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5/12/2004
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Understanding Chemistry
Go to Main Menu . . .
http://www.chemguide.co.uk/atommenu.html30/12/2004 11:00:04
Understanding Chemistry
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 . . .
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.
proton
neutron
electron
relative mass
1
1
1/1836
relative charge
+1
0
-1
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.
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
http://www.chemguide.co.uk/atoms/properties/gcse.html (2 of 7)30/12/2004 11:00:08
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
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:
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:
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.
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."
http://www.chemguide.co.uk/gcsebook.html (1 of 5)30/12/2004 11:00:11
GCSE chemistry
"It would certainly help to bridge the gap between GCSE and AS
level."
GCSE chemistry
Reactivity series
Salts
Simple analysis
GCSE chemistry
metals
GCSE chemistry
Go to Main Menu . . .
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.
atomic orbitals
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
atomic orbitals
atomic orbitals
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.
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.
atomic orbitals
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.
atomic orbitals
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.
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.
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
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.
1s22s22p63s23p64s1
Ca
1s22s22p63s23p64s2
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-
block element" don't quite have the same meaning, but it doesn't matter
in the present context.
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
1s22s22p63s23p63d54s2
Fe
1s22s22p63s23p63d64s2
Co
1s22s22p63s23p63d74s2
Ni
1s22s22p63s23p63d84s2
Cu
1s22s22p63s23p63d104s1
Zn
1s22s22p63s23p63d104s2
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.
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.
http://www.chemguide.co.uk/atoms/properties/elstructs.html (8 of 9)30/12/2004 11:00:22
Understanding Chemistry
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.
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.
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 . . .
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.
1s22s22p63s23px23py23pz1
Cl-
1s22s22p63s23px23py23pz2
1s22s22px22py12pz1
O2-
1s22s22px22py22pz2
1s22s22p63s1
Na+
1s22s22p6
1s22s22p63s23p64s2
Ca2+
1s22s22p63s23p6
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.
1s22s22p63s23p63d54s1
Cr3+
1s22s22p63s23p63d3
1s22s22p63s23p63d104s2
Zn2+
1s22s22p63s23p63d10
1s22s22p63s23p63d64s2
Fe3+
1s22s22p63s23p63d5
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.
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).
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.
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
1s22s22px1
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 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
Al
1s22s22p63s23px1
1s22s22px12py12pz1
1s22s22px22py12pz1
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.
1s22s1
Na
1s22s22p63s1
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.
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.
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
Zn
[Ar]3d104s2
In each case, the electron is coming from the same orbital, with identical
http://www.chemguide.co.uk/atoms/properties/ies.html (10 of 12)30/12/2004 11:00:33
screening, but the zinc has one extra proton in the nucleus and so the
attraction is greater.
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.
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.
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.
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: 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.
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.
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.
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.
http://www.chemguide.co.uk/atoms/bondingmenu.html (1 of 2)30/12/2004 11:00:38
Bonding menu
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.
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
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
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.
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.
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.
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.
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.
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.
ionic structures
Ions of the same charge are brought side-by-side and so the crystal
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ionic structures
ionic structures
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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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.
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.
Energy is released when the two co-ordinate bonds are formed, and so
the dimer is more stable than two separate AlCl3 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:
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.
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.
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.
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.
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:
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.
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.
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".
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.
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
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.
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
question of whether you've got a noble gas structure, and so you don't
worry about it.
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
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".
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.
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.
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:
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.
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.
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
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.
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.
Understanding Chemistry
Electronegativity . . .
An introduction to electronegativity as it applies to organic
chemistry, including its causes. Bond polarity.
Understanding Chemistry
Go to Main Menu . . .
Understanding Chemistry
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 . . .
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
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.
But, again these are exactly the same. Look at the models.
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.
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.
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:
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:
But the commonest of all is the benzene ring, C6H6, which has a special
symbol of its own.
given situations. You could also look at any support material published
by your Board.
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!
0.154 nm
0.134 nm
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.
CH3CH3
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.
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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In fact, the enthalpy change is -232 kJ mol-1 - which isn't far off what we
are predicting.
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.
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.
Understanding Chemistry
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.
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.
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.
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.
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.
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).
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.
BONDING IN ETHENE
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.
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.
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.
All double bonds (whatever atoms they might be joining) will consist of a
sigma bond and a pi bond.
To Main Menu . . .
ELECTRONEGATIVITY
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:
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.
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:
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
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.
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.
fluorine: 1s22s22px22py22pz1
chlorine: 1s22s22px22py22pz23s23px23py23pz1
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.
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).
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.
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.
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.
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
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
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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All the other mechanisms for symmetrical alkenes and the hydrogen
halides would be done in the same way.
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.
That leaves you with these two ions at this half-way stage of the reaction:
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.
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.
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:
H-F 568
H-Cl 432
H-Br 366
H-I
298
- 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!
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).
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.
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.
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:
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.
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.
totally irrelevant.
The mechanism
This is an example of electrophilic addition.
HF slowest reaction
HCl
HBr
HI
fastest reaction
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.
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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by a different mechanism.
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.
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.
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.
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.
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.
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.
In the case of hydrogen bromide, both steps of the propagation stage are
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exothermic.
This page guides you through the mechanism for the free radical addition
of hydrogen bromide to alkenes - often known as the "peroxide effect".
The oxygen-oxygen bond is quite weak, and breaks easily so that each
oxygen gets a single electron. Free radicals are formed.
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.
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.
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.
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.
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.
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.
The bromine radical now goes into another cycle exactly as before to
continue the chain reaction.
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.
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:
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.
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.
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.
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.
Understanding Chemistry
Go to Main Menu . . .
Understanding Chemistry
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".
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
CH3
ethyl
CH3CH2
CH3Cl + HCl
Notice that one of the hydrogen atoms in the methane has been replaced
by a chlorine atom. That's 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.
Cl
CH3
Understanding Chemistry
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.
This is what you need to understand for the purposes of the electrophilic
substitution mechanisms:
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.
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.
X+ and form a bond with it. This has the effect of breaking the
delocalisation, although not completely.
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
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.
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.
BONDING IN BENZENE
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.
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.
Note: To get the best out of this section you ought to read
the article on the Kekul structure for benzene.
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.
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.
or:
formed by reaction between the nitric acid and the sulphuric acid.
Stage two
This page guides you through the mechanism for the nitration of benzene
involving an electrophilic substitution reaction between benzene and
nitric acid.
The equation
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).
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:
The hydrogen is shown as "falling off" the ring as a hydrogen ion. This is
sloppy and unsatisfactory on two counts:
Showing exactly how the hydrogen is removed from the ring isn't difficult
- do it properly!
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.
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:
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.
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.
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.
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.
or better:
Stage two
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.
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.
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.
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: If you haven't already done so, you might like to look
at the Friedel-Crafts alkylation reaction before you go on.
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.
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.
For example, the propyl group becomes attached to the ring via its
middle carbon atom - and not its end one.
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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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.
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: We are only showing one of the lone pairs around the
chloride ion. The other three aren't involved in this reaction.
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-.
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.
Alternatively, the pi bond electrons could move the other way and form a
secondary carbocation.
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.
This page guides you through the mechanism for the electrophilic
addition of hydrogen halides such as hydrogen bromide to unsymmetrical
alkenes like propene.
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.
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:
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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Because the secondary ion is more energetically stable, it will form more
easily and so the reaction needs less activation energy.
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.
ELECTROPHILIC ADDITION TO
UNSYMMETRICAL ALKENES
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.
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
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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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.
In the slow mechanism which produces hardly any product, you get a
primary carbocation formed instead.
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.
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.
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.
or:
or:
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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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.
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 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-.
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.
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?
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.
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.
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 electrons from the pi bond move towards the slightly positive
bromine atom.
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.
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.
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.
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.
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
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.
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
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.
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.
brown colour to give a colourless liquid. In the case of the reaction with
propene, 1,2-dibromopropane is formed.
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
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.
This page guides you through the mechanism for the electrophilic
addition of bromine to unsymmetrical alkenes like propene.
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.
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.
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 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.
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.
Or:
Stage two
This page guides you through the mechanism for the electrophilic
substitution reaction between benzene and sulphuric acid (or sulphur
trioxide)
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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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:
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.
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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Note: You will find links to help you to contact your Exam
Board on the syllabuses page.
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
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.
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.
For example, the complete mechanism for substitution into the 4position is:
Stage one
Stage two
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.
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.
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.
Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2
2Cl
Cl2
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
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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Cl-Cl +
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.
Even worse, two phenylmethyl radicals could hit each other. Not
only does this remove radicals from the system, but produces an
unwanted side reaction.
2Cl
Cl2
CH4 + Cl2
CH3Cl + HCl
Chain initiation
The chain is initiated (started) by UV light breaking a chlorine molecule
into free radicals.
Cl2
2Cl
CH3
+ Cl2
+ HCl
CH3Cl + Cl
Cl2
+
CH3 +
CH3
CH3Cl
CH3CH3
To Main Menu . . .
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
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
be formed. It is just a wasted collision.
Cl + Cl-Cl
Cl
Cl-Cl +
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
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
2Cl
CH3
+ Cl2
+ HCl
CH3Cl + Cl
Cl2
+
CH3 +
CH3
CH3Cl
CH3CH3
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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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
CH2Cl + HCl
CH2Cl2 + Cl
CHCl2 + HCl
CHCl3 + Cl
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.
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!
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.
The mechanisms
Making (dichloromethyl)benzene
You will remember that the over-all equation for the first stage of the
reaction is
The new radical formed can then interact with a chlorine molecule in a
new propagation step . . .
Understanding Chemistry
ARENES MENU
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
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.
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.
There are delocalised electrons above and below the plane of the
ring.
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.
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.
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.
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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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.
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.
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 +.
An instant later the electrons may well have moved up to the other end,
reversing the polarity of the molecule.
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.
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.
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.
-269C
neon
argon
krypton
xenon
radon
-246C
-186C
-152C
-108C
-62C
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.
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
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.
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
This sort of bond could be thought of as being a "pure" covalent bond where the electrons are shared evenly between the two atoms.
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.
electronegativity
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.
Summary
electronegativity
electronegativity
electronegativity
electronegativity
electronegativity
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
In the case of aluminium chloride, the electron pairs are dragged back
towards the aluminium to such an extent that the bonds becomes
covalent.
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.
The increase in boiling point happens because the molecules are getting
larger with more electrons, and so van der Waals dispersion forces
become greater.
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.
However complicated the negative ion, there will always be lone pairs
that the hydrogen atoms from the water molecules can hydrogen bond to.
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.
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.
MOLECULAR STRUCTURES
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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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.
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.
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.
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".
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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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
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.
The double bond is shown conventionally by two lines joining the atoms.
Each line represents one pair of shared electrons.
Carbon dioxide, CO2
Ethene, C2H4
Ethene has a double bond between the two carbon atoms.
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.
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.
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.
This page explains the acidity of simple organic acids and looks at the
factors which affect their relative strengths.
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:
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!
So . . . if the same bond is being broken in each case, why do these three
compounds have such widely different acid strengths?
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.
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:
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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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.
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.
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.
3.75
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
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
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
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.
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.
This time two of the sp2 hybrid orbitals contain lone pairs of electrons.
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.
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.
Note: You can read about addition reactions or additionelimination reactions of carbonyl compounds elswhere on this
site.
Understanding Chemistry
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 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.
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.
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.
Attack from one side will lead to one of the two isomers, and attack from
the other side will lead to the other.
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.
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.
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
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.
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+.
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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+.
If you must do it that way, then write the hydrogen ion as H+(aq) - not
just as H+.
Attack from above will lead to one of the two isomers, and attack from
below will lead to the other.
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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.
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.
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!
To Main Menu . . .
optical isomerism
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.
optical isomerism
Optical isomerism
Why optical isomers?
Optical isomers are named like this because of their effect on plane
polarised light.
optical isomerism
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.
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.
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.
optical isomerism
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.
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.
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.
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.
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
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
optical isomerism
structural isomerism
STRUCTURAL ISOMERISM
This page explains what structural isomerism is, and looks at some of the
various ways that structural isomers can arise.
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.
structural isomerism
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.
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.
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
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:
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.
structural isomerism
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.
structural isomerism
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.
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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.
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:
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.
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.
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.
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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Summary
To get geometric isomers you must have:
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!
isomer
cis
-80
60
trans
-50
48
This is common. You can see the same effect with the cis and trans
isomers of but-2-ene:
isomer
cis-but-2-ene
-139
trans-but-2-ene
-106
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.
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.
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.
This page gives a simple explanation of what plane polarised light is and
the way it is affected by optically active compounds.
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.
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.
How can you tell that the plane of polarisation has been rotated?
You use a polarimeter.
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.
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.
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.
Adding water:
This time, the negative ion takes a hydrogen ion from a water molecule.
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.
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.
Understanding Chemistry
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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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.
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.
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.
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.
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.
molecule
type
CH3CH2CH3
alkane
-42
CH3CHO
aldehyde
+21
CH3CH2OH
alcohol
+78
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.
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.
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:
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
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
means
an
en
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:
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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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.
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-.
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.
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.
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:
Incidentally, you might equally well have decided that the right-hand
carbon was the number 1 carbon, and drawn the structure as:
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.
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.
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.
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.
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.
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).
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).
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.
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.
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.
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.
Acid anhydrides
Another acid derivative! An acid anhydride is what you get if you
dehydrate an acid - that is, remove water from it.
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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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.
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.
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.
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.
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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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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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.
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.
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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phenol
Phenol has an -OH group attached to a benzene ring and so has a
formula C6H5OH.
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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Understanding Chemistry
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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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 . . .
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.
Alkanes Menu
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.
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.
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.
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!
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.
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
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
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.
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) . . .
Alkenes Menu
an introduction to alkenes
INTRODUCING ALKENES
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.
an introduction to alkenes
an introduction to alkenes
an introduction to alkenes
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.
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.
an introduction to alkenes
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.
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.
an introduction to alkenes
an introduction to alkenes
To make a few test tubes of ethene, you can use this apparatus:
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.
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 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.
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.
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.
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.
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.
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!
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:
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
but-1-ene
cis-but-2-ene
trans-but-2-ene
Understanding Chemistry
product is possible.
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.
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 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.
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.
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:
but-1-ene
cis-but-2-ene
trans-but-2-ene
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.
Elimination
Halogenoalkanes also undergo elimination reactions in the presence of
sodium or potassium hydroxide.
substitution or elimination?
primary
mainly substitution
secondary
tertiary
mainly 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
Note: The explanations for these effects are well beyond the
demands of UK A level syllabuses. Some things you just
have to know!
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 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.
You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:
If your examiners want you to show the transition state, draw the
mechanism like this:
Or if you want the full equation rather than the ionic one:
The mechanism
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The mechanism
Should you need it, the two stages of the SN1 mechanism are:
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.
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:
Understanding Chemistry
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
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:
413
C-F
C-Cl
C-Br
C-I
467
346
290
228
Notice that each of these contains at least one lone pair of electrons,
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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.
The movement goes on until the -Nu is firmly attached to the carbon, and
the bromine has been expelled as a Br- ion.
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:
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
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.
Since any other approach is prevented by the bromine atom, the reaction
has to go by an alternative mechanism.
The alternative mechanism
The reaction happens in two stages. In the first, a small proportion of the
halogenoalkane ionises to give a carbocation and a bromide ion.
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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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.
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.
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.
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.
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.
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 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:
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 mechanism
This mechanism involves an initial ionisation of the halogenoalkane:
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.
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,
you would end up with a neutral species and a negative ion on the
right. Charges must balance in equations, so something is wrong.
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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 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.
You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:
The mechanism
Here is the mechanism for the reaction involving bromoethane:
slow step (in this case, the only step) of the reaction, it is known as an
SN2 reaction.
If your examiners want you to show the transition state, draw the
mechanism like this:
Or if you want the full equation rather than the ionic one:
The mechanism
This mechanism involves an initial ionisation of the halogenoalkane:
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:
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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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.
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.
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
cyanide ion. The lone pair on the cyanide ion is strongly attracted to the
positive carbon, moves towards it, and forms a bond.
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 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.
There is then the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
The mechanism
The mechanism involves two steps. The first is a simple nucleophilic
substitution reaction:
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.
Followed by:
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The mechanism
This mechanism involves an initial ionisation of the halogenoalkane:
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.
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
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.
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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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: 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.
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 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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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:
In this first step, the bromine is again displaced as a bromide ion and you
get a salt formed called triethylammonium bromide.
An ammonia molecule can then remove the hydrogen from the nitrogen
in the reversible reaction:
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-.
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.
and active lone pair attracts the new hydrogen from the water.
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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the ease with which the lone pair picks up a hydrogen ion,
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.
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:
For example:
pKb
CH3NH2
3.36
CH3CH2NH2
3.27
CH3CH2CH2NH2
3.16
CH3CH2CH2CH2NH2
3.39
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 . . .
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.
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.
Understanding Chemistry
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.
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Amines Menu
Understanding Chemistry
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
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.
an introduction to amines
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:
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:
type
formula
primary
CH3NH2
-6.3
primary
CH3CH2NH2
16.6
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.
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.
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.
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.
an introduction to amines
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.
Understanding Chemistry
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 Main Menu . . .
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 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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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.
-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.
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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preparation of amines
MAKING AMINES
preparation of amines
There is then the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
preparation of amines
There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
preparation of amines
There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
This time there isn't any hydrogen left on the nitrogen to be removed. The
reaction stops here.
preparation of amines
preparation of amines
preparation of amines
MAKING 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.
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:
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.
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:
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).
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
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:
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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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!
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.
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.
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:
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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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 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.
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.
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:
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.
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:
That means that an oxidising agent takes electrons from that other
substance.
So an oxidising agent must gain electrons.
Redox menu
Understanding Chemistry
REDOX MENU
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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.
electron-half-equations
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.
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.
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)
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!
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.
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:.
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.
To Main Menu . . .
Understanding Chemistry
Discusses entropy and entropy changes in as simple a way as possible and looks at the way total entropy change governs the feasibility of a
reaction. Goes on to look at free energy changes and how they can be
calculated and used to predict feasibility.
Go to Main Menu . . .
Understanding Chemistry
Go to Main Menu . . .
Understanding Chemistry
This page explores the trends in some atomic and physical properties of
the Group 2 elements - beryllium, magnesium, calcium, strontium and
barium. You will find separate sections below covering the trends in
atomic radius, first ionisation energy, electronegativity and melting point.
Even if you aren't currently interested in all these things, it would
probably pay you to read the whole page. The same ideas tend to recur
throughout the atomic properties, and you may find that earlier
explanations help to you understand later ones.
You can see that the atomic radius increases as you go down the Group.
Notice that beryllium has a particularly small atom compared with the rest
of the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by
1s22s2
Mg
1s22s22p63s2
Note: If you aren't sure about writing electronic structures
using s and p notation it might be a good idea to follow this
link before you go on. Use the BACK button on your browser
to return quickly to this page.
In each case, the two outer electrons feel a net pull of 2+ from the
nucleus. The positive charge on the nucleus is cut down by the
negativeness of the inner electrons.
This is equally true for all the other atoms in Group 2. Work it out for
calcium if you aren't convinced.
The only factor which is going to affect the size of the atom is therefore
the number of layers of inner electrons which have to be fitted in around
the atom. Obviously, the more layers of electrons you have, the more
space they will take up - electrons repel each other. That means that the
atoms are bound to get bigger as you go down the Group.
Note: You may think that this is all a bit long-winded! It is,
after all, fairly obvious that atoms will get bigger if you add
more layers of electrons. Why, then, bother about exploring
the net pull on the electrons from the centre of the atom?
It is a matter of setting up good habits. If you are talking
about atoms in the same Group, the net pull from the centre
will always be the same - and you could ignore it without
creating problems. That isn't true if you try to compare atoms
from different parts of the Periodic Table. If you don't get into
the habit of thinking about all the possible factors, you are
going to make mistakes.
Notice that first ionisation energy falls as you go down the group.
Explaining the decrease in first ionisation energy
Ionisation energy is governed by
Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a
bonding pair of electrons. It is usually measured on the Pauling scale, on
which the most electronegative element (fluorine) is given an
electronegativity of 4.0.
Note: You might argue that the fall doesn't apply throughout
the Group because both calcium and strontium have an
electronegativity of 1.0. This is probably most easily
explained by the fact that electronegativities are only
recorded to 1 decimal place. If, for example, calcium was
1.04 and strontium was 0.95 (made-up numbers!), both
would appear to have an electronegativity of 1.0.
The electron pair ends up so close to the chlorine that there is essentially
a transfer of an electron to the chlorine - ions are formed.
The large pull from the chlorine nucleus is why chlorine is much more
electronegative than magnesium is.
Now compare this with the beryllium-chlorine bond.
The net pull from each end of the bond is the same as before, but you
have to remember that the beryllium atom is smaller than a magnesium
atom. That means that the electron pair is going to be closer to the net 2
+ charge from the beryllium end, and so more strongly attracted to it.
In this case, the electron pair doesn't get attracted close enough to the
chlorine for an ionic bond to be formed. Because of its small size,
beryllium forms covalent bonds, not ionic ones. The attraction between
the beryllium nucleus and a bonding pair is always too great for ions to
be formed.
Summarising the trend down the Group
As the metal atoms get bigger, any bonding pair gets further and further
away from the metal nucleus, and so is less strongly attracted towards it.
In other words, as you go down the Group, the elements become less
electronegative.
As you go down the Group, the bonds formed between these elements
and other things such as chlorine become more and more ionic. The
bonding pair is increasingly attracted away from the Group 2 element
towards the chlorine (or whatever).
You will see that (with the exception of magnesium) the melting point
falls as you go down the Group.
Explaining the trends in melting point (or not!)
Thankfully, none of the current A'level syllabuses ask you to explain the
pattern in the melting points. Trying to explain patterns in melting point is
notoriously difficult, and simple explanations usually come to grief if you
look at them closely.
It would be tempting to say that (apart from magnesium) the lower
melting points as you go down the Group reflect weaker metallic bonds,
but this is dangerous. The metallic bond isn't fully broken on melting.
Boiling point is usually a better guide to the strengths of the forces
involved.
You will sometimes come across an explanation for the low melting point
of magnesium in terms of the way the atoms pack in the crystal. It isn't
very difficult to pick holes in this argument and, in any case, the boiling
point of magnesium is also surprisingly low - and packing is completely
irrelevant when you are thinking about a liquid. In the case of
magnesium, there must be some factor producing a relatively weak
metallic bond. (I have no idea what that might be!)
You will see that there is no obvious pattern in the boiling points implying that there is no simple pattern in the strengths of the metallic
bonds.
Another measure of the strengths of the metallic bonds might be
atomisation energy. This is the energy needed to produce 1 mole of
separated atoms in the gas state starting from the element in its standard
state (the state you would expect it to be in at approximately room
temperature and pressure).
And again there is no simple pattern. Don't worry about any of this for
A'level purposes, but be very wary of any explanation which looks
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deceptively simple!
Understanding Chemistry
You should be able to find what you want via the menu systems or using
the Google site search in the Main Menu. However, it may well be that I
haven't written exactly what you want yet - in which case, you will need to
look elsewhere. Please bear with me - writing new stuff takes a long time!
Helping yourself
To get the best from the site you must have a clear idea of what you
need to know. You will often find comments suggesting that you should
refer to your syllabus or to recent exam papers. It is important that you
have these to hand.
UK A level students can easily download syllabuses from their Exam
Boards, and should be able to find other useful things on those websites.
You can find links to these sites via the Main Menu.
If you are working in another examination system, you still need to know
exactly what is expected of you, but will have to find that information for
yourself.
Go to Main Menu . . .
Understanding Chemistry
Exactly this same structure is found in silicon and germanium and in one
of the allotropes of tin - "grey tin" or "alpha-tin".
The common allotrope of tin ("white tin" or "beta-tin") is metallic and has
its atoms held together by metallic bonds. The structure is a distorted
close-packed arrangement. In close-packing, each atom is surrounded
by 12 near-neighbours.
By the time you get to lead, the atoms are arranged in a straightforward
12-co-ordinated metallic structure.
There is therefore a clear trend from the typical covalency found in nonmetals to the metallic bonding in metals, with the change-over obvious in
the two entirely different structures found in tin.
The low value for tin's melting point compared with lead is presumably
due to tin forming a distorted 12-co-ordinated structure rather than a pure
one. The tin values in the chart refer to metallic white tin.
Brittleness
There is a much clearer non-metal / metal difference shown if you look at
the brittleness of the elements.
Carbon as diamond is, of course, very hard - reflecting the strength of the
covalent bonds. However, if you hit it with a hammer, it shatters. Once
you apply enough energy to break the existing carbon-carbon bonds,
that's it!
Silicon, germanium and grey tin (all with the same structure as diamond)
are also brittle solids.
However, white tin and lead have metallic structures. The atoms can roll
over each other without any permanent disruption of the metallic bonds leading to typical metallic properties like being malleable and ductile.
Lead in particular is a fairly soft metal.
Electrical conductivity
Carbon as diamond doesn't conduct electricity. In diamond the electrons
are all tightly bound and not free to move.
Note: The data in this chart again comes from the University
of Sheffield's Webelements site. Again, there is an awful lot
of variability in the data depending on where you get it from.
But in no case that I have found is there any trend to lower
electronegativities as you go down the Group. Older data
sources give a fall from carbon (2.5) to silicon (1.8), but then
give all the other elements in the Group the same value (all
1.8).
If anyone reading this has a simple explanation for the lack of
correlation between the trend to metallic behaviour and the
electronegativity values, could you please contact me via the
address on the about this site page.
Ionisation energies
If you are thinking about the formation of positive ions, the obvious place
to start looking is how ionisation energies change as you go down Group
4.
Ionisation energies are defined as the energy needed to carry out each
of the following changes. They are quoted in kJ mol-1.
First ionisation energy:
. . . and so on.
You can see that the ionisation energies tend to fall as you go down the
Group - although there is a slight increase at lead. The main trend is
because:
If you look at the amount of ionisation energy needed to form 4+ ions, the
pattern is similar, but not entirely clear cut. Again, the values are all in kJ
mol-1.
What is clear looking at these two charts is that you have to put in large
amounts of ionisation energy to form 2+ ions, and huge amounts to form
4+ ions.
However, in each case there is a fall in ionisation energy as you go down
the Group which makes it more likely that tin and lead could form positive
ions - however, there is no indication from these figures that they are
likely to form positive ions.
The ionisation energies of carbon at the top of the Group are so huge
that there is no possibility of it forming simple positive ions.
Note: Even for tin and lead, you have to put in huge
amounts of energy to form either 2+ or 4+ ions. So why do
they form ions at all?
You have to remember that there are lots of other energy
terms involved in the formation of an ionic compound apart
from ionisation energy. Some of these give out large amounts
of energy - for example, lattice enthalpy if you are forming an
ionic solid, or hydration enthalpy if you are forming a solution.
You will need to read about Born-Haber cycles in order to
understand this fully. These aren't covered formally on this
site, but you will find them discussed in detail in my chemistry
calculations book.
In the diagram some carbon atoms only seem to be forming two bonds
(or even one bond), but that's not really the case. We are only showing a
small bit of the whole structure.
This is a giant covalent structure - it continues on and on in three
dimensions. It is not a molecule, because the number of atoms joined up
in a real diamond is completely variable - depending on the size of the
crystal.
has a very high melting point (almost 4000C). Very strong carboncarbon covalent bonds have to be broken throughout the structure
before melting occurs.
is very hard. This is again due to the need to break very strong
covalent bonds operating in 3-dimensions.
doesn't conduct electricity. All the electrons are held tightly
between the atoms, and aren't free to move.
is insoluble in water and organic solvents. There are no possible
Notice that you can't really draw the side view of the layers to the same
scale as the atoms in the layer without one or other part of the diagram
being either very spread out or very squashed.
In that case, it is important to give some idea of the distances involved.
The distance between the layers is about 2.5 times the distance between
the atoms within each layer.
The layers, of course, extend over huge numbers of atoms - not just the
few shown above.
You might argue that carbon has to form 4 bonds because of its 4
unpaired electrons, whereas in this diagram it only seems to be forming 3
bonds to the neighbouring carbons. This diagram is something of a
simplification, and shows the arrangement of atoms rather than the
bonding.
The important thing is that the delocalised electrons are free to move
anywhere within the sheet - each electron is no longer fixed to a
particular carbon atom. There is, however, no direct contact between the
delocalised electrons in one sheet and those in the neighbouring sheets.
The atoms within a sheet are held together by strong covalent bonds stronger, in fact, than in diamond because of the additional bonding
caused by the delocalised electrons. So what holds the sheets together?
In graphite you have the ultimate example of van der Waals dispersion
forces. As the delocalised electrons move around in the sheet, very large
temporary dipoles can be set up which will induce opposite dipoles in the
sheets above and below - and so on throughout the whole graphite
crystal.
Note: If you aren't sure about van der Waals forces follow
this link before you go on. Use the BACK button on your
browser to return to this page.
metal structures
METALLIC STRUCTURES
This page decribes the structure of metals, and relates that structure to
the physical properties of the metal.
12-co-ordination
Most metals are close packed - that is, they fit as many atoms as
possible into the available volume. Each atom in the structure has 12
touching neighbours. Such a metal is described as 12-co-ordinated.
Each atom has 6 other atoms touching it in each layer.
There are also 3 atoms touching any particular atom in the layer above
and another 3 in the layer underneath.
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metal structures
This second diagram shows the layer immediately above the first layer.
There will be a corresponding layer underneath. (There are actually two
different ways of placing the third layer in a close packed structure, but
that goes beyond the requirements of current A'level syllabuses.)
8-co-ordination
Some metals (notably those in Group 1 of the Periodic Table) are packed
less efficiently, having only 8 touching neighbours. These are 8-coordinated.
The left hand diagram shows that no atoms are touching each other
within a particular layer . They are only touched by the atoms in the
layers above and below. The right hand diagram shows the 8 atoms (4
above and 4 below) touching the darker coloured one.
Dislocations
It would be misleading to suppose that all the atoms in a piece of metal
are arranged in a regular way. Any piece of metal is made up of a large
number of "crystal grains", which are regions of perfect regularity. At the
grain boundaries atoms have become misaligned.
metal structures
Electrical conductivity
Metals conduct electricity. The delocalised electrons are free to move
throughout the structure in 3-dimensions. They can cross grain
boundaries. Even though the pattern may be disrupted at the boundary,
as long as atoms are touching each other, the metallic bond is still
present.
Liquid metals also conduct electricity, showing that although the metal
atoms may be free to move, the delocalisation remains in force until the
metal boils.
metal structures
Thermal conductivity
Metals are good conductors of heat. Heat energy is picked up by the
electrons as additional kinetic energy (it makes them move faster). The
energy is transferred throughout the rest of the metal by the moving
electrons.
If a larger stress is put on, the atoms roll over each other into a new
position, and the metal is permanently changed.
metal structures
metal structures
metallic bonding
METALLIC BONDING
This page introduces the bonding in metals. It explains how the metallic
bond arises and why its strength varies from metal to metal.
metallic bonding
metallic bonding
This page explains how you can decide what sort of structure a
substance has by looking at its physical properties. It starts with a very
simple look at solids, liquids and gases.
Solids
In the solid, the particles are touching, and the only motion allowed to
them is vibration. The particles may be arranged regularly (in which case,
the solid is crystalline), or at random (giving waxy solids like candles or
some forms of polythene, for example).
The particles are held in the solid by forces which depend on the actual
substance - ionic bonds, covalent bonds, metallic bonds, hydrogen
bonds or van der Waals attractions.
Melting and freezing
If energy is supplied by heating the solid, the heat energy causes greater
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vibrations until the particles eventually loosen from each other to form a
liquid. The heat energy required to convert 1 mole of solid into a liquid at
its melting point is called the enthalpy of fusion.
When a liquid freezes, the reverse happens. At some temperature, the
motion of the particles is slow enough for the forces of attraction to be
able to hold the particles as a solid. As the new bonds are formed, heat
energy is evolved.
Liquids
In a liquid, the particles are mainly touching, but some gaps have
appeared in the structure. These gaps allow the particles to move, and
so the particles are arranged randomly. Unless melting has broken up a
substance consisting only of covalent bonds (a giant covalent structure),
the forces that held the solid particles together are also present in the
liquid, but in a somewhat loosened form.
Boiling and condensing
If more heat energy is supplied, the particles eventually move fast
enough to break all the attractions between them, and the liquid boils.
The heat energy required to convert 1 mole of liquid into a gas at its
boiling point is called the enthalpy of vaporisation.
If the gas is cooled, at some temperature the gas particles will slow down
enough for the attractions to become effective enough to condense it
back into a liquid. Again, as those forces are re-established, heat energy
is released.
Gases
In a gas, the particles are entirely free to move. At ordinary pressures,
the distance between individual particles is of the order of ten times the
diameter of the particles. At that distance, any attractions between the
particles are fairly negligible.
This page describes the structures of the Period 3 elements from sodium
to argon, and shows how these structures can be used to explain the
physical properties of the elements.
In a moment we shall explain all the ups and downs in this graph.
Electrical conductivity
Sodium, magnesium and aluminium are all good conductors of electricity.
Silicon is a semiconductor. None of the rest conduct electricity.
However, as you go down the Group, there are more and more examples
where the oxidation state is +2, such as SnCl2, PbO, and Pb2+.
With tin, the +4 state is still more stable than the +2, but by the time you
get to lead, the +2 state is the more stable - and dominates the chemistry
of lead.
Tin(II) ions also reduce iron(III) ions to iron(II) ions. For example, tin(II)
chloride solution will reduce iron(III) chloride solution to iron(II) chloride
solution. In the process, the tin(II) ions are oxidised to the more stable tin
(IV) ions.
large increase between tin and lead must be because the 6s2 pair is
significantly more difficult to remove in lead than the corresponding 5s2
pair in tin.
Again, the values are all in kJ mol-1, and the two charts are to
approximately the same scale.
The reasons for all this lie in the Theory of Relativity. With the heavier
elements like lead, there is what is known as a relativistic contraction
of the electrons which tends to draw the electrons closer to the nucleus
than you would expect. Because they are closer to the nucleus, they are
more difficult to remove. The heavier the element, the greater this effect.
This affects s electrons much more than p electrons.
In the case of lead, the relativistic contraction makes it energetically more
difficult to remove the 6s electrons than you might expect. The energy
releasing terms when ions are formed (like lattice enthalpy or hydration
enthalpy) obviously aren't enough to compensate for this extra energy.
That means that it doesn't make energetic sense for lead to form 4+ ions.
There are only two unpaired electrons. Before carbon forms bonds,
though, it normally promotes one of the s electrons to the empty p orbital.
This page takes a brief look at the tetrachlorides of carbon, silicon and
lead, and also at lead(II) chloride. It looks at their structures, stability and
reactions with water.
