes and ammonia

Once the carbocation is formed, however, it would react immediately it


came into contact with an ammonia molecule. The lone pair on the
nitrogen is strongly attracted towards the positive carbon, and moves
towards it to create a new bond.

How fast the reaction happens overall is going to be governed by how


fast the halogenoalkane ionises - because that's a slow process.
Because this initial slow step only involves one species, the mechanism
is described as SN1 - substitution, nucleophilic, one species taking part in
the initial slow step.
A salt is formed, and again you need to know whether your examiners
want you to go on beyond this to the formation of the free amine. If they
do, one of the hydrogens attached to the nitrogen is removed by another
ammonia molecule.

Where would you like to go now?


To look at further substitution in these reactions . . .
To menu of nucleophilic substitution reactions. . .
To menu of other types of mechanism. . .
To Main Menu . . .

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Explaining nucleophilic substitution between halogenoalkanes and ammonia

Jim Clark 2000

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multiple nucleophilic substitution - halogenoalkanes and ammonia

MULTIPLE NUCLEOPHILIC SUBSTITUTION IN


THE REACTION BETWEEN
HALOGENOALKANES AND AMMONIA

This page looks at further substitution in the nucleophilic substitution


reaction between halogenoalkanes and ammonia following the formation
of the primary amine. You could also think of this as a description of how
primary, secondary and tertiary amines act as nucleophiles in a
sequence of reactions with a halogenoalkane.
Only primary halogenoalkanes are considered on this page. One current
A' level syllabus (AQA) is likely to ask about these reactions, and that
only asks about primary halogenoalkanes in this context.

Warning! Don't even think about reading this page unless


you are confident about the nucleophilic substitution reaction
involving a primary halogenoalkane and ammonia giving a
primary amine. You need only worry about the SN2 reaction.
The reactions on the current page follow on from those
described on that page. They are no harder, but they do look
more difficult. They are certainly much more tedious! It is
important that you understand what is explained on this page.
Life is too valuable to waste it learning each of the reactions
described here. If you understand what's happening, you can
work out the equations if you need to.

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multiple nucleophilic substitution - halogenoalkanes and ammonia

Why do you get multiple substitution?


The initial substitution - a reminder
The lone pair on the nitrogen atom in an ammonia molecule is attracted
towards the + carbon in the halogenoalkane - in this example,
bromoethane. It forms a bond with it - in the process expelling the
bromine as a bromide ion.

A salt is formed - ethylammonium bromide.


There is then the possibility of another ammonia molecule removing a
hydrogen from the positive ion to give a primary amine - ethylamine. A
primary amine has the general formula RNH2. This reaction is reversible,
and you will only get significant amounts of the free amine if you use a
large excess of ammonia.

The product as a nucleophile


At the end of the initial substitution there will be a certain amount of free
primary amine formed - the CH3CH2NH2 in the example above. There
may not be very much of it, but there will be some. If that small amount
reacts with something else, the reverse reaction can't happen any longer.
The free amine will continue to be produced, and what was originally a
reversible reaction becomes a one-way reaction - provided the free
amine is removed by some other reaction as soon as it is formed.
Now compare the structures of ammonia and ethylamine:

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multiple nucleophilic substitution - halogenoalkanes and ammonia

You can think of the primary amine as a slightly modified ammonia


molecule. It has a lone pair on the nitrogen atom and an even bigger charge than in ammonia.
That means that the primary amine is going to be a better nucleophile
than ammonia is. You can therefore get a reaction between it and a
molecule of the halogenoalkane.

Note: If you are interested in why the nitrogen in ethylamine


has a greater degree of negative charge than the one in
ammonia, you could follow this link and read about organic
bases.

Making a secondary amine from a primary amine


What is a secondary amine?
A secondary amine has the general formula R2NH. It is like an ammonia
molecule (NH3) in which two of the hydrogens have been replaced by
alkyl groups.
The mechanism

The lone pair on the nitrogen in the primary amine attacks the + carbon
exactly the same as the ammonia did. Bromine is lost as a bromide ion,
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multiple nucleophilic substitution - halogenoalkanes and ammonia

and the immediate product is a salt called diethylammonium bromide (CH3CH2)2NH2+ Br-. This is essentially ammonium bromide in which two
of the hydrogens attached to the nitrogen have been replaced by ethyl
groups.
This then reacts with ammonia in a reversible reaction, exactly as we've
seen before:

The organic product is a secondary amine - diethylamine. It is secondary


because there are two alkyl groups attached to the nitrogen atom.

Making a tertiary amine from the secondary amine


What is a tertiary amine?
A tertiary amine has the general formula R3N. It is like an ammonia
molecule in which all three of the hydrogens have been replaced by alkyl
groups.
The mechanism
The secondary amine still has an active lone pair of electrons on the
nitrogen atom. That, in turn, can attack bromoethane if it happens to
collide with it. The two step sequence is exactly as before:

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multiple nucleophilic substitution - halogenoalkanes and ammonia

In this first step, the bromine is again displaced as a bromide ion and you
get a salt formed called triethylammonium bromide.

Note: It has been necessary to rearrange the formula of the


secondary amine in order to keep the appearance of the
mechanism the same as the previous ones. Look carefully at
it to be sure there isn't anything nasty going on!

An ammonia molecule can then remove the hydrogen from the nitrogen
in the reversible reaction:

The organic product of this reaction is the tertiary amine, triethylamine. It


is tertiary because of the three alkyl groups attached to the nitrogen.

The final stage - making a quaternary ammonium salt


What is a quaternary ammonium salt?
A quaternary ammonium salt is an ammonium salt (for example, NH4+
Br-) in which all the hydrogens have been replaced by an alkyl group - for
example, (CH3CH2)4N+ Br-.
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multiple nucleophilic substitution - halogenoalkanes and ammonia

The mechanism
The tertiary amine still has an active lone pair on the nitrogen and, once
again, that can attack the + carbon in the bromoethane.

But this time there is nowhere else for the reaction to go. There is no
longer a hydrogen atom on the nitrogen that an ammonia molecule could
remove, and so the reaction finally comes to an end.
The product is a salt called tetraethylammonium bromide, (CH3CH2)4N+
Br-.

If you react bromoethane and ammonia, what do you


actually get?
You will always get a mixture of all the above products unless you use a
very large excess of bromoethane so that there is enough of it to carry
the sequence all the way through to the quaternary ammonium salt.
You could favour formation of the primary amine (or its salt) by using a
very large excess of ammonia. That way there is always a greater
chance of a bromoethane molecule being hit by an ammonia molecule
than any other possible nucleophile. Even so, there will always, by
chance, be some collisions leading to the follow-on products.

Where would you like to go now?


To menu of nucleophilic substitution reactions. . .

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multiple nucleophilic substitution - halogenoalkanes and ammonia

To menu of other types of mechanism. . .


To Main Menu . . .

Jim Clark 2000

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Explaining the strength of organic bases

ORGANIC BASES

This page explains why simple organic bases are basic and looks at the
factors which affect their relative strengths. For A'level purposes, all the
bases we are concerned with are primary amines - compounds in which
one of the hydrogens in an ammonia molecule, NH3, is replaced either
by an alkyl group or a benzene ring.

Why are primary amines basic?