Structures
Carbon, silicon and lead tetrachlorides
These all have the formula XCl4.
They are all simple covalent molecules with a typical tetrahedral shape.
All of them are liquids at room temperature. (Although at room
temperature, lead(IV) chloride will tend to decompose to give lead(II)
chloride and chlorine gas - see below.)
Lead(II) chloride, PbCl2
Lead(II) chloride is a white solid, melting at 501C. It is very slightly
soluble in cold water, but more soluble in hot water. You can think of lead
(II) chloride as being mainly ionic in character.
Stability
At the top of Group 4, the most stable oxidation state shown by the
elements is +4. This is the oxidation state shown by carbon and silicon in
CCl4 and SiCl4. These therefore have no tendency to split up to give
dichlorides.
However, the relative stability of the +4 oxidation state falls as you go
down the Group, and the +2 oxidation state becomes the most stable by
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Silicon tetrachloride
The situation is different with silicon tetrachloride.
The silicon atom is bigger, and so there is more room around it for the
water molecule to attack, and the transition state will be less cluttered.
But silicon has the additional advantage that there are empty 3d orbitals
available to accept a lone pair from the water molecule. Carbon doesn't
have 2d orbitals because there are no such things. There are no empty 2-
Liquid SiCl4 fumes in moist air for this reason - it is reacting with water
vapour in the air.
Lead(II) chloride
Unlike the tetrachlorides, lead(II) chloride can be thought of as ionic. It is
sparingly soluble in cold water, but more soluble in hot water. Looked at
simply, solubility in water involves the break-up of the ionic lattice and the
hydration of the lead(II) and chloride ions to give Pb2+(aq) and Cl-(aq).
This page takes a brief look at the oxides of carbon, silicon, germanium,
tin and lead. It concentrates on the structural differences between carbon
dioxide and silicon dioxide, and on the trends in acid-base behaviour of
the oxides as you go down Group 4.
None of the other elements in Group 4 form double bonds with oxygen,
and so that forces completely different structures on them.
When carbon forms bonds with oxygen, it first promotes one of the
electrons in the 2s level into the empty 2p level. This produces 4
unpaired electrons.
What these look like in the atom (using the same colour coding) is:
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Notice that the two green lobes are two different hybrid orbitals arranged as far apart from each other as possible. Don't confuse them
with the shape of a p orbital.
So that's how the carbon is organised just before it bonds. Now we need
to look at the oxygen.
Oxygen's electronic structure is 1s22s22px22py12pz1.
Hybridisation occurs in the oxygen as well. This time, sp2 hybrids are
formed with the s orbital and two of the p orbitals being rearranged to
give 3 orbitals of equal energy - leaving a temporarily unaffected p orbital.
This time two of the sp2 hybrid orbitals contain lone pairs of electrons.
Now line up the two oxygens and the carbon prior to bonding them.
Notice that the left-hand oxygen has been rotated through 90:
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Then bring them together so that the pale green hybrid orbitals overlap
end-to-end to form simple covalent bonds. These are properly called
sigma bonds, and are shown as orange in the next diagram.
This brings the various p orbitals close enough together that they overlap
sideways.
This means that silicon dioxide is a giant covalent structure. The strong
bonds in three dimensions make it a hard, high melting point solid.
Carbon monoxide
Carbon monoxide is usually treated as if it was a neutral oxide, but in fact
it is very, very slightly acidic. It doesn't react with water, but it will react
with hot concentrated sodium hydroxide solution to give a solution of
sodium methanoate.
The fact that the carbon monoxide reacts with the basic hydroxide ion
shows that it must be acidic.
Silicon dioxide also reacts with sodium hydroxide solution, but only if it is
hot and concentrated. Sodium silicate solution is formed.
You may also be familiar with one of the reactions happening in the Blast
Furnace extraction of iron - in which calcium oxide (from the limestone
which is one of the raw materials) reacts with silicon dioxide to produce a
liquid slag, calcium silicate. This is also an example of the acidic silicon
dioxide reacting with a base.
The dioxides
These dioxides are again amphoteric - showing both basic and acidic
properties.
The basic nature of the dioxides
The dioxides react with concentrated hydrochloric acid first to give
compounds of the type XCl4:
These will react with excess chloride ions in the hydrochloric acid to give
complexes such as XCl62-.
In the case of lead(IV) oxide, the reaction has to be done with ice-cold
hydrochloric acid. If the reaction is done any warmer, the lead(IV)
chloride decomposes to give lead(II) chloride and chlorine gas. This is an
effect of the preferred oxidation state of lead being +2 rather than +4.
Some sources suggest that the lead(IV) oxide needs molten sodium
hydroxide. In that case, the equation is different.
Understanding Chemistry
This page explores the trends in some atomic and physical properties of
the Group 7 elements (the halogens) - fluorine, chlorine, bromine and
iodine. You will find separate sections below covering the trends in
atomic radius, electronegativity, electron affinity, and melting and boiling
points. There is also a section on the bond enthalpies (strengths) of
halogen-halogen bonds (for example, Cl-Cl) and of hydrogen-halogen
bonds (e.g. H-Cl)
Even if you aren't currently interested in all these things, it would
probably pay you to read the whole page. The same ideas tend to recur
throughout the atomic properties, and you may find that earlier
explanations help to you understand later ones.
You can see that the atomic radius increases as you go down the Group.
Explaining the increase in atomic radius
The radius of an atom is governed by
2,7
Cl
2,8,7
In each case, the outer electrons feel a net pull of 7+ from the nucleus.
The positive charge on the nucleus is cut down by the negativeness of
the inner electrons.
This is equally true for all the other atoms in Group 7. The outer electrons
always feel a net pull of 7+ from the centre.
The only factor which is going to affect the size of the atom is therefore
the number of layers of inner electrons which have to be fitted in around
the atom. Obviously, the more layers of electrons you have, the more
space they will take up - electrons repel each other. That means that the
atoms are bound to get bigger as you go down the Group.
Trends in Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a
bonding pair of electrons. It is usually measured on the Pauling scale, on
which the most electronegative element (fluorine) is given an
electronegativity of 4.0.
Notice that electronegativity falls as you go down the Group. The atoms
become less good at attracting bonding pairs of electrons.
Explaining the decrease in electronegativity
This is easily shown using simple dots-and-crosses diagrams for
hydrogen fluoride and hydrogen chloride.
The bonding pair of electrons between the hydrogen and the halogen
feels the same net pull of 7+ from both the fluorine and the chlorine. (This
is exactly the same sort of argument as you have seen in the atomic
radius section above.) However, in the chlorine case, the nucleus is
further away from that bonding pair. That means that it won't be as
strongly attracted as in the fluorine case.
The larger pull from the closer fluorine nucleus is why fluorine is more
electronegative than chlorine is.
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Notice that the trend down the Group isn't tidy. The tendency is for the
electron affinities to decrease (in the sense that less heat is given out),
but the fluorine value is out of line.
The electron affinity is a measure of the attraction between the incoming
electron and the nucleus. The higher the attraction, the higher the
electron affinity.
In the bigger atom, the attraction from the more positive nucleus is offset
by the additional screening electrons, so each incoming electron feels
the effect of a net 7+ charges from the centre - exactly as when you are
thinking about atomic radius or electronegativity.
As the atom gets bigger, the incoming electron is further from the
nucleus and so feels less attraction. The electron affinity therefore falls
as you go down the Group.
But what about fluorine? That is a very small atom, with the incoming
electron quite close to the nucleus. Why isn't its electron affinity bigger
than chlorine's?
There is another effect operating. When the new electron comes into the
atom, it is entering a region of space already very negatively charged
because of the existing electrons. There is bound to be some repulsion,
offsetting some of the attraction from the nucleus.
In the case of fluorine, because the atom is very small, the existing
electron density is very high. That means that the extra repulsion is
particularly great and lessens the attraction from the nucleus enough to
lower the electron affinity below that of chlorine.
You will see that both melting points and boiling points rise as you go
down the Group.
If you explore the graphs, you will find that fluorine and chlorine are
gases at room temperature, bromine is a liquid and iodine a solid.
Nothing very surprising there!
Explaining the trends in melting point and boiling point
All of the halogens exist as diatomic molecules - F2, Cl2, and so on. The
intermolecular attractions between one molecule and its neighbours are
van der Waals dispersion forces.
As the molecules get bigger there are obviously more electrons which
can move around and set up the temporary dipoles which create these
attractions.
The stronger intermolecular attractions as the molecules get bigger
means that you have to supply more heat energy to turn them into either
a liquid or a gas - and so their melting and boiling points rise.
As with all halogens, the bonding pair will feel a net pull of 7+ from both
ends of the bond - the charge on the nucleus offset by the inner
electrons. That will still be the same whatever the size of the halogen
atoms.
As the atoms get bigger, the bonding pair gets further from the nuclei and
so you would expect the strength of the bond to fall.
The bond enthalpies of the Cl-Cl, Br-Br and I-I bonds fall just as you
would expect, but the F-F bond is way out of line!
Because fluorine atoms are so small, you might expect a very strong
bond - in fact, it is remarkably weak. There must be another factor at
work as well.
As well as the bonding pair of electrons between the two atoms, each
atom has 3 non-bonding pairs of electrons in the outer level - lone pairs.
Where the bond gets very short (as in F-F), the lone pairs on the two
atoms get close enough together to set up a significant amount of
repulsion.
As the halogen atom gets bigger, the bonding pair gets more and more
distant from the nucleus. The attraction is less, and the bond gets weaker
- exactly what is shown by the data. There is nothing complicated
happening in this case.
electron affinity
ELECTRON AFFINITY
This page explains what electron affinity is, and then looks at the factors
that affect its size. It assumes that you know about simple atomic
orbitals, and can write electronic structures for simple atoms.
electron affinity
-328 kJ mol-1
Cl
-349 kJ mol-1
Br
-324 kJ mol-1
-295 kJ mol-1
Is there a pattern?
Yes - as you go down the group, first electron affinities become less (in
the sense that less energy is evolved when the negative ions are
formed). Fluorine breaks that pattern, and will have to be accounted for
separately.
The electron affinity is a measure of the attraction between the incoming
electron and the nucleus - the stronger the attraction, the more energy is
released.
The factors which affect this attraction are exactly the same as those
relating to ionisation energies - nuclear charge, distance and screening.
electron affinity
electron affinity
electron affinity
in both.
That means that the net pull from the nucleus is less in Group 6 than in
Group 7, and so the electron affinities are less.
electron affinity
It is the energy needed to carry out this change per mole of X-.
Why is energy needed to do this?
You are forcing an electron into an already negative ion. It's not going to
go in willingly!
1st EA = -142 kJ mol-1
2nd EA = +844 kJ mol-1
The positive sign shows that you have to put in energy to perform this
change. The second electron affinity of oxygen is particularly high
because the electron is being forced into a small, very electron-dense
space.
This page explores the trend in oxidising ability of the Group 7 elements
(the halogens) - fluorine, chlorine, bromine and iodine. We are going to
look at the ability of one halogen to oxidise the ions of another one, and
how that changes as you go down the Group.
The facts
We are going to look at the reactions between one halogen (chlorine,
say) and the ions of another one (iodide ions, perhaps). The iodide ions
will be in a solution of a salt like sodium or potassium iodide. The sodium
or potassium ions will be spectator ions, and are completely irrelevant to
the reaction.
In the chlorine and iodide ion case, the reaction would be:
The iodide ions have lost electrons to form iodine molecules. They have
been oxidised.
The chlorine molecules have gained electrons to form chloride ions. They
have been reduced.
This is obviously a redox reaction in which chlorine is acting as an
oxidising agent.
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Fluorine
We'll have to exclude fluorine from this descriptive bit, because it is too
strong an oxidising agent. Fluorine oxidises water to oxygen and so it is
impossible to do simple solution reactions with it.
The iodine appears either as a red solution if you are mean with the
amount of chlorine you use, or as a dark grey precipitate if the chlorine is
in excess.
Note: The reason for the red solution is that iodine dissolves
in potassium iodide (or other soluble iodides) by reacting to
give a red ion, I3-. If the chlorine is in excess, obviously there
isn't anything left for the iodine to react with, and so it
remains as a dark grey precipitate.
Bromine can only oxidise iodide ions to iodine. It isn't a strong enough
oxidising agent to convert chloride ions into chlorine. (You have just seen
exactly the reverse of that happening.)
A red solution of iodine is formed (see the note above) until the bromine
is in excess. Then you get a dark grey precipitate.
Iodine won't oxidise any of the other halide ions (unless you happened to
have some extremely radioactive and amazingly rare astatide ions astatine is at the bottom of this Group).
To summarise
This all means that oxidising ability falls as you go down the Group.
As you go down the Group, the ease with which these hydrated ions are
formed falls, and so the halogens become less good as oxidising agents
- less ready to take electrons from something else.
The reason that the hydrated ions form less readily as you go down the
Group is a fairly complicated mixture of several factors. Unfortunately,
this is often over-simplified to give what is actually a faulty and
misleading explanation. We'll deal with this first before giving a proper
explanation.
The faulty explanation
This is normally given for the trend in oxidising ability of chlorine, bromine
and iodine, and goes like this:
How easily the element forms its ions depends on how strongly the new
electrons are attracted. As the atoms get bigger, the new electrons find
themselves further from the nucleus, and more and more screened from
it by the inner electrons (offsetting the effect of the greater nuclear
charge). The bigger atoms are therefore less good at attracting new
electrons and forming ions.
That sounds reasonable! What's wrong with it?
What we are describing is the trend in electron affinity as you go from
chlorine to bromine to iodine. Electron affinity tends to fall as you go
down the Group. This is described in detail on another page.
The snag comes if you try to expand the argument to include fluorine.
Fluorine has a much higher tendency to form its hydrated ion than
chlorine does. BUT . . . the tendency of the fluorine atom to gain an
electron is less than that of chlorine - as measured by its electron affinity!
That makes a nonsense of the whole argument.
So, what is going wrong? The mistake is to look at only one part of a
much more complicated process. The argument about atoms accepting
electrons applies to isolated atoms in the gas state picking up electrons
to make isolated ions - also in the gas state. That's not what we should
be talking about.
In reality:
Atomisation energy
This is the energy needed to produce 1 mole of isolated gaseous
atoms starting from an element in its standard state (gas for
chlorine, and liquid for bromine, for example - both of them as X2).
For a gas like chlorine, this is simply half of the bond enthalpy
(because breaking a Cl-Cl bond produces 2 chlorine atoms, not 1).
For a liquid like bromine or a solid like iodine, it also includes the
energy that is needed to convert them into gases.
Electron affinity
The first electron affinity is the energy released when 1 mole of
gaseous atoms each acquire an electron to form 1 mole of
gaseous 1- ions.
In symbol terms:
atomisation
energy
(kJ mol-1)
electron
affinity
(kJ mol-1)
hydration
enthalpy
(kJ mol-1)
overall
(kJ mol1)
+79
-328
-506
-755
Cl
+121
-349
-364
-592
Br
+112
-324
-335
-547
+107
-295
-293
-481
There's quite a lot of data here to look at. Concentrate first on the final
column which shows the overall heat evolved when all the other
processes happen. It is calculated by adding the figures in the previous 3
columns.
You can see that the amount of heat evolved falls quite dramatically from
the top to the bottom of the Group, with the biggest fall from fluorine to
chlorine.
Fluorine produces a lot of heat when it forms its hydrated ion, chlorine
less so, and so on down the Group.
The main reason, though, is the very high hydration enthalpy of the
fluoride ion. That is because the ion is very small. There is a very strong
attraction between the fluoride ions and water molecules. The stronger
the attraction, the more heat is evolved when the hydrated ions are
formed.
Why the fall in oxidising ability from chlorine to bromine to iodine?
The fall in atomisation energy between these three elements is fairly
slight, and would tend to make the overall change more negative as you
go down the Group. The explanation doesn't lie there!
It is helpful to look at the changes in electron affinity and hydration
enthalpy as you go down the Group. Using the figures from the previous
table:
change in electron
affinity
(kJ mol-1)
change in hydration
enthalpy
(kJ mol-1)
Cl to Br
+25
+29
Br to I
+29
+42
going from
You can see that both of these effects matter, but that the more
important one - the one that changes the most - is the change in the
hydration enthalpy.
As you go down the Group, the ions become less attractive to water
molecules as they get bigger. Although the ease with which an atom
attracts an electron matters, it isn't actually as important as the hydration
enthalpy of the negative ion formed.
The faulty explanation misses the mark even if you restrict it to chlorine,
bromine and iodine!
Hydrogen fluoride's boiling point is higher than you might expect because
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Fluorine is the most electronegative of all the elements and the bond
between it and hydrogen is very polar. The hydrogen atom carries quite a
lot of positive charge ( +); the fluorine is fairly negatively charged ( -).
In addition, each fluorine atom has 3 very active lone pairs of electrons.
Fluorine's outer electrons are at the 2-level, and the lone pairs represent
small highly charged regions of space. Hydrogen bonds form between
the + hydrogen on one HF molecule and a lone pair on the fluorine of
another one.
The other hydrogen halides don't form hydrogen bonds. The other
halogens aren't as electronegative as fluorine, and so the bonds in HX
are less polar. As well as that, their lone pairs are at higher energy
levels. That makes the lone pairs bigger, and so they don't carry such an
intensely concentrated negative charge for the hydrogens to be attracted
to.
. . . and the full one showing the formation of the salt, sodium
dihydrogenphosphate(V) is:
The H3O+ ion is the hydroxonium ion (also known as the hydronium ion
or the oxonium ion). This is the ion that we are actually talking about
when we write H+(aq).
When hydrogen chloride dissolves in water (to produce hydrochloric
acid), almost 100% of the hydrogen chloride molecules react in this way.
Hydrochloric acid is therefore a strong acid. A strong acid is one which
is fully ionised in solution.
Hydrobromic acid and hydriodic acid as strong acids
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Hydrogen bromide and hydrogen iodide dissolve in (and react with) water
in exactly the same way as hydrogen chloride does. Hydrogen bromide
reacts to give hydrobromic acid; hydrogen iodide gives hydriodic acid.
Both of these are also strong acids.
Hydrofluoric acid as an exception
By contrast, although hydrogen fluoride dissolves freely in water,
hydrofluoric acid is only a weak acid - similar in strength to organic acids
like methanoic acid. The reason for this is quite complicated.
Warning! Are you sure you need to know the reason for
this? The explanation is far more complicated than books at
this level tend to suggest. To understand it properly you need
to be familiar with energy cycles, entropy, free energy and
equilibrium constants.
The explanation starts fairly easily, but gets harder and
harder as you go on!
bond enthalpy
(kJ mol-1)
H-F
+562
H-Cl
+431
H-Br
+366
H-I
+299
In order for ions to form when the hydrogen fluoride reacts with water,
you first have to break the H-F bond. It would seem reasonable to say
that the relative reluctance of hydrogen fluoride to react with water is due
to the large amount of energy needed to break that bond.
It might seem reasonable, but if you dig a little deeper, that explanation
falls apart!
Looking at the energetics of the process from HX(g) to X-(aq)
We need to consider the energetics of this sequence:
All of these terms are involved in the overall enthalpy change as you
convert HX(g) into its ions in water.
However, the terms involving the hydrogen will be the same for every
hydrogen halide. So if we are just trying to draw comparisons, we only
need to look at the terms shown in red in the diagram.
bond
enthalpy of
HX
(kJ mol-1)
electron
affinity of X
(kJ mol-1)
hydration
enthalpy of X(kJ mol-1)
sum of
these
(kJ mol1)
HF
+562
-328
-506
-272
HCl
+431
-349
-364
-282
HBr
+366
-324
-335
-293
HI
+299
-295
-293
-289
The large bond enthalpy of the H-F bond is compensated for by the large
hydration enthalpy of the fluoride ion. There is a very strong attraction
between the very small fluoride ion and the water molecules. This
releases a lot of heat (the hydration enthalpy) when the fluoride ion
becomes wrapped in water molecules.
The fact that there isn't much difference between the overall values
means that we still aren't looking in the right place for the explanation of
why hydrofluoric acid is weak!
Looking at other attractions in the system
The mistake we are making so far is in starting from the wrong place!
The energy terms we have been looking at start from HX as a gas. In
fact, we should be thinking of it starting in solution - but not yet reacted
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Unfortunately, at this point I've been unable to find any figures for that
first stage. However, in each case, that initial separation of the HX from
water molecules will be endothermic. Energy is needed to break the
intermolecular attractions between the HX molecules and water.
That energy will be much greater in the case of hydrogen fluoride
because it forms hydrogen bonds with the water molecules. The other
hydrogen halides only form the weaker van der Waals dispersion forces
or dipole-dipole attractions.
Note: If you aren't sure about van der Waals forces, you
could follow this link.
Use the BACK button on your browser to return to this page.
Putting all this together, here are the overall enthalpy changes (including
all the stages in the energy cycle) for the reactions:
enthalpy change
(kJ mol-1)
HF
-13
HCl
-59
HBr
-63
H-I
-57
You can see that the enthalpy change for HF is much lower than that for
the other three hydrogen halides - but it is still an exothermic change. We
still haven't got fully to the bottom of why hydrofluoric acid is a weak acid!
Entropy and free energy considerations
What decides the extent to which a reaction happens isn't enthalpy
change but is a term called free energy change.
Free energy change is calculated from the enthalpy change, the
temperature of the reaction and the entropy change during the reaction.
The only way of making sense of entropy without getting bogged down in
some serious maths is to think of it as a measure of the amount of
disorder in a system. Entropy is given the symbol S. If a system becomes
more disordered, then its entropy increases. If it becomes more ordered,
its entropy decreases.
The key equation is:
T S
(kJ mol-1)
HF
-29
HCl
-13
HBr
-4
H-I
+4
Notice that at the top of the Group, the systems are becoming more
ordered when the HX reacts with the water. The entropy of the system
(the amount of disorder) is decreasing - particularly with the hydrogen
fluoride.
The reason for this is that the very strong attractions between H3O+ and
F-(aq) ions imposes a lot of order on the system, as also does the
attraction between the water molecules and the various ions present.
These attractions (of both kinds) will be at their greatest in the case of
the very small fluoride ions.
Putting all this together, what is the effect on the free energy change, and
therefore the value of the equilibrium constant for the reaction?
Ka
H
(kJ mol-1)
T S
(kJ mol-1)
G
(kJ mol-1)
(mol dm-3)
HF
-13
-29
+16
1.6 x 10-3
HCl
-59
-13
-46
1.2 x 108
HBr
-63
-4
-59
2.2 x 1010
HI
-57
+4
-61
5.0 x 1010
The values for these estimated equilibrium constants for HCl, HBr and HI
are so high that you can think of the reaction as being essentially "oneway". The ionisation is virtually 100% complete. These are all strong
acids - but getting somewhat stronger as you go down the Group.
By contrast, the estimated equilibrium constant of hydrofluoric acid is
pretty small. Hydrofluoric acid only ionises to a very small extent in water.
It is a weak acid.
It is possible to check the accuracy of our explanation by comparing the
real value of the equilibrium constant with the estimated one.
You might think that these values aren't all that similar, but in fact they
are in remarkable agreement! Because of the way the maths works, a
very small change in G has a very large effect on Ka.
To have the values in close agreement, G would only have to increase
from +16 to +18.5 kJ mol-1. Given the uncertainty about the values used
to calculate G, our calculated value could easily be that much out.
To be honest, the calculated values for Ka shouldn't really have been
quoted beyond 1 significant figure. I've quoted them slightly more
accurately than they deserve in order to pick out the trend in the three
strong acids.
Summary: Why is hydrofluoric acid a weak acid?
The two main factors are:
A final thought
A Peanuts cartoon showed one of the others (Linus?) asking the awful
Lucy why the sky was blue. The conversation went something like this:
Linus: "Why is the sky blue?"
This page describes and explains the redox reactions involving halide
ions and concentrated sulphuric acid. It uses these reactions to discuss
the trend in reducing ability of the ions as you go from fluoride to chloride
to bromide to iodide.
The Facts
There are two different types of reaction which might go on when
concentrated sulphuric acid is added to a solid ionic halide like sodium
fluoride, chloride, bromide or iodide. The concentrated sulphuric acid can
act both as an acid and as an oxidising agent.
Concentrated sulphuric acid acting as an acid
The concentrated sulphuric acid gives a hydrogen ion to the halide ion to
produce a hydrogen halide. Because this is a gas, it immediately
escapes from the system. If the hydrogen halide is exposed to moist air,
you see it as steamy fumes.
As an example, concentrated sulphuric acid reacts with solid sodium
chloride in the cold to produce hydrogen chloride and sodium
hydrogensulphate.
All of the halide ions (fluoride, chloride, bromide and iodide) behave
similarly.
The bromide ions reduce the sulphuric acid to sulphur dioxide gas. This
is a decrease of oxidation state of the sulphur from +6 in the sulphuric
acid to +4 in the sulphur dioxide.
You can combine these two half-equations to give the overall ionic
equation for the reaction:
Note: If you aren't confident about redox reactions, electronhalf equations, and oxidation states you really ought to follow
this link before you go any further.
What you see in this reaction are the steamy fumes of hydrogen bromide
contaminated with the brown colour of bromine vapour. The sulphur
dioxide is a colourless gas, so you couldn't observe its presence directly.
With iodide ions
Iodide ions are stronger reducing agents than bromide ions are. They are
oxidised to iodine by the concentrated sulphuric acid.
The reduction of the sulphuric acid is more complicated than before. The
iodide ions are powerful enough reducing agents to reduce it
and all the way to hydrogen sulphide (sulphur oxidation state = -2).
This time what you see is a trace of steamy fumes of hydrogen iodide,
but mainly lots of iodine. The reaction is exothermic and so purple iodine
vapour is formed, and probably dark grey solid iodine condensing around
the top of the tube. There will also be red colours where the iodine
comes into contact with the solid iodide.
The red colour is due to the I3- ion formed by reaction between I2
molecules and I- ions.
You won't see the colourless hydrogen sulphide gas, but might pick up its
"bad egg" smell if you were foolish enough to smell the intensely
poisonous gases evolved!
An over-simplified explanation
This only works (and even then, not very well!) if you ignore fluoride ions.
The argument goes like this:
When a halide ion acts as a reducing agent, it gives electrons to
something else. That means that the halide ion itself has to lose
electrons.
The bigger the halide ion, the further the outer electrons are from the
nucleus, and the more they are screened from it by inner electrons. It
therefore gets easier for the halide ions to lose electrons as you go down
the Group because there is less attraction between the outer electrons
and the nucleus.
It sounds convincing, but it only tells part of the story. We need to look in
some detail at the energetics of the change.
Look carefully at the diagram so that you see how this all fits together:
heat needed
to break up
NaX lattice
(kJ mol-1)
heat needed
to remove
electron from
halide ion
(kJ mol-1)
heat released in
forming
halogen
molecules
(kJ mol-1)
sum of
these
(kJ mol-1)
+902
+328
-79
+1151
Cl
+771
+349
-121
+999
Br
+733
+324
-112
+945
+684
+295
-107
+872
Fluorine
Fluoride ions are very difficult to oxidise to fluorine. The table shows that
this isn't anything to do with the amount of energy needed to remove an
electron from a fluoride ion. It is actually easier to remove an electron
from a fluoride ion than from a chloride ion. In this case, to make the
generalisation that an electron gets easier to remove as the ion gets
bigger is just plain wrong!
Fluoride ions are so small that the electrons feel an abnormal amount of
repulsion from each other. This outweighs the effect of their closeness to
the nucleus and makes them easier to remove than you might expect.
There are two important reasons why fluoride ions are so difficult to
oxidise.
The first is the comparatively very high lattice enthalpy of the solid
fluoride. This is due to the small size of the fluoride ion, which means that
the positive and negative ions are very close together and so strongly
attracted to each other.
The other factor is the small amount of heat which is released when the
fluorine atoms combine to make fluorine molecules. (Scroll back and look
at the table again.)
This is because of the low bond enthalpy of the F-F bond. The reason for
this low bond enthalpy is discusssed on a separate page.
Note: If you haven't read about this recently, you will find it
on the page about atomic and physical properties of the
halogens
This page describes and explains the tests for halide ions (fluoride,
chloride, bromide and iodide) using silver nitrate solution followed by
ammonia solution.
ion present
observation
F-
no precipitate
Cl-
white precipitate
Br-
I-
The chloride precipitate is obviously white, but the other two aren't really
very different from each other. You couldn't be sure which you had
unless you compared them side-by-side.
All of the precipitates change colour if they are exposed to light - taking
on grey or purplish tints.
The absence of a precipitate with fluoride ions doesn't prove anything
unless you already know that you must have a halogen present and are
simply trying to find out which one. All the absence of a precipitate shows
is that you haven't got chloride, bromide or iodide ions present.
The chemistry of the test
The precipitates are the insoluble silver halides - silver chloride, silver
bromide or silver iodide.
original precipitate
observation
AgCl
AgBr
AgI
than the solubility product, you don't get a precipitate. If the product of
the concentrations would exceed this value, you do get a precipitate.
Essentially, the product of the ionic concentrations can never be greater
than the solubility product value. Enough of the solid is precipitated so
that the ionic product is lowered to the value of the solubility product.
Look at the way the solubility products vary from silver chloride to silver
iodide. (You can't quote a solubility product value for silver fluoride
because it is too soluble. Solubility products only work with compounds
which are very, very sparingly soluble.)
Ksp
(mol2dm-6)
AgCl
1.8 x 10-10
AgBr
7.7 x 10-13
AgI
8.3 x 10-17
You can see that the compounds are all pretty insoluble, but become
even less soluble as you go from the chloride to the bromide to the iodide.
What is the ammonia doing?
The ammonia combines with silver ions to produce a complex ion called
the diamminesilver(I) ion, [Ag(NH3)2]+. This is a reversible reaction, but
the complex is very stable, and the position of equilibrium lies well to the
right.
A solution in contact with one of the silver halide precipitates will contain
a very small concentration of dissolved silver ions. The effect of adding
the ammonia is to lower this concentration still further.
What happens if you multiply this new silver ion concentration by the
halide ion concentration? If the answer is less than the solubility product,
the precipitate will dissolve.
That happens with the silver chloride, and with the silver bromide if
concentrated ammonia is used. The more concentrated ammonia tips the
equilibrium even further to the right, lowering the silver ion concentration
even more.
The silver iodide is so insoluble that the ammonia won't lower the silver
ion concentration enough for the precipitate to dissolve.
ion present
observation
F-
Cl-
Br-
I-
Understanding Chemistry
This page explains the terms complex ion and ligand, and looks at the
bonding between the ligands and the central metal ion. It discusses
various sorts of ligand (including some quite complicated ones), and
describes what is meant by co-ordination number.
The molecules or ions surrounding the central metal ion are called
ligands.
The nature of ligands
Simple ligands include water, ammonia and chloride ions.
What all these have got in common is active lone pairs of electrons in the
outer energy level. These are used to form co-ordinate bonds with the
metal ion.
All ligands are lone pair donors. In other words, all ligands function as
Lewis bases.
Note: If you haven't come across the term Lewis base, and
want to find out more, you could follow this link to a page on
theories of acids and bases. It isn't, however, particularly
important to the rest of this page that you know anything
more than the fact that a substance which forms a coordinate bond by donating a lone pair of electrons to
something else is known as a Lewis base.
If you follow this link, use the BACK button on your browser
to return quickly to this page.
That means that all the 3-level orbitals are now empty. The aluminium
uses of six of these to accept lone pairs from six water molecules.
It re-organises (hybridises) the 3s, the three 3p, and two of the 3d
orbitals to produce six new orbitals all with the same energy.
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:
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.
Because the aluminium is forming 6 bonds, the co-ordination number
of the aluminium is said to be 6. The co-ordination number of a complex
ion counts the number of co-ordinate bonds being formed by the metal
ion at its centre.
In a simple case like this, that obviously also counts the number of
ligands - but that isn't necessarily so, as you will see later. Some ligands
can form more than one co-ordinate bond with the metal ion.
Fe(H2O)6 3+
This example is chosen because it is very similar to the last one - except
that it involves a transition metal.
Iron has the electronic structure
1s22s22p63s23p63d64s2
When it forms an Fe3+ ion it loses the 4s electrons and one of the 3d
electrons to leave
1s22s22p63s23p63d5
Looking at this as electrons-in-boxes, at the bonding level:
Now, be careful! The single electrons in the 3d level are NOT involved in
the bonding in any way. Instead, the ion uses 6 orbitals from the 4s, 4p
and 4d levels to accept lone pairs from the water molecules.
Before they are used, the orbitals are re-organised (hybridised) to
produce 6 orbitals of equal energy.
Once the co-ordinate bonds have been formed, the ion looks exactly the
same as the equivalent aluminium ion.
Because the iron is forming 6 bonds, the co-ordination number of the iron
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is 6.
Only one of the 4 lone pairs on each chloride ion is shown. The other
three are pointing away from the copper ion, and aren't involved in the
bonding.
That gives you the complex ion:
In the examples we've already looked at, each ligand only forms one
bond with the central metal ion to give the complex ion. Such a ligand is
said to be unidentate. That means literally that it only has one tooth!
It only has one pair of electrons that it can use to bond to the metal - any
other lone pairs are pointing in the wrong direction.
Some ligands, however, have rather more teeth! These are known
generally as multidentate or polydentate ligands, but can be broken down
into a number of different types.
Bidentate ligands
Bidentate ligands have two lone pairs, both of which can bond to the
central metal ion.
The two commonly used examples are 1,2-diaminoethane (old name:
ethylenediamine - often given the abbreviation "en"), and the
ethanedioate ion (old name: oxalate).
In the ethanedioate ion, there are lots more lone pairs than the two
shown, but these are the only ones we are interested in.
You can think of these bidentate ligands rather as if they were a pair of
headphones, carrying lone pairs on each of the "ear pieces". These will
then fit snuggly around a metal ion.
Ni (NH2CH2CH2NH2)3 2+
You might find this abbreviated to [Ni(en)3] 2+.
In this case, the "ear pieces" are the nitrogen atoms of the NH2 groups and the "bit that goes over your head " is the -CH2CH2- group. If you
were going to draw this in an exam, you would obviously want to draw it
properly - but for learning purposes, drawing all the atoms makes the
diagram look unduly complicated!
Notice that the arrangement of the bonds around the central metal ion is
exactly the same as it was with the ions with 6 water molecules attached.
The only difference is that this time each ligand uses up two of the
positions - at right angles to each other.
Because the nickel is forming 6 co-ordinate bonds, the co-ordination
number of this ion is 6, despite the fact that it is only joined to 3 ligands.
Co-ordination number counts the number of bonds, not the number of
ligands.
Cr (C2O4)3 3This is the complex ion formed by attaching 3 ethanedioate (oxalate) ions
to a chromium(III) ion. The shape is exactly the same as the previous
nickel complex. The only real difference is the number of charges. The
original chromium ion carried 3+ charges, and each ethanedioate ion
carried 2-. (3+) + (3 x 2-) = 3-.
The structure of the ion looks like this:
Again, if you drew this in an exam, you would want to show all the atoms
properly. If you need to be able to do this, practice drawing it so that it
looks clear and tidy! Refer back to the diagram of the ethanedioate ion
further up the page to help you.
A quadridentate ligand
A quadridentate ligand has four lone pairs, all of which can bond to the
central metal ion.
An example of this occurs in haemoglobin (American: hemoglobin).
The functional part of this is an iron(II) ion surrounded by a complicated
molecule called haem (heme). This is a sort of hollow ring of carbon and
hydrogen atoms, at the centre of which are 4 nitrogen atoms with lone
pairs on them.
Haem is one of a group of similar compounds called porphyrins. They
all have the same sort of ring system, but with different groups attached
to the outside of the ring. You aren't going to need to know the exact
structure of the haem at this level.
We could simplify the haem with the trapped iron ion as:
Each of the lone pairs on the nitrogen can form a co-ordinate bond with
the iron(II) ion - holding it at the centre of the complicated ring of atoms.
The iron forms 4 co-ordinate bonds with the haem, but still has space to
form two more - one above and one below the plane of the ring.
The protein globin attaches to one of these positions using a lone pair
on one of the nitrogens in one of its amino acids. The interesting bit is the
other position.
A hexadentate ligand
A hexadentate ligand has 6 lone pairs of electrons - all of which can form
co-ordinate bonds with the same metal ion. The best example is EDTA.
EDTA is used as a negative ion - EDTA4-. The diagram shows the
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structure of the ion with the important atoms and lone pairs picked out.
The EDTA ion entirely wraps up a metal ion using all 6 of the positions
that we have seen before. The co-ordination number is again 6 because
of the 6 co-ordinate bonds being formed by the central metal ion. The
diagram below shows this happening with a copper(II) ion.
Drawing the product of this clearly while showing all the atoms defeats
me completely! Here is a simplified version. Make sure that you can see
how this relates to the full structure above.
The overall charge, of course, comes from the 2+ on the original copper
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In the sodium hydroxide case, hydrogen ions from the acid are reacting
with hydroxide ions from the sodium hydroxide - in line with the Arrhenius
theory.
However, in the ammonia case, there don't appear to be any hydroxide
ions!
You can get around this by saying that the ammonia reacts with the
water it is dissolved in to produce ammonium ions and hydroxide ions:
In this case, there aren't any hydrogen ions or hydroxide ions in solution because there isn't any solution. The Arrhenius theory wouldn't count this
as an acid-base reaction, despite the fact that it is producing the same
product as when the two substances were in solution. That's silly!
Conjugate pairs
When hydrogen chloride dissolves in water, almost 100% of it reacts with
the water to produce hydroxonium ions and chloride ions. Hydrogen
chloride is a strong acid, and we tend to write this as a one-way reaction:
In fact, the reaction between HCl and water is reversible, but only to a
very minor extent. In order to generalise, consider an acid HA, and think
of the reaction as being reversible.
But there is also a back reaction between the hydroxonium ion and the Aion:
The reversible reaction contains two acids and two bases. We think of
them in pairs, called conjugate pairs.
When the acid, HA, loses a proton it forms a base, A-. When the base,
A-, accepts a proton back again, it obviously refoms the acid, HA. These
two are a conjugate pair.
Members of a conjugate pair differ from each other by the presence or
absence of the transferable hydrogen ion.
If you are thinking about HA as the acid, then A- is its conjugate base.
If you are thinking about A- as the base, then HA is its conjugate acid.
The water and the hydroxonium ion are also a conjugate pair. Thinking of
the water as a base, the hydroxonium ion is its conjugate acid because it
has the extra hydrogen ion which it can give away again.
Thinking about the hydroxonium ion as an acid, then water is its
conjugate base. The water can accept a hydrogen ion back again to
reform the hydroxonium ion.
A second example of conjugate pairs
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This is the reaction between ammonia and water that we looked at earlier:
The theory
The Bronsted-Lowry theory says that they are acting as bases because
they are combining with hydrogen ions. The reason they are combining
with hydrogen ions is that they have lone pairs of electrons - which is
what the Lewis theory says. The two are entirely consistent.
So how does this extend the concept of a base? At the moment it doesn't
- it just looks at it from a different angle.
But what about other similar reactions of ammonia or water, for
example? On the Lewis theory, any reaction in which the ammonia or
water used their lone pairs of electrons to form a co-ordinate bond would
be counted as them acting as a base.
Here is a reaction which you will find talked about on the page dealing
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with co-ordinate bonding. Ammonia reacts with BF3 by using its lone pair
to form a co-ordinate bond with the empty orbital on the boron.
Lewis acids
Lewis acids are electron pair acceptors. In the above example, the BF3 is
acting as the Lewis acid by accepting the nitrogen's lone pair. On the
Bronsted-Lowry theory, the BF3 has nothing remotely acidic about it.
This is an extension of the term acid well beyond any common use.
What about more obviously acid-base reactions - like, for example, the
reaction between ammonia and hydrogen chloride gas?
This page explains the terms strong and weak as applied to acids. As a
part of this it defines and explains what is meant by pH, Ka and pKa.
It is important that you don't confuse the words strong and weak with the
terms concentrated and dilute.
As you will see below, the strength of an acid is related to the proportion
of it which has reacted with water to produce ions. The concentration
tells you about how much of the original acid is dissolved in the solution.
It is perfectly possible to have a concentrated solution of a weak acid, or
a dilute solution of a strong acid. Read on . . .
Strong acids
Explaining the term "strong acid"
We are going to use the Bronsted-Lowry definition of an acid.
Note: If you don't know what the Bronsted-Lowry theory of
acids is, you should read about theories of acids and bases
on another page in this section. You don't need to spend time
reading about Lewis acids and bases for the purposes of this
present page.
Use the BACK button on your browser when you are ready to
return to this page.
These reactions are all reversible, but in some cases, the acid is so good
at giving away hydrogen ions that we can think of the reaction as being
one-way. The acid is virtually 100% ionised.
For example, when hydrogen chloride dissolves in water to make
hydrochloric acid, so little of the reverse reaction happens that we can
write:
At any one time, virtually 100% of the hydrogen chloride will have
reacted to produce hydroxonium ions and chloride ions. Hydrogen
chloride is described as a strong acid.
A strong acid is one which is virtually 100% ionised in solution.
Other common strong acids include sulphuric acid and nitric acid.
You may find the equation for the ionisation written in a simplified form:
This shows the hydrogen chloride dissolved in the water splitting to give
hydrogen ions in solution and chloride ions in solution.
This version is often used in this work just to make things look easier. If
you use it, remember that the water is actually involved, and that when
you write H+(aq) what you really mean is a hydroxonium ion, H3O+.
Weak acids
Explaining the term "weak acid"
A weak acid is one which doesn't ionise fully when it is dissolved in water.
Ethanoic acid is a typical weak acid. It reacts with water to produce
hydroxonium ions and ethanoate ions, but the back reaction is more
successful than the forward one. The ions react very easily to reform the
acid and the water.
At any one time, only about 1% of the ethanoic acid molecules have
converted into ions. The rest remain as simple ethanoic acid molecules.
Most organic acids are weak. Hydrogen fluoride (dissolving in water to
produce hydrofluoric acid) is a weak inorganic acid that you may come
across elsewhere.
However, if you think about this carefully, there is something odd about it.
At the bottom of the expression, you have a term for the concentration of
the water in the solution. That's not a problem - except that the number is
going to be very large compared with all the other numbers.
In 1 dm3 of solution, there are going to be about 55 moles of water.
If you had a weak acid with a concentration of about 1 mol dm-3, and
only about 1% of it reacted with the water, the number of moles of water
is only going to fall by about 0.01. In other words, if the acid is weak the
concentration of the water is virtually constant.
In that case, there isn't a lot of point in including it in the expression as if
it were a variable. Instead, a new equilibrium constant is defined which
leaves it out. This new equilibrium constant is called Ka.
You may find the Ka expression written differently if you work from the
simplified version of the equilibrium reaction:
Ka (mol dm-3)
hydrofluoric acid
5.6 x 10-4
methanoic acid
1.6 x 10-4
ethanoic acid
1.7 x 10-5
hydrogen sulphide
8.9 x 10-8
These are all weak acids because the values for Ka are very small. They
are listed in order of decreasing acid strength - the Ka values get smaller
An introduction to pKa
pKa bears exactly the same relationship to Ka as pH does to the
hydrogen ion concentration:
If you use your calculator on all the Ka values in the table above and
convert them into pKa values, you get:
Ka (mol dm-3)
pKa
hydrofluoric acid
5.6 x 10-4
3.3
methanoic acid
1.6 x 10-4
3.8
ethanoic acid
1.7 x 10-5
4.8
hydrogen sulphide
8.9 x 10-8
7.1
acid
Note: Notice that unlike Ka, pKa doesn't have any units.
Notice that the weaker the acid, the larger the value of pKa. It is now
easy to see the trend towards weaker acids as you go down the table.
Remember this:
The lower the value for pKa, the stronger the acid.
The higher the value for pKa, the weaker the acid.
Note: If you need to know about Ka and pKa, you are quite
likely to need to be able to do calculations with them. You will
probably need to be able to calculate the pH of a weak acid
from its concentration and Ka or pKa. You may need to
reverse this and calculate a value for pKa from pH and
concentration. I can't help you with these calculations on this
site, but they are all covered in detail in my chemistry
calculations book.
This page looks at the basic ideas underpinning the idea of a chemical
equilibrium. It talks about reversible reactions and how they behave if the
system is closed. This leads to the idea of a dynamic equilibrium, and
what the common term "position of equilibrium" means.
Reversible reactions
A reversible reaction is one which can be made to go in either direction
depending on the conditions.
If you pass steam over hot iron the steam reacts with the iron to produce
a black, magnetic oxide of iron called triiron tetroxide, Fe3O4.
Under different conditions, the products of this reaction will also react
together. Hydrogen passed over hot triiron tetroxide reduces it to iron.
Steam is also produced.
This time the steam produced in the reaction is swept away by the
stream of hydrogen.
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These reactions are reversible, but under the conditions normally used,
they become one-way reactions. The products aren't left in contact with
each other, so the reverse reaction can't happen.
Reversible reactions happening in a closed system
A closed system is one in which no substances are either added to the
system or lost from it. Energy can, however, be transferred in or out at
will.
In the example we've been looking at, you would have to imagine iron
being heated in steam in a closed container. Heat is being added to the
system, but none of the substances in the reaction can escape. The
system is closed.
As the triiron tetroxide and hydrogen start to be formed, they will also
react again to give the original iron and steam. So, if you analysed the
mixture after a while, what would you find?
You would find that you had established what is known as a dynamic
equilibrium. To explain what that means, we are going to use a much
simpler example . . .
Dynamic equilibria
Getting a visual feel for a dynamic equilibrium
Imagine a substance which can exist in two forms - a blue form or an
orange form - and that each form can react to give the other one. We are
going to let them react in a closed system. Neither form can escape.
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Assume that the blue form turns into the orange one much faster than
the other way round. In any given time, these are the chances of the two
changes happening:
You can simulate this very easily with some coloured paper cut up into
small pieces (a different colour on each side), and a dice.
The following are the real results of a "reaction" I did myself. I started
with 16 blue squares and looked at each one in turn and decided
whether it should change colour by throwing a dice.
A blue square was turned into an orange square (the bit of paper was
turned over!) if I threw a 4, 5 or 6
An orange square was turned into a blue square only if I threw a 6 while I
was looking at that particular square.
Once I had looked at all 16 squares, I started the process all over again but obviously with a different starting pattern. The diagrams show the
results of doing this 11 times (plus the original 16 blue squares).
You can see that the "reaction" is continuing all the time. The exact
pattern of orange and blue is constantly changing. However, the overall
numbers of orange and of blue squares remain remarkably constant most commonly, 12 orange ones to 4 blue ones.
It is important to realise that this doesn't just mean that the reaction is
reversible. It means that you have a reversible reaction in a state of
dynamic equilibrium.
The "forward reaction" and the "back reaction"
The change from left to right in the equation (in this case from blue to
orange as it is written) is known as the forward reaction. The change
from right to left is the back reaction.
Position of equilibrium
In the example we've used, the equilibrium mixture contained more
orange squares than blue ones. Position of equilibrium is a way of
expressing this. You can say things like:
Once again, you can see that exactly the same position of equilibrium is
being established as when we started with the blue squares. You get
exactly the same equilibrium mixture irrespective of which side of the
equation you start from - provided the conditions are the same in both
cases.
How did it get to that state? Let's assume that we started with A and B.
At the beginning of the reaction, the concentrations of A and B were at
their maximum. That means that the rate of the reaction was at its fastest.
As A and B react, their concentrations fall. That means that they are less
likely to collide and react, and so the rate of the forward reaction falls as
time goes on.
In the beginning, there isn't any C and D, so there can't be any reaction
between them. As time goes on, though, their concentrations in the
mixture increase and they are more likely to collide and react.
With time, the rate of the reaction between C and D increases:
Eventually, the rates of the two reactions will become equal. A and B will
be converting into C and D at exactly the same rate as C and D convert
back into A and B again.
A summary
A dynamic equilibrium occurs when you have a reversible reaction in a
closed system. Nothing can be added to the system or taken away from
it apart from energy.
At equilibrium, the quantities of everything present in the mixture remain
constant, although the reactions are still continuing. This is because the
rates of the forward and the back reactions are equal.
If you change the conditions in a way which changes the relative rates of
the forward and back reactions you will change the position of equilibrium
- in other words, change the proportions of the various substances
present in the equilibrium mixture. This is explored in detail on other
pages in this equilibrium section.
Understanding Chemistry
Mathematical bits
Kc . . .
Explains equilibrium constants expressed in terms of
concentrations.
Kp . . .
Explains equilibrium constants expressed in terms of partial
pressures. Includes an explanation of the terms partial pressure
and mole fraction. Before you read this page, you should have a
reasonable understanding of Kc.
The effect of changing conditions . . .
Looks at the way that equilibrium constants are changed (or not!)
as you change the conditions for a reaction (concentration,
temperature, pressure or catalyst), and how this ties in with Le
Chatelier's Principle. This page assumes that you are fully
confident about writing expressions for both kinds of equilibrium
constants.
Le Chatelier's Principle
LE CHATELIER'S PRINCIPLE
Le Chatelier's Principle
Le Chatelier's Principle
Important
This isn't in any way an explanation of why the position of equilibrium
moves in the ways described. All Le Chatelier's Principle gives you is a
quick way of working out what happens.
Le Chatelier's Principle
In this case, there are 3 molecules on the left-hand side of the equation,
but only 2 on the right. By forming more C and D, the system causes the
pressure to reduce.
Increasing the pressure on a gas reaction shifts the position of
equilibrium towards the side with fewer molecules.
Important
Again, this isn't an explanation of why the position of equilibrium moves
in the ways described. You will find a rather mathematical treatment of
Le Chatelier's Principle
This shows that 250 kJ is evolved (hence the negative sign) when 1 mole
of A reacts completely with 2 moles of B. For reversible reactions, the
value is always given as if the reaction was one-way in the forward
direction.
The back reaction (the conversion of C and D into A and B) would be
endothermic by exactly the same amount.
Le Chatelier's Principle
Le Chatelier's Principle
Summary
Important
Again, this isn't in any way an explanation of why the position of
equilibrium moves in the ways described. It is only a way of helping you
to work out what happens.
Le Chatelier's Principle
Le Chatelier's Principle
Changing concentrations
The facts
Equilibrium constants aren't changed if you change the concentrations
of things present in the equilibrium. The only thing that changes an
equilibrium constant is a change of temperature.
The position of equilibrium is changed if you change the concentration
of something present in the mixture. According to Le Chatelier's
Principle, the position of equilibrium moves in such a way as to tend to
undo the change that you have made.
Suppose you have an equilibrium established between four substances
A, B, C and D.
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If you have moved the position of the equilibrium to the right (and so
increased the amount of C and D), why hasn't the equilibrium constant
increased?
This is actually the wrong question to ask! We need to look at it the other
way round.
Let's assume that the equilibrium constant mustn't change if you
decrease the concentration of C - because equilibrium constants are
constant at constant temperature. Why does the position of equilibrium
move as it does?
If you decrease the concentration of C, the top of the Kc expression gets
smaller. That would change the value of Kc. In order for that not to
happen, the concentrations of C and D will have to increase again, and
those of A and B must decrease. That happens until a new balance is
reached when the value of the equilibrium constant expression reverts to
what it was before.
Changing pressure
This only applies to systems involving at least one gas.
The facts
Equilibrium constants aren't changed if you change the pressure of the
system. The only thing that changes an equilibrium constant is a change
of temperature.
The position of equilibrium may be changed if you change the
pressure. According to Le Chatelier's Principle, the position of equilibrium
moves in such a way as to tend to undo the change that you have made.
That means that if you increase the pressure, the position of equilibrium
will move in such a way as to decrease the pressure again - if that is
possible. It can do this by favouring the reaction which produces the
fewer molecules. If there are the same number of molecules on each
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Note: If you aren't happy with this, read the beginning of the
page about Kp before you go on.
Use the BACK button on your browser to return to this page.
Replacing all the partial pressure terms by mole fractions and total
pressure gives you this:
If you sort this out, most of the "P"s cancel out - but one is left at the
bottom of the expression.
There isn't a single "P" left in the expression. Changing the pressure
can't make any difference to the Kp expression. The position of
equilibrium doesn't need to move to keep Kp constant.
Changing temperature
The facts
Equilibrium constants are changed if you change the temperature of
the system. Kc or Kp are constant at constant temperature, but they vary
as the temperature changes.
Look at the equilibrium involving hydrogen, iodine and hydrogen iodide:
temperature
Kp
500 K
160
700 K
54
You can see that as the temperature increases, the value of Kp falls.
This is typical of what happens with any equilibrium where the forward
reaction is exothermic. Increasing the temperature decreases the value
of the equilibrium constant.
Where the forward reaction is endothermic, increasing the temperature
increases the value of the equilibrium constant.
Adding a catalyst
The facts
Equilibrium constants aren't changed if you add (or change) a catalyst.
The only thing that changes an equilibrium constant is a change of
temperature.
The position of equilibrium is not changed if you add (or change) a
catalyst.
Explanation
A catalyst speeds up both the forward and back reactions by exactly the
same amount. Dynamic equilibrium is established when the rates of the
forward and back reactions become equal. If a catalyst speeds up both
reactions to the same extent, then they will remain equal without any
need for a shift in position of equilibrium.
equilibrium constants - Kp
EQUILIBRIUM CONSTANTS: Kp
equilibrium constants - Kp
Partial pressure
The partial pressure of one of the gases in a mixture is the pressure
which it would exert if it alone occupied the whole container.
The partial pressure of gas A is often given the symbol PA. The partial
pressure of gas B would be PB - and so on.
There are two important relationships involving partial pressures. The
first is again fairly obvious.
The total pressure of a mixture of gases is equal to the sum of the partial
pressures.
Gas A is creating a pressure (its partial pressure) when its molecules hit
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equilibrium constants - Kp
the walls of its container. Gas B does the same. When you mix them up,
they just go on doing what they were doing before. The total pressure is
due to both molecules hitting the walls - in other words, the sum of the
partial pressures.
The more important relationship is the second one:
Learn it!
That means that if you had a mixture made up of 20 moles of nitrogen,
60 moles of hydrogen and 20 moles of ammonia (a total of 100 moles of
gases) at 200 atmospheres pressure, the partial pressures would be
calculated like this:
gas
mole fraction
partial pressure
nitrogen
20/100 = 0.2
hydrogen
60/100 = 0.6
ammonia
20/100 = 0.2
equilibrium constants - Kp
If you allow this reaction to reach equilibrium and then measure (or work
out) the equilibrium partial pressures of everything, you can combine
these into the equilibrium constant, Kp.
Just like Kc, Kp always has the same value (provided you don't change
the temperature), irrespective of the amounts of A, B, C and D you
started with.
Kp has exactly the same format as Kc, except that partial pressures are
used instead of concentrations. The gases on the right-hand side of the
chemical equation are at the top of the expression, and those on the left
at the bottom.
equilibrium constants - Kp
Kp is given by:
Kc in heterogeneous equilibria
A typical example of a heterogeneous equilibrium will involve gases in
contact with solids.
Writing an expression for Kp for a heterogeneous equilibrium
Exactly as happens with Kc, you don't include any term for a solid in the
equilibrium expression.
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equilibrium constants - Kp
Everything is exactly the same as before in the expression for Kp, except
that you leave out the solid carbon.
The only thing in this equilibrium which isn't a solid is the carbon dioxide.
That is all that is left in the equilibrium constant expression.
Calculations involving Kp
On the Kc page, I've already discussed the fact that the internet isn't a
good medium for learning how to do calculations.
If you want lots of worked examples and problems to do yourself centred
around Kp, you might be interested in my book on chemistry calculations.
equilibrium constants - Kp
equilibrium constants - Kc
EQUILIBRIUM CONSTANTS: Kc
Kc in homogeneous equilibria
This is the more straightforward case. It applies where everything in the
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equilibrium constants - Kc
No state symbols have been given, but they will be all (g), or all (l), or all
(aq) if the reaction was between substances in solution in water.
If you allow this reaction to reach equilibrium and then measure the
equilibrium concentrations of everything, you can combine these
concentrations into an expression known as an equilibrium constant.
The equilibrium constant always has the same value (provided you don't
change the temperature), irrespective of the amounts of A, B, C and D
you started with. It is also unaffected by a change in pressure or whether
or not you are using a catalyst.
equilibrium constants - Kc
Compare this with the chemical equation for the equilibrium. The
convention is that the substances on the right-hand side of the equation
are written at the top of the Kc expression, and those on the left-hand
side at the bottom.
The indices (the powers that you have to raise the concentrations to - for
example, squared or cubed or whatever) are just the numbers that
appear in the equation.
equilibrium constants - Kc
equilibrium constants - Kc
If you compare this with the previous example, you will see that all that
has happened is that the expression has turned upside-down. Its value at
room temperature will be approximately 1/4 (0.25).
It is really important to write down the equilibrium reaction whenever you
talk about an equilibrium constant. That is the only way that you can be
sure that you have got the expression the right way up - with the righthand substances on the top and the left-hand ones at the bottom.
The Contact Process equilibrium
You will remember that the equation for this is:
equilibrium constants - Kc
Kc in heterogeneous equilibria
Typical examples of a heterogeneous equilibrium include:
The equilibrium established if steam is in contact with red hot carbon.
Here we have gases in contact with a solid.
If you shake copper with silver nitrate solution, you get this equilibrium
involving solids and aqueous ions:
equilibrium constants - Kc
Both the copper on the left-hand side and the silver on the right are
solids. Both are left out of the equilibrium constant expression.
The only thing in this equilibrium which isn't a solid is the carbon dioxide.
That is all that is left in the equilibrium constant expression.
Calculations involving Kc
There are all sorts of calculations you might be expected to do which are
centred around equilibrium constants. You might be expected to
calculate a value for Kc including its units (which vary from case to case).
Alternatively you might have to calculate equilibrium concentrations from
a given value of Kc and given starting concentrations.
This is simply too huge a topic to be able to deal with satisfactorily on the
internet. It isn't the best medium for learning how to do chemistry
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equilibrium constants - Kc
types of catalysis
TYPES OF CATALYSIS
This page looks at the the different types of catalyst (heterogeneous and
homogeneous) with examples of each kind, and explanations of how
they work. You will also find a description of one example of
autocatalysis - a reaction which is catalysed by one of its products.
types of catalysis
You might wonder why phase differs from the term physical state (solid,
liquid or gas). It includes solids, liquids and gases, but is actually a bit
more general. It can also apply to two liquids (oil and water, for example)
which don't dissolve in each other. You could see the boundary between
the two liquids.
If you want to be fussy about things, the diagrams actually show more
phases than are labelled. Each, for example, also has the glass beaker
as a solid phase. All probably have a gas above the liquid - that's another
phase. We don't count these extra phases because they aren't a part of
the reaction.
Heterogeneous catalysis
This involves the use of a catalyst in a different phase from the reactants.
types of catalysis
types of catalysis
types of catalysis
bond between the carbon atoms breaks and the electrons are used to
bond it to the nickel surface.
If a hydrogen atom diffuses close to one of the bonded carbons, the bond
between the carbon and the nickel is replaced by one between the
carbon and hydrogen.
That end of the original ethene now breaks free of the surface, and
eventually the same thing will happen at the other end.
types of catalysis
As before, one of the hydrogen atoms forms a bond with the carbon, and
that end also breaks free. There is now space on the surface of the
nickel for new reactant molecules to go through the whole process again.
types of catalysis
Catalytic converters
Catalytic converters change poisonous molecules like carbon monoxide
and various nitrogen oxides in car exhausts into more harmless
molecules like carbon dioxide and nitrogen. They use expensive metals
like platinum, palladium and rhodium as the heterogeneous catalyst.
The metals are deposited as thin layers onto a ceramic honeycomb. This
maximises the surface area and keeps the amount of metal used to a
minimum.
Taking the reaction between carbon monoxide and nitrogen monoxide as
typical:
In the same sort of way as the previous example, the carbon monoxide
and nitrogen monoxide will be adsorbed on the surface of the catalyst,
where they react. The carbon dioxide and nitrogen are then desorbed.
types of catalysis
This example is slightly different from the previous ones because the
gases actually react with the surface of the catalyst, temporarily changing
it. It is a good example of the ability of transition metals and their
compounds to act as catalysts because of their ability to change their
oxidation state.
This is a good example of the way that a catalyst can be changed during
the course of a reaction. At the end of the reaction, though, it will be
chemically the same as it started.
types of catalysis
Homogeneous catalysis
This has the catalyst in the same phase as the reactants. Typically
everything will be present as a gas or contained in a single liquid phase.
The examples contain one of each of these . . .
Examples of homogeneous catalysis
The reaction between persulphate ions and iodide ions
This is a solution reaction that you may well only meet in the context of
catalysis, but it is a lovely example!
Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful
oxidising agents. Iodide ions are very easily oxidised to iodine. And yet
the reaction between them in solution in water is very slow.
If you look at the equation, it is easy to see why that is:
types of catalysis
The iron(III) ions are strong enough oxidising agents to oxidise iodide
ions to iodine. In the process, they are reduced back to iron(II) ions again.
The oxygen radicals can then combine with ordinary oxygen molecules
to make ozone.
Ozone can also be split up again into ordinary oxygen and an oxygen
radical by absorbing ultraviolet light.
types of catalysis
This formation and breaking up of ozone is going on all the time. Taken
together, these reactions stop a lot of harmful ultraviolet radiation
penetrating the atmosphere to reach the surface of the Earth.
The catalytic reaction we are interested in destroys the ozone and so
stops it absorbing UV in this way.
Chlorofluorocarbons (CFCs) like CF2Cl2, for example, were used
extensively in aerosols and as refrigerants. Their slow breakdown in the
atmosphere produces chlorine atoms - chlorine free radicals. These
catalyse the destruction of the ozone.
This happens in two stages. In the first, the ozone is broken up and a
new free radical is produced.
Because the chlorine radical keeps on being regenerated, each one can
destroy thousands of ozone molecules.
Autocatalysis
The oxidation of ethanedioic acid by manganate(VII) ions
In autocatalysis, the reaction is catalysed by one of its products. One of
the simplest examples of this is in the oxidation of a solution of
ethanedioic acid (oxalic acid) by an acidified solution of potassium
manganate(VII) (potassium permanganate).
types of catalysis
Concentrations are high at the beginning and so the reaction is fast shown by a rapid fall in the reactant concentration. As things get used
up, the reaction slows down and eventually stops as one or more of the
reactants are completely used up.
An example of autocatalysis gives a curve like this:
types of catalysis
You can see the slow (uncatalysed) reaction at the beginning. As catalyst
begins to be formed in the mixture, the reaction speeds up - getting
faster and faster as more and more catalyst is formed. Eventually, of
course, the rate falls again as things get used up.
Warning!
Don't assume that a rate curve which looks like this necessarily shows an
example of autocatalysis. There are other effects which might produce a
similar graph.
For example, if the reaction involved a solid reacting with a liquid, there
might be some sort of surface coating on the solid which the liquid has to
penetrate before the expected reaction can happen.
A more common possibility is that you have a strongly exothermic
reaction and aren't controlling the temperature properly. The heat
evolved during the reaction speeds the reaction up.
types of catalysis
To Main Menu . . .
This page describes and explains the way that adding a catalyst affects
the rate of a reaction. It assumes that you are already familiar with basic
ideas about the collision theory of reaction rates, and with the MaxwellBoltzmann distribution of molecular energies in a gas.
The facts
What are catalysts?
A catalyst is a substance which speeds up a reaction, but is chemically
unchanged at the end of the reaction. When the reaction has finished,
you would have exactly the same mass of catalyst as you had at the
beginning.
Some examples
Some common examples which you may need for other parts of your
syllabus include:
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reaction
catalyst
Nitration of benzene
iron
nickel
The explanation
The key importance of activation energy
Collisions only result in a reaction if the particles collide with enough
energy to get the reaction started. This minimum energy required is
called the activation energy for the reaction.
Only those particles represented by the area to the right of the activation
energy will react when they collide. The great majority don't have enough
energy, and will simply bounce apart.
Catalysts and activation energy
To increase the rate of a reaction you need to increase the number of
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A word of caution!
Be very careful if you are asked about this in an exam. The correct form
of words is
"A catalyst provides an alternative route for the reaction with a
lower activation energy."
It does not "lower the activation energy of the reaction". There is a subtle
difference between the two statements that is easily illustrated with a
simple analogy.
Suppose you have a mountain between two valleys so that the only way
for people to get from one valley to the other is over the mountain. Only
the most active people will manage to get from one valley to the other.
Now suppose a tunnel is cut through the mountain. Many more people
will now manage to get from one valley to the other by this easier route.
You could say that the tunnel route has a lower activation energy than
going over the mountain.
But you haven't lowered the mountain! The tunnel has provided an
alternative route but hasn't lowered the original one. The original
mountain is still there, and some people will still choose to climb it.
In the chemistry case, if particles collide with enough energy they can still
react in exactly the same way as if the catalyst wasn't there. It is simply
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that the majority of particles will react via the easier catalysed route.
Reactions where a single species falls apart in some way are slightly
simpler because you won't be involved in worrying about the orientation
of collisions. Reactions involving collisions between more than two
species are going to be extremely uncommon (see below).
As a result of the collision between the two molecules, the double bond
between the two carbons is converted into a single bond. A hydrogen
atom gets attached to one of the carbons and a chlorine atom to the
other.
The reaction can only happen if the hydrogen end of the H-Cl bond
approaches the carbon-carbon double bond. Any other collision between
the two molecules doesn't work. The two simply bounce off each other.
Of the collisions shown in the diagram, only collision 1 may possibly lead
on to a reaction.
If you haven't read the page about the mechanism of the reaction, you
may wonder why collision 2 won't work as well. The double bond has a
high concentration of negative charge around it due to the electrons in
the bonds. The approaching chlorine atom is also slightly negative
because it is more electronegative than hydrogen. The repulsion simply
causes the molecules to bounce off each other.
If the particles collide with less energy than the activation energy, nothing
important happens. They bounce apart. You can think of the activation
energy as a barrier to the reaction. Only those collisions which have
energies equal to or greater than the activation energy result in a
reaction.
Any chemical reaction results in the breaking of some bonds (needing
energy) and the making of new ones (releasing energy). Obviously some
bonds have to be broken before new ones can be made. Activation
energy is involved in breaking some of the original bonds.
Where collisions are relatively gentle, there isn't enough energy available
to start the bond-breaking process, and so the particles don't react.
The area under the curve is a measure of the total number of particles
present.
Note: The reason for this lies in some maths beyond the
scope of an A'level chemistry course. It is important that you
remember that the area under the curve gives a count of the
number of particles even if you don't understand why!
Notice that the large majority of the particles don't have enough energy to
react when they collide. To enable them to react we either have to
change the shape of the curve, or move the activation energy further to
the left. This is described on other pages.
This page describes and explains the way that changing the temperature
affects the rate of a reaction. It assumes that you are already familiar
with basic ideas about the collision theory, and with the MaxwellBoltzmann distribution of molecular energies in a gas.
The facts
What happens?
As you increase the temperature the rate of reaction increases. As a
rough approximation, for many reactions happening at around room
temperature, the rate of reaction doubles for every 10C rise in
temperature.
You have to be careful not to take this too literally. It doesn't apply to all
reactions. Even where it is approximately true, it may be that the rate
doubles every 9C or 11C or whatever. The number of degrees needed
to double the rate will also change gradually as the temperature
increases.
Examples
Some reactions are virtually instantaneous - for example, a precipitation
reaction involving the coming together of ions in solution to make an
insoluble solid, or the reaction between hydrogen ions from an acid and
hydroxide ions from an alkali in solution. So heating one of these won't
make any noticeable difference to the rate of the reaction.
Almost any other reaction you care to name will happen faster if you heat
it - either in the lab, or in industry.
The explanation
Increasing the collision frequency
Particles can only react when they collide. If you heat a substance, the
particles move faster and so collide more frequently. That will speed up
the rate of reaction.
That seems a fairly straightforward explanation until you look at the
numbers!
It turns out that the frequency of two-particle collisions in gases is
proportional to the square root of the kelvin temperature. If you increase
the temperature from 293 K to 303 K (20C to 30C), you will increase
the collision frequency by a factor of:
Only those particles represented by the area to the right of the activation
energy will react when they collide. The great majority don't have enough
energy, and will simply bounce apart.
To speed up the reaction, you need to increase the number of the very
energetic particles - those with energies equal to or greater than the
activation energy. Increasing the temperature has exactly that effect - it
changes the shape of the graph.
In the next diagram, the graph labelled T is at the original temperature.
The graph labelled T+t is at a higher temperature.
If you now mark the position of the activation energy, you can see that
although the curve hasn't moved very much overall, there has been such
a large increase in the number of the very energetic particles that many
more now collide with enough energy to react.
Remember that the area under a curve gives a count of the number of
particles. On the last diagram, the area under the higher temperature
curve to the right of the activation energy looks to have at least doubled therefore at least doubling the rate of the reaction.
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Summary
Increasing the temperature increases reaction rates because of the
disproportionately large increase in the number of high energy collisions.
It is only these collisions (possessing at least the activation energy for
the reaction) which result in a reaction.
This page looks at the way that rate constants vary with temperature and
activation energy as shown by the Arrhenius equation.