Ammonia as a weak base
All of the compounds we are concerned with are derived from ammonia
and so we'll start by looking at the reason for its basic properties.
For the purposes of this topic, we are going to take the definition of a
base as "a substance which combines with hydrogen ions (protons)". We
are going to get a measure of this by looking at how easily the bases
take hydrogen ions from water molecules when they are in solution in
water.
Ammonia in solution sets up this equilibrium:

An ammonium ion is formed together with hydroxide ions. Because the


ammonia is only a weak base, it doesn't hang on to the extra hydrogen
ion very effectively and so the reaction is reversible. At any one time,
about 99% of the ammonia is present as unreacted molecules. The
position of equilibrium lies well to the left.
The ammonia reacts as a base because of the active lone pair on the
nitrogen. Nitrogen is more electronegative than hydrogen and so attracts
the bonding electrons in the ammonia molecule towards itself. That
means that in addition to the lone pair, there is a build-up of negative
charge around the nitrogen atom. That combination of extra negativity
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Explaining the strength of organic bases

and active lone pair attracts the new hydrogen from the water.

Comparing the strengths of weak bases


The strengths of weak bases are measured on the pKb scale. The
smaller the number on this scale, the stronger the base is.
Three of the compounds we shall be looking at, together with their pKb
values are:

Remember - the smaller the number the stronger the base. Comparing
the other two to ammonia, you will see that methylamine is a stronger
base, whereas phenylamine is very much weaker.
Methylamine is typical of aliphatic primary amines - where the -NH2
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Explaining the strength of organic bases

group is attached to a carbon chain. All aliphatic primary amines are


stronger bases than ammonia.
Phenylamine is typical of aromatic primary amines - where the -NH2
group is attached directly to a benzene ring. These are very much
weaker bases than ammonia.

Explaining the differences in base strengths


The factors to consider
Two of the factors which influence the strength of a base are:

the ease with which the lone pair picks up a hydrogen ion,

the stability of the ions being formed.

Why are aliphatic primary amines stronger bases than ammonia?


Methylamine
Methylamine has the structure:

The only difference between this and ammonia is the presence of the
CH3 group in the methylamine. But that's important! Alkyl groups have a
tendency to "push" electrons away from themselves. That means that
there will be a small amount of extra negative charge built up on the
nitrogen atom. That extra negativity around the nitrogen makes the lone
pair even more attractive towards hydrogen ions.

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Explaining the strength of organic bases

Making the nitrogen more negative helps the lone pair to pick up a
hydrogen ion.
What about the effect on the positive methylammonium ion formed? Is
this more stable than a simple ammonium ion?
Compare the methylammonium ion with an ammonium ion:

In the methylammonium ion, the positive charge is spread around the ion
by the "electron-pushing" effect of the methyl group. The more you can
spread charge around, the more stable an ion becomes. In the
ammonium ion there isn't any way of spreading the charge.
To summarise:

The nitrogen is more negative in methylamine than in ammonia,


and so it picks up a hydrogen ion more readily.
The ion formed from methylamine is more stable than the one
formed from ammonia, and so is less likely to shed the hydrogen
ion again.

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Explaining the strength of organic bases

Taken together, these mean that methylamine is a stronger base than


ammonia.

Note: This is a bit of a simplification for A' level purposes. As


bases get more complex, another factor concerning the
stability of the ions formed becomes important. That
concerns the way they interact with water molecules in the
solution. You don't need to worry about that at this level.

The other aliphatic primary amines


The other alkyl groups have "electron-pushing" effects very similar to the
methyl group, and so the strengths of the other aliphatic primary amines
are very similar to methylamine.

Note: If you want more information about the inductive effect


of alkyl groups, you could read about carbocations
(carbonium ions) in the mechanism section of this site.

For example:
pKb
CH3NH2

3.36

CH3CH2NH2

3.27

CH3CH2CH2NH2

3.16

CH3CH2CH2CH2NH2

3.39

Why are aromatic primary amines much weaker bases than


ammonia?
An aromatic primary amine is one in which the -NH2 group is attached
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Explaining the strength of organic bases

directly to a benzene ring. The only one you are likely to come across is
phenylamine.
Phenylamine has the structure:

The lone pair on the nitrogen touches the delocalised ring electrons . . .

. . . and becomes delocalised with them:

That means that the lone pair is no longer fully available to combine with
hydrogen ions. The nitrogen is still the most electronegative atom in the
molecule, and so the delocalised electrons will be attracted towards it,
but the intensity of charge around the nitrogen is nothing like what it is in,
say, an ammonia molecule.

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Explaining the strength of organic bases

The other problem is that if the lone pair is used to join to a hydrogen ion,
it is no longer available to contribute to the delocalisation. That means
that the delocalisation would have to be disrupted if the phenylamine acts
as a base. Delocalisation makes molecules more stable, and so
disrupting the delocalisation costs energy and won't happen easily.
Taken together - the lack of intense charge around the nitrogen, and the
need to break some delocalisation - this means that phenylamine is a
very weak base indeed.

Where would you like to go now?


To the acids and bases menu. . .
To menu of basic organic chemistry. . .
To Main Menu . . .

You might also be interested in:


The properties and reactions of:
aliphatic amines . . .
phenylamine (aniline) . . .

Jim Clark 2000

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Organic acids and bases menu

Understanding Chemistry

ORGANIC ACIDS AND BASES MENU

Organic acids . . .
Explains why organic acids are acidic, and what affects their
strengths.
Organic bases . . .
Explains why primary amines are basic, and what affects their
strengths.

Go to menu of basic organic chemistry. . .


Go to Main Menu . . .

Jim Clark 2000

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Amines Menu

Understanding Chemistry

ALIPHATIC AMINES MENU

This only covers amines where the functional group is not attached
directly to a benzene ring. There is a link towards the bottom of the page
to a separate section about phenylamine (aniline) if you are interested.

Background . . .
An introduction to amines including the various types of amine
(primary, secondary and tertiary) and their physical properties.
Preparation of amines . . .
Their preparation from halogenoalkanes (haloalkanes or alkyl
halides) and from nitriles.
Amines as bases . . .
The importance of the lone pair on the nitrogen in the reactions of
amines as bases. Their reactions with acids, water and copper(II)
ions.
Amines as nucleophiles . . .
The importance of the lone pair on the nitrogen in the reactions of
amines as nucleophiles. Their reactions with halogenoalkanes
(haloalkanes or alkyl halides), with acyl chlorides (acid chlorides)
and with acid anhydrides.
The reaction of amines with nitrous acid (nitric(III) acid) . . .
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Amines Menu

The use of nitrous acid in testing for amines.

Information about phenylamine (aniline) . . .


The preparation and physical and chemical properties of the
aromatic amine, phenylamine (aniline). This section also includes
the preparation and properties of diazonium salts.

Go to menu of other organic compounds . . .


Go to Main Menu . . .

Jim Clark 2004

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an introduction to amines

INTRODUCING AMINES

This page explains what amines are, and what the difference is between
primary, secondary and tertiary amines. It looks in some detail at their
simple physical properties such as solubility and boiling points. Details of
the chemical reactions of amines are described on separate pages.

Note: This page only deals with amines where the functional
group is not attached directly to a benzene ring. Aromatic
amines such as phenylamine (aniline) are sufficiently
different that they are covered in a separate section. Follow
this link if you are mainly interested in phenylamine.

What are amines?


The easiest way to think of amines is as near relatives of ammonia, NH3.
In amines, the hydrogen atoms in the ammonia have been replaced one
at a time by hydrocarbon groups. On this page, we are only looking at
cases where the hydrocarbon groups are simple alkyl groups.

The different kinds of amines


Amines fall into different classes depending on how many of the
hydrogen atoms are replaced.
Primary amines
In primary amines, only one of the hydrogen atoms in the ammonia
molecule has been replaced. That means that the formula of the primary
amine will be RNH2 where "R" is an alkyl group.
Examples include:
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an introduction to amines

Naming amines can be quite confusing because there are so many


variations on the names. For example, the simplest amine, CH3NH2, can
be called methylamine, methanamine or aminomethane.