Note: If you aren't sure what a rate constant is, you should
read the page about orders of reaction before you go on. This
present page is at the hard end of the rates of reaction work
on this site. If you aren't reasonably confident about the basic
rates of reaction work, explore the rates of reaction menu first.
Note: If you don't remember this, you must read the page
about orders of reaction before you go on. Use the BACK
button on your browser to return to this page.
The rate equation shows the effect of changing the concentrations of the
reactants on the rate of the reaction. What about all the other things (like
temperature and catalysts, for example) which also change rates of
reaction? Where do these fit into this equation?
These are all included in the so-called rate constant - which is only
actually constant if all you are changing is the concentration of the
reactants. If you change the temperature or the catalyst, for example, the
rate constant changes.
This is shown mathematically in the Arrhenius equation.
The Arrhenius equation
steric factor.
A is a term which includes factors like the frequency of collisions
and their orientation. It varies slightly with temperature, although
not much. It is often taken as constant across small temperature
ranges.
By this time you've probably forgotten what the original Arrhenius
equation looked like! Here it is again:
"ln" is a form of logarithm. Don't worry about what it means. If you need
to use this equation, just find the "ln" button on your calculator.
By raising the temperature just a little bit (to 303 K), this increases:
You can see that the fraction of the molecules able to react has almost
doubled by increasing the temperature by 10C. That causes the rate of
reaction to almost double. This is the value in the rule-of-thumb often
used in simple rate of reaction work.
If you compare that with the corresponding value where the activation
energy was 50 kJ mol-1, you will see that there has been a massive
increase in the fraction of the molecules which are able to react. There
are almost 30000 times more molecules which can react in the presence
of the catalyst compared to having no catalyst (using our assumptions
about the activation energies).
It's no wonder catalysts speed up reactions!
Rate equations
Measuring a rate of reaction
There are several simple ways of measuring a reaction rate. For
example, if a gas was being given off during a reaction, you could take
some measurements and work out the volume being given off per
second at any particular time during the reaction.
A rate of 2 cm3 s-1 is obviously twice as fast as one of 1 cm3 s-1.
However, for this more formal and mathematical look at rates of reaction,
the rate is usually measured by looking at how fast the concentration of
one of the reactants is falling at any one time.
For example, suppose you had a reaction between two substances A
and B. Assume that at least one of them is in a form where it is sensible
to measure its concentration - for example, in solution or as a gas.
For this reaction you could measure the rate of the reaction by finding out
how fast the concentration of, say, A was falling per second.
You might, for example, find that at the beginning of the reaction, its
concentration was falling at a rate of 0.0040 mol dm-3 s-1.
Note: Read mol dm-3 s-1 as "moles per cubic decimetre (or
litre) per second".
Orders of reaction
I'm not going to define what order of reaction means straight away - I'm
going to sneak up on it!
Orders of reaction are always found by doing experiments. You can't
deduce anything about the order of a reaction just by looking at the
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Generalising this
By doing experiments involving a reaction between A and B, you would
find that the rate of the reaction was related to the concentrations of A
and B in this way:
In this case, the order of reaction with respect to both A and B is 1. The
overall order of reaction is 2 - found by adding up the individual orders.
Example 2:
This reaction is first order with respect to A and zero order with respect
to B, because the concentration of B doesn't affect the rate of the
Many text books make these sums look really difficult. In fact for A' level
purposes, the calculations are usually fairly trivial. You will find them
explained in detail in my chemistry calculations book.
Note: There are several reasons why there are very few
calculations on this site. It is much easier to learn to do sums
from a carefully organised book than from a website; I would
be in breach of my contract with my publishers if I included
material similar to what is in the book; and I need to sell a few
books to generate some income!
If you are interested in my chemistry calculations book you
might like to follow this link.
This page describes and explains the way that changing the
concentration of a solution affects the rate of a reaction. Be aware that
this is an introductory page only. If you are interested in orders of
reaction, you will find separate pages dealing with these. You can access
these via the rates of reaction menu (link at the bottom of the page).
The facts
What happens?
For many reactions involving liquids or gases, increasing the
concentration of the reactants increases the rate of reaction. In a few
cases, increasing the concentration of one of the reactants may have little
noticeable effect of the rate. These cases are discussed and explained
further down this page.
Don't assume that if you double the concentration of one of the reactants
that you will double the rate of the reaction. It may happen like that, but
the relationship may well be more complicated.
Some examples
The examples on this page all involve solutions. Changing the
concentration of a gas is achieved by changing its pressure. This is
covered on a separate page.
The explanation
Cases where changing the concentration affects the rate of the
reaction
This is the common case, and is easily explained.
Collisions involving two particles
The same argument applies whether the reaction involves collision
between two different particles or two of the same particle.
In order for any reaction to happen, those particles must first collide. This
is true whether both particles are in solution, or whether one is in solution
and the other a solid. If the concentration is higher, the chances of
collision are greater.
Note: If you aren't sure about this, then read the page about
collision theory and activation energy before you go on. Use
the BACK button on your browser to return to this page.
Suppose that at any one time 1 in a million particles have enough energy
to equal or exceed the activation energy. If you had 100 million particles,
100 of them would react. If you had 200 million particles in the same
volume, 200 of them would now react. The rate of reaction has doubled
by doubling the concentration.
The best specific examples of reactions of this type comes from organic
chemistry. These involve the reaction between a tertiary halogenoalkane
(alkyl halide) and a number of possible substances - including hydroxide
ions. These are examples of nucleophilic substitution using a mechanism
known as SN1.
This page describes and explains the way that changing the pressure of
a gas changes the rate of a reaction.
The facts
What happens?
Increasing the pressure on a reaction involving reacting gases increases
the rate of reaction. Changing the pressure on a reaction which involves
only solids or liquids has no effect on the rate.
An example
In the manufacture of ammonia by the Haber Process, the rate of
reaction between the hydrogen and the nitrogen is increased by the use
of very high pressures.
In fact, the main reason for using high pressures is to improve the
percentage of ammonia in the equilibrium mixture, but there is a useful
effect on rate of reaction as well.
Note: If you want to explore equilibria you will find the topic
covered in a separate section of the site.
The explanation
The relationship between pressure and concentration
Increasing the pressure of a gas is exactly the same as increasing its
concentration. If you have a given mass of gas, the way you increase its
pressure is to squeeze it into a smaller volume. If you have the same
mass in a smaller volume, then its concentration is higher.
You can also show this relationship mathematically if you have come
across the ideal gas equation:
Note: If you aren't sure about this, then read the page about
collision theory and activation energy before you go on. Use
the BACK button on your browser to return to this page.
Suppose that at any one time 1 in a million particles have enough energy
to equal or exceed the activation energy. If you had 100 million particles,
100 of them would react. If you had 200 million particles in the same
volume, 200 of them would now react. The rate of reaction has doubled
by doubling the pressure.
Understanding Chemistry
Rates of Reaction
Basic ideas about rates of reaction . . .
Covers collision theory, and describes and explains the effects of
surface area, concentration, pressure, temperature and catalysts
on reaction rates. Also takes an introductory look at the rate
equation for a reaction - particularly order of reaction and the rate
constant.
Catalysis . . .
A detailed look at various types of catalytic action with a wide
range of examples taken from A level syllabuses.
Equilibria
Chemical equilibria . . .
An introduction to the ideas surrounding chemical equilibria
including the concept of a dynamic equilibrium, Le Chatelier's
Principle, and a detailed look at the equilibrium aspects of the
Haber Process, the Contact Process and the manufacture of
ethanol from ethene. Plus an introductory look at equilibrium
constants, Kc and Kp.
Redox equilibria . . .
Go to Main Menu . . .
Understanding Chemistry
This page describes and explains the effect of changing the surface area
of a solid on the rate of a reaction it is involved in. This applies to
reactions involving a solid and a gas, or a solid and a liquid. It includes
cases where the solid is acting as a catalyst.
The facts
What happens?
The more finely divided the solid is, the faster the reaction happens. A
powdered solid will normally produce a faster reaction than if the same
mass is present as a single lump. The powdered solid has a greater
surface area than the single lump.
Some examples
Calcium carbonate and hydrochloric acid
In the lab, powdered calcium carbonate reacts much faster with dilute
hydrochloric acid than if the same mass was present as lumps of marble
or limestone.
Catalytic converters
Catalytic converters use metals like platinum, palladium and rhodium to
convert poisonous compounds in vehicle exhausts into less harmful
things. For example, a reaction which removes both carbon monoxide
and an oxide of nitrogen is:
Because the exhaust gases are only in contact with the catalyst for a
very short time, the reactions have to be very fast. The extremely
expensive metals used as the catalyst are coated as a very thin layer
onto a ceramic honeycomb structure to maximise the surface area.
The explanation
You are only going to get a reaction if the particles in the gas or liquid
collide with the particles in the solid. Increasing the surface area of the
solid increases the chances of collision taking place.
Catalysis menu
Understanding Chemistry
CATALYSIS MENU
Catalysis menu
This page takes a brief look at the catalysts used in the Contact Process
to manufacture sulphuric acid, in the Haber Process to manufacture
ammonia, and in the conversion of ammonia into nitric acid.
If you want full details of the Contact Process or the Haber Process, you
will find links below. Full details of the manufacture of nitric acid are given
on this page because they don't appear elsewhere on this site.
A flow scheme for this part of the process looks like this:
The reasons for all these conditions will be explored in detail further
down the page.
Converting the sulphur trioxide into sulphuric acid
This can't be done by simply adding water to the sulphur trioxide - the
reaction is so uncontrollable that it creates a fog of sulphuric acid.
Instead, the sulphur trioxide is first dissolved in concentrated sulphuric
acid:
sulphuric acid - twice as much as you originally used to make the fuming
sulphuric acid.
amount of sulphur trioxide made each day. The 1 : 1 mixture turns out to
give you the best possible overall yield of sulphur trioxide.
The temperature
Equilibrium considerations
You need to shift the position of the equilibrium as far as possible to the
right in order to produce the maximum possible amount of sulphur
trioxide in the equilibrium mixture.
The forward reaction (the production of sulphur trioxide) is exothermic.
The pressure
Equilibrium considerations
Notice that there are 3 molecules on the left-hand side of the equation,
but only 2 on the right.
According to Le Chatelier's Principle, if you increase the pressure the
system will respond by favouring the reaction which produces fewer
molecules. That will cause the pressure to fall again.
In order to get as much sulphur trioxide as possible in the equilibrium
mixture, you need as high a pressure as possible. High pressures also
increase the rate of the reaction. However, the reaction is done at
pressures close to atmospheric pressure!
Economic considerations
Even at these relatively low pressures, there is a 99.5% conversion of
sulphur dioxide into sulphur trioxide. The very small improvement that
you could achieve by increasing the pressure isn't worth the expense of
producing those high pressures.
The catalyst
Equilibrium considerations
The catalyst has no effect whatsoever on the position of the equilibrium.
Adding a catalyst doesn't produce any greater percentage of sulphur
trioxide in the equilibrium mixture. Its only function is to speed up the
reaction.
Rate considerations
In the absence of a catalyst the reaction is so slow that virtually no
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reaction happens in any sensible time. The catalyst ensures that the
reaction is fast enough for a dynamic equilibrium to be set up within the
very short time that the gases are actually in the reactor.
This page describes the Haber Process for the manufacture of ammonia
from nitrogen and hydrogen, and then goes on to explain the reasons for
the conditions used in the process. It looks at the effect of temperature,
pressure and catalyst on the composition of the equilibrium mixture, the
rate of the reaction and the economics of the process.
The temperature
Equilibrium considerations
You need to shift the position of the equilibrium as far as possible to the
right in order to produce the maximum possible amount of ammonia in
the equilibrium mixture.
The forward reaction (the production of ammonia) is exothermic.
The pressure
Equilibrium considerations
Notice that there are 4 molecules on the left-hand side of the equation,
but only 2 on the right.
According to Le Chatelier's Principle, if you increase the pressure the
system will respond by favouring the reaction which produces fewer
molecules. That will cause the pressure to fall again.
In order to get as much ammonia as possible in the equilibrium mixture,
you need as high a pressure as possible. 200 atmospheres is a high
pressure, but not amazingly high.
Rate considerations
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The catalyst
Equilibrium considerations
The catalyst has no effect whatsoever on the position of the equilibrium.
Adding a catalyst doesn't produce any greater percentage of ammonia in
the equilibrium mixture. Its only function is to speed up the reaction.
Rate considerations
In the absence of a catalyst the reaction is so slow that virtually no
reaction happens in any sensible time. The catalyst ensures that the
reaction is fast enough for a dynamic equilibrium to be set up within the
very short time that the gases are actually in the reactor.
Catalytic cracking
Cracking is the name given to breaking up large hydrocarbon molecules
into smaller and more useful bits. This is achieved by using high
pressures and temperatures without a catalyst, or lower temperatures and
pressures in the presence of a catalyst.
The source of the large hydrocarbon molecules is often the naphtha
fraction or the gas oil fraction from the fractional distillation of crude oil
(petroleum). These fractions are obtained from the distillation process as
liquids, but are re-vaporised before cracking.
The hydrocarbons are mixed with a very fine catalyst powder. These days
the catalysts are zeolites (complex aluminosilicates) - these are more
efficient than the older mixtures of aluminium oxide and silicon dioxide.
The whole mixture is blown rather like a liquid through a reaction chamber
at a temperature of about 500C. Because the mixture behaves like a
liquid, this is known as fluid catalytic cracking (or fluidised catalytic
cracking).
Although the mixture of gas and fine solid behaves as a liquid, this is
nevertheless an example of heterogeneous catalysis - the catalyst is in a
different phase from the reactants.
Or, showing more clearly what happens to the various atoms and bonds:
This is only one way in which this particular molecule might break up. The
ethene and propene are important materials for making plastics or
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Isomerisation
Hydrocarbons used in petrol (gasoline) are given an octane rating which
relates to how effectively they perform in the engine. A hydrocarbon with a
high octane rating burns more smoothly than one with a low octane rating.
Molecules with "straight chains" have a tendency to pre-ignition. When the
petrol / air mixture is compressed they tend to explode, and then explode
a second time when the spark is passed through them. This double
explosion produces knocking in the engine.
Reforming
Reforming is another process used to improve the octane rating of
hydrocarbons to be used in petrol, but is also a useful source of aromatic
compounds for the chemical industry. Aromatic compounds are ones
based on a benzene ring.
This page looks at the use of acid catalysts in some organic reactions. It
covers the nitration of benzene, the hydration of ethene to manufacture
ethanol, and the reactions both to produce esters and to hydrolyse them
under acidic conditions. You will find links to the full mechanisms for
each of these reactions if you want them.
or:
Note: If you aren't happy about the names of esters, you will
find them discussed if you follow this link.
Use the BACK button on your browser to return to this page
afterwards.
The ethyl ethanoate has the lowest boiling point of anything in the
mixture, and so is distilled off as soon as it is formed. This helps to
reduce the reverse reaction.
The equation for the reaction is simply the esterification equation written
backwards.
The dilute acid used as the catalyst also provides the water for the
reaction. You need a large excess of water in order to increase the
chances of the forward reaction happening and the ester hydrolysing.
You would normally hydrolyse esters quite differently by heating them
with sodium hydroxide solution (alkaline hydrolysis). This isn't an
example of a catalytic reaction because the hydroxide ions are used up
during the reaction.
Only 5% of the ethene is converted into ethanol at each pass through the
reactor. By removing the ethanol from the equilibrium mixture and
recycling the ethene, it is possible to achieve an overall 95% conversion.
A flow scheme for the reaction looks like this:
The temperature
Equilibrium considerations
You need to shift the position of the equilibrium as far as possible to the
right in order to produce the maximum possible amount of ethanol in the
equilibrium mixture.
The forward reaction (the production of ethanol) is exothermic.
You need the gases to reach equilibrium within the very short time that
they will be in contact with the catalyst in the reactor.
The compromise
300C is a compromise temperature producing an acceptable proportion
of ethanol in the equilibrium mixture, but in a very short time. Under
these conditions, about 5% of the ethene reacts to give ethanol at each
pass over the catalyst.
The pressure
Equilibrium considerations
Notice that there are 2 molecules on the left-hand side of the equation,
but only 1 on the right.
According to Le Chatelier's Principle, if you increase the pressure the
system will respond by favouring the reaction which produces fewer
molecules. That will cause the pressure to fall again.
In order to get as much ethanol as possible in the equilibrium mixture,
you need as high a pressure as possible. High pressures also increase
the rate of the reaction. However, the pressure used isn't all that high.
Problems with high pressures
There are two quite separate problems in this case:
The catalyst
Equilibrium considerations
The catalyst has no effect whatsoever on the position of the equilibrium.
Adding a catalyst doesn't produce any greater percentage of ethanol in
the equilibrium mixture. Its only function is to speed up the reaction.
Rate considerations
In the absence of a catalyst the reaction is so slow that virtually no
reaction happens in any sensible time. The catalyst ensures that the
reaction is fast enough for a dynamic equilibrium to be set up within the
very short time that the gases are actually in the reactor.
The mechanism
The over-all process is known as free radical addition.
Chain initiation
The chain is initiated by free radicals, Ra , produced by reaction
between some of the ethene and the oxygen initiator.
Chain propagation
Each time a free radical hits an ethene molecule a new longer free
radical is formed.
etc
Chain termination
Eventually two free radicals hit each other producing a final molecule.
The process stops here because no new free radicals are formed.
To Main Menu . . .
The sigma bond between the carbon atoms isn't affected by any of this.
The free radical, Ra , 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.
You can show this using "curly arrow" notation if you want to:
Note: If you aren't sure about about curly arrow notation you
can follow this link.
Use the BACK button on your browser to return to this page.
This is energetically worth doing because the new bond between the
radical and the carbon is stronger than the pi bond which is broken. You
would get more energy out when the new bond is made than was used to
break the old one. The more energy that is given out, the more stable the
system becomes.
What we've now got is a bigger free radical - lengthened by CH2CH2.
That can react with another ethene molecule in the same way:
So now the radical is even bigger. That can react with another ethene and so on and so on. The polymer chain gets longer and longer.
Chain termination
The chain doesn't, however, grow indefinitely. Sooner or later two free
radicals will collide together.
That immediately stops the growth of two chains and produces one of the
final molecules in the poly(ethene). It is important to realise that the poly
(ethene) is going to be a mixture of molecules of different sizes, made in
this sort of random way.
Simplifying all this for exam purposes
The over-all process is known as free radical addition.
Chain initiation
The chain is initiated by free radicals, Ra , produced by reaction
between some of the ethene and the oxygen initiator.
Chain propagation
Each time a free radical hits an ethene molecule a new longer free
radical is formed.
etc
Chain termination
Eventually two free radicals hit each other producing a final molecule.
The process stops here because no new free radicals are formed.
This page describes the mechanism for the hydration of ethene to make
ethanol using phosphoric(V) acid as the catalyst.
All the steps in the mechanism below are shown as one-way reactions
because it makes the mechanism look less confusing. It doesn't affect
the argument, but in fact all the steps are reversible.
Step 1
All of the hydrogen atoms in the phosphoric(V) acid are fairly positively
charged because they are attached to a very electronegative oxygen
atom.
Step 2
The carbocation (carbonium ion) formed reacts with one of the lone pairs
on a water molecule. A carbocation is one which carries a positive
charge on a carbon atom.
Step 3
Finally, one of the hydrogens on the oxygen is removed by reaction with
the dihydrogenphosphate(V) ion, H2PO4-, formed in the first step.
Note: This link will lead you to the reverse of this hydration
process, the dehydration of ethanol.
The catalyst used on that page is concentrated sulphuric acid
rather than phosphoric(V) acid, because that is the acid often
used in the lab. You could write either of these mechanisms
(in either direction) perfectly well using the structure of either
of these acids.
Use the BACK button on your browser if you want to return to
this page afterwards.
Alcohols Menu
Understanding Chemistry
ALCOHOLS MENU
Background . . .
An introduction to the alcohols and their physical properties.
The manufacture of alcohols . . .
The manufacture of alcohols from alkenes, and the production of
ethanol by fermentation.
Dehydrating alcohols to make alkenes . . .
Various lab methods of converting alcohols into alkenes.
The reaction between alcohols and sodium . . .
Details of the reaction, and some simple properties of the alkoxide
ions formed.
Replacing the OH group by halogen atoms . . .
The reactions between alcohols and phosphorus halides (such as
phosphorus(V) chloride) or sulphur dichloride oxide (thionyl
chloride), and mixtures such as sodium bromide and concentrated
sulphuric acid. Includes testing for the OH group using PCl5.
The oxidation of alcohols . . .
The oxidation of alcohols using acidified potassium dichromate(VI)
solution, and its use in making aldehydes, ketones and carboxylic
Alcohols Menu
an introduction to alcohols
INTRODUCING ALCOHOLS
This page explains what alcohols are, and what the difference is between
primary, secondary and tertiary alcohols. It looks in some detail at their
simple physical properties such as solubility and boiling points. Details of
the chemical reactions of alcohols are described on separate pages.
an introduction to alcohols
Notice that it doesn't matter how complicated the attached alkyl group is.
In each case there is only one linkage to an alkyl group from the CH2
group holding the -OH group.
There is an exception to this. Methanol, CH3OH, is counted as a primary
alcohol even though there are no alkyl groups attached to the carbon
with the -OH group on it.
Secondary alcohols
In a secondary (2) alcohol, the carbon with the -OH group attached is
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an introduction to alcohols
joined directly to two alkyl groups, which may be the same or different.
Examples:
Tertiary alcohols
In a tertiary (3) alcohol, the carbon atom holding the -OH group is
attached directly to three alkyl groups, which may be any combination of
same or different.
Examples:
an introduction to alcohols
They are compared with the equivalent alkane (methane to butane) with
the same number of carbon atoms.
Notice that:
an introduction to alcohols
Hydrogen bonding
Hydrogen bonding occurs between molecules where you have a
hydrogen atom attached to one of the very electronegative elements fluorine, oxygen or nitrogen.
In the case of alcohols, there are hydrogen bonds set up between the
slightly positive hydrogen atoms and lone pairs on oxygens in other
molecules.
The hydrogen atoms are slightly positive because the bonding electrons
are pulled away from them towards the very electronegative oxygen
atoms.
an introduction to alcohols
In alkanes, the only intermolecular forces are van der Waals dispersion
forces. Hydrogen bonds are much stronger than these and therefore it
takes more energy to separate alcohol molecules than it does to
separate alkane molecules.
That's the main reason that the boiling points are higher.
an introduction to alcohols
In order to mix the two, you would have to break the hydrogen bonds
between the water molecules and the hydrogen bonds between the
ethanol molecules. It needs energy to do both of these things.
However, when the molecules are mixed, new hydrogen bonds are made
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an introduction to alcohols
The energy released when these new hydrogen bonds are made more or
less compensates for that needed to break the original ones.
In addition, there is an increase in the disorder of the system - an
increase in entropy. That is another factor in deciding whether things
happen or not.
an introduction to alcohols
The hydrocarbon chains are forcing their way between water molecules
and so breaking hydrogen bonds between those water molecules.
The -OH end of the alcohol molecules can form new hydrogen bonds
with water molecules, but the hydrocarbon "tail" doesn't form hydrogen
bonds
That means that quite a lot of the original hydrogen bonds being broken
aren't replaced by new ones.
All you get in place of those original hydrogen bonds are van der Waals
dispersion forces between the water and the hydrocarbon "tails". These
attractions are much weaker. That means that you don't get enough
energy back to compensate for the hydrogen bonds being broken. Even
allowing for the increase in disorder, the process becomes less feasible.
As the length of the alcohol increases, this situation just gets worse, and
so the solubility falls.
an introduction to alcohols
manufacture of alcohols
Only 5% of the ethene is converted into ethanol at each pass through the
reactor. By removing the ethanol from the equilibrium mixture and
recycling the ethene, it is possible to achieve an overall 95% conversion.
A flow scheme for the reaction looks like this:
manufacture of alcohols
manufacture of alcohols
manufacture of alcohols
The effect of this is that there are bound to be some alcohols which it is
impossible to make by reacting alkenes with steam because the addition
would be the wrong way around.
manufacture of alcohols
Maltose has the same molecular formula as sucrose but contains two
glucose units joined together, whereas sucrose contains one glucose
and one fructose unit.
Yeast is then added and the mixture is kept warm (say 35C) for perhaps
several days until fermentation is complete. Air is kept out of the mixture
to prevent oxidation of the ethanol produced to ethanoic acid (vinegar).
Enzymes in the yeast first convert carbohydrates like maltose or sucrose
into even simpler ones like glucose and fructose, both C6H12O6, and
then convert these in turn into ethanol and carbon dioxide.
You can show these changes as simple chemical equations, but the
biochemistry of the reactions is much, much more complicated than this
suggests.
manufacture of alcohols
Hydration of ethene
Type of process
A batch process.
Everything is put into a
container and then left
until fermentation is
complete. That batch
is then cleared out and
a new reaction set up.
This is inefficient.
A continuous flow
process. A stream of
reactants is passed
continuously over a
catalyst. This is a
more efficient way of
doing things.
Rate of reaction
Very slow.
Very rapid.
Quality of
product
Reaction
conditions
Uses gentle
temperatures and
atmospheric pressure.
Uses high
temperatures and
pressures, needing
lots of energy input.
Use of resources
Uses renewable
resources based on
plant material.
manufacture of alcohols
dehydration of alcohols
To make a few test tubes of ethene, you can use this apparatus:
dehydration of alcohols
dehydration of alcohols
dehydration of alcohols
This page describes the reaction between alcohols and metallic sodium,
and takes a very brief look at the properties of the alkoxide which is
formed. We will look at the reaction between sodium and ethanol as being
typical, but you could substitute any other alcohol you wanted to - the
reaction would be the same.
Although at first sight you might think this was something new and
complicated, in fact it is exactly the same (apart from being a more gentle
reaction) as the reaction between sodium and water - something you
have probably known about for years.
Compare the two:
Sodium ethoxide is just like sodium hydroxide, except that the hydrogen
has been replaced by an ethyl group. Sodium hydroxide contains OHions; sodium ethoxide contains CH3CH2O- ions.
Note: The reason that the ethoxide formula is written with the
oxygen on the right unlike the hydroxide ion is simply a matter
of clarity. If you write it the other way around, it doesn't
immediately look as if it comes from ethanol. You will find the
same thing happens when you write formulae for organic salts
like sodium ethanoate, for example.
alcohol.
Note: You will find the mechanism for this reaction in the
mechanism section of this site.
Use the BACK button on your browser to return to this page.
The ethoxide ion behaves in exactly the same way. If you knew the
mechanism for the hydroxide ion reaction you could work out exactly what
happens in the reaction between a halogenoalkane and ethoxide ion.
Compare this equation with the last one.
The only difference is that where there was a hydrogen atom at the righthand end of the product molecule, you now have an alkyl group.
Two alkyl (or other hydrocarbon) groups bridged by an oxygen atom is
called an ether. This particular one is 1-ethoxypropane or ethyl propyl
ether. This reaction is a good way of making ethers in the lab.
Substitution or elimination?
There are two different sorts of reaction that you can get depending on
the conditions used and the type of halogenoalkane. Primary, secondary
and tertiary halogenoalkanes behave differently in this respect.
Substitution reactions
In a substitution reaction, the halogen atom is replaced by an -OH group
to give an alcohol.
For example:
Elimination reactions
Halogenoalkanes also undergo elimination reactions in the presence of
sodium or potassium hydroxide.
substitution or elimination?
primary
mainly substitution
secondary
tertiary
mainly 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:
higher temperatures
lower temperatures
Note: The explanations for these effects are well beyond the
demands of UK A level syllabuses. Some things you just
have to know!
INTRODUCING HALOGENOALKANES
(haloalkanes or alkyl halides)
Notice that it doesn't matter how complicated the attached alkyl group is. In
each case there is only one linkage to an alkyl group from the CH2 group
holding the halogen.
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 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:
Notice that three of these have boiling points below room temperature
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(taken as being about 20C). These will be gases at room temperature. All
the others you are likely to come across are liquids.
Remember:
chloroethane is a gas.
4.0
Cl 3.0
Br 2.8
I
2.5
This means that in addition to the dispersion forces there will be forces due
to the attractions between the permanent dipoles (except in the iodide
case).
The size of those dipole-dipole attractions will fall as the bonds get less
polar (as you go from chloride to bromide to iodide, for example).
Nevertheless, the boiling points rise! This shows that the effect of the
permanent dipole-dipole attractions is much less important than that of the
temporary dipoles which cause the dispersion forces.
The large increase in number of electrons by the time you get to the iodide
completely outweighs the loss of any permanent dipoles in the molecules.
The examples show that the boiling points fall as the isomers go from a
primary to a secondary to a tertiary halogenoalkane. This is a simple result
of the fall in the effectiveness of the dispersion forces.
The temporary dipoles are greatest for the longest molecule. The
attractions are also stronger if the molecules can lie closely together. The
tertiary halogenoalkane is very short and fat, and won't have much close
contact with its neighbours.
Solubility of halogenoalkanes
Solubility in water
The halogenoalkanes are at best only very slightly soluble in water.
In order for a halogenoalkane to dissolve in water you have to break
attractions between the halogenoalkane molecules (van der Waals
dispersion and dipole-dipole interactions) and break the hydrogen bonds
between water molecules. Both of these cost energy.
Notice that bond strength falls as you go from C-F to C-I, and notice how
much stronger the carbon-fluorine bond is than the rest.
Note: You will find almost as many different values for bond
strengths (or bond enthalpies or bond energies) as there are
different sources! Don't worry about this - the pattern is always
the same. This is why you have got a chart here rather than
actual numbers.
In order for anything to react with the halogenoalkanes, the carbonhalogen bond has got to be broken. Because that gets easier as you go
from fluoride to chloride to bromide to iodide, the compounds get more
reactive in that order.
Iodoalkanes are the most reactive and fluoroalkanes are the least. In fact,
fluoroalkanes are so unreactive that we shall pretty well ignore them
completely from now on in this section!
The electronegativities of carbon and iodine are equal and so there will be
no separation of charge on the bond.
You might have thought that either of these would be more effective in the
case of the carbon-fluorine bond with the quite large amounts of positive
and negative charge already present. But that's not so - quite the opposite
is true!
The thing that governs the reactivity is the strength of the bonds which
have to be broken. If is difficult to break a carbon-fluorine bond, but easy to
break a carbon-iodine one.
Understanding Chemistry
HALOGENOALKANES MENU
(Also known as haloalkanes or alkyl halides)
Background . . .
An introduction to the halogenoalkanes, their reactivity and their
physical properties.
Making halogenoalkanes . . .
Making halogenoalkanes in the lab from alcohols.
The reaction with hydroxide ions . . .
The reaction with hydroxide ions from, for example, sodium
hydroxide solution leading to substitution and elimination reactions.
The reaction with cyanide ions . . .
The reaction with cyanide ions from, for example, a solution of
potassium cyanide in alcohol.
The reaction with ammonia . . .
The reaction with ammonia to produce various kinds of amines.
Reactions involving silver nitrate solution . . .
Includes testing for halogenoalkanes, and the use of silver nitrate
solution as a guide to the reactivity of the various halogenoalkanes.
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Grignard reagents . . .
An introduction to Grignard reagents, including making them from
halogenoalkanes and some of their simple reactions.
Uses of halogenoalkanes . . .
Including the problems associated with CFCs.
Making chloroalkanes
It is possible to make tertiary chloroalkanes successfully from the
corresponding alcohol and concentrated hydrochloric acid, but to make
primary or secondary ones you really need to use a different method - the
reaction rates are too slow.
A tertiary chloroalkane can be made by shaking the corresponding alcohol
with concentrated hydrochloric acid at room temperature.
Making bromoalkanes
Rather than using hydrobromic acid, you usually treat the alcohol with a
mixture of sodium or potassium bromide and concentrated sulphuric acid.
This produces hydrogen bromide which reacts with the alcohol. The
mixture is warmed to distil off the bromoalkane. You will find practical
details of a reaction of this kind further down the page.
Making iodoalkanes
In this case the alcohol is reacted with a mixture of sodium or potassium
iodide and concentrated phosphoric(V) acid, H3PO4, and the iodoalkane is
distilled off. The mixture of the iodide and phosphoric(V) acid produces
hydrogen iodide which reacts with the alcohol.
There are also side reactions involving the POCl3 reacting with the alcohol.
Making bromoalkanes and iodoalkanes
These are both made in the same general way. Instead of using
phosphorus(III) bromide or iodide, the alcohol is heated under reflux with a
mixture of red phosphorus and either bromine or iodine.
The phosphorus first reacts with the bromine or iodine to give the
phosphorus(III) halide.
Bromoethane has a low boiling point but is denser than water and almost
insoluble in it. To prevent it from evaporating, it is often collected under
water in a flask surrounded by ice. Sometimes it is simply collected in a
tube surrounded by ice without any water.
The reaction flask is heated gently until no more droplets of bromoethane
collect.
Purifying the bromoethane
Impurities in the bromoethane include:
The water you discard will contain almost all of the hydrogen bromide, and
quite a lot of any bromine, sulphur dioxide and ethanol present as
impurities.
Stage 2
To get rid of any remaining acidic impurities (including the bromine and
sulphur dioxide), return the bromoethane to the separating funnel and
shake it with either sodium carbonate or sodium hydrogencarbonate
solution.
This reacts with any acids present liberating carbon dioxide and forming
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soluble salts.
Separate and retain the lower bromoethane layer as before.
Stage 3
Now wash the bromoethane with water in a separating funnel to remove
any remaining inorganic impurities (excess sodium carbonate solution,
etc). This time, transfer the lower bromoethane layer to a dry test tube.
Stage 4
Add some anhydrous calcium chloride to the tube, shake well and leave to
stand. The anhydrous calcium chloride is a drying agent and removes any
remaining water. It also absorbs ethanol, and so any remaining ethanol
may be removed as well (depending on how much calcium chloride you
use).
Stage 5
Transfer the dry bromoethane to a distillation flask and fractionally distil it,
collecting what distils over at between 35 and 40C.
In principle, this should remove any remaining organic impurities. In
practice, though, any ethoxyethane (which is perhaps the most likely
impurity left at this stage) has a boiling point very, very close to that of
bromoethane. It is unlikely that you will be able to separate the two.
If there is any ethanol left which hadn't been absorbed by the calcium
chloride, that would certainly be removed because its boiling point is much
higher.
What's left?
In my experience with A level students, virtually nothing if you are working
on a small scale!! Every time you go through a purification stage, you
inevitably lose some of what you are trying to collect.
You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:
Nitriles Menu
Understanding Chemistry
NITRILES MENU
Background . . .
An introduction to nitriles including their physical properties.
Preparation of nitriles . . .
Their preparation from halogenoalkanes, amides, and aldehydes
and ketones.
The hydrolysis of nitriles . . .