The commonest name at this level is methylamine and, similarly, the


second compound drawn above is usually called ethylamine.
Where there might be confusion about where the -NH2 group is attached
to a chain, the simplest way of naming the compound is to use the
"amino" form.
For example:

Secondary amines
In a secondary amine, two of the hydrogens in an ammonia molecule
have been replaced by hydrocarbon groups. At this level, you are only
likely to come across simple ones where both of the hydrocarbon groups
are alkyl groups and both are the same.
For example:

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an introduction to amines

There are other variants on the names, but this is the commonest and
simplest way of naming these small secondary amines.

Tertiary amines
In a tertiary amine, all of the hydrogens in an ammonia molecule have
been replaced by hydrocarbon groups. Again, you are only likely to come
across simple ones where all three of the hydrocarbon groups are alkyl
groups and all three are the same.
The naming is similar to secondary amines. For example:

Physical properties of amines


Boiling points
The table shows the boiling points of some simple amines.

type

formula

boiling point (C)

primary

CH3NH2

-6.3

primary

CH3CH2NH2

16.6

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an introduction to amines

primary

CH3CH2CH2NH2

48.6

secondary

(CH3)2NH

7.4

tertiary

(CH3)3N

3.5

We will need to look at this with some care to sort out the patterns and
reasons. Concentrate first on the primary amines.
Primary amines
It is useful to compare the boiling point of methylamine, CH3NH2, with
that of ethane, CH3CH3.
Both molecules contain the same number of electrons and have, as near
as makes no difference, the same shape. However, the boiling point of
methylamine is -6.3C, whereas ethane's boiling point is much lower at 88.6C.
The reason for the higher boiling points of the primary amines is that they
can form hydrogen bonds with each other as well as van der Waals
dispersion forces and dipole-dipole interactions.

Note: If you aren't happy about intermolecular forces


(including van der Waals dispersion forces and hydrogen
bonds) then you really ought to follow this link before you go
on. The next bit won't make much sense to you if you aren't
familiar with the various sorts of intermolecular forces.
Use the BACK button on your browser to return to this page.

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an introduction to amines

Hydrogen bonds can form between the lone pair on the very
electronegative nitrogen atom and the slightly positive hydrogen atom in
another molecule.

The hydrogen bonding isn't as efficient as it is in, say, water, because


there is a shortage of lone pairs. Some slightly positive hydrogen atoms
won't be able to find a lone pair to hydrogen bond with. There are twice
as many suitable hydrogens are there are lone pairs.
The boiling points of the primary amines increase as you increase chain
length because of the greater amount of van der Waals dispersion forces
between the bigger molecules.

Secondary amines
For a fair comparison you would have to compare the boiling point of
dimethylamine with that of ethylamine. They are isomers of each other each contains exactly the same number of the same atoms.
The boiling point of the secondary amine is a little lower than the
corresponding primary amine with the same number of carbon atoms.
Secondary amines still form hydrogen bonds, but having the nitrogen
atom in the middle of the chain rather than at the end makes the
permanent dipole on the molecule slightly less.
The lower boiling point is due to the lower dipole-dipole attractions in the
dimethylamine compared with ethylamine.

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an introduction to amines

Tertiary amines
This time to make a fair comparison you would have to compare
trimethylamine with its isomer 1-aminopropane.
If you look back at the table further up the page, you will see that the
trimethylamine has a much lower boiling point (3.5C) than 1aminopropane (48.6C).
In a tertiary amine there aren't any hydrogen atoms attached directly to
the nitrogen. That means that hydrogen bonding between tertiary amine
molecules is impossible. That's why the boiling point is much lower.

Solubility in water
The small amines of all types are very soluble in water. In fact, the ones
that would normally be found as gases at room temperature are normally
sold as solutions in water - in much the same way that ammonia is
usually supplied as ammonia solution.
All of the amines can form hydrogen bonds with water - even the tertiary
ones.
Although the tertiary amines don't have a hydrogen atom attached to the
nitrogen and so can't form hydrogen bonds with themselves, they can
form hydrogen bonds with water molecules just using the lone pair on the
nitrogen.

Solubility falls off as the hydrocarbon chains get longer - noticeably so


after about 6 carbons. The hydrocarbon chains have to force their way

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an introduction to amines

between water molecules, breaking hydrogen bonds between water


molecules.
However, they don't replace them by anything as strong, and so the
process of forming a solution becomes less and less energetically
feasible as chain length grows.

Smell
The very small amines like methylamine and ethylamine smell very
similar to ammonia - although if you compared them side by side, the
amine smells are slightly more complex.
As the amines get bigger, they tend to smell more "fishy", or they smell of
decay.
If you are familiar with the smell of hawthorn blossom (and similarly
smelling things like cotoneaster blossom), this is the smell of
trimethylamine - a sweet and rather sickly smell like the early stages of
decaying flesh.

Where would you like to go now?


To the amines menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2004

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Phenylamine (aniline) Menu

Understanding Chemistry

PHENYLAMINE (ANILINE) MENU

Background . . .
An introduction to phenylamine (aniline) and its physical properties.
Preparation . . .
Making phenylamine from benzene via nitrobenzene.
Reactions of phenylamine as a primary amine . . .
This covers the reactions that phenylamine has in common with
other primary amines - its reactions as a base, its acylation with
acyl chlorides and acid anhydrides, and its reaction with
halogenoalkanes.
Making diazonium salts . . .
The reaction of phenylamine with nitrous acid to produce
diazonium ions.
Reactions of diazonium salts . . .
Using them to make phenol and iodobenzene, and the coupling
reactions with phenol, naphthalen-2-ol (2-naphthol) and
phenylamine.

Go to menu of other organic compounds . . .


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Phenylamine (aniline) Menu

Go to Main Menu . . .

You might also be interested in:


properties and reactions of aliphatic amines. . .
Covers the physical and chemical properties of amines where the
amine group is attached to a carbon chain (or just a methyl group)
rather than a benzene ring.

Jim Clark 2004

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an introduction to phenylamine (aniline)

INTRODUCING PHENYLAMINE

This page looks at the structure and physical properties of phenylamine also known as aniline or aminobenzene. Phenylamine has an -NH2
group attached directly to a benzene ring.

The structure of phenylamine


Phenylamine is a primary amine - a compound in which one of the
hydrogen atoms in an ammonia molecule has been replaced by a
hydrocarbon group.
However, in comparison with simple primary amines like methylamine,
the properties of phenylamine are slightly different. This is because the
lone pair on the nitrogen atom interacts with the delocalised electrons in
the benzene ring.
The simplest way to draw the structure of phenylamine is:

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an introduction to phenylamine (aniline)

Warning! You need to understand about the bonding in


benzene in order to make sense of this next bit.
If you follow this link, you may have to explore several other
pages before you are ready to come back here again. Use
the BACK button (or HISTORY file or GO menu) on your
browser to return to this page.

There is an interaction between the delocalised electrons in the benzene


ring and the lone pair on the nitrogen atom. The lone pair overlaps with
the delocalised ring electron system . . .

. . . giving a structure rather like this:

The donation of the nitrogen's lone pair into the ring system increases
the electron density around the ring. That makes the ring much more
reactive than it is in benzene itself.
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an introduction to phenylamine (aniline)

Note: The ring reactions of phenylamine aren't on any of the


current UK A level chemistry syllabuses, so I haven't followed
this up anywhere on this site.

It also reduces the availability of the lone pair on the nitrogen to take part
in other reactions. In particular, it makes phenylamine much more weakly
basic than primary amines where the -NH2 group isn't attached to a
benzene ring. That will be explored elsewhere in this section. (See the
phenylamine menu - link at the bottom of this page.)

Physical properties
Pure phenylamine is a colourless liquid, but it darkens rapidly on
exposure to light and air. It is normally a brown oily liquid.
Melting and boiling points
It is useful to compare phenylamine's melting and boiling points with
those of methylbenzene (toluene). Both molecules contain a similar
number of electrons and are a very similar shape. That means that the
intermolecular attractions due to van der Waals dispersion forces are
going to be very similar.

Note: If you aren't happy about intermolecular forces


(including van der Waals dispersion forces and hydrogen
bonds) then you really ought to follow this link before you go
on. This section won't make much sense to you if you aren't
familiar with the various sorts of intermolecular forces.
Use the BACK button on your browser to return to this page.

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an introduction to phenylamine (aniline)

melting point (C) boiling point (C)


C6H5NH2

-6.2

184

C6H5CH3

-95.0

111

The reason for the higher values for phenylamine is in part due to
permanent dipole-dipole attractions due to the electronegativity of the
nitrogen - but is mainly due to hydrogen bonding.
Hydrogen bonds can form between a lone pair on a nitrogen on one
molecule and the hydrogen on the -NH2 group of one of its neighbours.

Note: If you are amazingly wide-awake, you might wonder


how the lone pair can form hydrogen bonds if it is delocalised
into the ring electrons. The truth is that the delocalisation isn't
complete. You can think of the lone pair as still being there,
but not as effective as it would otherwise be.

Solubility in water
Phenylamine is slightly soluble in water - about 3.6 g (depending on
where you get the data from!) of phenylamine will dissolve in 100 g of
water at 20C. Mixtures containing more phenylamine than this separate
into two layers, with the phenylamine forming the bottom one.
Phenylamine is somewhat soluble in water because of its ability to form
hydrogen bonds with the water.
However, the benzene rings in the phenylamine break more hydrogen
bonds between water molecules than are reformed between water and
the -NH2 groups. The water molecules also disrupt fairly strong van der
Waals attractions between the phenylamine molecules.
Both of these effects mean that dissolving phenylamine in water isn't very
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an introduction to phenylamine (aniline)

energetically profitable, and so stop the phenylamine from being very


soluble.

Where would you like to go now?


To the phenylamine menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

You might also be interested in:


properties and reactions of aliphatic amines. . .
Covers the physical and chemical properties of amines where the
amine group is attached to a carbon chain (or just a methyl group)
rather than a benzene ring.

Jim Clark 2004

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preparation of amines

MAKING AMINES

This page looks at the preparation of amines from halogenoalkanes (also


known as haloalkanes or alkyl halides) and from nitriles.
It only deals with amines where the functional group is not attached
directly to a benzene ring. Aromatic amines such as phenylamine (aniline)
are usually made differently and are discussed on a separate page.

Note: Follow this link if you are mainly interested in the


preparation of phenylamine.

Making amines from halogenoalkanes


The halogenoalkane is heated with a concentrated solution of ammonia in
ethanol. The reaction is carried out in a sealed tube. You couldn't heat this
mixture under reflux, because the ammonia would simply escape up the
condenser as a gas.
We'll talk about the reaction using 1-bromoethane as a typical
halogenoalkane.
You get a mixture of amines formed together with their salts. The reactions
happen one after another.

Making a primary amine


The reaction happens in two stages. In the first stage, a salt is formed - in
this case, ethylammonium bromide. This is just like ammonium bromide,
except that one of the hydrogens in the ammonium ion is replaced by an
ethyl group.

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preparation of amines

There is then the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the ethylammonium ion to


leave a primary amine - ethylamine.
The more ammonia there is in the mixture, the more the forward reaction is
favoured.

Note: You will find considerable disagreement in textbooks


and other sources about the exact nature of the products in this
reaction. Some of the information you'll come across is simply
wrong!
You can read the arguments about the products of this reaction
by following this link.
Warning! That page is in the mechanism section of the site.
Return to the current page using the BACK button on your
browser. If you use the links at the bottom of that page, you
could get seriously lost!

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preparation of amines

Making a secondary amine


The reaction doesn't stop at a primary amine. The ethylamine also reacts
with bromoethane - in the same two stages as before.
In the first stage, you get a salt formed - this time, diethylammonium
bromide. Think of this as ammonium bromide with two hydrogens replaced
by ethyl groups.

There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the diethylammonium ion to


leave a secondary amine - diethylamine. A secondary amine is one which
has two alkyl groups attached to the nitrogen.

Making a tertiary amine


And still it doesn't stop! The diethylamine also reacts with bromoethane - in
the same two stages as before.
In the first stage, you get triethylammonium bromide.

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preparation of amines

There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the triethylammonium ion to


leave a tertiary amine - triethylamine. A tertiary amine is one which has
three alkyl groups attached to the nitrogen.

Making a quaternary ammonium salt


The final stage! The triethylamine reacts with bromoethane to give
tetraethylammonium bromide - a quaternary ammonium salt (one in which
all four hydrogens have been replaced by alkyl groups).

This time there isn't any hydrogen left on the nitrogen to be removed. The
reaction stops here.

Note: This whole reaction sequence is a complete pain if you


are going to have to learn it. It is much, much easier to work it
out if you need to, provided you understand the mechanisms
for the reactions.
You can explore the mechanisms for the various stages of the
reaction by following this link. This will lead you to several
pages in the mechanism section of this site. If all you want to
do is make some sense of the above reactions, it would
probably pay you to just read the parts of those pages
concerned with primary halogenoalkanes like bromoethane.

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preparation of amines

What do you actually get if you react bromoethane with ammonia?


Whatever you do, you get a mixture of all of the products (including the
various amines and their salts) shown on this page.
To get mainly the quaternary ammonium salt, you can use a large excess
of bromoethane. If you look at the reactions going on, each one needs
additional bromoethane. If you provide enough, then the chances are that
the reaction will go to completion, given enough time.
On the other hand, if you use a very large excess of ammonia, the
chances are always greatest that a bromoethane molecule will hit an
ammonia molecule rather than one of the amines being formed. That will
help to prevent the formation of secondary (etc) amines - although it won't
stop it entirely.

Making primary amines from nitriles


Nitriles are compounds containing the -CN group, and can be reduced in
various ways. Two possible methods are described here.

Reducing nitriles using LiAlH4


One possible reducing agent is lithium tetrahydridoaluminate(III) - often
just called lithium tetrahydridoaluminate or lithium aluminium hydride.
The nitrile reacts with the lithium tetrahydridoaluminate in solution in
ethoxyethane (diethyl ether, or just "ether") followed by treatment of the
product of that reaction with a dilute acid.
Overall, the carbon-nitrogen triple bond is reduced to give a primary amine.
For example, with ethanenitrile you get ethylamine:

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Notice that this is a simplified equation - perfectly acceptable to UK A level


examiners. [H] means "hydrogen from a reducing agent".

Note: If you know about the reduction of aldehydes and


ketones, you may know that they are also reduced by the
similar compound NaBH4.
However, NaBH4 isn't a strong enough reducing agent to
reduce nitriles.

The reduction of nitriles using hydrogen and a metal catalyst


The carbon-nitrogen triple bond in a nitrile can also be reduced by reaction
with hydrogen gas in the presence of a variety of metal catalysts.
Commonly quoted catalysts are palladium, platinum or nickel.
The reaction will take place at a raised temperature and pressure. It is
impossible to give exact details because it will vary from catalyst to
catalyst.
For example, ethanenitrile can be reduced to ethylamine by reaction with
hydrogen in the presence of a palladium catalyst.

Note: Notice that this time the hydrogen is written normally as


H2. This is a proper equation involving hydrogen gas - not a
simplification.

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preparation of amines

Where would you like to go now?


To the amines menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2004

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the preparation of phenylamine (aniline)

MAKING PHENYLAMINE

This page looks in outline at the preparation of phenylamine (also known


as aniline or aminobenzene) starting from benzene. The benzene is first
converted to nitrobenzene which is in turn reduced to phenylamine.