The hydrolysis of nitriles using acids or alkalis.
The reduction of nitriles . . .
The reduction of nitriles to primary amines.
Nitriles Menu
an introduction to nitriles
INTRODUCING NITRILES
This page explains what nitriles are and looks at their simple physical
properties such as solubility and boiling points.
Notice the triple bond between the carbon and nitrogen in the -CN group.
The three simplest nitriles are:
CH3CN
ethanenitrile
CH3CH2CN
propanenitrile
CH3CH2CH2CN
butanenitrile
When you are counting the length of the carbon chain, don't forget the
carbon in the -CN group. If the chain is branched, this carbon usually
counts as the number 1 carbon.
an introduction to nitriles
Physical properties
Boiling points
The small nitriles are liquids at room temperature.
nitrile
CH3CN
82
CH3CH2CN
97
CH3CH2CH2CN
116 - 118
an introduction to nitriles
These boiling points are very high for the size of the molecules - similar
to what you would expect if they were capable of forming hydrogen
bonds.
However, they don't form hydrogen bonds - they don't have a hydrogen
atom directly attached to an electronegative element.
They are just very polar molecules. The nitrogen is very electronegative
and the electrons in the triple bond are very easily pulled towards the
nitrogen end of the bond.
Nitriles therefore have strong permanent dipole-dipole attractions as well
as van der Waals dispersion forces between their molecules.
Solubility in water
Ethanenitrile is completely soluble in water, and the solubility then falls
as chain length increases.
nitrile
CH3CN
CH3CH2CN
CH3CH2CH2CN
solubility at 20C
miscible
10 g per 100 cm3 of water
3 g per 100 cm3 of water
an introduction to nitriles
The reason for the solubility is that although nitriles can't hydrogen bond
with themselves, they can hydrogen bond with water molecules.
One of the slightly positive hydrogen atoms in a water molecule is
attracted to the lone pair on the nitrogen atom in a nitrile and a hydrogen
bond is formed.
an introduction to nitriles
MAKING NITRILES
You could write the full equation rather than the ionic one, but it slightly
obscures what's going on:
In every example of this kind, the -OH group will be on the number 2
carbon atom - the one next to the -CN group.
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 reaction
happens at room temperature.
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 you want the mechanism for this reaction, you will
find it explained if you follow this link.
Use the BACK button on your browser to return to this page.
These are useful reactions because they not only increase the number of
carbon atoms in a chain, but also introduce another reactive group as
well as the -CN group. The -OH group behaves just like the -OH group in
any alcohol with a similar structure.
For example, starting from a hydroxynitrile made from an aldehyde, you
can quite easily produce relatively complicated molecules like 2-amino
acids - the amino acids which are used to construct proteins.
Note: You will find practical details of this reaction on the page
about preparation of halogenoalkanes. You don't need to read
the beginning of that page because it is just a modification of
this one!
Use the BACK button on your browser to return to this page.
There are also side reactions involving the POCl3 reacting with the alcohol.
Other reactions involving phosphorus halides
Instead of using phosphorus(III) bromide or iodide, the alcohol is usually
heated under reflux with a mixture of red phosphorus and either bromine
or iodine.
The phosphorus first reacts with the bromine or iodine to give the
phosphorus(III) halide.
The current page summarises the main facts about the reactions. If you
need details about the mechanisms, you will find a link below.
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.
There is then the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
There is again the possibility of a reversible reaction between this salt and
excess ammonia in the mixture.
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This time there isn't any hydrogen left on the nitrogen to be removed. The
reaction stops here.
hydrolysis of nitriles
HYDROLYSING NITRILES
This page looks at the hydrolysis of nitriles under either acidic or alkaline
conditions to make carboxylic acids or their salts.
hydrolysis of nitriles
Why is the free acid formed rather than the ammonium salt? The
ethanoate ions in the ammonium ethanoate react with hydrogen ions
from the hydrochloric acid to produce ethanoic acid. Ethanoic acid is only
a weak acid and so once it has got the hydrogen ion, it tends to hang on
to it.
hydrolysis of nitriles
reduction of nitriles
This page looks at the reduction of nitriles to primary amines using either
lithium tetrahydridoaluminate(III) (lithium aluminium hydride) or hydrogen
and a metal catalyst.
reduction of nitriles
reduction of nitriles
reduction of nitriles
This page looks at the reduction of aldehydes and ketones by two similar
reducing agents - lithium tetrahydridoaluminate(III) (also known as lithium
aluminium hydride) and sodium tetrahydridoborate(III) (sodium
borohydride).
Reaction details
Using lithium tetrahydridoaluminate (lithium aluminium hydride)
Lithium tetrahydridoaluminate is much more reactive than sodium
tetrahydridoborate. It reacts violently with water and alcohols, and so any
reaction must exclude these common solvents.
The reactions are usually carried out in solution in an ether such as
ethoxyethane (diethyl ether). The reaction happens at room temperature,
and takes place in two separate stages.
In the first stage, a salt is formed containing a complex aluminium ion. The
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The product is then treated with a dilute acid (such as dilute sulphuric acid
or dilute hydrochloric acid) to release the alcohol from the complex ion.
Note: You can see why UK A level examiners are happy with
the equations showing H in square brackets!
On the other hand, you may well be expected to know that the
reaction is done initially in solution in ethoxyethane followed
by treatment with acid.
In the second stage of the reaction, water is added and the mixture is
boiled to release the alcohol from the complex.
Again, the alcohol formed can be recovered from the mixture by fractional
distillation.
This page looks at how silver nitrate solution can be used as part of a test
for halogenoalkanes (haloalkanes or alkyl halides), and also as a means
of measuring their relative reactivities.
ion present
observation
Cl-
white precipitate
Br-
I-
original precipitate
AgCl
observation
precipitate dissolves to give a colourless
solution
AgBr
AgI
Obviously, the time taken for a precipitate of silver bromide to appear will
depend on how much of everything you use and the temperature at which
the reaction is carried out. But the pattern of results is always the same.
For example:
Again, the actual times taken will vary with reaction conditions, but the
pattern will always be the same.
For example:
precipitate.
It is more difficult to explain the reason for this, because it needs a fairly
intimate knowledge of the mechanisms involved in the reactions. It
reflects the change in the way that the halide ion is produced as you go
from primary to secondary to tertiary halogenoalkanes.
Note: You can read about the different mechanisms for this
reaction in the mechanism section of this site if you are
interested.
Use the BACK button on your browser to return to this page.
grignard reagents
This page takes an introductory look at how Grignard reagents are made
from halogenoalkanes (haloalkanes or alkyl halides), and introduces some
of their reactions.
grignard reagents
Any reactions using the Grignard reagent are carried out with the mixture
produced from this reaction. You can't separate it out in any way.
grignard reagents
Almost all sources quote the formation of a basic halide such as Mg(OH)
Br as the other product of the reaction. That's actually misleading because
these compounds react with dilute acids. What you end up with would be
a mixture of ordinary hydrated magnesium ions, halide ions and sulphate
or chloride ions - depending on which dilute acid you added.
grignard reagents
R and R' can be the same or different, and can be an alkyl group or
hydrogen.
If one (or both) of the R groups are hydrogens, the compounds are called
aldehydes. For example:
If both of the R groups are alkyl groups, the compounds are called
ketones. Examples include:
grignard reagents
Dilute acid is then added to this to hydrolyse it. (I am using the normally
accepted equation ignoring the fact that the Mg(OH)Br will react further
with the acid.)
grignard reagents
Assuming that you are starting with CH3CH2MgBr and using the general
equation above, the alcohol you get always has the form:
Since both R groups are hydrogen atoms, the final product will be:
A primary alcohol is formed. A primary alcohol has only one alkyl group
attached to the carbon atom with the -OH group on it.
You could obviously get a different primary alcohol if you started from a
different Grignard reagent.
grignard reagents
Again, think about how that relates to the general case. The alcohol
formed is:
So this time the final product has one CH3 group and one hydrogen
attached:
A secondary alcohol has two alkyl groups (the same or different) attached
to the carbon with the -OH group on it.
You could change the nature of the final secondary alcohol by either:
grignard reagents
This time when you replace the R groups in the general formula for the
alcohol produced you get a tertiary alcohol.
A tertiary alcohol has three alkyl groups attached to the carbon with the OH attached. The alkyl groups can be any combination of same or
different.
You could ring the changes on the product by
grignard reagents
Note: If you are interested, you could follow this link to the
bonding in a carbonyl group. Reading the last couple of
paragraphs on that page would be enough in the present
context.
Use the BACK button on your browser to return to this page.
grignard reagents
uses of halogenoalkanes
USES OF HALOGENOALKANES
CCl3F
CFC-12
CCl2F2
How to work out the formula from the CFC number: You
add 90 to the CFC number to give a new number. For
example, CFC-11 generates the number 101 (11+90)
The first digit of the new number tells you how many carbon
atoms there are. The second number tells you the number of
hydrogens, and the third the number of fluorines. You
calculate the number of chlorines from the formula Cl = 2(C
+1)-H-F.
uses of halogenoalkanes
Uses of CFCs
CFCs are non-flammable and not very toxic. They therefore had a large
number of uses.
They were used as refrigerants, propellants for aerosols, for generating
foamed plastics like expanded polystyrene or polyurethane foam, and as
solvents for dry cleaning and for general degreasing purposes.
Unfortunately, CFCs are largely responsible for destroying the ozone
layer. In the high atmosphere, the carbon-chlorine bonds break to give
chlorine free radicals. It is these radicals which destroy ozone. CFCs are
now being replaced by less environmentally harmful compounds.
Note: You will find the mechanism for the depletion of ozone
by the chlorine radicals produced from CFCs on the
introduction to catalysis page in the physical chemistry
section of this site.
Use the BACK button on your browser to return to this page.
CFCs can also cause global warming. One molecule of CFC-11, for
example, has a global warming potential about 5000 times greater than a
molecule of carbon dioxide.
On the other hand, there is far more carbon dioxide in the atmosphere
than CFCs, so global warming isn't the major problem associated with
them.
uses of halogenoalkanes
Hydrochlorofluorocarbons, HCFCs
These are carbon compounds which contain hydrogen as well as
halogen atoms. For example:
HCFC-22
CHClF2
The formula can be worked out from the number in the name in exactly
the same way as for CFCs.
These have a shorter life in the atmosphere than CFCs, and much of
them is destroyed in the low atmosphere and so doesn't reach the ozone
layer. HCFC-22 has only about one-twentieth of the effect on the ozone
layer as a typical CFC.
Hydrofluorocarbons, HFCs
These are compounds containing only hydrogen and fluorine attached to
carbon. For example:
HFC-134a
CH2F-CF3
Because these HCFCs don't contain any chlorine, they have zero effect
on the ozone layer. HFC-134a is now widely used in refrigerants, for
blowing foamed plastics and as a propellant in aerosols.
Hydrocarbons
Again, these have no effect on the ozone layer, but they do have a downside. They are highly flammable and are involved in environmental
problems such as the formation of photochemical smog.
uses of halogenoalkanes
uses of halogenoalkanes
polymerisation of alkenes
polymerisation of alkenes
Note: If you want the mechanism for this reaction, you can
get it by following this link to the mechanism section of the
site.
Use the BACK button on your browser if you want to return to
this page.
One chain is held to its neighbours in the structure by van der Waals
dispersion forces. Those attractions will be greater if the chains are close
to each other. The amorphous regions where the chains are inefficiently
packed lower the effectiveness of the van der Waals attractions and so
lower the melting point and strength of the polymer. They also lower the
density of the polymer (hence: "low density poly(ethene)").
polymerisation of alkenes
Note: Follow this link if you don't understand van der Waals
forces.
Use the BACK button on your browser to return to this page.
Low density poly(ethene) is used for familiar things like plastic carrier
bags and other similar low strength and flexible sheet materials.
polymerisation of alkenes
chains - the crystallinity is 95% or better. This better packing means that
van der Waals attractions between the chains are greater and so the
plastic is stronger and has a higher melting point. Its density is also
higher because of the better packing and smaller amount of wasted
space in the structure.
High density poly(ethene) is used to make things like plastic milk bottles
and similar containers, washing up bowls, plastic pipes and so on. Look
for the letters HDPE near the recycling symbol.
Poly(propene) (polypropylene): PP
Poly(propene) is manufactured using Ziegler-Natta and other modern
catalysts. There are three variants on the structure of poly(propene)
which you may need to know about, but we'll start from the beginning
with a general structure which fits all of them.
polymerisation of alkenes
Now line lots of them up in a row and join them together. Notice that the
double bonds are all replaced by single bonds in the process.
polymerisation of alkenes
Note: Dotted lines show bonds going back into the screen or
paper, and wedge shapes show them coming out towards
you. If you aren't very happy about the various ways of
drawing organic structures it might be worth following this link
before you go on.
Use the BACK button on your browser to return to this page.
This very regular arrangement of the CH3 groups makes it possible for
the chains to pack close together and so maximise the amount of van der
Waals bonding between them. That means that isotactic poly(propene) is
quite strong either as a solid object or when it is drawn into fibres.
This is the common form of poly(propene) which is used to make plastic
crates and ropes amongst many other things. Look for the letters PP
near the recycling symbol.
Atactic poly(propene)
In atactic poly(propene) the CH3 groups are orientated randomly along
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polymerisation of alkenes
the chain.
This lack of regularity makes it impossible for the chains to lie closely
together and so the van der Waals attractions between them are weaker.
Atactic poly(propene) is much softer with a lower melting point.
It is formed as a waste product during the manufacture of isotactic poly
(propene) and its uses are limited. It is used, for example, in road paint,
in making roofing materials like "roofing felt", and in some sealants and
adhesives.
Syndiotactic poly(propene)
Syndiotactic poly(propene) is a relatively new material and is another
regularly arranged version of poly(propene). In this case, every alternate
CH3 group is orientated in the same way.
This regularity means that the chains can pack closely, and van der
Waals attractions will be fairly strong. However, the attractions aren't as
strong as in isotactic poly(propene). This makes syndiotactic poly
(propene) softer and gives it a lower melting point.
Because syndiotactic poly(propene) is relatively new, at the time of
writing uses were still being developed. It has uses in packaging - for
example, in plastic film for shrink wrapping food. There are also medical
uses - for example, in medical tubing and for medical bags and pouches.
There are a wide range of other potential uses - either on its own, or in
mixtures with isotactic poly(propene).
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polymerisation of alkenes
It doesn't matter which carbon you attach the chlorine to in the original
molecule. Just be consistent on both sides of the equation.
The polymerisation process produces mainly atactic polymer molecules with the chlorines orientated randomly along the chain. The structure is
no different from atactic poly(propene) - just replace the CH3 groups by
chlorine atoms.
polymerisation of alkenes
Because of the way the chlorine atoms stick out from the chain at
random, and because ot their large size, it is difficult for the chains to lie
close together. Poly(chloroethene) is mainly amorphous with only small
areas of crystallinity.
Properties and uses
You normally expect amorphous polymers to be more flexible than
crystalline ones because the forces of attraction between the chains tend
to be weaker. However, pure poly(chloroethene) tends to be rather hard
and rigid.
This is because of the presence of additional dipole-dipole interactions
due to the polarity of the carbon-chlorine bonds. Chlorine is more
electronegative than carbon, and so attracts the electrons in the bond
towards itself. That makes the chlorine atoms slightly negative and the
carbons slightly positive.
These permanent dipoles add to the attractions due to the temporary
dipoles which produce the dispersion forces.
polymerisation of alkenes
Poly(tetrafluoroethene): PTFE
You may have come across this under the brand names of Teflon or
Fluon.
Structure
Structurally, PTFE is just like poly(ethene) except that each hydrogen in
the structure is replaced by a fluorine atom.
The PTFE chains tend to pack well and PTFE is fairly crystalline.
Because of the fluorine atoms, the chains also contain more electrons
(for an equal length) than a corresponding poly(ethene) chain. Taken
together (the good packing and the extra electrons) that means that the
van der Waals dispersion forces will be stronger than in even high
density poly(ethene).
polymerisation of alkenes
polymerisation of alkenes
Understanding Chemistry
Background . . .
An introduction to the aryl halides and their physical properties.
The preparation of aryl halides . . .
Making chlorobenzene and bromobenzene by reacting chlorine or
bromine with benzene, and making iodobenzene from
benzenediazonium chloride.
The reactions of aryl halides . . .
. . . or more particularly the reasons for their lack of reaction
relative to halogenoalkanes (haloalkanes or alkyl halides).
This page looks at the structure and physical properties of three simple
aryl halides - chlorobenzene, bromobenzene and iodobenzene. An aryl
halide has a halogen atom attached directly to a benzene ring.
Physical properties
Boiling points
Chlorobenzene, bromobenzene and iodobenzene are all oily liquids. The
boiling points increase as the halogen atom gets bigger.
boiling point (C)
C6H5Cl
132
C6H5Br
156
C6H5I
189
The main attractions between the molecules will be van der Waals
dispersion forces. These increase as the number of electrons in the
molecule increases. This is the reason that the boiling points increase as
the halogen atom gets bigger.
There will also be permanent dipole-dipole attractions involved in the
chlorobenzene and bromobenzene, but very little in the iodobenzene.
Iodine has much the same electronegativity as carbon.
These dipole-dipole attractions must be very unimportant relative to the
dispersion forces because the most polar molecule (the chlorobenzene)
has the lowest boiling point of the three.
Solubility in water
The aryl halides are insoluble in water. They are denser than water and
form a separate lower layer.
The molecules are quite large compared with a water molecule. In order
for chlorobenzene 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 chlorobenzene
molecules. Both of these cost energy.
The only new forces between the chlorobenzene 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 chlorobenzene), and so
you wouldn't get much energy released when they form.
It simply isn't energetically profitable for chlorobenzene (and the others)
to dissolve in water.
This page only looks at the ways of making the aryl halides,
chlorobenzene, bromobenzene and iodobenzene, as required by some
UK A level syllabuses. It is not intended to be an overall survey of the
topic.
Making chlorobenzene
Benzene reacts with chlorine in the presence of a catalyst, replacing one
of the hydrogen atoms on the ring by a chlorine atom.
The reaction happens at room temperature. The catalyst is either
aluminium chloride or iron.
Strictly speaking iron isn't a catalyst, because it gets permanently
changed during the reaction. It reacts with some of the chlorine to form
iron(III) chloride, FeCl3.
This compound acts as the catalyst and behaves exactly like aluminium
chloride, AlCl3, in this reaction.
The reaction between benzene and chlorine in the presence of either
aluminium chloride or iron gives chlorobenzene.
Note: Follow this link if you want the mechanism for the
chlorination of benzene.
Use the BACK button on your browser to return to this page
later.
Making bromobenzene
The reaction between benzene and bromine in the presence of either
aluminium bromide (rather than aluminium chloride) or iron gives
bromobenzene. Iron is usually used because it is cheaper and more
readily available. If you use iron, it is first converted into iron(III) bromide
by the reaction between the iron and bromine.
or:
Making iodobenzene
Iodobenzene can be made from the reaction of benzene with iodine if
they are heated under reflux in the presence of concentrated nitric acid,
but it is normally made from benzenediazonium chloride solution. That's
what we will concentrate on here.
If you add cold potassium iodide solution to ice-cold benzenediazonium
chloride solution, nitrogen gas is given off, and you get oily droplets of
iodobenzene formed.
There is a simple reaction between the diazonium ions present in the
benzenediazonium chloride solution and the iodide ions from the
potassium iodide solution.
This page only looks at one aspect of the chemistry of the aryl halides
such as chlorobenzene - the fact that they are very unreactive compared
with halogenoalkanes (haloalkanes or alkyl halides). This is the only bit
of their chemistry asked for by any UK A level syllabuses.
oxidation of alcohols
OXIDATION OF ALCOHOLS
oxidation of alcohols
Primary alcohols
Primary alcohols can be oxidised to either aldehydes or carboxylic acids
depending on the reaction conditions. In the case of the formation of
carboxylic acids, the alcohol is first oxidised to an aldehyde which is then
oxidised further to the acid.
Partial oxidation to aldehydes
You get an aldehyde if you use an excess of the alcohol, and distil off the
aldehyde as soon as it forms.
The excess of the alcohol means that there isn't enough oxidising agent
present to carry out the second stage. Removing the aldehyde as soon
as it is formed means that it doesn't hang around waiting to be oxidised
anyway!
If you used ethanol as a typical primary alcohol, you would produce the
aldehyde ethanal, CH3CHO.
The full equation for this reaction is fairly complicated, and you need to
understand about electron-half-equations in order to work it out.
oxidation of alcohols
oxidation of alcohols
Alternatively, you could write separate equations for the two stages of the
reaction - the formation of ethanal and then its subsequent oxidation.
Secondary alcohols
Secondary alcohols are oxidised to ketones - and that's it. For example, if
you heat the secondary alcohol propan-2-ol with sodium or potassium
dichromate(VI) solution acidified with dilute sulphuric acid, you get
propanone formed.
Playing around with the reaction conditions makes no difference
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oxidation of alcohols
If you look back at the second stage of the primary alcohol reaction, you
will see that an oxygen "slotted in" between the carbon and the hydrogen
in the aldehyde group to produce the carboxylic acid. In this case, there
is no such hydrogen - and the reaction has nowhere further to go.
Tertiary alcohols
Tertiary alcohols aren't oxidised by acidified sodium or potassium
dichromate(VI) solution. There is no reaction whatsoever.
If you look at what is happening with primary and secondary alcohols,
you will see that the oxidising agent is removing the hydrogen from the OH group, and a hydrogen from the carbon atom attached to the -OH.
Tertiary alcohols don't have a hydrogen atom attached to that carbon.
You need to be able to remove those two particular hydrogen atoms in
order to set up the carbon-oxygen double bond.
oxidation of alcohols
oxidation of alcohols
You would then add a few drops of the alcohol to a test tube containing
potassium dichromate(VI) solution acidified with dilute sulphuric acid.
The tube would be warmed in a hot water bath.
Results for the various kinds of alcohol
Picking out the tertiary alcohol
In the case of a primary or secondary alcohol, the orange solution turns
green. With a tertiary alcohol there is no colour change.
After heating:
Note: You will find these tests for aldehydes by following this
link.
Use the BACK button on your browser to return to this page.
oxidation of alcohols
In my experience, these tests can be a bit of a bother to carry out and the
results aren't always as clear-cut as the books say. A much simpler but
fairly reliable test is to use Schiff's reagent. Schiff's reagent isn't
specifically mentioned by any of the UK A level syllabuses, but I have
always used it.
Schiff's reagent is a fuchsin dye decolourised by passing sulphur dioxide
through it. In the presence of even small amounts of an aldehyde, it turns
bright magenta.
It must, however, be used absolutely cold, because ketones react with it
very slowly to give the same colour. If you heat it, obviously the change
is faster - and potentially confusing.
While you are warming the reaction mixture in the hot water bath, you
can pass any vapours produced through some Schiff's reagent.
oxidation of alcohols
Background
Why do aldehydes and ketones behave differently?
You will remember that the difference between an aldehyde and a ketone
is the presence of a hydrogen atom attached to the carbon-oxygen
double bond in the aldehyde. Ketones don't have that hydrogen.
Because ketones don't have that particular hydrogen atom, they are
resistant to oxidation. Only very strong oxidising agents like potassium
manganate(VII) solution (potassium permanganate solution) oxidise
ketones - and they do it in a destructive way, breaking carbon-carbon
bonds.
Provided you avoid using these powerful oxidising agents, you can easily
tell the difference between an aldehyde and a ketone. Aldehydes are
easily oxidised by all sorts of different oxidising agents: ketones aren't.
You will find details of these reactions further down the page.
Specific examples
In each of the following examples, we are assuming that you know that
you have either an aldehyde or a ketone. There are lots of other things
which could also give positive results.
Note: Follow this link to find out how to test for the carbonoxygen double bond in aldehydes and ketones.
Use the BACK button on your browser to return to this page.
Assuming that you know it has to be one or the other, in each case, a
ketone does nothing. Only an aldehyde gives a positive result.
ketone
aldehyde
Note: You may wonder why I have gone to all the trouble of
working out a complete equation for this reaction (and the
next ones) rather than using symbols like [O] which are
frequently used in organic chemistry.
The problem is that what is important in using these reactions
as tests is the colour change in the oxidising agent. In this
particular reaction, you have to explain, for example, why the
solution turns green. Any equation that you write has got to
show the production of the chromium(III) ions.
If you aren't sure exactly how the two half-equations are
combined to give the final equation, follow the last link (further
up the page) to learn how to do it - and then come back and
have a go yourself to check that you can get the right answer.
ketone
aldehyde
Note: If you actually get a silver mirror it is very satisfying but a grey precipitate is enough to show that the test has
worked. Whether you get a silver mirror or not seems a matter
of luck. I have watched really careful students clean
everything scrupulously and take great care over quantities,
and still get no more than a trace of a mirror. On the other
hand students who have just thrown everything together in
the first grubby test tube that came to hand can get a
wonderful mirror. Life isn't always fair!
ketone
aldehyde
The equations for these reactions are always simplified to avoid having to
write in the formulae for the tartrate or citrate ions in the copper
complexes. The electron-half-equations for both Fehling's solution and
Benedict's solution can be written as:
Note: If you are really alert, you might wonder where the
hydroxide ions come from if you are talking about Benedict's
solution, which is made alkaline using sodium carbonate.
Sodium carbonate solution is alkaline because the carbonate
ions react reversibly with water to produce hydroxide ions
(and hydrogencarbonate ions).
ADDITION-ELIMINATION REACTIONS OF
ALDEHYDES AND KETONES
This page looks at the reaction of aldehydes and ketones with 2,4dinitrophenylhydrazine (Brady's reagent) as a test for the carbon-oxygen
double bond. It also looks briefly at some other similar reactions which
are all known as addition-elimination (or condensation) reactions.
Provided you take care to draw the two starting molecules lined up right,
working out the structure of the product is easy.
The product is known as a "2,4-dinitrophenylhydrazone". Notice that all
that has changed is the ending from "-ine" to "-one". That's possibly
confusing!
The product from the reaction with ethanal would be called ethanal 2,4dinitrophenylhydrazone; from propanone, you would get propanone 2,4dinitrophenylhydrazone - and so on. That's not too difficult!
The reaction is known as a condensation reaction. A condensation
reaction is one in which two molecules join together with the loss of a
small molecule in the process. In this case, that small molecule is water.
In terms of mechanisms, this is a nucleophilic addition-elimination
reaction. The 2,4-dinitrophenylhydrazine first adds across the carbonoxygen double bond (the addition stage) to give an intermediate
compound which then loses a molecule of water (the elimination stage).
First, you can just use it to test for the presence of the carbonoxygen double bond. You only get an orange or yellow precipitate
from a carbon-oxygen double bond in an aldehyde or ketone.
Secondly, you can use it to help to identify the specific aldehyde or
ketone.
The precipitate is filtered and washed with, for example, methanol
and then recrystallised from a suitable solvent which will vary
depending on the nature of the aldehyde or ketone. For example,
you can recrystallise the products from the small aldehydes and
ketones from a mixture of ethanol and water.
The crystals are dissolved in the minimum quantity of hot solvent.
When the solution cools, the crystals are re-precipitated and can
be filtered, washed with a small amount of solvent and dried. They
should then be pure.
If you then find the melting point of the crystals, you can compare
it with tables of the melting points of 2,4-dinitrophenylhydrazones
of all the common aldehydes and ketones to find out which one
you are likely to have got.
with hydrazine
with phenylhydrazine
with hydroxylamine
ESTERIFICATION
Notice that the ester is named the opposite way around from the way the
formula is written. The "ethanoate" bit comes from ethanoic acid. The
"ethyl" bit comes from the ethyl group on the end.
Notice that the acid is named by counting up the total number of carbon
atoms in the chain - including the one in the -COOH group. So, for
example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the
propanoate group.
Note: You can find more about naming acids and esters by
following this link to a different part of this site.
Use the BACK button on your browser to return to this page.
So, for example, if you were making ethyl ethanoate from ethanoic acid
and ethanol, the equation would be:
This page looks in detail at the mechanism for the formation of esters
from carboxylic acids and alcohols in the presence of concentrated
sulphuric acid acting as the catalyst. It uses the formation of ethyl
ethanoate from ethanoic acid and ethanol as a typical example.
The mechanism
All the steps in the mechanism below are shown as one-way reactions
because it makes the mechanism look less confusing. The reverse
reaction is actually done sufficiently differently that it affects the way the
mechanism is written. You will find a link to the hydrolysis of esters
further down the page if you are interested.
Note: The explanation assumes that you know about the use
of curly arrows in organic reaction mechanisms. If you aren't
happy about these follow this link before you go any further.
(To be honest, if you are that unsure about the conventions
used in reaction mechanisms, you probably shouldn't be
reading this page anyway - you will find it distinctly scary!)
Use the BACK button on your browser to return to this page.
Step 1
In the first step, the ethanoic acid takes a proton (a hydrogen ion) from
the concentrated sulphuric acid. The proton becomes attached to one of
the lone pairs on the oxygen which is double-bonded to the carbon.
The transfer of the proton to the oxygen gives it a positive charge, but it is
actually misleading to draw the structure in this way (although nearly
everybody does!).
The positive charge is delocalised over the whole of the right-hand end of
the ion, with a fair amount of positiveness on the carbon atom. In other
words, you can think of an electron pair shifting to give this structure:
You could also imagine another electron pair shift producing a third
structure:
The double headed arrows are telling you that each of the individual
structures makes a contribution to the real structure of the ion. They
don't mean that the bonds are flipping back and forth between one
structure and another. The various structures are known as resonance
structures or canonical forms.
There will be some degree of positive charge on both of the oxygen
atoms, and also on the carbon atom. Each of the bonds between the
carbon and the two oxygens will be the same - somewhere between a
single bond and a double bond.
For the purposes of the rest of this discussion, we are going to use the
structure where the positive charge is on the carbon atom.
Step 2
The positive charge on the carbon atom is attacked by one of the lone
pairs on the oxygen of the ethanol molecule.
Step 3
What happens next is that a proton (a hydrogen ion) gets transferred
from the bottom oxygen atom to one of the others. It gets picked off by
one of the other substances in the mixture (for example, by attaching to a
lone pair on an unreacted ethanol molecule), and then dumped back onto
one of the oxygens more or less at random.
The net effect is:
Step 4
Now a molecule of water is lost from the ion.
The product ion has been drawn in a shape to reflect the product which
we are finally getting quite close to!
The structure for the latest ion is just like the one we discusssed at length
back in step 1. The positive charge is actually delocalised all over that
end of the ion, and there will also be contributions from structures where
the charge is on the either of the oxygens:
Step 5
The hydrogen is removed from the oxygen by reaction with the
hydrogensulphate ion which was formed way back in the first step.
And there we are! The ester has been formed, and the sulphuric acid
catalyst has been regenerated.
This page looks in detail at the mechanism for the hydrolysis of esters in
the presence of a dilute acid (such as hydrochloric acid or sulphuric acid)
acting as the catalyst. It uses ethyl ethanoate as a typical ester.
The mechanism
All the steps in the mechanism below are shown as one-way reactions
because it makes the mechanism look less confusing. The reverse
reaction is actually done sufficiently differently that it affects the way the
mechanism is written. You will find a link to the esterification reaction
further down the page if you are interested.
Note: The explanation assumes that you know about the use
of curly arrows in organic reaction mechanisms. If you aren't
happy about these follow this link before you go any further.
(To be honest, if you are that unsure about the conventions
used in reaction mechanisms, you probably shouldn't be
reading this page anyway - you will find it distinctly scary!)
Use the BACK button on your browser to return to this page.
Step 1
The actual catalyst in this case is the hydroxonium ion, H3O+, present in
all solutions of acids in water.
In the first step, the ester takes a proton (a hydrogen ion) from the
hydroxonium ion. The proton becomes attached to one of the lone pairs
on the oxygen which is double-bonded to the carbon.
The transfer of the proton to the oxygen gives it a positive charge, but the
charge is actually delocalised (spread around) much more widely than
this shows.
One way of representing this delocalisation is to draw a number of
structures called resonance structures or canonical forms joined by
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None of these formulae represents the true structure of the ion - but each
gives you some information about it. For example, notice where the
positive charge is in the three structures. What this means in reality is
that the positive charge is spread around over those three atoms - the
two oxygens and the carbon.
The next stage of the mechanism involves an attack on the carbon, and
so it is convenient to use the structure showing the positive charge on
that carbon in the next step.
Step 2
The positive charge on the carbon atom is attacked by one of the lone
pairs on the oxygen of a water molecule.
Step 3
What happens next is that a proton (a hydrogen ion) gets transferred
from the bottom oxygen atom to one of the others. It gets picked off by
one of the other substances in the mixture (for example, by attaching to a
lone pair on a water molecule), and then dumped back onto one of the
oxygens more or less at random.
Eventually, by chance, it will join to the oxygen with the ethyl group
attached. When that happens, the net effect is:
Step 4
Now a molecule of ethanol is lost from the ion. That's one of the products
of the reaction.
The structure for the latest ion is just like the one we discusssed at length
back in step 1. The positive charge is actually delocalised all over that
end of the ion. The real structure will be a hybrid of these:
And there we are! We have produced the ethanoic acid (the other product
of the reaction) and the hydroxonium ion catalyst has been regenerated.
Understanding Chemistry
Background . . .
An introduction to carboxylic acids and their salts, including their
bonding and their physical properties.
Preparation of carboxylic acids . . .
Their preparation by the oxidation of primary alcohols and
aldehydes, and by the hydrolysis of nitriles.
Simple reactions of carboxylic acids as acids . . .
Reactions with metals, sodium hydroxide, carbonates and
hydrogencarbonates, ammonia and amines.
Making esters from carboxylic acids . . .
Reactions with alcohols to produce esters.
Reduction of carboxylic acids . . .
The reduction of carboxylic acids to primary alcohols using lithium
tetrahydridoaluminate(III) (lithium aluminium hydride).
Making acyl chlorides (acid chlorides) . . .
Replacing the -OH in the -COOH group with chlorine using
phosphorus(V) chloride, phosphorus(III) chloride or sulphur
dichloride oxide (thionyl chloride).
This page explains what carboxylic acids are, and looks at the ions that
they form in their salts. It also considers their simple physical properties
such as solubility and boiling points. Details of the chemical reactions of
carboxylic acids are described on separate pages.
The name counts the total number of carbon atoms in the longest chain including the one in the -COOH group. If you have side groups attached
to the chain, notice that you always count from the carbon atom in the COOH group as being number 1.
Depending on whether or not you wanted to stress the ionic nature of the
compound, this would be simplified to CH3COO- Na+ or just CH3COONa.
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Notice:
The bond between the sodium and the ethanoate is ionic. Don't
draw a line between the two (implying a covalent bond). That's
absolutely wrong!