Benzene to nitrobenzene
Benzene is nitrated by replacing one of the hydrogen atoms on the
benzene ring by a nitro group, NO2.
The benzene is treated with a mixture of concentrated nitric acid and
concentrated sulphuric acid at a temperature not exceeding 50C. The
mixture is held at this temperature for about half an hour. Yellow oily
nitrobenzene is formed.

You could write this in a more condensed form as:

The concentrated sulphuric acid is acting as a catalyst and so isn't


written into the equations.
The temperature is kept relatively low to prevent more than one nitro
group being substituted onto the ring.

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the preparation of phenylamine (aniline)

Note: Follow this link if you want the mechanism for the
nitration of benzene.
Use the BACK button (or the HISTORY file or GO menu) on
your browser to return to this page later.

Nitrobenzene to phenylamine
The conversion is done in two main stages:
Stage 1: conversion of nitrobenzene into phenylammonium ions
Nitrobenzene is reduced to phenylammonium ions using a mixture of tin
and concentrated hydrochloric acid. The mixture is heated under reflux in
a boiling water bath for about half an hour.
Under the acidic conditions, rather than getting phenylamine directly, you
instead get phenylammonium ions formed. The lone pair on the nitrogen
in the phenylamine picks up a hydrogen ion from the acid.
The electron-half-equation for this reaction is:

The nitrobenzene has been reduced by gaining electrons in the presence


of the acid.
The electrons come from the tin, which forms both tin(II) and tin(IV) ions.

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the preparation of phenylamine (aniline)

Note: I have given these as electron-half-equations rather


than attempting full equations in order to try to show what is
happening. Combining them into full equations leads you to
some really scary equations where it is difficult to see what is
going on. The problem is made much worse because the tin
ions formed go on to react with chloride ions from the
hydrochloric acid to form complex ions such as [SnCl6]2-.
If you aren't sure about electron-half-equations you could
follow this link - but it really isn't important for UK A level
purposes to worry too much about this in the present context.
You are unlikely to need much more than the conditions for
the reaction.
Use the BACK button on your browser to return to this page if
you should decide to follow this link.

Stage 2: conversion of the phenylammonium ions into phenylamine


All you need to do is to remove the hydrogen ion from the -NH3+ group.
Sodium hydroxide solution is added to the product of the first stage of the
reaction.

The phenylamine is formed together with a complicated mixture of tin


compounds from reactions between the sodium hydroxide solution and
the complex tin ions formed during the first stage.
The phenylamine is finally separated from this mixture. The separation is
long, tedious and potentially dangerous - involving steam distillation,
solvent extraction and a final distillation.
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the preparation of phenylamine (aniline)

Note: The conversion of nitrobenzene into phenylamine is


so time-consuming, complicated, and hazardous at this level
that I'm not going to make any attempt to describe this in
detail. If you want details, refer to any good practical organic
chemistry textbook.

Summary
What you are likely to need for UK A level chemistry purposes can be
summed up by:

You are almost bound to need the mechanism for the nitration reaction
as well.

Where would you like to go now?


To the phenylamine menu . . .
To the menu of other organic compounds . . .
To Main Menu . . .

Jim Clark 2004

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Writing ionic equations for redox reactions

WRITING IONIC EQUATIONS FOR REDOX


REACTIONS

This page explains how to work out electron-half-reactions for oxidation


and reduction processes, and then how to combine them to give the
overall ionic equation for a redox reaction. This is an important skill in
inorganic chemistry.
Don't worry if it seems to take you a long time in the early stages. It is a
fairly slow process even with experience. Take your time and practice as
much as you can.

Electron-half-equations
What is an electron-half-equation?
When magnesium reduces hot copper(II) oxide to copper, the ionic
equation for the reaction is:

Note: I am going to leave out state symbols in all the


equations on this page. This topic is awkward enough anyway
without having to worry about state symbols as well as
everything else. Practice getting the equations right, and then
add the state symbols in afterwards if your examiners are likely
to want them.
How do you know whether your examiners will want you to
include them? The best way is to look at their mark schemes.
You should be able to get these from your Exam Board's
website. There are links on the syllabuses page.

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Writing ionic equations for redox reactions

You can split the ionic equation into two parts, and look at it from the point
of view of the magnesium and of the copper(II) ions separately. This
shows clearly that the magnesium has lost two electrons, and the copper
(II) ions have gained them.

These two equations are described as "electron-half-equations" or "halfequations" or "ionic-half-equations" or "half-reactions" - lots of variations all
meaning exactly the same thing!
Any redox reaction is made up of two half-reactions: in one of them
electrons are being lost (an oxidation process) and in the other one those
electrons are being gained (a reduction process).

Note: If you aren't happy about redox reactions in terms of


electron transfer, you MUST read the introductory page on
redox reactions before you go on.

Working out electron-half-equations and using them to build ionic


equations
In the example above, we've got at the electron-half-equations by starting
from the ionic equation and extracting the individual half-reactions from it.
That's doing everything entirely the wrong way round!
In reality, you almost always start from the electron-half-equations and use
them to build the ionic equation.
Example 1: The reaction between chlorine and iron(II) ions
Chlorine gas oxidises iron(II) ions to iron(III) ions. In the process, the
chlorine is reduced to chloride ions.
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Writing ionic equations for redox reactions

You would have to know this, or be told it by an examiner. In building


equations, there is quite a lot that you can work out as you go along, but
you have to have somewhere to start from!
You start by writing down what you know for each of the half-reactions. In
the chlorine case, you know that chlorine (as molecules) turns into chloride
ions:

The first thing to do is to balance the atoms that you have got as far as you
possibly can:

ALWAYS check that you have the existing atoms balanced before you do
anything else. If you forget to do this, everything else that you do
afterwards is a complete waste of time!
Now you have to add things to the half-equation in order to make it
balance completely.
All you are allowed to add are:

electrons

water

hydrogen ions (unless the reaction is being done under alkaline


conditions - in which case, you can add hydroxide ions instead)

In the chlorine case, all that is wrong with the existing equation that we've
produced so far is that the charges don't balance. The left-hand side of the
equation has no charge, but the right-hand side carries 2 negative charges.
That's easily put right by adding two electrons to the left-hand side. The
final version of the half-reaction is:

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Writing ionic equations for redox reactions

Now you repeat this for the iron(II) ions. You know (or are told) that they
are oxidised to iron(III) ions. Write this down:

The atoms balance, but the charges don't. There are 3 positive charges on
the right-hand side, but only 2 on the left.
You need to reduce the number of positive charges on the right-hand side.
That's easily done by adding an electron to that side:

Combining the half-reactions to make the ionic equation for the reaction
What we've got at the moment is this:

It is obvious that the iron reaction will have to happen twice for every
chlorine molecule that reacts. Allow for that, and then add the two halfequations together.

But don't stop there!! Check that everything balances - atoms and charges.
It is very easy to make small mistakes, especially if you are trying to
multiply and add up more complicated equations.
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Writing ionic equations for redox reactions

You will notice that I haven't bothered to include the electrons in the addedup version. If you think about it, there are bound to be the same number on
each side of the final equation, and so they will cancel out. If you aren't
happy with this, write them down and then cross them out afterwards!

Example 2: The reaction between hydrogen peroxide and manganate


(VII) ions
The first example was a simple bit of chemistry which you may well have
come across. The technique works just as well for more complicated (and
perhaps unfamiliar) chemistry.
Manganate(VII) ions, MnO4-, oxidise hydrogen peroxide, H2O2, to oxygen
gas. The reaction is done with potassium manganate(VII) solution and
hydrogen peroxide solution acidified with dilute sulphuric acid.
During the reaction, the manganate(VII) ions are reduced to manganese(II)
ions.
Let's start with the hydrogen peroxide half-equation. What we know is:

The oxygen is already balanced. What about the hydrogen?


All you are allowed to add to this equation are water, hydrogen ions and
electrons. If you add water to supply the extra hydrogen atoms needed on
the right-hand side, you will mess up the oxygens again - that's obviously
wrong!
Add two hydrogen ions to the right-hand side.

Now all you need to do is balance the charges. You would have to add 2
electrons to the right-hand side to make the overall charge on both sides
zero.

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Writing ionic equations for redox reactions

Now for the manganate(VII) half-equation:


You know (or are told) that the manganate(VII) ions turn into manganese
(II) ions. Write that down.

The manganese balances, but you need four oxygens on the right-hand
side. These can only come from water - that's the only oxygen-containing
thing you are allowed to write into one of these equations in acid
conditions.

By doing this, we've introduced some hydrogens. To balance these, you


will need 8 hydrogen ions on the left-hand side.

Now that all the atoms are balanced, all you need to do is balance the
charges. At the moment there are a net 7+ charges on the left-hand side
(1- and 8+), but only 2+ on the right. Add 5 electrons to the left-hand side
to reduce the 7+ to 2+.

This is the typical sort of half-equation which you will have to be able to
work out. The sequence is usually:

Balance the atoms apart from oxygen and hydrogen.

Balance the oxygens by adding water molecules.

Balance the hydrogens by adding hydrogen ions.

Balance the charges by adding electrons.

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Writing ionic equations for redox reactions

Combining the half-reactions to make the ionic equation for the reaction
The two half-equations we've produced are:

You have to multiply the equations so that the same number of electrons
are involved in both. In this case, everything would work out well if you
transferred 10 electrons.

But this time, you haven't quite finished. During the checking of the
balancing, you should notice that there are hydrogen ions on both sides of
the equation:

You can simplify this down by subtracting 10 hydrogen ions from both
sides to leave the final version of the ionic equation - but don't forget to
check the balancing of the atoms and charges!

You will often find that hydrogen ions or water molecules appear on both
sides of the ionic equation in complicated cases built up in this way.
Always check, and then simplify where possible.
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Writing ionic equations for redox reactions

Example 3: The oxidation of ethanol by acidified potassium


dichromate(VI)
This technique can be used just as well in examples involving organic
chemicals. Potassium dichromate(VI) solution acidified with dilute
sulphuric acid is used to oxidise ethanol, CH3CH2OH, to ethanoic acid,
CH3COOH.
The oxidising agent is the dichromate(VI) ion, Cr2O72-. This is reduced to
chromium(III) ions, Cr3+.
We'll do the ethanol to ethanoic acid half-equation first. Using the same
stages as before, start by writing down what you know:

Balance the oxygens by adding a water molecule to the left-hand side:

Add hydrogen ions to the right-hand side to balance the hydrogens:

And finally balance the charges by adding 4 electrons to the right-hand


side to give an overall zero charge on each side:

The dichromate(VI) half-equation contains a trap which lots of people fall


into!
Start by writing down what you know:

What people often forget to do at this stage is to balance the chromiums. If

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Writing ionic equations for redox reactions

you don't do that, you are doomed to getting the wrong answer at the end
of the process! When you come to balance the charges you will have to
write in the wrong number of electrons - which means that your multiplying
factors will be wrong when you come to add the half-equations . . . A
complete waste of time!

Now balance the oxygens by adding water molecules . . .

. . . and the hydrogens by adding hydrogen ions:

Now all that needs balancing is the charges. Add 6 electrons to the lefthand side to give a net 6+ on each side.

Combining the half-reactions to make the ionic equation for the reaction
What we have so far is:

What are the multiplying factors for the equations this time? The simplest
way of working this out is to find the smallest number of electrons which
both 4 and 6 will divide into - in this case, 12. That means that you can
multiply one equation by 3 and the other by 2.

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Writing ionic equations for redox reactions

Note: Don't worry too much if you get this wrong and choose
to transfer 24 electrons instead. All that will happen is that your
final equation will end up with everything multiplied by 2. Your
examiners might well allow that.

The multiplication and addition looks like this:

Now you will find that there are water molecules and hydrogen ions
occurring on both sides of the ionic equation. You can simplify this to give
the final equation:

Note: You have now seen a cross-section of the sort of


equations which you could be asked to work out. Now you
need to practice so that you can do this reasonably quickly and
very accurately! Aim to get an averagely complicated example
done in about 3 minutes.
If you want a few more examples, and the opportunity to
practice with answers available, you might be interested in
looking in chapter 1 of my book on Chemistry Calculations.

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Writing ionic equations for redox reactions

Reactions done under alkaline conditions


Working out half-equations for reactions in alkaline solution is decidedly
more tricky than those above. You are fairly unlikely to be asked to do this
at A' level, and for that reason I've covered these on a separate page (link
below). It would be worthwhile checking your syllabus and past papers
before you start worrying about these!

Where would you like to go now?


How to work out half-equations for reactions under alkaline
conditions . . .
To the Redox menu . . .
To the Inorganic Chemistry menu . . .
To Main Menu . . .

Jim Clark 2002

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Definitions of oxidation and reduction (redox)

DEFINITIONS OF OXIDATION AND REDUCTION


(REDOX)

This page looks at the various definitions of oxidation and reduction


(redox) in terms of the transfer of oxygen, hydrogen and electrons. It also
explains the terms oxidising agent and reducing agent.

Oxidation and reduction in terms of oxygen transfer


Definitions

Oxidation is gain of oxygen.

Reduction is loss of oxygen.

For example, in the extraction of iron from its ore:

Because both reduction and oxidation are going on side-by-side, this is


known as a redox reaction.
Oxidising and reducing agents
An oxidising agent is substance which oxidises something else. In the
above example, the iron(III) oxide is the oxidising agent.
A reducing agent reduces something else. In the equation, the carbon
monoxide is the reducing agent.

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Definitions of oxidation and reduction (redox)

Oxidising agents give oxygen to another substance.

Reducing agents remove oxygen from another substance.

Oxidation and reduction in terms of hydrogen transfer


These are old definitions which aren't used very much nowadays. The
most likely place you will come across them is in organic chemistry.
Definitions

Oxidation is loss of hydrogen.

Reduction is gain of hydrogen.

Notice that these are exactly the opposite of the oxygen definitions.
For example, ethanol can be oxidised to ethanal:

You would need to use an oxidising agent to remove the hydrogen from
the ethanol. A commonly used oxidising agent is potassium dichromate
(VI) solution acidified with dilute sulphuric acid.

Note: The equation for this is rather complicated for this


introductory page. If you are interested, you will find a similar
example (ethanol to ethanoic acid) on the page dealing with
writing equations for redox reactions.

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Definitions of oxidation and reduction (redox)

Ethanal can also be reduced back to ethanol again by adding hydrogen


to it. A possible reducing agent is sodium tetrahydridoborate, NaBH4.
Again the equation is too complicated to be worth bothering about at this
point.

An update on oxidising and reducing agents

Oxidising agents give oxygen to another substance or remove


hydrogen from it.
Reducing agents remove oxygen from another substance or give
hydrogen to it.

Oxidation and reduction in terms of electron transfer


This is easily the most important use of the terms oxidation and reduction
at A' level.
Definitions

Oxidation is loss of electrons.

Reduction is gain of electrons.

It is essential that you remember these definitions. There is a very easy


way to do this. As long as you remember that you are talking about
electron transfer:

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Definitions of oxidation and reduction (redox)

A simple example
The equation shows a simple redox reaction which can obviously be
described in terms of oxygen transfer.