Although the name is written with the sodium first, the formula is
always written in one of the ways shown. This is something you
just have to get used to.
The boiling points of carboxylic acids of similar size are higher still.
For example:
propan-1-ol
CH3CH2CH2OH
97.2C
ethanoic acid
CH3COOH
118C
These are chosen for comparison because they have identical relative
molecular masses and almost the same number of electrons (which
This immediately doubles the size of the molecule and so increases the
van der Waals dispersion forces between one of these dimers and its
neighbours - resulting in a high boiling point.
Solubility in water
In the presence of water, the carboxylic acids don't dimerise. Instead,
hydrogen bonds are formed between water molecules and individual
molecules of acid.
The carboxylic acids with up to four carbon atoms will mix with water in
any proportion. When you mix the two together, the energy released
when the new hydrogen bonds form is much the same as is needed to
break the hydrogen bonds in the pure liquids.
The solubility of the bigger acids decreases very rapidly with size. This is
because the longer hydrocarbon "tails" of the molecules get between
water molecules and break hydrogen bonds. In this case, these broken
hydrogen bonds are only replaced by much weaker van der Waals
dispersion forces.
Understanding Chemistry
Background . . .
An introduction to amino acids including their physical properties.
Acid-base reactions of amino acids . . .
Amino acids as zwitterions and the influence of this on their
reactions with acids and bases.
The structure of proteins . . .
A brief introduction to protein structure including primary,
secondary and tertiary structure.
Hydrolysis of proteins . . .
Hydrolysing proteins using hydrochloric acid.
This page explains what amino acids are, concentrating on the 2-amino
acids that are biologically important. It looks in some detail at their simple
physical properties such as solubility and melting points.
Physical properties
Melting points
The amino acids are crystalline solids with surprisingly high melting
points. It is difficult to pin the melting points down exactly because the
amino acids tend to decompose before they melt. Decomposition and
melting tend to be in the 200 - 300C range.
For the size of the molecules, this is very high. Something unusual must
be happening.
If you look again at the general structure of an amino acid, you will see
that it has both a basic amine group and an acidic carboxylic acid group.
This is the form that amino acids exist in even in the solid state. Instead
of the weaker hydrogen bonds and other intermolecular forces that you
might have expected, you actually have much stronger ionic attractions
between one ion and its neighbours.
These ionic attractions take more energy to break and so the amino
acids have high melting points for the size of the molecules.
Solubility
Amino acids are generally soluble in water and insoluble in non-polar
organic solvents such as hydrocarbons.
This again reflects the presence of the zwitterions. In water, the ionic
attractions between the ions in the solid amino acid are replaced by
strong attractions between polar water molecules and the zwitterions.
This is much the same as any other ionic substance dissolving in water.
The extent of the solubility in water varies depending on the size and
nature of the "R" group.
Optical activity
If you look yet again at the general formula for an amino acid, you will
see that (apart from glycine, 2-aminoethanoic acid) the carbon at the
centre of the structure has four different groups attached. In glycine, the
"R" group is another hydrogen atom.
This is equally true if you draw the structure of the zwitterion instead of
this simpler structure.
Because of these four different groups attached to the same carbon
atom, amino acids (apart from glycine) are chiral.
All the naturally occurring amino acids have the right-hand structure in
this diagram. This is known as the "L-" configuration. The other one is
known as the "D-" configuration.
You almost certainly don't need to know this for UK A level chemistry
purposes, but if you are interested, you can recognise the Lconfiguration by imagining that you are looking down from above on the
right-hand structure in the last diagram. If you read around the other
groups in a clockwise direction, you get the word CORN.
You can't tell by looking at a structure whether that isomer will rotate the
plane of polarisation of plane polarised light clockwise or anticlockwise.
All the naturally occurring amino acids have the same L- configuration,
but they include examples which rotate the plane clockwise (+) and those
which do the opposite (-).
For example:
(+)alanine
(-)cysteine
(-)tyrosine
(+)valine
It is quite common for natural systems to only work with one of the optical
isomers (enantiomers) of an optically active substance like the amino
acids. 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.
To Main Menu . . .
This page looks at what happens to amino acids as you change the pH
by adding either acids or alkalis to their solutions.
For simplicity, the page only looks at amino acids which contain a single NH2 group and a single -COOH group.
This is the form that amino acids exist in even in the solid state. If you
dissolve the amino acid in water, a simple solution also contains this ion.
You could show that the amino acid now existed as a negative ion using
electrophoresis.
In its simplest form, electrophoresis can just consist of a piece of
moistened filter paper on a microscope slide with a crocodile clip at each
end attached to a battery. A drop of amino acid solution is placed in the
centre of the paper.
Although the amino acid solution is colourless, its position after a time
can be found by spraying it with a solution of ninhydrin. If the paper is
allowed to dry and then heated gently, the amino acid shows up as a
coloured spot.
The amino acid would be found to travel towards the anode (the positive
electrode).
This time, during electrophoresis, the amino acid would move towards the
cathode (the negative electrode).
So when you have added just the right amount of alkali, the amino acid
no longer has a net positive or negative charge. That means that it
wouldn't move towards either the cathode or anode during
electrophoresis.
The pH at which this lack of movement during electrophoresis happens is
known as the isoelectric point of the amino acid. This pH varies from
amino acid to amino acid.
If you go on adding hydroxide ions, you will get the reaction we've
already seen, in which a hydrogen ion is removed from the -NH3+ group.
You can, of course, reverse the whole process by adding an acid to the
ion we've just finished up with.
That ion contains two basic groups - the -NH2 group and the -COOgroup. The -NH2 group is the stronger base, and so picks up hydrogen
ions first. That leads you back to the zwitterion again.
. . . and, of course, you can keep going by then adding a hydrogen ion to
the -COO- group.
When an amino acid dissolves in water, the situation is a little bit more
complicated than we tend to pretend at this level. The zwitterion interacts
with water molecules - acting as both an acid and a base.
As an acid:
The -NH3+ group is a weak acid and donates a hydrogen ion to a water
molecule. Because it is only a weak acid, the position of equilibrium will
lie to the left.
As a base:
The -COO- group is a weak base and takes a hydrogen ion from a water
molecule. Again, the equilibrium lies to the left.
When you dissolve an amino acid in water, both of these reactions are
happening.
But . . .
The positions of the two equilibria aren't identical - they vary depending
on the influence of the "R" group. In practice, for the simple amino acids
we have been talking about, the position of the first equilibrium lies a bit
further to the right than the second one.
That means that there will be rather more of the negative ion from the
amino acid in the solution than the positive one.
In those circumstances, if you carried out electrophoresis on the
unmodified solution, there would be a slight drift of amino acid towards
the positive electrode (the anode).
To stop that, you need to cut down the amount of the negative ion so that
the concentrations of the two ions are identical. You can do that by
adding a very small amount of acid to the solution, moving the position of
the first equilibrium further to the left.
Typically, the pH has to be lowered to about 6 to achieve this. For
glycine, for example, the isoelectric point is pH 6.07; for alanine, 6.11;
and for serine, 5.68.
protein structure
This page explains how amino acids combine to make proteins and what
is meant by the primary, secondary and tertiary structures of proteins.
Quaternary structure isn't covered. It only applies to proteins consisting
of more than one polypeptide chain, and isn't required for UK A level
chemistry purposes.
That means that the two simplest amino acids, glycine and alanine,
would be shown as:
protein structure
Or:
In each case, the linkage shown in blue in the structure of the dipeptide
is known as a peptide link. In chemistry, this would also be known as an
amide link, but since we are now in the realms of biochemistry and
biology, we'll use their terms.
If you joined three amino acids together, you would get a tripeptide. If
you joined lots and lots together (as in a protein chain), you get a
polypeptide.
A protein chain will have somewhere in the range of 50 to 2000 amino
acid residues. You have to use this term because strictly speaking a
peptide chain isn't made up of amino acids. When the amino acids
combine together, a water molecule is lost. The peptide chain is made up
from what is left after the water is lost - in other words, is made up of
amino acid residues.
By convention, when you are drawing peptide chains, the -NH2 group
which hasn't been converted into a peptide link is written at the left-hand
end. The unchanged -COOH group is written at the right-hand end.
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protein structure
The "R" groups come from the 20 amino acids which occur in proteins.
The peptide chain is known as the backbone, and the "R" groups are
known as side chains.
If you look carefully, you will spot the abbreviations for glycine (Gly) and
alanine (Ala) amongst the others.
The wider definition of primary structure includes all the features of a
protein which are a result of covalent bonds. Obviously, all the peptide
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protein structure
If two cysteine side chains end up next to each other because of folding
in the peptide chain, they can react to form a sulphur bridge. This is
another covalent link and so some people count it as a part of the
primary structure of the protein.
Because of the way sulphur bridges affect the way the protein folds,
other people count this as a part of the tertiary structure (see below).
This is obviously a potential source of confusion!
protein structure
protein structure
The alpha-helix
In an alpha-helix, the protein chain is coiled like a loosely-coiled spring.
The "alpha" means that if you look down the length of the spring, the
coiling is happening in a clockwise direction as it goes away from you.
protein structure
protein structure
complete turn of the spiral has 3.6 (approximately) amino acid residues
in it.
If you had a whole number of amino acid residues per turn, each group
would have an identical group underneath it on the turn below. Hydrogen
bonding can't happen under those circumstances.
Each turn has 3 complete amino acid residues and two atoms from the
next one. That means that each turn is offset from the ones above and
below, such that the N-H and C=O groups are brought into line with each
other.
Beta-pleated sheets
In a beta-pleated sheet, the chains are folded so that they lie alongside
each other. The next diagram shows what is known as an "anti-parallel"
sheet. All that means is that next-door chains are heading in opposite
directions. Given the way this particular folding happens, that would
seem to be inevitable.
protein structure
protein structure
protein structure
protein structure
Hydrogen bonds
Notice that we are now talking about hydrogen bonds between side
groups - not between groups actually in the backbone of the chain.
Lots of amino acids contain groups in the side chains which have a
hydrogen atom attached to either an oxygen or a nitrogen atom. This is a
classic situation where hydrogen bonding can occur.
For example, the amino acid serine contains an -OH group in the side
chain. You could have a hydrogen bond set up between two serine
residues in different parts of a folded chain.
protein structure
You could easily imagine similar hydrogen bonding involving -OH groups,
or -COOH groups, or -CONH2 groups, or -NH2 groups in various
combinations - although you would have to be careful to remember that a
-COOH group and an -NH2 group would form a zwitterion and produce
stronger ionic bonding instead of hydrogen bonds.
protein structure
Sulphur bridges
Sulphur bridges which form between two cysteine residues have already
been discussed under primary structures. Wherever you choose to place
them doesn't affect how they are formed!
protein hydrolysis
This page looks briefly at the hydrolysis of proteins into their constituent
amino acids using hydrochloric acid.
Now imagine doing the same thing with a simple dipeptide made of any
two amino acids.
Instead of ammonium ions, you get positive ions made from the -NH2
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protein hydrolysis
protein hydrolysis
This page looks at ways of making carboxylic acids in the lab by the
oxidation of primary alcohols or aldehydes, and by the hydrolysis of
nitriles.
If you start with an aldehyde, you are obviously just doing this second
stage.
Starting from the primary alcohol, you could combine these into one
single equation to give:
For example, if you were converting ethanol into ethanoic acid, the
simplified equation would be:
It is possible that you might want to write proper equations for these
reactions rather than these simplified ones. You can work these out from
electron-half-equations. How you do this is described in detail elsewhere
on the site.
The complete equation for the conversion of a primary alcohol to a
carboxylic acid is:
The name is based on the total number of carbons in the longest chain including the one in the -CN group. Where you have things substituted
into the chain (as in the third example), the -CN carbon counts as
number 1.
Where do nitriles come from?
Nitriles are produced in two important reactions - both of which result in
an increase in the length of the carbon chain because of the extra carbon
in the -CN group.
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Alkaline hydrolysis
The nitrile is heated under reflux with an alkali such as sodium hydroxide
solution.
This time you wouldn't, of course, get a carboxylic acid produced - any
acid formed would react with the sodium hydroxide present to give a salt.
You also wouldn't get ammonium ions because they would react with
sodium hydroxide to produce ammonia.
Starting from ethanenitrile, you would therefore get a solution containing
ethanoate ions (for example, sodium ethanoate if you used sodium
hydroxide solution) and ammonia.
You have to remember to convert the ions into the free carboxylic acid,
because that's what we are trying to make. To liberate the weak acid,
ethanoic acid, you just have to supply hydrogen ions from a strong acid
such as hydrochloric acid. You add enough hydrochloric acid to the
mixture to make it acidic.
Combustion
Like any other hydrocarbons, benzene and methylbenzene burn in a
plentiful supply of oxygen to give carbon dioxide and water. For example:
For benzene:
. . . and methylbenzene:
You almost invariably get incomplete combustion, and the arenes can be
recognised by the smokiness of their flames.
Hydrogenation
Hydrogenation is an addition reaction in which hydrogen atoms are
added all the way around the benzene ring. A cycloalkane is formed. For
example:
With benzene:
. . . and methylbenzene:
Sulphonation
Sulphonation involves replacing one of the hydrogens on a benzene ring
by the sulphonic acid group, -SO3H.
The sulphonation of benzene
There are two equivalent ways of sulphonating benzene:
Or:
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and:
Oxidation of alkenes
Experimental details
Alkenes react with potassium manganate(VII) solution in the cold. The
colour change depends on whether the potassium manganate(VII) is used
under acidic or alkaline conditions.
If the potassium manganate(VII) solution is acidified with dilute sulphuric
acid, the purple solution becomes colourless.
If the potassium manganate(VII) solution is made slightly alkaline (often by
adding sodium carbonate solution), the purple solution first becomes dark
green and then produces a dark brown precipitate.
Chemistry of the reaction
We'll look at the reaction with ethene. Other alkenes react in just the same
way.
Manganate(VII) ions are a strong oxidising agent, and in the first instance
oxidise ethene to ethane-1,2-diol (old name: ethylene glycol).
Looking at the equation purely from the point of view of the organic reaction:
This last reaction is also the one you would get if the reaction was done
under neutral conditions. You will notice that there are neither hydrogen
ions nor hydroxide ions on the left-hand side of the equation.
Complications
(. . . and you thought this was already complicated enough?)
The product, ethane-1,2-diol, is itself quite easily oxidised by manganate
(VII) ions, and so the reaction won't stop at this point unless the potassium
manganate(VII) solution is very dilute, very cold, and preferably not under
acidic conditions.
That means that this reaction has little use as a way of preparing ethane1,2-diol. Its only real use is in testing for carbon-carbon double bonds - and
even then it isn't very good!
Note: You will find details of the use of bromine water in testing
for carbon-carbon double bonds in the page about the reactions
of alkenes with halogens.
halogenation of alkenes
halogenation of alkenes
halogenation of alkenes
halogenation of alkenes
MANUFACTURING ARENES
Catalytic reforming
What is reforming?
Reforming takes straight chain hydrocarbons in the C6 to C8 range from
the gasoline or naphtha fractions and rearranges them into compounds
containing benzene rings. Hydrogen is produced as a by-product of the
reactions.
For example, hexane, C6H14, loses hydrogen and turns into benzene. As
long as you draw the hexane bent into a circle, it is easy to see what is
happening.
The process
The feedstock
The feedstock is a mixture of the naphtha or gasoline fractions and
hydrogen. The hydrogen is there to help prevent the formation of carbon
by decomposition of the hydrocarbons at the high temperatures used.
The carbon would otherwise contaminate the catalyst.
The catalyst
A typical catalyst is a mixture of platinum and aluminium oxide. With a
platinum catalyst, the process is sometimes described as "platforming".
Temperature and pressure
The temperature is about 500C, and the pressure varies either side of
20 atmospheres.
This page looks at the facts about the nitration of benzene and
methylbenzene. The mechanisms for these reactions are covered
elsewhere on the site, and you will find links to these.
Notice that the new nitro group goes into the 3 position on the ring. Nitro
groups "direct" new groups into the 3 and 5 positions. The reasons for
this "directing effect" are beyond UK A level.
It is also possible to get a third nitro group attached to the ring (in the 5
position). However, nitro groups make the ring much less reactive than
the original benzene ring. Two nitro groups on the ring make its reactions
so slow that virtually no trinitrobenzene is produced under these
conditions.
Note: Follow this link if you want the mechanism for the
nitration of benzene.
You will find the mechanism for the nitration of nitrobenzene
(the reaction producing 1,3-dinitrobenzene) at the bottom of
the page you will get to by following this second link.
If you choose to follow either of these links, use the BACK
button (or the HISTORY file or GO menu) on your browser to
return to this page later.
Just as with benzene, you will get a certain amount of dinitro compound
formed under the conditions of the reaction, but virtually no trinitro
product because the reactivity of the ring decreases for every nitro group
added. From an experimental point of view this is just as well.
Trinitromethylbenzene used to be called trinitrotoluene or TNT!
The reason for the 2,4-directing effect of the methyl group is beyond UK
A level, but the increased reaction rate can be explained up to a point.
The reactivity of a benzene ring is governed by the electron density
around the ring. Methyl groups tend to "push" electrons towards the ring increasing the density, and so making the ring more attractive to
attacking reagents.
This is actually a simplification. In order to understand the rate effect
properly you have to think about the stability of the intermediate ions
formed during the reactions, because this affects the activation energy of
the reactions. This is also the basis for the directing effect and is again
beyond UK A level.
entirely logical!
Thirdly, you can end up with completely different names for
compounds which are structurally similar. For example, if you
think about substituting chlorines into these positions instead
of nitro groups you will have to completely change the names
for purely alphabetical reasons. That's silly!
I may well be in a minority of one on this, but I am sticking to
my guns on it. In fact, IUPAC is much more flexible about
these things than they are sometimes given credit for. I doubt
if it would worry them, although it might upset your teachers
or lecturers. Obviously, if you are working in a system which
still calls methylbenzene "toluene", none of this bothers you!
These compounds act as the catalyst and behave exactly like aluminium
chloride, AlCl3, or aluminium bromide, AlBr3, 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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or:
Note: Follow this link if you want the mechanism for the
halogenation of benzene.
Use the BACK button on your browser to return to this page
later.
Addition reactions
In the presence of ultraviolet light (but without a catalyst present), hot
benzene will also undergo an addition reaction with chlorine or bromine.
The ring delocalisation is permanently broken and a chlorine or bromine
atom adds on to each carbon atom.
For example, if you bubble chlorine gas through hot benzene exposed to
UV light for an hour, you get 1,2,3,4,5,6-hexachlorocyclohexane.
Note: You will find the mechanism for this reaction half way
down the page you will get to by following this link.
Use the BACK button on your browser to return to this page
later.
Addition reactions
I haven't been able to track down anything similar to the reaction
between benzene and chlorine in which six chlorine atoms add around
the ring.
That perhaps isn't surprising. Chlorine adds to benzene in the presence
of ultraviolet light. With methylbenzene under those conditions, you get
substitution in the methyl group. That is energetically easier because it
doesn't involve breaking the delocalised electron system.
Whether you would get addition to the ring if you used a large excess of
chlorine and did the reaction for a long time, I don't know. Once all the
hydrogens in the methyl group had been substituted, perhaps you might
then get addition to the ring as well.
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Friedel-Crafts acylation
Friedel-Crafts acylation of benzene
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, and in this case the reaction is sometimes called
"ethanoylation". In the example which follows we are substituting a
CH3CO- group into the ring, but you could equally well use any other acyl
group.
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. The mixture is heated to about 60C
for about 30 minutes.
Note: You will find the mechanism for this reaction in the
mechanisms section of this site.
Use the BACK button on your browser to return to this page
later.
Friedel-Crafts alkylation
Friedel-Crafts alkylation of benzene
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 reacts at room temperature with a chloroalkane (for example,
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or:
Note: The problem in this case lies in the fact that the methyl
groups attaching to the ring can fall off again and reattach
somewhere else in the presence of the aluminium chloride.
You can get equilibria set up between the various isomers.
The reason for the 2,4- directing effect of the methyl group in
methylbenzene lies in the fact that the 2- and 4- isomers form
faster than the 3- isomer. However, in this case, the 3isomer is the most thermodynamically stable of the three. If
you raise the temperature, or allow more time, the equilibria
set up favour the most stable product.
You do NOT have to worry about this for A level purposes.
or:
Again, 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.
Note: You will find the mechanism for this reaction in the
mechanisms section of this site. This will show exactly what
the HCl and aluminium chloride are doing in the reaction.
Use the BACK button on your browser to return to this page
later.
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 reaction
happens at room temperature.
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 you want the mechanism for this reaction, you will
find it explained if you follow this link.
Use the BACK button on your browser to return to this page.
the -OH group which behaves like a simple alcohol and can be
replaced by other things like chlorine, which can in turn be
replaced to give, for example, an -NH2 group;
the -CN group which is easily converted into a carboxylic acid
group -COOH.
The reactions
This reaction only works well for aldehydes. In the case of ketones, one
of the hydrocarbon groups attached to the carbonyl group needs to be a
methyl group. Bulky groups attached to the carbonyl group get in the way
of the reaction happening.
The aldehyde or ketone is shaken with a saturated solution of sodium
hydrogensulphite in water. Where the product is formed, it separates as
white crystals.
ketones that it works for). The addition compound can be split easily to
regenerate the aldehyde or ketone by treating it with either dilute acid or
dilute alkali.
If you have an impure aldehyde, for example, you could shake it with a
saturated solution of sodium hydrogensulphite to produce the crystals.
These crystals could easily be filtered and washed to remove any other
impurities. Addition of dilute acid, for example, would then regenerate the
original aldehyde.
It would, of course, still need to be separated from the excess acid and
assorted inorganic products of the reaction - but that is beyond the scope
of this page!
However, if you are going to use this second equation, you must include
state symbols. They imply that the hydrogen ion is actually attached to a
water molecule.
If you mix dilute ethanoic acid with sodium hydroxide solution, for
example, you simply get a colourless solution containing sodium
ethanoate. The only sign that a change has happened is that the
temperature of the mixture will have increased.
This change could well be represented by the ionic equation above, but if
you want it, the full equation for this particular reaction is:
If you pour some dilute ethanoic acid onto some white sodium carbonate
or sodium hydrogencarbonate crystals, there is an immediate fizzing as
carbon dioxide is produced. You end up with a colourless solution of
sodium ethanoate.
With sodium carbonate, the full equation is:
In this case, the marble chip would react noticeably more slowly with
ethanoic acid than with hydrochloric acid.
With ammonia
Ethanoic acid reacts with ammonia in exactly the same way as any other
acid does. It transfers a hydrogen ion to the lone pair on the nitrogen of
the ammonia and forms an ammonium ion.
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With amines
Amines are compounds in which one or more of the hydrogen atoms in
an ammonia molecule have been replaced by a hydrocarbon group such
as an alkyl group. For simplicity, we'll just look at compounds where only
one of the hydrogen atoms has been replaced. These are called primary
amines.
Simple primary amines include:
The small amines are very similar indeed to ammonia in many ways. For
example, they smell very much like ammonia and are just as soluble in
water. Because all you have done to an ammonia molecule is swap a
hydrogen for an alkyl group, the lone pair is still there on the nitrogen
atom.
That means that they will react with acids (including carboxylic acids) in
just the same way as ammonia does.
However complicated the amine, because all of them have got a lone
pair on the nitrogen atom, you would get the same sort of reaction.
Note: If you want to find out more about amines you could
explore the amines menu by following this link.
Notice that the ester is named the opposite way around from the way the
formula is written. The "ethanoate" bit comes from ethanoic acid. The
"ethyl" bit comes from the ethyl group on the end.
Note: You can find more about naming acids and esters by
following this link to a different part of this site.
Use the BACK button on your browser to return to this page.
Making esters
The chemistry of the reaction
Esters are produced when carboxylic acids are heated with alcohols in
the presence of an acid catalyst. The catalyst is usually concentrated
sulphuric acid. Dry hydrogen chloride gas is used in some cases, but
these tend to involve aromatic esters (ones containing a benzene ring). If
you are a UK A level student you won't have to worry about these.
The esterification reaction is both slow and reversible. The equation for
the reaction between an acid RCOOH and an alcohol R'OH (where R
and R' can be the same or different) is:
So, for example, if you were making ethyl ethanoate from ethanoic acid
and ethanol, the equation would be:
The reaction
The reducing agent
Lithium tetrahydridoaluminate has the structure:
covalent) bond using the lone pair on a hydride ion (H-) to form a bond with
an empty orbital on the aluminium.
Note: Follow this link if you aren't sure what a primary alcohol
is.
Use the BACK button on your browser to return to this page.
Reaction conditions
Lithium tetrahydridoaluminate reacts violently with water and so the
reactions are carried out in solution in dry ethoxyethane (diethyl ether or
just "ether"). The reaction happens at room temperature.
At the end of the reaction, the product is a complex aluminium salt. This is
converted into the alcohol by treatment with dilute sulphuric acid.
This page looks at ways of swapping the -OH group in the -COOH group
of a carboxylic acid for a chlorine atom. This produces useful compounds
called acyl chlorides (acid chlorides).
It covers the use of phosphorus(V) chloride and phosphorus(III) chloride
as well as sulphur dichloride oxide (thionyl chloride).
Acyl chlorides are very reactive, and can be used to make a wide range
of other things. That's why they are important.
Note: If you are want to find out more about acyl chlorides,
you can explore the acyl chlorides menu by following this link.
Use the BACK button on your browser to return to this page.
Understanding Chemistry
Background . . .
An introduction to acyl chlorides including a general look at their
reactivity.
Preparation of acyl chlorides . . .
Their preparation from carboxylic acids.
Reactions of acyl chlorides involving oxygen compounds . . .
The reactions of acyl chlorides with water, alcohols and phenols.
Reactions of acyl chlorides involving nitrogen compounds . . .
The reactions of acyl chlorides with ammonia and primary amines.
Using acyl chlorides in Friedel-Crafts reactions . . .
The use of acyl chlorides in substituting an acyl group into a
benzene ring.
This page explains what acyl chlorides are and looks at their simple
physical properties such as boiling points. It introduces their chemical
reactivity in a general way, but details of specific reactions are given on
separate pages - see the acyl chlorides menu (link at the bottom of the
page).
There are a number of related compounds in which the -OH group in the
acid is replaced by something else. Compounds like this are described
as acid derivatives.
Acyl chlorides (also known as acid chlorides) are one example of an acid
derivative. In this case, the -OH group has been replaced by a chlorine
atom.
ethanoic acid
ethanoyl chloride
CH3COCl
propanoic acid
propanoyl chloride
CH3CH2COCl
butanoic acid
butanoyl chloride
CH3CH2CH2COCl
If you have something substituted into the hydrocarbon chain, the carbon
in the -COCl group counts as the number 1 carbon.
For example, 2-methylbutanoyl chloride is:
Solubility in water
Acyl chlorides can't be said to dissolve in water because they react (often
violently) with it. The strong reaction means that it is impossible to get a
simple aqueous solution of an acyl chloride.
Boiling points
Note: You can find details of all these reactions from the
acyl chlorides menu (link below).
If you are interested in exploring the general mechanism for
these reactions, you will find it by following this link to another
part of the site dealing with nucleophilic addition-elimination
reactions. If you want mechanisms for specific reactions you
could explore other pages from the nucleophilic additionelimination menu as well - but read the general mechanism
first.
Background
What are acyl chlorides?
Acyl chlorides (also known as acid chlorides) are one of a number of
types of compounds known as "acid derivatives". This is ethanoic acid:
If you remove the -OH group and replace it by a -Cl, you have produced
an acyl chloride.
This molecule is known as ethanoyl chloride and for the rest of this topic
will be taken as typical of acyl chlorides in general.
Acyl chlorides are extremely reactive. They are open to attack by
nucleophiles - with the overall result being a replacement of the chlorine
by something else.
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 nucleophiles that we shall be
looking at all depend on lone pairs on either an oxygen atom or a
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nitrogen atom.
Nucleophiles based on oxygen atoms
We shall be talking about water and alcohols, taking ethanol as a typical
alcohol.
Notice how similar these two molecules are around the oxygen atom.
That's what turns out to be important.
Nucleophiles based on nitrogen atoms
We shall be considering ammonia and primary amines, taking ethylamine
as a typical primary amine. A primary amine contains the -NH2 group
attached to either an alkyl group (as it is here) or a benzene ring. As far
as these reactions are concerned, the nature of any hydrocarbon
attached to the nitrogen makes no difference. The nitrogen atom is the
important bit.
Again, notice how similar these two molecules are around the nitrogen
atom - and also how similar they are to the previous ones containing
oxygen. Both types of molecule have an active lone pair of electrons
attached to one of the most electronegative elements. All of these
molecules also have at least one hydrogen atom attached to the oxygen
or nitrogen.
Why are acyl chlorides attacked by nucleophiles?
The carbon atom in the -COCl group has both an oxygen atom and a
chlorine atom attached to it. Both of these are very electronegative. They
both pull electrons towards themselves, leaving the carbon atom quite
positively charged.
In each case, the net effect is that you replace the -Cl by -Nu, and
hydrogen chloride is formed as well.
Since the initial attack is by a nucleophile, and the overall result is
substitution, it would seem reasonable to describe the reaction as
nucleophilic substitution. However, the reaction happens in two distinct
stages. The first involves an addition reaction, which is followed by an
elimination reaction where HCl is produced. So the mechanism is also
known as nucleophilic addition / elimination.
Note: You will find both terms in use - and to confuse the
issue still further, these are also examples of condensation
reactions. A condensation reaction is one in which two
molecules join together to make a bigger one, and in the
process shed a little molecule.
The only Exam Board to require these mechanisms (AQA)
calls them addition / elimination reactions.
Notice the positive charge that forms on the nucleophile. Just accept this
for the moment. It's much easier to explain why that charge must be
there if you have a real example in front of you. This is fully explained in
the pages on the reactions involving water, ammonia and so on.
The elimination stage of the mechanism
This happens in two steps. In the first step, the carbon-oxygen double
bond reforms. To make room for it, the electrons in the carbon-chlorine
bond are repelled until they are entirely on the chlorine atom - forming a
chloride ion.
Finally, the chloride ion plucks the hydrogen off the original nucleophile.
It removes it as a hydrogen ion, leaving the pair of electrons behind on
the oxygen or nitrogen atom in that nucleophile. That cancels the positive
charge.
Understanding Chemistry
This page gives you the facts and a simple, uncluttered mechanism for
the nucleophilic addition / elimination reaction between acyl chlorides
(acid chlorides) and water. If you want the mechanism explained to you
in detail, there is a link at the bottom of the page.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way. Simply replace the CH3 group in
what follows by anything else you want.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic
attack on the fairly positive carbon atom by one of the lone pairs on the
oxygen of a water molecule.
Note: Only one of the two lone pairs on the oxygen in water
is shown. This is to avoid cluttering an already complicated
diagram with things that aren't relevant.
The second stage (the elimination stage) happens in two steps. In the
first, the carbon-oxygen double bond reforms and a chloride ion is
pushed off.
Explaining the reaction between acyl chlorides and water - addition / elimination
This page guides you through the mechanism for the nucleophilic
addition / elimination reaction between acyl chlorides (acid chlorides) and
water.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way. Simply replace the CH3 group in
what follows by anything else you want.
Explaining the reaction between acyl chlorides and water - addition / elimination
The mechanism
The reaction happens in two main stages - an addition stage, followed by
an elimination stage.
In the addition stage, a water molecule becomes attached to the carbon
in the ethanoyl chloride.
As the lone pair on the water approaches the fairly positive carbon in the
ethanoyl chloride, it moves to form a bond with it. In the process, the two
electrons in one of the carbon-oxygen bonds are repelled entirely onto
the oxygen, leaving that oxygen negatively charged.
Explaining the reaction between acyl chlorides and water - addition / elimination
Note: Only one of the two lone pairs on the oxygen in water
is shown because only one of them is involved in the
reaction. There's no reason why you couldn't write both in if
you want to - it just clutters the diagram.
Notice that the oxygen atom in the water has gained a positive charge.
The underlying reason for this is that when the lone pair forms a bond
with the carbon, electrons are moving away from the oxygen. What
matters, though, is that you remember to show the positive charge in an
exam. Think of it like this:
If you leave out the positive charge, two things are wrong with the
equation:
The charges don't balance. You start with two overall neutral
molecules and, if you forgot the positive charge, you would end up
with a negative ion. There has got to be a positive charge
somewhere to balance the negative one.
The oxygen looks wrong! Oxygen normally forms two bonds, but
here it is forming three. Oxygen can only form three bonds if it
carries a positive charge. (A positively charged oxygen atom has
the same electronic structure as nitrogen - which normally forms
three bonds.)
You can put both things right with a positive charge on the oxygen.
Explaining the reaction between acyl chlorides and water - addition / elimination
The elimination stage stage of the reaction happens in two steps. In the
first, the carbon-oxygen double bond reforms. As the electron pair moves
back to form a bond with the carbon, the pair of electrons in the carbonchlorine bond are forced entirely onto the chlorine to give a chloride ion.
Finally, the chloride ion forms a bond with one of the hydrogens on the
oxygen - removing it as a hydrogen ion. The electrons in the hydrogenoxgyen bond move back onto the oxygen, cancelling the positive charge.
This page gives you the facts and a simple, uncluttered mechanism for the
nucleophilic addition / elimination reaction between acyl chlorides (acid
chlorides) and alcohols. If you want the mechanism explained to you in
detail, there is a link at the bottom of the page.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl chloride
will behave in the same way. Simply replace the CH3 group in what follows
by anything else you want. Similarly, ethanol is taken as a typical alcohol. If
you are interested in another alcohol, you can replace the CH3CH2 group
by any other alkyl group.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic
attack on the fairly positive carbon atom by one of the lone pairs on the
oxygen of an ethanol molecule.
Note: Only one of the two lone pairs on the oxygen in the
ethanol is shown. This is to avoid cluttering an already
complicated diagram with things that aren't relevant.
The second stage (the elimination stage) happens in two steps. In the first,
the carbon-oxygen double bond reforms and a chloride ion is pushed off.
Explaining the reaction between acyl chlorides and alcohols - addition / elimination
This page guides you through the mechanism for the nucleophilic
addition / elimination reaction between acyl chlorides (acid chlorides) and
alcohols.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way. Ethanol is taken as a typical
alcohol. Again, any other alcohol will behave in the same way.
Explaining the reaction between acyl chlorides and alcohols - addition / elimination
The mechanism
The reaction happens in two main stages - an addition stage, followed by
an elimination stage.
In the addition stage, an ethanol molecule becomes attached to the
carbon in the ethanoyl chloride.