Copper(II) oxide and magnesium oxide are both ionic. The metals
obviously aren't. If you rewrite this as an ionic equation, it turns out that
the oxide ions are spectator ions and you are left with:

A last comment on oxidising and reducing agents


If you look at the equation above, the magnesium is reducing the copper
(II) ions by giving them electrons to neutralise the charge. Magnesium is
a reducing agent.
Looking at it the other way round, the copper(II) ions are removing
electrons from the magnesium to create the magnesium ions. The copper
(II) ions are acting as an oxidising agent.
Warning!
This is potentially very confusing if you try to learn both what oxidation
and reduction mean in terms of electron transfer, and also learn
definitions of oxidising and reducing agents in the same terms.
Personally, I would recommend that you work it out if you need it. The
argument (going on inside your head) would go like this if you wanted to
know, for example, what an oxidising agent did in terms of electrons:

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Definitions of oxidation and reduction (redox)

An oxidising agent oxidises something else.

Oxidation is loss of electrons (OIL RIG).

That means that an oxidising agent takes electrons from that other
substance.
So an oxidising agent must gain electrons.

Or you could think it out like this:

An oxidising agent oxidises something else.

That means that the oxidising agent must be being reduced.

Reduction is gain of electrons (OIL RIG).

So an oxidising agent must gain electrons.

Understanding is a lot safer than thoughtless learning!

Where would you like to go now?


To the Redox menu . . .
To the Inorganic Chemistry menu . . .
To Main Menu . . .

Jim Clark 2002

http://www.chemguide.co.uk/inorganic/redox/definitions.html (5 of 5)30/12/2004 11:11:23

Redox menu

Understanding Chemistry

REDOX MENU

Definitions of oxidation and reduction . . .


Covers definitions of oxidation and reduction in terms of transfer of
oxygen, hydrogen and electrons.
Writing equations for redox reactions . . .
How to construct ionic equations for redox reactions by working
out electron half equations and then combining them.
Oxidation states (oxidation numbers) . . .
How to work out oxidation states (oxidation numbers) and use
them to decide simply what is being oxidised and what is being
reduced in a reaction.

Go to inorganic chemistry menu . . .


Go to Main Menu . . .

Jim Clark 2002

http://www.chemguide.co.uk/inorganic/redoxmenu.html30/12/2004 11:11:24

Oxidation states (oxidation numbers)

OXIDATION STATES (OXIDATION NUMBERS)

This page explains what oxidation states (oxidation numbers) are and
how to calculate them and make use of them.
Oxidation states are straightforward to work out and to use, but it is quite
difficult to define what they are in any quick way.

Explaining what oxidation states (oxidation numbers) are


Oxidation states simplify the whole process of working out what is being
oxidised and what is being reduced in redox reactions. However, for the
purposes of this introduction, it would be helpful if you knew about:

oxidation and reduction in terms of electron transfer

electron-half-equations

Note: If you aren't sure about either of these things, you


might want to look at the pages on redox definitions and
electron-half-equations. It would probably be best to read on
and come back to these links if you feel you need to.

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Oxidation states (oxidation numbers)

We are going to look at some examples from vanadium chemistry. If you


don't know anything about vanadium, it doesn't matter in the slightest.
Vanadium forms a number of different ions - for example, V2+ and V3+. If
you think about how these might be produced from vanadium metal, the 2
+ ion will be formed by oxidising the metal by removing two electrons:

The vanadium is now said to be in an oxidation state of +2.


Removal of another electron gives the V3+ ion:

The vanadium now has an oxidation state of +3.


Removal of another electron gives a more unusual looking ion, VO2+.

The vanadium is now in an oxidation state of +4. Notice that the oxidation
state isn't simply counting the charge on the ion (that was true for the first
two cases but not for this one).
The positive oxidation state is counting the total number of electrons
which have had to be removed - starting from the element.
It is also possible to remove a fifth electron to give another ion (easily
confused with the one before!). The oxidation state of the vanadium is
now +5.

Every time you oxidise the vanadium by removing another electron from
it, its oxidation state increases by 1.
Fairly obviously, if you start adding electrons again the oxidation state
will fall. You could eventually get back to the element vanadium which
would have an oxidation state of zero.

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Oxidation states (oxidation numbers)

What if you kept on adding electrons to the element? You can't actually
do that with vanadium, but you can with an element like sulphur.

The sulphur has an oxidation state of -2.


Summary
Oxidation state shows the total number of electrons which have been
removed from an element (a positive oxidation state) or added to an
element (a negative oxidation state) to get to its present state.
Oxidation involves an increase in oxidation state
Reduction involves a decrease in oxidation state
Recognising this simple pattern is the single most important thing about
the concept of oxidation states. If you know how the oxidation state of an
element changes during a reaction, you can instantly tell whether it is
being oxidised or reduced without having to work in terms of electron-halfequations and electron transfers.

Working out oxidation states


You don't work out oxidation states by counting the numbers of electrons
transferred. It would take far too long. Instead you learn some simple
rules, and do some very simple sums!

The oxidation state of an uncombined element is zero. That's


obviously so, because it hasn't been either oxidised or reduced
yet! This applies whatever the structure of the element - whether it
is, for example, Xe or Cl2 or S8, or whether it has a giant structure
like carbon or silicon.
The sum of the oxidation states of all the atoms or ions in a neutral
compound is zero.
The sum of the oxidation states of all the atoms in an ion is equal

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Oxidation states (oxidation numbers)

to the charge on the ion.

The more electronegative element in a substance is given a


negative oxidation state. The less electronegative one is given a
positive oxidation state. Remember that fluorine is the most
electronegative element with oxygen second.
Some elements almost always have the same oxidation states in
their compounds:

element

usual oxidation
state

exceptions

Group 1 metals

always +1

Group 2 metals

always +2

Oxygen

usually -2

except in peroxides
and F2O (see below)

Hydrogen

usually +1

except in metal
hydrides where it is 1 (see below)

Fluorine

always -1

Chlorine

usually -1

except in
compounds with O
or F (see below)

The reasons for the exceptions


Hydrogen in the metal hydrides
Metal hydrides include compounds like sodium hydride, NaH. In this, the
hydrogen is present as a hydride ion, H-. The oxidation state of a simple
ion like hydride is equal to the charge on the ion - in this case, -1.

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Oxidation states (oxidation numbers)

Alternatively, you can think of it that the sum of the oxidation states in a
neutral compound is zero. Since Group 1 metals always have an
oxidation state of +1 in their compounds, it follows that the hydrogen
must have an oxidation state of -1 (+1 -1 = 0).
Oxygen in peroxides
Peroxides include hydrogen peroxide, H2O2. This is an electrically
neutral compound and so the sum of the oxidation states of the hydrogen
and oxygen must be zero.
Since each hydrogen has an oxidation state of +1, each oxygen must
have an oxidation state of -1 to balance it.
Oxygen in F2O
The problem here is that oxygen isn't the most electronegative element.
The fluorine is more electronegative and has an oxidation state of -1. In
this case, the oxygen has an oxidation state of +2.
Chlorine in compounds with fluorine or oxygen
There are so many different oxidation states that chlorine can have in
these, that it is safer to simply remember that the chlorine doesn't have
an oxidation state of -1 in them, and work out its actual oxidation state
when you need it. You will find an example of this below.

Warning!
Don't get too bogged down in these exceptions. In most of the cases you
will come across, they don't apply!

Examples of working out oxidation states


What is the oxidation state of chromium in Cr2+?
That's easy! For a simple ion like this, the oxidation state is the charge on
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Oxidation states (oxidation numbers)

the ion - in other words: +2 (Don't forget the + sign.)


What is the oxidation state of chromium in CrCl3?
This is a neutral compound so the sum of the oxidation states is zero.
Chlorine has an oxidation state of -1. If the oxidation state of chromium is
n:
n + 3(-1) = 0
n = +3 (Again, don't forget the + sign!)
What is the oxidation state of chromium in Cr(H2O)63+?
This is an ion and so the sum of the oxidation states is equal to the
charge on the ion. There is a short-cut for working out oxidation states in
complex ions like this where the metal atom is surrounded by electrically
neutral molecules like water or ammonia.
The sum of the oxidation states in the attached neutral molecule must be
zero. That means that you can ignore them when you do the sum. This
would be essentially the same as an unattached chromium ion, Cr3+. The
oxidation state is +3.
What is the oxidation state of chromium in the dichromate ion, Cr2O72-?
The oxidation state of the oxygen is -2, and the sum of the oxidation
states is equal to the charge on the ion. Don't forget that there are 2
chromium atoms present.
2n + 7(-2) = -2
n = +6

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Oxidation states (oxidation numbers)

Warning: Because these are simple sums it is tempting to


try to do them in your head. If it matters (like in an exam)
write them down using as many steps as you need so that
there is no chance of making careless mistakes. Your
examiners aren't going to be impressed by your mental
arithmetic - all they want is the right answer!
If you want some more examples to practice on, you will find
them in most text books, including my chemistry calculations
book.

What is the oxidation state of copper in CuSO4?


Unfortunately, it isn't always possible to work out oxidation states by a
simple use of the rules above. The problem in this case is that the
compound contains two elements (the copper and the sulphur) whose
oxidation states can both change.
The only way around this is to know some simple chemistry! There are
two ways you might approach it. (There might be others as well, but I
can't think of them at the moment!)

You might recognise this as an ionic compound containing copper


ions and sulphate ions, SO42-. To make an electrically neutral
compound, the copper must be present as a 2+ ion. The oxidation
state is therefore +2.
You might recognise the formula as being copper(II) sulphate. The
"(II)" in the name tells you that the oxidation state is 2 (see below).
You will know that it is +2 because you know that metals form
positive ions, and the oxidation state will simply be the charge on
the ion.

Using oxidation states

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Oxidation states (oxidation numbers)

In naming compounds
You will have come across names like iron(II) sulphate and iron(III)
chloride. The (II) and (III) are the oxidation states of the iron in the two
compounds: +2 and +3 respectively. That tells you that they contain Fe2+
and Fe3+ ions.
This can also be extended to the negative ion. Iron(II) sulphate is FeSO4.
There is also a compound FeSO3 with the old name of iron(II) sulphite.
The modern names reflect the oxidation states of the sulphur in the two
compounds.
The sulphate ion is SO42-. The oxidation state of the sulphur is +6 (work
it out!). The ion is more properly called the sulphate(VI) ion.
The sulphite ion is SO32-. The oxidation state of the sulphur is +4 (work
that out as well!). This ion is more properly called the sulphate(IV) ion.
The ate ending simply shows that the sulphur is in a negative ion.
So FeSO4 is properly called iron(II) sulphate(VI), and FeSO3 is iron(II)
sulphate(IV). In fact, because of the easy confusion between these
names, the old names sulphate and sulphite are normally still used in
introductory chemistry courses.

Note: Even these aren't the full name! The oxygens in the
negative ions should also be identified. FeSO4 is properly
called iron(II) tetraoxosulphate(VI). It all gets a bit out of hand
for everyday use for common ions.

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Oxidation states (oxidation numbers)

Using oxidation states to identify what's been oxidised and what's


been reduced
This is easily the most common use of oxidation states.
Remember:
Oxidation involves an increase in oxidation state
Reduction involves a decrease in oxidation state
In each of the following examples, we have to decide whether the
reaction involves redox, and if so what has been oxidised and what
reduced.
Example 1:
This is the reaction between magnesium and hydrochloric acid or
hydrogen chloride gas:

Have the oxidation states of anything changed? Yes they have - you
have two elements which are in compounds on one side of the equation
and as uncombined elements on the other. Check all the oxidation states
to be sure:.

The magnesium's oxidation state has increased - it has been oxidised.


The hydrogen's oxidation state has fallen - it has been reduced. The
chlorine is in the same oxidation state on both sides of the equation - it
hasn't been oxidised or reduced.
Example 2:
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Oxidation states (oxidation numbers)

The reaction between sodium hydroxide and hydrochloric acid is:

Checking all the oxidation states:

Nothing has changed. This isn't a redox reaction.


Example 3:
This is a sneaky one! The reaction between chlorine and cold dilute
sodium hydroxide solution is:

Obviously the chlorine has changed oxidation state because it has ended
up in compounds starting from the original element. Checking all the
oxidation states shows:

The chlorine is the only thing to have changed oxidation state. Has it
been oxidised or reduced? Yes! Both! One atom has been reduced
because its oxidation state has fallen. The other has been oxidised.
This is a good example of a disproportionation reaction. A
disproportionation reaction is one in which a single substance is both
oxidised and reduced.

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Oxidation states (oxidation numbers)

Using oxidation states to work out reacting proportions


This is sometimes useful where you have to work out reacting
proportions for use in titration reactions where you don't have enough
information to work out the complete ionic equation.
Remember that each time an oxidation state changes by one unit, one
electron has been transferred. If one substance's oxidation state in a
reaction falls by 2, that means that it has gained 2 electrons.
Something else in the reaction must be losing those electrons. Any
oxidation state fall by one substance must be accompanied by an equal
oxidation state increase by something else.
This example is based on information in an old AQA A' level question.
Ions containing cerium in the +4 oxidation state are oxidising agents.
(They are more complicated than just Ce4+.) They can oxidise ions
containing molybdenum from the +2 to the +6 oxidation state (from Mo2+
to MoO42-). In the process the cerium is reduced to the +3 oxidation state
(Ce3+). What are the reacting proportions?
The oxidation state of the molybdenum is increasing by 4. That means
that the oxidation state of the cerium must fall by 4 to compensate.
But the oxidation state of the cerium in each of its ions only falls from +4
to +3 - a fall of 1. So there must obviously be 4 cerium ions involved for
each molybdenum ion.
The reacting proportions are 4 cerium-containing ions to 1 molybdenum
ion.

Where would you like to go now?


To the Redox menu . . .
To the Inorganic Chemistry menu . . .
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Oxidation states (oxidation numbers)

To Main Menu . . .

Jim Clark 2002

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calculations in as / a level chemistry

Understanding Chemistry

CALCULATIONS IN AS / A LEVEL CHEMISTRY


There are virtually no calculations on
this site, but you might be interested
in the author's book covering all the
calculations required by the UK A'
level syllabuses.
If you have found this site helpful,
you should find the book will help
you as well.
Students working in other countries
should also find the book useful.
Compare what you are expected to
know with the list of things that the
book covers (see below).
On this page you will find a description of how the book is organised,
together with a full list of the contents. You will also find a direct link to
the book on the Amazon.co.uk site.
School Science Review, March 2001
"This is an excellent book, . . ." " . . . a 'must have' for teachers and
students alike."
Times Educational Supplement, 27 April 2001
". . fills a large gap in the market and provides excellent
coverage . ."
"I shall recommend this to my students as a self-study aid and will
certainly use it myself."

http://www.chemguide.co.uk/book.html (1 of 5)30/12/2004 11:11:35

calculations in as / a level chemistry

How to get hold of the book


You can, of course, buy the book through normal book sellers, but if if
you want to buy online, you will find a direct link to Amazon.co.uk coming
up. (Note that Amazon mistakenly refers to the book as "Calculations in
A Level Chemistry".)
Non-UK students can also buy the book from Amazon.co.uk, but will
obviously have to pay a slightly higher delivery charge.

Note: If your usual source of books is Amazon.com, you


should compare the pr