As the lone pair on the oxygen approaches the fairly positive carbon in
the ethanoyl chloride, it moves to form a bond with it. In the process, the
two electrons in one of the carbon-oxygen bonds are repelled entirely
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Explaining the reaction between acyl chlorides and alcohols - addition / elimination
Note: Only one of the two lone pairs on the oxygen in the
ethanol is shown because only one of them is involved in the
reaction. There's no reason why you couldn't write both in if
you want to - it just clutters the diagram.
Notice that the oxygen atom in the ethanol has gained a positive charge.
The underlying reason for this is that when the lone pair forms a bond
with the carbon, electrons are moving away from the oxygen. What
matters, though, is that you remember to show the positive charge in an
exam. Think of it like this:
If you leave out the positive charge, two things are wrong with the
equation:
The charges don't balance. You start with two overall neutral
molecules and, if you forgot the positive charge, you would end up
with a negative ion. There has got to be a positive charge
somewhere to balance the negative one.
The oxygen looks wrong! Oxygen normally forms two bonds, but
here it is forming three. Oxygen can only form three bonds if it
carries a positive charge. (A positively charged oxygen atom has
the same electronic structure as nitrogen - which normally forms
three bonds.)
You can put both things right with a positive charge on the oxygen.
Explaining the reaction between acyl chlorides and alcohols - addition / elimination
The elimination stage stage of the reaction happens in two steps. In the
first, the carbon-oxygen double bond reforms. As the electron pair moves
back to form a bond with the carbon, the pair of electrons in the carbonchlorine bond are forced entirely onto the chlorine to give a chloride ion.
Finally, the chloride ion forms a bond with the hydrogen on the oxygen removing it as a hydrogen ion. The electrons in the hydrogen-oxgyen
bond move back onto the oxygen, cancelling the positive charge.
Explaining the reaction between acyl chlorides and alcohols - addition / elimination
This page gives you the facts and a simple, uncluttered mechanism for
the nucleophilic addition / elimination reaction between acyl chlorides
(acid chlorides) and ammonia. If you want the mechanism explained to
you in detail, there is a link at the bottom of the page.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way. Simply replace the CH3 group in
what follows by anything else you want.
Notice that, unlike the reactions between ethanoyl chloride and water or
ethanol, hydrogen chloride isn't produced - at least, not in any quantity.
Any hydrogen chloride formed would immediately react with excess
ammonia to give ammonium chloride.
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic
attack on the fairly positive carbon atom by the lone pair on the nitrogen
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The second stage (the elimination stage) happens in two steps. In the
first, the carbon-oxygen double bond reforms and a chloride ion is
pushed off.
and
The ammonium ion, together with the chloride ion already there, makes
up the ammonium chloride formed in the reaction.
Explaining the reaction between acyl chlorides and ammonia - addition / elimination
This page guides you through the mechanism for the nucleophilic
addition / elimination reaction between acyl chlorides (acid chlorides) and
ammonia.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way.
Explaining the reaction between acyl chlorides and ammonia - addition / elimination
The carbon atom in the -COCl group has both an oxygen atom and a
chlorine atom attached to it. Both of these are very electronegative. They
both pull electrons towards themselves, leaving the carbon atom quite
positively charged. It is that carbon atom which is attacked by the lone
pair on the nitrogen atom in an ammonia molecule.
The ethanoyl chloride molecule is also planar (flat) around that carbon
atom, and that leaves plenty of room for a nucleophile to attack either
from above or below the plane of the molecule.
The mechanism
The reaction happens in two main stages - an addition stage, followed by
an elimination stage.
In the addition stage, an ammonia molecule becomes attached to the
carbon in the ethanoyl chloride.
As the lone pair on the nitrogen approaches the fairly positive carbon in
the ethanoyl chloride, it moves to form a bond with it. In the process, the
two electrons in one of the carbon-oxygen bonds are repelled entirely
onto the oxygen, leaving it negatively charged.
Notice that the nitrogen atom has gained a positive charge. The
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Explaining the reaction between acyl chlorides and ammonia - addition / elimination
underlying reason for this is that when the lone pair forms a bond with
the carbon, electrons are moving away from the nitrogen. What matters,
though, is that you remember to show the positive charge in an exam.
Think of it like this:
If you leave out the positive charge, two things are wrong with the
equation:
The charges don't balance. You start with two overall neutral
molecules and, if you forgot the positive charge, you would end up
with a negative ion. There has got to be a positive charge
somewhere to balance the negative one.
The nitrogen looks wrong! Nitrogen normally forms three bonds,
but here it is forming four. Nitrogen can only form four bonds if it
carries a positive charge. (A positively charged nitrogen atom has
the same electronic structure as carbon - which normally forms
four bonds.)
You can put both things right with a positive charge on the nitrogen.
The elimination stage stage of the reaction happens in two steps. In the
first, the carbon-oxygen double bond reforms. As the electron pair moves
back to form a bond with the carbon, the pair of electrons in the carbonchlorine bond are forced entirely onto the chlorine to give a chloride ion.
Explaining the reaction between acyl chlorides and ammonia - addition / elimination
The hydrogen chloride produced would at once react with any excess
ammonia present to form ammonium chloride.
The other (more likely) possibility is that the hydrogen ion gets removed
directly by an ammonia molecule. This forms an ammonium ion. The
ammonium ion together with the chloride ion formed in the previous
stage makes up the ammonium chloride produced in the reaction.
Explaining the reaction between acyl chlorides and ammonia - addition / elimination
This page gives you the facts and a simple, uncluttered mechanism for
the nucleophilic addition / elimination reaction between acyl chlorides
(acid chlorides) and amines. If you want the mechanism explained to you
in detail, there is a link at the bottom of the page.
Ethanoyl chloride is taken as a typical acyl chloride. Any other acyl
chloride will behave in the same way. Simply replace the CH3 group in
what follows by anything else you want.
Similarly, ethylamine is taken as a typical amine. Any other amine will
behave in the same way. Replacing the CH3CH2 group by any other
hydrocarbon group won't affect the mechanism in any way.
Notice that, unlike the reactions between ethanoyl chloride and water or
ethanol, hydrogen chloride isn't produced - at least, not in any quantity.
Any hydrogen chloride formed would immediately react with excess
The mechanism
The first stage (the addition stage of the reaction) involves a nucleophilic
attack on the fairly positive carbon atom by the lone pair on the nitrogen
atom in the ethylamine.
The second stage (the elimination stage) happens in two steps. In the
first, the carbon-oxygen double bond reforms and a chloride ion is
pushed off.
and
The ethylammonium ion, together with the chloride ion already there,
makes up the ethylammonium chloride formed in the reaction.
Explaining the reaction between acyl chlorides and amines - addition / elimination
This page guides you through the mechanism for the nucleophilic
addition / elimination reaction between acyl chlorides (acid chlorides) and
amines.
Ethanoyl chloride is taken as a typical acyl chloride. Similarly, ethylamine
is taken as a typical amine. Changing either the acyl choride or the
amine won't affect the mechanism in any way.
Explaining the reaction between acyl chlorides and amines - addition / elimination
Explaining the reaction between acyl chlorides and amines - addition / elimination
The mechanism
The reaction happens in two main stages - an addition stage, followed by
an elimination stage.
In the addition stage, an ethylamine molecule becomes attached to the
carbon in the ethanoyl chloride.
As the lone pair on the nitrogen approaches the fairly positive carbon in
the ethanoyl chloride, it moves to form a bond with it. In the process, the
two electrons in one of the carbon-oxygen bonds are repelled entirely
onto the oxygen, leaving it negatively charged.
Notice that the nitrogen atom has gained a positive charge. The
underlying reason for this is that when the lone pair forms a bond with
the carbon, electrons are moving away from the nitrogen. What matters,
though, is that you remember to show the positive charge in an exam.
Think of it like this:
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Explaining the reaction between acyl chlorides and amines - addition / elimination
If you leave out the positive charge, two things are wrong with the
equation:
The charges don't balance. You start with two overall neutral
molecules and, if you forgot the positive charge, you would end up
with a negative ion. There has got to be a positive charge
somewhere to balance the negative one.
The nitrogen looks wrong! Nitrogen normally forms three bonds,
but here it is forming four. Nitrogen can only form four bonds if it
carries a positive charge. (A positively charged nitrogen atom has
the same electronic structure as carbon - which normally forms
four bonds.)
You can put both things right with a positive charge on the nitrogen.
The elimination stage stage of the reaction happens in two steps. In the
first, the carbon-oxygen double bond reforms. As the electron pair moves
back to form a bond with the carbon, the pair of electrons in the carbonchlorine bond are forced entirely onto the chlorine to give a chloride ion.
Explaining the reaction between acyl chlorides and amines - addition / elimination
The hydrogen chloride produced would at once react with any excess
ethylamine present to form ethylammonium chloride.
The other (more likely) possibility is that the hydrogen ion gets removed
directly by an ethylamine molecule. This forms an ethylammonium ion.
The ethylammonium ion together with the chloride ion formed in the
previous stage makes up the ethylammonium chloride produced in the
reaction.
Explaining the reaction between acyl chlorides and amines - addition / elimination
This page looks at ways of swapping the -OH group in the -COOH group
of a carboxylic acid for a chlorine atom to make acyl chlorides (acid
chlorides), and is a very slightly modified version of a page in the section
on reactions of carboxylic acids.
It covers the use of phosphorus(V) chloride, phosphorus(III) chloride and
sulphur dichloride oxide (thionyl chloride).
oxide.
This page looks at the reactions of acyl chlorides (acid chlorides) with
water, alcohols and phenol. These reactions are all considered together
because their chemistry is so similar.
page.
Note: If you are want the mechanism for this reaction, you
will find it by following this link to another part of the site
dealing with nucleophilic addition-elimination reactions.
Use the BACK button on your browser to return to this page.
The organic product this time is an ester. For example, with ethanol you
would get the ester ethyl ethanoate:
Especially if you write the equation in this second way, it is obvious that
you have just produced another ester - in this case, called phenyl
ethanoate.
But beware! You may come across the structure drawn in a variety of
other ways which make it look much more as if it was a derivative of
phenol (which of course it is!).
For example:
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You might also find it with the -OH group at the top and the -COOH
group next door and either to the left or right of it. Life can get very
confusing!
When this reacts with ethanoyl chloride, it is ethanoylated (or acylated, if
you want to use the more general term) to give:
You might find all sorts of other variants on drawing this as well.
This molecule is aspirin.
Note: Although you can make aspirin this way, the 2hydroxybenzoic acid is normally ethanoylated commercially
using ethanoic anhydride rather than ethanoyl chloride. There
are various reasons for this, which are explored at the bottom
of the corresponding page about the reactions of acid
anhydrides with oxygen compounds.
Use the BACK button on your browser if you want to return to
this page later.
This page looks at the reactions of acid anhydrides with water, alcohols
and phenols (including the manufacture of aspirin). These reactions are all
considered together because their chemistry is so similar.
There is also a great similarity between acid anhydrides and acyl
chlorides (acid chlorides) as far as these reactions are concerned.
Concentrate on these similarities as you go through this page because it
should help you to remember.
Note: If you aren't sure about using this symbol for a benzene
ring, you could follow this link to find out all about it. It is likely
to take you some time, though, and you may have to visit
several other pages as well.
It isn't particularly important in the context of the current page.
All you need to know is that at each corner of the hexagon
there is a carbon atom, together with a hydrogen atom apart
from where the -OH group is attached.
If you choose to follow the link, use the BACK button (or the
HISTORY file or GO menu) on your browser to return to this
page.
Ethanoic anhydride is the only one you are likely to come across for UK A
level purposes.
If you compare this with the acyl chloride equation, you can see that the
only difference is that ethanoic acid is produced as the second product of
the reaction rather than hydrogen chloride.
These reactions are just the same as the corresponding acyl chloride
reactions except:
The product this time (apart from the ethanoic acid always produced) is an
ester. For example, with ethanol you would get the ester ethyl ethanoate:
Especially if you write the equation in this second way, it is obvious that
you have just produced another ester - in this case, called phenyl
ethanoate.
The equivalent acyl chloride reaction is:
But beware! You may come across the structure of the ester drawn in a
variety of other ways which make it look much more as if it was a
derivative of phenol (which of course it is!).
For example:
Looking at it this way, notice that the hydrogen of the phenol -OH group
has been replaced by an acyl group - an alkyl group attached to a carbonoxygen double bond.
You can say that the phenol has been acylated or has undergone
acylation.
Because of the nature of this particular acyl group, it is also described as
ethanoylation. The hydrogen is being replaced by an ethanoyl group,
CH3CO-.
You might also find it with the -OH group at the top and the -COOH group
next door and either to the left or right of it. Life can get very confusing!
When this reacts with ethanoic anhydride, it is ethanoylated (or acylated, if
you want to use the more general term) to give:
You might find all sorts of other variants on drawing this as well.
This molecule is aspirin.
Although this reaction can also be done with ethanoyl chloride, aspirin is
manufactured by reacting 2-hydroxybenzoic acid with ethanoic anhydride
at 90C.
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The reasons for using ethanoic anhydride rather than ethanoyl chloride
include:
Understanding Chemistry
Background . . .
An introduction to acid anhydrides including a general look at their
reactivity.
Reactions of acid anhydrides with oxygen compounds . . .
The reactions of acid anhydrides with water, alcohols and phenols
(including the manufacture of aspirin).
Reactions of acid anhydrides with nitrogen compounds . . .
The reactions of acid anhydrides with ammonia and primary
amines.
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This page explains what acid anhydrides are and looks at their simple
physical properties such as boiling points. It introduces their chemical
reactivity in a general way, but details of specific reactions are given on
separate pages - see the acid anhydrides menu (link at the bottom of the
page).
Solubility in water
Ethanoic anhydride can't be said to dissolve in water because it reacts
with it to give ethanoic acid. There is no such thing as an aqueous
solution of ethanoic anhydride.
Boiling point
Ethanoic anhydride boils at 140C. This is because it is a fairly big polar
molecule and so has both van der Waals dispersion forces and dipoledipole attractions.
It doesn't, however, form hydrogen bonds. That means that its boiling
point isn't as high as a carboxylic acid of similar size. For example,
pentanoic acid (the most similarly sized acid) boils at 186C.
Just like the hydrogen chloride, this might afterwards go on to react with
other things present.
The reactions (of both acyl chlorides and acid anhydrides) involve things
like water, alcohols and phenols, or ammonia and amines. All of these
particular cases contain a very electronegative element with an active
lone pair of electrons - either oxygen or nitrogen.
Note: You can find details of all these reactions from the
acid anhydrides menu (link below).
This page looks at the reactions of acid anhydrides with ammonia and with
primary amines. These reactions are considered together because their
chemistry is so similar.
There is also a great similarity between acid anhydrides and acyl chlorides
(acid chlorides) as far as these reactions are concerned. Concentrate on
these similarities as you go through this page because it should help you
to remember.
Note: If you aren't sure about using this symbol for a benzene
ring, you could follow this link to find out all about it. It is likely
to take you some time, though, and you may have to visit
several other pages as well.
It isn't particularly important in the context of the current page.
All you need to know is that at each corner of the hexagon
there is a carbon atom, together with a hydrogen atom apart
from where the -NH2 group is attached.
If you choose to follow the link, use the BACK button (or the
HISTORY file or GO menu) on your browser to return to this
page.
So . . . in each case, you initially get hydrogen chloride gas - the hydrogen
coming from the -NH2 group, and the chlorine from the ethanoyl chloride.
Everything left over just gets joined together.
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But ammonia and amines are basic, and react with the hydrogen chloride
to produce a salt. So the second stage of the reaction is:
If you compare this with the acyl chloride equation, you can see that the
only difference is that ethanoic acid is produced as the second product of
the reaction rather than hydrogen chloride.
Then the ethanoic acid reacts with excess ammonia or amine to give a salt
- this time an ethanoate.
This looks more difficult than the acyl chloride case because of the way the
salt is written. You get an ethanoate ion and a positive ion with this
structure:
This is easier to understand with real compounds - as you will see below.
In summary:
These reactions are just the same as the corresponding acyl chloride
reactions except:
. . . and you can combine all this together to give one overall equation:
You need to follow this through really carefully, because the two products
of the reaction overall can look confusingly similar.
The corresponding reaction with an acyl chloride is:
If you stop and think about it, this is obviously the same molecule as in the
equation above, but it stresses the phenylamine part of it much more.
Looking at it this way, notice that one of the hydrogens of the -NH2 group
has been replaced by an acyl group - an alkyl group attached to a carbonoxygen double bond.
You can say that the phenylamine has been acylated or has undergone
acylation.
Because of the nature of this particular acyl group, it is also described as
ethanoylation. The hydrogen is being replaced by an ethanoyl group,
CH3CO-.
This page looks at the reactions of acyl chlorides (acid chlorides) with
ammonia and with primary amines. These reactions are considered
together because their chemistry is so similar.
Note: If you aren't sure about using this symbol for a benzene
ring, you could follow this link to find out all about it. It is likely
to take you some time, though, and you may have to visit
several other pages as well.
It isn't particularly important in the context of the current page.
All you need to know is that at each corner of the hexagon
there is a carbon atom, together with a hydrogen atom apart
from where the -NH2 group is attached.
If you want to know more about what primary amines are, you
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So . . . in each case, you initially get hydrogen chloride gas - the hydrogen
coming from the -NH2 group, and the chlorine from the ethanoyl chloride.
Everything left over just gets joined together.
But ammonia and amines are basic, and react with the hydrogen chloride
to produce a salt. So the second stage of the reaction is:
This is easier to understand with real compounds - as you will see below.
. . . and you can combine all this together to give one overall equation:
Note: If you are want the mechanism for this reaction, you will
find it by following this link to another part of the site dealing
with nucleophilic addition-elimination reactions.
Use the BACK button on your browser to return to this page.
The reaction looks exactly the same as the one with ammonia. The
methylamine is again used as a concentrated solution in water. There is a
violent reaction producing a white solid mixture of N-methylethanamide
and methylammonium chloride.
If you stop and think about it, this is obviously the same molecule as in the
equation above, but it stresses the phenylamine part of it much more.
Looking at it this way, notice that one of the hydrogens of the -NH2 group
has been replaced by an acyl group - an alkyl group attached to a carbonoxygen double bond.
You can say that the phenylamine has been acylated or has undergone
acylation.
Because of the nature of this particular acyl group, it is also described as
ethanoylation. The hydrogen is being replaced by an ethanoyl group,
CH3CO-.
This page looks at the reaction of acyl chlorides (acid chlorides) with
benzene in the presence of an aluminium chloride catalyst. This is known
as a Friedel-Crafts acylation.
In the simplified formula for the product, the phenyl group is usually
written on the left-hand side and the alkyl group to the right of the carbonoxygen double bond - but I doubt if it really matters!
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 product is called phenylethanone (old name, acetophenone).
Note: If you are want the mechanism for this reaction, you
will find it by following this link to another part of the site
dealing with electrophilic substitution reactions.
Use the BACK button on your browser to return to this page.
This indirect route is the best way of getting an alkyl group attached to a
benzene ring.
It is possible to attach an alkyl group directly to the ring, but it is
The reaction
The solid sodium salt of a carboxylic acid is mixed with solid soda lime,
and the mixture is heated.
For example, if you heat sodium ethanoate with soda lime, you get
methane gas formed:
This reaction can be done with certain carboxylic acids themselves, but
the acid would have to be solid. For example, benzene can be made by
heating soda lime with solid benzoic acid (benzenecarboxylic acid),
C6H5COOH.
You can think of this as first a reaction between the acid and the soda
lime to make sodium benzoate, and then a decarboxylation as in the first
example.
Esters Menu
Understanding Chemistry
ESTERS MENU
Background . . .
An introduction to esters, including large esters like animal or
vegetable fats and oils.
Preparation of esters . . .
Their preparation from alcohols (and phenols) reacting with
carboxylic acids, acyl chlorides and acid anhydrides as appropriate.
The hydrolysis of esters . . .
The hydrolysis of esters using water, acids or alkalis (including
soap making).
Polyesters . . .
A summary of the chemistry of simple polyesters like Terylene,
including their formation, structure, hydrolysis and uses.
Esters Menu
an introduction to esters
INTRODUCING ESTERS
This page explains what esters are and looks at their simple physical
properties such as solubility and boiling points. It includes an introduction
to more complicated naturally-occurring esters like animal and vegetable
fats and oils.
Notice that the ester is named the opposite way around from the way the
formula is written. The "ethanoate" bit comes from ethanoic acid. The
"ethyl" bit comes from the ethyl group on the end.
an introduction to esters
Notice that the acid is named by counting up the total number of carbon
atoms in the chain - including the one in the -COOH group. So, for
example, CH3CH2COOH is propanoic acid, and CH3CH2COO is the
propanoate group.
an introduction to esters
Note: You can find more about naming acids and esters by
following this link to a different part of this site.
Use the BACK button on your browser to return to this page.
an introduction to esters
Note: The colour coding refers to the name of the ester and
not strictly to the structure. When the ester is made, the water
that is lost comes from the whole -OH group of the acid and
just a single hydrogen from the alcohol. That means that as
far as the structure is concerned the oxygen attached to the
ethyl group actually ought to be coloured red. Don't worry
about this at this level.
Now lets make the alcohol a bit more complicated by having more than
one -OH group. The diagram below shows the structure of propane-1,2,3triol (old name: glycerol).
Just as with the ethanol in the previous equation, I've drawn this back-tofront to make the next diagrams clearer. Normally, it is drawn with the OH groups on the right-hand side.
If you make an ester of this with ethanoic acid, you could attach three
ethanoate groups.
an introduction to esters
Now, make the acid chains much longer, and you finally have a fat.
Note: The colour coding is still there only to help you to see
how the formulae are built up. In each case, if you want to be
strictly accurate, the final oxygen in each row should actually
be colour-coded red because it comes from the propane1,2,3-triol.
Although I have shown all the chains in the last structure as
the same for simplicity, there is no reason why the three
chains in any particular fat or oil molecule have to be the
same.
an introduction to esters
You might possibly have come across the terms "omega 6" and "omega
3" in the context of fats and oils.
Linoleic acid is an omega 6 acid. It just means that the first carboncarbon double bond starts on the sixth carbon from the CH3 end.
Linolenic acid is an omega 3 acid for the same reason.
an introduction to esters
Because of their relationship with fats and oils, all of the acids above are
sometimes described as fatty acids.
Physical properties
Simple esters
I am thinking here about things like ethyl ethanoate.
Boiling points
The small esters have boiling points which are similar to those of
aldehydes and ketones with the same number of carbon atoms.
Like aldehydes and ketones, they are polar molecules and so have
dipole-dipole interactions as well as van der Waals dispersion forces.
However, they don't form hydrogen bonds, and so their boiling points
aren't anything like as high as an acid with the same number of carbon
atoms.
For example:
molecule
type
CH3COOCH2CH3
ester
77.1
CH3CH2CH2COOH
carboxylic acid
164
an introduction to esters
Solubility in water
The small esters are fairly soluble in water but solubility falls with chain
length.
For example:
ester
formula
ethyl methanoate
HCOOCH2CH3
10.5
ethyl ethanoate
CH3COOCH2CH3
8.7
ethyl propanoate
CH3CH2COOCH2CH3
1.7
The reason for the solubility is that although esters 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 one of the oxygen atoms
in an ester for a hydrogen bond to be formed.
There will also, of course, be dispersion forces and dipole-dipole
attractions between the ester and the water molecules.
an introduction to esters
an introduction to esters
Unsaturated fats and oils have at least one carbon-carbon double bond
in at least one chain.
There isn't any rotation about a carbon-carbon double bond and so that
locks a permanent kink into the chain. That makes packing molecules
close together more difficult. If they don't pack so well, the van der Waals
forces won't work as well.
This effect is much worse for molecules where the hydrocarbon chains
either end of the double bond are arranged cis to each other - in other
words, both of them on the same side of the double bond:
an introduction to esters
If they are on opposite sides of the double bond (the trans form) the
effect isn't as marked. It is, however, rather more than the diagram below
suggests because of the changes in bond angles around the double
bond compared with the rest of the chain.
Trans fats and oils have higher melting points than cis ones because the
packing isn't affected quite as much. Naturally occurring unsaturated fats
and oils tend to be the cis form.
an introduction to esters
Note: Follow this link if you aren't sure about cis and trans
forms around a carbon-carbon double bond.
Use the BACK button on your browser to return to this page.
preparation of esters
MAKING ESTERS
This page describes ways of making esters in the lab from alcohols and
phenols using carboxylic acids, acyl chlorides (acid chlorides) or acid
anhydrides as appropriate.
So, for example, if you were making ethyl ethanoate from ethanoic acid
and ethanol, the equation would be:
preparation of esters
preparation of esters
preparation of esters
preparation of esters
The phenoxide ion reacts more rapidly with benzoyl chloride than the
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preparation of esters
original phenol does, but even so you have to shake it with benzoyl
chloride for about 15 minutes. Solid phenyl benzoate is formed.
The reaction with phenol is similar, but will be slower. Phenyl ethanoate is
formed together with ethanoic acid.
preparation of esters
This reaction isn't important itself, but a very similar reaction is involved in
the manufacture of aspirin (covered in detail on another page - link below).
If the phenol is first converted into sodium phenoxide by adding sodium
hydroxide solution, the reaction is faster. Phenyl ethanoate is again
formed, but this time the other product is sodium ethanoate rather than
ethanoic acid.
preparation of esters
hydrolysis of esters
HYDROLYSING ESTERS
hydrolysis of esters
hydrolysis of esters
Notice that you get the sodium salt formed rather than the carboxylic acid
itself.
This mixture is relatively easy to separate. Provided you use an excess of
sodium hydroxide solution, there won't be any ester left - so you don't
have to worry about that.
The alcohol formed can be distilled off. That's easy!
If you want the acid rather than its salt, all you have to do is to add an
excess of a strong acid like dilute hydrochloric acid or dilute sulphuric acid
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hydrolysis of esters
If the large esters present in animal or vegetable fats and oils are heated
with concentrated sodium hydroxide solution exactly the same reaction
happens as with the simple esters.
A salt of a carboxylic acid is formed - in this case, the sodium salt of a big
acid such as octadecanoic acid (stearic acid). These salts are the
important ingredients of soap - the ones that do the cleaning.
An alcohol is also produced - in this case, the more complicated alcohol,
propane-1,2,3-triol (glycerol).
hydrolysis of esters
POLYESTERS
Poly(ethylene terephthalate)
What is a polyester?
A polyester is a polymer (a chain of repeating units) where the individual
units are held together by ester linkages.
The diagram shows a very small bit of the polymer chain and looks pretty
complicated. But it isn't very difficult to work out - and that's the best thing
to do: work it out, not try to remember it. You will see how to do that in a
moment.
The usual name of this common polyester is poly(ethylene
terephthalate). The everyday name depends on whether it is being used
as a fibre or as a material for making things like bottles for soft drinks.
When it is being used as a fibre to make clothes, it is often just called
polyester. It may sometimes be known by a brand name like Terylene.
When it is being used to make bottles, for example, it is usually called
PET.
Now imagine lining these up alternately and making esters with each
acid group and each alcohol group, losing a molecule of water every time
an ester linkage is made.
That would produce the chain shown above (although this time written
without separating out the carbon-oxygen double bond - write it
whichever way you like).
In the first stage, before polymerisation happens, you get a fairly simple
ester formed between the acid and two molecules of ethane-1,2-diol.
Hydrolysis of polyesters
Simple esters are easily hydrolysed by reaction with dilute acids or
alkalis.
Polyesters are attacked readily by alkalis, but much more slowly by dilute
acids. Hydrolysis by water alone is so slow as to be completely
unimportant. (You wouldn't expect your polyester fleece to fall to pieces if
you went out in the rain!)
If you spill dilute alkali on a fabric made from polyester, the ester linkages
are broken. Ethane-1,2-diol is formed together with the salt of the
carboxylic acid.
Because you produce small molecules rather than the original polymer,
the fibres are destroyed, and you end up with a hole!
For example, if you react the polyester with sodium hydroxide solution:
Lots of secondary alcohols give this reaction, but those that do all
have a methyl group attached to the carbon with the -OH group.
This is being given as a flow scheme rather than full equations. You
aren't likely to need the equation for the oxidation stage for UK A level
purposes. The equations for the other two steps are given on a page
about reactions of aldehydes and ketones. Follow the first link below if
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The first stage involves substitution of all three hydrogens in the methyl
group by iodine atoms. The presence of hydroxide ions is important for
the reaction to happen - they take part in the mechanism for the reaction
(not required for UK A level).
In the second stage, the bond between the C I3 and the rest of the
molecule is broken to produce triiodomethane (iodoform) and the salt of
an acid.
Putting all this together gives the overall equation for the reaction:
uses of alcohols
USES OF ALCOHOLS
This page has a brief look at some of the more important uses of the
simple alcohols like methanol, ethanol and propan-2-ol.
Uses of ethanol
Drinks
The "alcohol" in alcoholic drinks is simply ethanol.
Industrial methylated spirits (meths)
Ethanol is usually sold as industrial methylated spirits which is ethanol
with a small quantity of methanol added and possibly some colour.
Methanol is poisonous, and so the industrial methylated spirits is unfit to
drink. This avoids the high taxes which are levied on alcoholic drinks
(certainly in the UK!).
As a fuel
Ethanol burns to give carbon dioxide and water and can be used as a
fuel in its own right, or in mixtures with petrol (gasoline). "Gasohol" is a
petrol / ethanol mixture containing about 10 - 20% ethanol.
Because ethanol can be produced by fermentation, this is a useful way
for countries without an oil industry to reduce imports of petrol.
As a solvent
Ethanol is widely used as a solvent. It is relatively safe, and can be used
to dissolve many organic compounds which are insoluble in water. It is
used, for example, in many perfumes and cosmetics.
uses of alcohols
Uses of methanol
As a fuel
Methanol again burns to form carbon dioxide and water.
Uses of propan-2-ol
Propan-2-ol is widely used in an amazing number of different situations
as a solvent. Details on this are probably not required by UK A level
syllabuses, but if you need them, an internet search on propan-2-ol
solvent uses will give you more examples than you can cope with! (There
is a Google search box at the bottom of the Main Menu.)
uses of alcohols
This page looks a few odds and ends of examples of catalysts used in
organic chemistry. It includes the formation of epoxyethane from ethene,
and several reactions from benzene chemistry - Friedel-Crafts reactions
and halogenation. You will find links to other parts of the site for the
mechanisms of the benzene reactions.
Other examples of catalysts in organic chemistry can be found from the
catalysis menu. There is a link to that menu at the bottom of the page if
you have come direct to this page via a search engine.
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.
or:
or:
or:
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:
Understanding Chemistry
Background
The differing reactivities of metals
When metals react, they give away electrons and form positive ions. This
particular topic sets about comparing the ease with which a metal does
this to form hydrated ions in solution - for example, Mg2+(aq) or Cu2+(aq).
We might want to compare the ease with which these two changes take
place:
Everybody who has done chemistry for more than a few months knows
that magnesium is more reactive than copper. The first reaction happens
much more readily than the second one. What this topic does is to try to
express this with some numbers.
Looking at this from an equilibrium point of view
Suppose you have a piece of magnesium in a beaker of water. There will
be some tendency for the magnesium atoms to shed electrons and go
into solution as magnesium ions. The electrons will be left behind on the
magnesium.
A dynamic equilibrium will be established when the rate at which ions are
leaving the surface is exactly equal to the rate at which they are joining it
again. At that point there will be a constant negative charge on the
magnesium, and a constant number of magnesium ions present in the
solution around it.
Simplifying the diagram to get rid of the "bites" out of the magnesium,
you would be left with a situation like this:
Don't forget that this is just a snapshot of a dynamic equilibrium. Ions are
continually leaving and rejoining the surface.
How would this be different if you used a piece of copper instead of a
piece of magnesium?
Copper is less reactive and so forms its ions less readily. Any ions which
do break away are more likely to reclaim their electrons and stick back
on to the metal again. You will still reach an equilibrium position, but
there will be less charge on the metal, and fewer ions in solution.
Notice the way that the two equilibria are written. By convention, all these
equilibria are written with the electrons on the left-hand side of the
equation. If you stick with this convention without fail, you will find that it
makes the rest of this topic much easier to visualise.
Everything else concerning electrode potentials is simply an attempt to
attach some numbers to these differing positions of equilibrium.
In principle, that is quite easy to do. In the magnesium case, there is a lot
of difference between the negativeness of the metal and the positiveness
of the solution around it. In the copper case, the difference is much less.
This potential difference could be recorded as a voltage - the bigger the
difference between the positiveness and the negativeness, the bigger the
voltage. Unfortunately, that voltage is impossible to measure!
Although you can't measure their absolute height, what you can do is to
measure their height relative to the convenient post. Suppose that in this
case, the person turned out to be 15 cm taller than the post.
You could repeat this for a range of people . . .
person
+20
+15
-15
Although you don't know any of their absolute heights, you can usefully
rank them in order, and do some very simple sums to work out exactly
how much taller one is than another. For example, C is 5 cm taller than A.
All we need to know is that the magnesium equilibrium lies further to the
left than the copper one. We need to know that magnesium sheds
electrons and forms ions more readily than copper does.
That means that we don't need to be able to measure the absolute
voltage between the metal and the solution. It is enough to compare the
voltage with a standardised system called a reference electrode.
The system used is called a standard hydrogen electrode.
What is happening?
As the hydrogen gas flows over the porous platinum, an equilibrium is set
up between hydrogen molecules and hydrogen ions in solution. The
reaction is catalysed by the platinum.
This is the equilibrium that we are going to compare all the others with.
Standard conditions
which generates a voltage. Each of the two beakers and their contents
are described as half cells.
The salt bridge
The salt bridge is included to complete the electrical circuit but without
introducing any more bits of metal into the system. It is just a glass tube
filled with an electrolyte like potassium nitrate solution. The ends are
"stoppered" by bits of cotton wool. This stops too much mixing of the
contents of the salt bridge with the contents of the two beakers.
The electrolyte in the salt bridge is chosen so that it doesn't react with the
contents of either beaker.
What happens?
These two equilibria are set up on the two electrodes (the magnesium
and the porous platinum):
Magnesium has a much greater tendency to form its ions than hydrogen
does. The position of the magnesium equilibrium will be well to the left of
that of the hydrogen equilibrium.
That means that there will be a much greater build-up of electrons on the
piece of magnesium than on the platinum. Stripping all the rest of the
diagram out, apart from the essential bits:
solution.
Copper forms its ions less readily than hydrogen does. Of the two
equilibria . . .
. . . the hydrogen one lies further to the left. That means that there will be
less build-up of electrons on the copper than there is on the platinum of
the hydrogen electrode.
high resistance.
This is to avoid any flow of current through the circuit. If there was a low
resistance in the circuit, electrons would flow from where there are a lot
of them (around the magnesium, for example) to where there are less
(on the hydrogen electrode).
If any current flows, the voltage measured drops. In order to make proper
comparisons, it is important to measure the maximum possible voltage in
any situation. This is called the electromotive force or emf.
The emf of a cell measured under standard conditions is given the
symbol Ecell.
Cell conventions
A quick way of drawing a cell
Drawing a full diagram to represent a cell takes too long. Instead, the cell
in which a magnesium electrode is coupled to a hydrogen electrode is
represented like this:
You will often find variants on the way the hydrogen electrode is
represented, such as:
E (volts)
Mg2+ / Mg
-2.37
Zn2+ / Zn
-0.76
Cu2+ / Cu
+0.34
Ag+ / Ag
+0.80
If you compare these with the E values, you can see that the ones
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whose positions of equilibrium lie furthest to the left have the most
negative E values. That is because they form ions more readily - and
leave more electrons behind on the metal, making it more negative.
Those which don't shed electrons as readily have positions of equilibrium
further to the right. Their E values get progressively more positive.
A final summary
E values give you a way of comparing the positions of equilibrium when
these elements lose electrons to form ions in solution.
The more negative the E value, the further the equilibrium lies to
the left - the more readily the element loses electrons and forms
ions.
The more positive (or less negative) the E value, the further the
equilibrium lies to the right - the less readily the element loses
electrons and forms ions.
This page explains the origin of the electrochemical series, and shows
how it can be used to work out the ability of the various substances
included in it to act as oxidising or reducing agents.
E (volts)
-3.03
-2.92
-2.87
-2.71
-2.37
-1.66
-0.76
-0.44
-0.13
0
+0.34
+0.80
+1.50
When solid magnesium forms its ions, it loses electrons. The magnesium
is being oxidised.
Taking another example . . .
When the copper(II) ions gain electrons to form copper, they are being
reduced.
Reducing agents and oxidising agents
A reducing agent reduces something else. That must mean that it gives
electrons to it.
Magnesium is good at giving away electrons to form its ions. Magnesium
must be a good reducing agent.
to the left - the more readily the metal loses electrons. The more negative
the value, the stronger reducing agent the metal is.
The more positive the E value, the more the position of equilibrium lies
to the right - the less readily the metal loses electrons, and the more
readily its ions pick them up again. The more positive the value, the
stronger oxidising agent the metal ion is.
This page explains how non-metals like chlorine can be included in the
electrochemical series, and how other oxidising and reducing agents can
have their standard electrode potentials (redox potentials) measured and
fitted into the series.
Notice that the equilibrium is still written with the electrons on the left-hand
side of the equation. That's why the chlorine gas has to appear on the lefthand side rather than on the right (which is where the metals and hydrogen
appeared).
How can this equilibrium be connected into a circuit? The half-cell is built just
the same as a hydrogen electrode. Chlorine gas is bubbled over a platinum
electrode, which is immersed in a solution containing chloride ions with a
concentration of 1 mol dm-3.
The conventional way of writing the whole cell looks like this.
Notice the way that the chlorine half cell is written. The convention is that the
substance losing electrons is written closest to the electrode. In this case, the
chloride ions are losing electrons.
If you had the chlorine half cell on the left-hand side in a different situation,
then the convention still has to hold. The half cell would then be written:
The value is positive and moderately high as E values go. That means that
the position of the Cl2 / Cl - equilibrium lies more to the right than the
hydrogen equilibrium. Chlorine is much more likely to pick up electrons than
hydrogen ions are.
To measure the redox potential of this, you would simply insert a platinum
electrode into a beaker containing a solution containing both iron(II) and iron
(III) ions (1 mol dm-3 with respect to both), and couple this to a hydrogen
electrode.
The cell diagram would look like this:
Notice that the E value isn't as positive as the chlorine one. The position of
the iron(III) / iron(II) equilibrium isn't as far to the right as the chlorine
equilibrium. That means that Fe3+ ions don't pick up electrons as easily as
chlorine does. Chlorine is a stronger oxidising agent than Fe3+ ions.
Potassium dichromate(VI) as an oxidising agent
A commonly used oxidising agent, especially in organic chemistry, is
potassium dichromate(VI) solution acidified with dilute sulphuric acid. The
potassium ions are just spectator ions and aren't involved in the equilibrium
in any way.
The equilibrium is more complicated this time because it contains more
things:
The half cell would have a piece of platinum dipping into a solution containing
all the ions (dichromate(VI) ions, hydrogen ions and chromium(III) ions) all at
1 mol dm-3.
There is yet another convention when it comes to writing these more
complicated cell diagrams. Where there is more than one thing on either side
of the equilibrium, square brackets are written around them to keep them
tidy. The substances losing electrons are written next to the electrode, just as
before.
equilibrium
E
(volts)
-3.03
-2.92
-2.87
-2.71
-2.37
-1.66
-0.76
-0.44
-0.13
0
+0.34
+0.77
+0.80
+1.33
+1.36
+1.50
combinations.
An update on oxidising agents
Remember:
The more positive the E value, the further the position of equilibrium
lies to the right.
That means that the more positive the E value, the more likely the
substances on the left-hand side of the equations are to pick up
electrons.
A substance which picks up electrons from something else is an
oxidising agent.
The more positive the E value, the stronger the substances on the lefthand side of the equation are as oxidising agents.
There will be more to say about this later in this series of pages.
The two equilibria which are set up in the half cells are:
The negative sign of the zinc E value shows that it releases electrons more
readily than hydrogen does. The positive sign of the copper E shows that it
releases electrons less readily than hydrogen.
That means that you can compare any two equilibria directly. For example,
in this case you can see that the zinc releases electrons more readily than
the copper does - the position of the zinc equilibrium lies further to the left
than the copper equilibrium.
Stripping everything else out of the diagram, and looking only at the build up
of electrons on the two pieces of metal:
Obviously, the voltmeter will show that the zinc is the negative electrode,
and copper is the (relatively) positive one. It will register a voltage showing
the difference between them.
This is exactly the same reaction that occurs when you drop a piece of zinc
into some copper(II) sulphate solution. The blue colour of the solution fades
as the copper(II) ions are converted into brown copper metal. The final
solution contains zinc sulphate. (The sulphate ions are spectator ions.)
You can add the two electron-half-equations above to give the overall ionic
equation for the reaction.
The only difference in this case is that the zinc gives the electrons directly to
the copper(II) ions rather than the electrons having to travel along a bit of
wire first.
The test tube reaction happens because of the relative tendency of the zinc
and copper to lose electrons to form ions. You can find out this relative
tendency by looking at the E values. That means that any redox reaction
could be discussed in a similar way.
The rest of the examples on this page illustrate this.
You can see that both of these E values are positive. Neither copper nor
silver produce ions and release electrons as easily as hydrogen does.
However, of the two, copper releases electrons more readily. In a cell, the
copper would have the greater build up of electrons, and be the negative
electrode. If the copper and zinc were connected by a bit of wire, electrons
would flow from the copper to the silver.
That, of course, will upset the two equilibria:
Electrons will continue to flow and the two equilibria will again turn into oneway reactions to give the electron-half-equations we've just used to build the
ionic equation. Showing that again:
Note: People sometimes worry whether the fact that one of the
equations has to be multiplied by two affects the argument in any
way. It doesn't! It makes no difference whatsoever to any stage
of the explanation in terms of shifts in the positions of the two
equilibria.
The equilibrium with the more negative (or less positive) E value will
move to the left.
The equilibrium with the more positive (or less negative) E value will
move to the right.
It sounds simple, but that is the key to using E values in most of the
situations you will come across.
The two equilibria become one-way reactions which you can use to build the
ionic equation:
Coming up next
The final page in the sequence simply expands on this one, and looks at
how you can use E values to predict whether or not redox reactions are
feasible. It would be a good idea to be fairly confident about the present
page before you went on to the final one.
The more negative the E value, the further the position of equilibrium lies
to the left. Remember that this is always relative to the hydrogen
equilibrium - and not in absolute terms.
The negative sign of the zinc E value shows that it releases electrons
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more readily than hydrogen does. The positive sign of the copper E value
shows that it releases electrons less readily than hydrogen.
Whenever you link two of these equilibria together (either via a bit of wire,
or by allowing one of the substances to give electrons directly to another
one in a test tube) electrons flow from one equilibrium to the other. That
upsets the equilibria, and Le Chatelier's Principle applies. The positions of
equilibrium move - and keep on moving if the electrons continue to be
transferred.
The two equilibria essentially turn into two one-way reactions:
The equilibrium with the more negative (or less positive) E value
will move to the left.
The equilibrium with the more positive (or less negative) E value
will move to the right.
You are starting with magnesium metal and hydrogen ions in the acid. The
sulphate ions are spectator ions and play no part in the reaction.
Think of it like this. There is no need to write anything down unless you
want to. With a small amount of practice, all you need to do is just look at
the numbers.
The diagram shows the way that the E values are telling us that the
equilibria will tend to move. Is this possible? No!
If we start from copper metal, the copper equilibrium is already completely
to the right. If it were to react at all, the equilibrium will have to move to the
left - directly opposite to what the E values are saying.
Similarly, if we start from hydrogen ions (from the dilute acid), the
hydrogen equilibrium is already as far to the left as possible. For it to react,
it would have to move to the right - against what the E values demand.
There is no possibility of a reaction.
In the next couple of examples, decide for yourself whether or not the
reaction is feasible before you read the text.
Will oxygen oxidise iron(II) hydroxide to iron(III) hydroxide under
alkaline conditions?
Think about this before you read on. Remember that the equilibrium with
the more negative E value will tend to move to the left. The other one
tends to move to the right. Is that possible?
Yes, it is possible. Given what we are starting with, both of these equilibria
can move in the directions required by the E values. The reaction is
feasible.
Given what you are starting from, these equilibrium shifts are impossible.
The manganese equilibrium has the more positive E value and so will
tend to move to the right. However, because we are starting from
manganese(II) ions, it is already as far to the right as possible. In order to
get any reaction, the equilibrium would have to move to the left. That is
against what the E values are saying.
This reaction isn't feasible.
Two examples where the E values seem to give the wrong answer
It sometimes happens that E values suggest that a reaction ought to
happen, but it doesn't. Occasionally, a reaction happens although the E
values seem to be the wrong way around. These next two examples
explain how that can happen. By coincidence, both involve the dichromate
(VI) ion in potassium dichromate(VI).
Will acidified potassium dichromate(VI) oxidise water?
The E values are:
The relative sizes of the E values show that the reaction is feasible:
However, in the test tube nothing happens however long you wait. An
acidified solution of potassium dichromate(VI) doesn't react with the water
that it is dissolved in. So what is wrong with the argument?
In fact, there is nothing wrong with the argument. The problem is that all
the E values show is that a reaction is possible. They don't tell you that it
will actually happen. There may be very large activation barriers to the
reaction which prevent it from taking place.
Always treat what E values tell you with some caution. All they tell you is
whether a reaction is feasible - they tell you nothing about how fast the
reaction will happen.
Will acidified potassium dichromate(VI) oxidise chloride ions to
chlorine?
The E values are:
Because the E values are so similar, you don't have to change them very
much to make the dichromate(VI) one the more positive. As soon as that
happens, it will react with the chloride ions to produce chlorine.
In most cases, there is enough difference between E values that you can
ignore the fact that you aren't doing a reaction under strictly standard
conditions. But sometimes it does make a difference. Be careful!
It is easier to explain this with a specific example. What could you use to
oxidise iron(II) ions to iron(III) ions? The E value for this reaction is:
To change iron(II) ions into iron(III) ions, you need to persuade this
equilibrium to move to the left. That means that when you couple it to a
second equilibrium, this iron E value must be the more negative (less
positive one).
You could use anything which has a more positive E value. For example,
you could use any of the these which we have already looked at over the
last page or two:
Dilute nitric acid:
Chlorine:
You have to be a little bit more careful this time, because the substance
losing electrons is found on the right-hand side of one of these redox
equilibria. Again, a specific example makes it clearer.
For example, what could you use to reduce chromium(III) ions to chromium
(II) ions? The E value is:
You need this equilibrium to move to the right. That means that when you
couple it with a second equilibrium, this chromium E value must be the
most positive (least negative).
In principle, you could choose anything with a more negative E value - for
example, zinc:
You would have to remember to start from metallic zinc, and not zinc ions.
You need this second equilibrium to be able to move to the left to provide
the electrons. If you started with zinc ions, it would already be on the left and would have no electrons to give away. Nothing could possibly happen
if you mixed chromium(III) ions and zinc ions.
That is fairly obvious in this simple case. If you were dealing with a more
complicated equilibrium, you would have to be careful to think it through
properly.
Understanding Chemistry
This page explains what is meant by the ionic product for water. It looks
at how the ionic product varies with temperature, and how that
determines the pH of pure water at different temperatures.
Kw and pKw
The important equilibrium in water
Water molecules can function as both acids and bases. One water
molecule (acting as a base) can accept a hydrogen ion from a second
one (acting as an acid). This will be happening anywhere there is even a
trace of water - it doesn't have to be pure.
A hydroxonium ion and a hydroxide ion are formed.
However, the hydroxonium ion is a very strong acid, and the hydroxide
ion is a very strong base. As fast as they are formed, they react to
poduce water again.
The net effect is that an equilibrium is set up.
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At any one time, there are incredibly small numbers of hydroxonium ions
and hydroxide ions present. Further down this page, we shall calculate
the concentration of hydroxonium ions present in pure water. It turns out
to be 1.00 x 10-7 mol dm-3 at room temperature.
You may well find this equilibrium written in a simplified form:
You may find them written with or without the state symbols. Whatever
version you come across, they all mean exactly the same thing!
You may wonder why the water isn't written on the bottom of these
equilibrium constant expressions. So little of the water is ionised at any
one time, that its concentration remains virtually unchanged - a constant.
Kw is defined to avoid making the expression unnecessarily complicated
by including another constant in it.
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The value of Kw
Like any other equilibrium constant, the value of Kw varies with
temperature. Its value is usually taken to be 1.00 x 10-14 mol2 dm-6 at
room temperature. In fact, this is its value at a bit less than 25C.
pKw
The relationship between Kw and pKw is exactly the same as that
between Ka and pKa, or [H+] and pH.
The Kw value of 1.00 x 10-14 mol2 dm-6 at room temperature gives you a
pKw value of 14. Try it on your calculator! Notice that pKw doesn't have
any units.
T (C)
Kw (mol2 dm-6)
pH
0.114 x 10-14
7.47
10
0.293 x 10-14
7.27
20
0.681 x 10-14
7.08
25
1.008 x 10-14
7.00
30
1.471 x 10-14
6.92
40
2.916 x 10-14
6.77
50
5.476 x 10-14
6.63
100
51.3 x 10-14
6.14
You can see that the pH of pure water falls as the temperature increases.
A word of warning!
If the pH falls as temperature increases, does this mean that water
becomes more acidic at higher temperatures? NO!
A solution is acidic if there is an excess of hydrogen ions over hydroxide
ions. In the case of pure water, there are always the same number of
hydrogen ions and hydroxide ions. That means that the water remains
neutral - even if its pH changes.
The problem is that we are all so familiar with 7 being the pH of pure
water, that anything else feels really strange. Remember that you
calculate the neutral value of pH from Kw. If that changes, then the
neutral value for pH changes as well.
At 100C, the pH of pure water is 6.14. That is the neutral point on the
pH scale at this higher temperature. A solution with a pH of 7 at this
temperature is slightly alkaline because its pH is a bit higher than the
neutral value of 6.14.
Similarly, you can argue that a solution with a pH of 7 at 0C is slightly
acidic, because its pH is a bit lower than the neutral value of 7.47 at this
temperature.
This page explains the terms strong and weak as applied to bases. As a
part of this it defines and explains Kb and pKb.
We are going to use the Bronsted-Lowry definition of a base as a
substance which accepts hydrogen ions (protons).
The usual way of comparing the strengths of bases is to see how readily
they produce hydroxide ions in solution. This may be because they
already contain hydroxide ions, or because they take hydrogen ions from
water molecules to produce hydroxide ions.
Strong bases
Explaining the term "strong base"
A strong base is something like sodium hydroxide or potassium
hydroxide which is fully ionic. You can think of the compound as being
100% split up into metal ions and hydroxide ions in solution.
Each mole of sodium hydroxide dissolves to give a mole of hydroxide
ions in solution.
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Some strong bases like calcium hydroxide aren't very soluble in water.
That doesn't matter - what does dissolve is still 100% ionised into
calcium ions and hydroxide ions. Calcium hydroxide still counts as a
strong base because of that 100% ionisation.
Working out the pH of a strong base
Remember that:
In the presence of extra hydroxide ions from, say, sodium hydroxide, the
equilibrium is still there, but the position of equilibrium has been shifted
well to the left according to Le Chatelier's Principle.
There will be far fewer hydrogen ions than there are in pure water, but
there will still be hydrogen ions present. The pH is a measure of the
concentration of these.
An outline of the method of working out the pH of a strong base
An example
To find the pH of 0.500 mol dm-3 sodium hydroxide solution:
Because the sodium hydroxide is fully ionic, each mole of it gives that
same number of moles of hydroxide ions in solution.
Now you use the value of Kw at the temperature of your solution. You
normally take this as 1.00 x 10-14 mol2 dm-6.
[H+] [OH-] = 1.00 x 10-14
This is true whether the water is pure or not. In this case we have a value
for the hydroxide ion concentration. Substituting that gives:
[H+] x 0.500 = 1.00 x 10-14
If you solve that for [H+], and then convert it into pH, you get a pH of 13.7.
Weak bases
Explaining the term "weak base"
Ammonia is a typical weak base. Ammonia itself obviously doesn't
contain hydroxide ions, but it reacts with water to produce ammonium
ions and hydroxide ions.
However, the reaction is reversible, and at any one time about 99% of
the ammonia is still present as ammonia molecules. Only about 1% has
actually produced hydroxide ions.
A weak base is one which doesn't convert fully into hydroxide ions in
solution.
In this case the equilibrium constant is called Kb. This is defined as:
Note: If you want to know why the water has been omitted
from the bottom of this expression, you will find it explained
on the page about strong and weak acids under the
corresponding constant, Ka.
Use the BACK button on your browser when you are ready to
return to this page.
pKb
The relationship between Kb and pKb is exactly the same as all the other
"p" terms in this topic:
The table shows some values for Kb and pKb for some weak bases.
Kb (mol dm-3)
pKb
C6H5NH2
4.17 x 10-10
9.38
NH3
1.78 x 10-5
4.75
CH3NH2
4.37 x 10-4
3.36
CH3CH2NH2
5.37 x 10-4
3.27
base
As you go down the table, the value of Kb is increasing. That means that
the bases are getting stronger.
As Kb gets bigger, pKb gets smaller. The lower the value of pKb, the
stronger the base.
This is exactly in line with the corresponding term for acids, pKa - the
smaller the value, the stronger the acid.
pH (TITRATION) CURVES
In this particular instance, this would also be the neutral point of the
titration, because sodium chloride solution has a pH of 7.
But that isn't necessarily true of all the salts you might get formed.
For example, if you titrate ammonia solution with hydrochloric acid, you
would get ammonium chloride formed. The ammonium ion is slightly
acidic, and so pure ammonium chloride has a slightly acidic pH.
That means that at the equivalence point (where you had mixed the
solutions in the correct proportions according to the equation), the
solution wouldn't actually be neutral. To use the term "neutral point" in
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Note: You can find out about indicators by following this link
(also available from the acid-base equilibria menu). You
should read the present page first though.
Simple pH curves
All the following titration curves are based on both acid and alkali having
a concentration of 1 mol dm-3. In each case, you start with 25 cm3 of one
of the solutions in the flask, and the other one in a burette.
Although you normally run the acid from a burette into the alkali in a
flask, you may need to know about the titration curve for adding it the
other way around as well. Alternative versions of the curves have been
described in most cases.
Titration curves for strong acid v strong base
We'll take hydrochloric acid and sodium hydroxide as typical of a strong
acid and a strong base.
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You can see that the pH only falls a very small amount until quite near
the equivalence point. Then there is a really steep plunge. If you
calculate the values, the pH falls all the way from 11.3 when you have
added 24.9 cm3 to 2.7 when you have added 25.1 cm3.
Again, the pH doesn't change very much until you get close to the
equivalence point. Then it surges upwards very steeply.
Because you have got a weak base, the beginning of the curve is
obviously going to be different. However, once you have got an excess of
acid, the curve is essentially the same as before.
At the very beginning of the curve, the pH starts by falling quite quickly
as the acid is added, but the curve very soon gets less steep. This is
because a buffer solution is being set up - composed of the excess
ammonia and the ammonium chloride being formed.
Notice that the equivalence point is now somewhat acidic ( a bit less than
pH 5), because pure ammonium chloride isn't neutral. However, the
equivalence point still falls on the steepest bit of the curve. That will turn
out to be important in choosing a suitable indicator for the titration.
Running alkali into the acid
At the beginning of this titration, you have an excess of hydrochloric acid.
The shape of the curve will be the same as when you had an excess of
acid at the start of a titration running sodium hydroxide solution into the
acid.
It is only after the equivalence point that things become different.
A buffer solution is formed containing excess ammonia and ammonium
chloride. This resists any large increase in pH - not that you would expect
a very large increase anyway, because ammonia is only a weak base.
Past the equivalence point you have a buffer solution containing sodium
ethanoate and ethanoic acid. This resists any large fall in pH.
Running alkali into the acid
The start of the graph shows a relatively rapid rise in pH but this slows
down as a buffer solution containing ethanoic acid and sodium ethanoate
is produced. Beyond the equivalence point (when the sodium hydroxide
is in excess) the curve is just the same as that end of the HCl - NaOH
graph.
It so happens that these two are both about equally weak - in that case,
the equivalence point is approximately pH 7.
Running acid into the alkali
This is really just a combination of graphs you have already seen. Up to
the equivalence point it is similar to the ammonia - HCl case. After the
equivalence point it is like the end of the ethanoic acid - NaOH curve.
Notice that there isn't any steep bit on this graph. Instead, there is just
what is known as a "point of inflexion". That lack of a steep bit means
that it is difficult to do a titration of a weak acid against a weak base.
If you had the two solutions of the same concentration, you would have
The graph is more complicated than you might think - and curious things
happen during the titration.
You expect carbonates to produce carbon dioxide when you add acids to
them, but in the early stages of this titration, no carbon dioxide is given
off at all.
Then - as soon as you get past the half-way point in the titration - lots of
carbon dioxide is suddenly released.
The graph is showing two end points - one at a pH of 8.3 (little more than
a point of inflexion), and a second at about pH 3.7. The reaction is
obviously happening in two distinct parts.
In the first part, complete at A in the diagram, the sodium carbonate is
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You can see that the reaction doesn't produce any carbon dioxide.
In the second part, the sodium hydrogencarbonate produced goes on to
react with more acid - giving off lots of CO2.
The reaction with sodium hydroxide takes place in two stages because
one of the hydrogens is easier to remove than the other. The two
successive reactions are:
If you run sodium hydroxide solution into ethanedioic acid solution, the
pH curve shows the end points for both of these reactions.
The curve is for the reaction between sodium hydroxide and ethanedioic
acid solutions of equal concentrations.
acid-base indicators
ACID-BASE INDICATORS
This page describes how simple acid-base indicators work, and how to
choose the right one for a particular titration.
acid-base indicators
acid-base indicators
The reason for the inverted commas around "neutral" is that there is no
reason why the two concentrations should become equal at pH 7. For
litmus, it so happens that the 50 / 50 colour does occur at close to pH 7 that's why litmus is commonly used to test for acids and alkalis. As you
will see below, that isn't true for other indicators.
Methyl orange
Methyl orange is one of the indicators commonly used in titrations. Its
structure is simple enough to be able to see what is happening as it loses
and gains hydrogen ions.
acid-base indicators
You have the same sort of equilibrium as in the litmus case - but the
colours are different.
You should be able to work out for yourself why the colour changes when
you add an acid or an alkali. The explanation is identical to the litmus
case - all that differs are the colours.
acid-base indicators
In the methyl orange case, the half-way stage where the mixture of red
and yellow produces an orange colour happens at pH 3.7 - nowhere near
neutral. This will be explored further down this page.
Phenolphthalein
Phenolphthalein is another commonly used indicator for titrations, and is
another weak acid.
In this case, the weak acid is colourless and its ion is bright pink. Adding
extra hydrogen ions shifts the position of equilibrium to the left, and turns
the indicator colourless. Adding hydroxide ions removes the hydrogen
ions from the equilibrium which tips to the right to replace them - turning
the indicator pink.
The half-way stage happens at pH 9.3. Since a mixture of pink and
colourless is simply a paler pink, this is difficult to detect with any
accuracy!
Because this is just like any other weak acid, you can write an
expression for Ka for it. We will call it Kind to stress that we are talking
about the indicator.
acid-base indicators
Think of what happens half-way through the colour change. At this point
the concentrations of the acid and its ion are equal. In that case, they will
cancel out of the Kind expression.
You can use this to work out what the pH is at this half-way point. If you
re-arrange the last equation so that the hydrogen ion concentration is on
the left-hand side, and then convert to pH and pKind, you get:
That means that the end point for the indicator depends entirely on what
its pKind value is. For the indicators we've looked at above, these are:
indicator
pKind
litmus
6.5
methyl orange
3.7
acid-base indicators
phenolphthalein
9.3
pH range
litmus
6.5
5-8
methyl orange
3.7
3.1 - 4.4
phenolphthalein
9.3
8.3 - 10.0
indicator
The litmus colour change happens over an unusually wide range, but it is
useful for detecting acids and alkalis in the lab because it changes colour
around pH 7. Methyl orange or phenolphthalein would be less useful.
acid-base indicators
acid-base indicators
You can see that neither indicator changes colour at the equivalence
point.
However, the graph is so steep at that point that there will be virtually no
difference in the volume of acid added whichever indicator you choose.
However, it would make sense to titrate to the best possible colour with
each indicator.
If you use phenolphthalein, you would titrate until it just becomes
colourless (at pH 8.3) because that is as close as you can get to the
equivalence point.
On the other hand, using methyl orange, you would titrate until there is
the very first trace of orange in the solution. If the solution becomes red,
you are getting further from the equivalence point.
acid-base indicators
acid-base indicators
You can see that neither indicator is any use. Phenolphthalein will have
finished changing well before the equivalence point, and methyl orange
falls off the graph altogether.
It may be possible to find an indicator which starts to change or finishes
changing at the equivalence point, but because the pH of the
equivalence point will be different from case to case, you can't generalise.
On the whole, you would never titrate a weak acid and a weak base in
the presence of an indicator.
acid-base indicators
acid-base indicators
buffer solutions
BUFFER SOLUTIONS
This page describes simple acidic and alkaline buffer solutions and
explains how they work.
buffer solutions
buffer solutions
Other things (like water and sodium ions) which are present aren't
important to the argument.
Adding an acid to this buffer solution
The buffer solution must remove most of the new hydrogen ions
otherwise the pH would drop markedly.
Hydrogen ions combine with the ethanoate ions to make ethanoic acid.
Although the reaction is reversible, since the ethanoic acid is a weak
acid, most of the new hydrogen ions are removed in this way.
Since most of the new hydrogen ions are removed, the pH won't change
very much - but because of the equilibria involved, it will fall a little bit.
Adding an alkali to this buffer solution
Alkaline solutions contain hydroxide ions and the buffer solution removes
most of these.
buffer solutions
This time the situation is a bit more complicated because there are two
processes which can remove hydroxide ions.
Removal by reacting with ethanoic acid
The most likely acidic substance which a hydroxide ion is going to collide
with is an ethanoic acid molecule. They will react to form ethanoate ions
and water.
Because most of the new hydroxide ions are removed, the pH doesn't
increase very much.
Removal of the hydroxide ions by reacting with hydrogen ions
Remember that there are some hydrogen ions present from the
ionisation of the ethanoic acid.
Hydroxide ions can combine with these to make water. As soon as this
happens, the equilibrium tips to replace them. This keeps on happening
until most of the hydroxide ions are removed.
buffer solutions
Again, because you have equilibria involved, not all of the hydroxide ions
are removed - just most of them. The water formed re-ionises to a very
small extent to give a few hydrogen ions and hydroxide ions.
Other things (like water and chloride ions) which are present aren't
important to the argument.
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buffer solutions
Most, but not all, of the hydrogen ions will be removed. The ammonium
ion is weakly acidic, and so some of the hydrogen ions will be released
again.
Removal of the hydrogen ions by reacting with hydroxide ions
Remember that there are some hydroxide ions present from the reaction
between the ammonia and the water.
Hydrogen ions can combine with these hydroxide ions to make water. As
soon as this happens, the equilibrium tips to replace the hydroxide ions.
This keeps on happening until most of the hydrogen ions are removed.
Again, because you have equilibria involved, not all of the hydrogen ions
are removed - just most of them.
buffer solutions
Because the ammonia formed is a weak base, it can react with the water
- and so the reaction is slightly reversible. That means that, again, most
(but not all) of the the hydroxide ions are removed from the solution.
Understanding Chemistry
Go to Main Menu . . .
This page looks at how the equilibrium between a liquid (or a solid) and
its vapour leads to the idea of a saturated vapour pressure. It also looks
at how saturated vapour pressure varies with temperature, and the
relationship between saturated vapour pressure and boiling point.
Notice that evaporation only takes place on the surface of the liquid.
That's quite different from boiling which happens when there is enough
energy to disrupt the attractive forces throughout the liquid. That's why, if
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you look at boiling water, you see bubbles of gas being formed all the
way through the liquid.
If you look at water which is just evaporating in the sun, you don't see
any bubbles. Water molecules are simply breaking away from the
surface layer.
Eventually, the water will all evaporate in this way. The energy which is
lost as the particles evaporate is replaced from the surroundings. As the
molecules in the water jostle with each other, new molecules will gain
enough energy to escape from the surface.
As the gaseous particles bounce around, some of them will hit the
surface of the liquid again, and be trapped there. There will rapidly be an
equilibrium set up in which the number of particles leaving the surface is
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If you squirt a few drops of liquid into the tube, it will rise to form a thin
layer floating on top of the mercury. Some of the liquid will evaporate and
you will get the equilibrium we've just been talking about - provided there
is still some liquid on top of the mercury. It is only an equilibrium if both
liquid and vapour are present.
The saturated vapour pressure of the liquid will force the mercury level
down a bit. You can measure the drop - and this gives a value for the
saturated vapour pressure of the liquid at this temperature. In this case,
the mercury has been forced down by a distance of 760 - 630 mm. The
saturated vapour pressure of this liquid at the temperature of the
experiment is 130 mmHg.
You could convert this into proper SI units (pascals) if you wanted to. 760
mmHg is equivalent to 101325 Pa.
A value of 130 mmHg is quite a high vapour pressure if we are talking
about room temperature. Water's saturated vapour pressure is about 20
mmHg at this temperature. A high vapour pressure means that the liquid
must be volatile - molecules escape from its surface relatively easily, and
aren't very good at sticking back on again either.
That will result in larger numbers of them in the gas state once
equilibrium is reached.
The liquid in the example must have significantly weaker intermolecular
forces than water.
Note: You could follow this link if you aren't sure about Le
Chatelier's Principle.
Use the BACK button on your browser to return to this page
later.
When the space above the liquid is saturated with vapour particles, you
have this equilibrium occurring on the surface of the liquid:
Note: This link will take you straight to the page about phase
diagrams where this is discussed in detail. Follow this link as
well if you are interested in the logical next step in this topic
which is a discussion of the phase diagrams of pure
substances, including water and carbon dioxide.
This page explains how to interpret the phase diagrams for simple pure
substances - including a look at the special cases of the phase diagrams
of water and carbon dioxide. This is going to be a long page, because I
have tried to do the whole thing as gently as possible.
Phase diagrams
A phase diagram lets you work out exactly what phases are present at
any given temperature and pressure. In the cases we'll be looking at on
this page, the phases will simply be the solid, liquid or vapour (gas)
states of a pure substance.
These diagrams (including this one) are nearly always drawn highly
distorted in order to see what is going on more easily. There are usually
two major distortions. We'll discuss these when they become relevant.
If you look at the diagram, you will see that there are three lines, three
areas marked "solid", "liquid" and "vapour", and two special points
marked "C" and "T".
The three areas
These are easy! Suppose you have a pure substance at three different
sets of conditions of temperature and pressure corresponding to 1, 2 and
3 in the next diagram.
Note: I'm using the terms vapour and gas as if they were
interchangeable. There are subtle differences between them
that I'm not ready to explain for a while yet. Be patient!
So what actually is this line separating the solid and liquid areas of the
diagram?
It simply shows the effect of pressure on melting point.
Anywhere on this line, there is an equilibrium between solid and liquid.
You can apply Le Chatelier's Principle to this equilibrium just as if it was
a chemical equilibrium. If you increase the pressure, the equilibrium will
move in such a way as to counter the change you have just made.
You can also play around with this by looking at what happens if you
decrease the pressure on a solid at constant temperature.
Note: I don't want to make any very big deal over this, but
this line is actually exactly the same as the graph for the
effect of temperature on the saturated vapour pressure of the
liquid. Saturated vapour pressure is dealt with on a separate
page. A liquid will boil when its saturated vapour pressure is
equal to the external pressure.
Suppose you measured the saturated vapour pressure of a
liquid at 50C, and it turned out to be 75 kPa. You could plot
that as one point on a vapour pressure curve, and then go on
to measure other saturated vapour pressures at different
temperatures and plot those as well.
Now, suppose that you had the liquid exposed to a total
external pressure of 75 kPa, and gradually increased the
temperature. The liquid would boil when its saturated vapour
pressure became equal to the external pressure - in this case
at 50C. If you have the complete vapour pressure curve, you
could equally well find the boiling point corresponding to any
other external pressure.
That means that the plot of saturated vapour pressure
against temperature is exactly the same as the curve relating
boiling point and external pressure - they are just two ways of
looking at the same thing.
If all you are interested in doing is interpreting one of these
phase diagrams, you probably don't have to worry too much
about this.
This works fine as long as the gas is below the critical temperature.
What, though, if your temperature was above the critical temperature?
There wouldn't be any line to cross!
That is because, above the critical temperature, it is impossible to
condense a gas into a liquid just by increasing the pressure. All you get
is a highly compressed gas. The particles have too much energy for the
intermolecular attractions to hold them together as a liquid.
The critical temperature obviously varies from substance to substance
and depends on the strength of the attractions between the particles. The
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You could read the sublimation temperature off the diagram. It will be the
temperature at which the line is crossed.
solid-liquid equilibrium
liquid-vapour equilibrium
solid-vapour equilibrium
Where all three lines meet, you must have a unique combination of
temperature and pressure where all three phases are in equilibrium
together. That's why it is called a triple point.
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There is only one difference between this and the phase diagram that
we've looked at up to now. The solid-liquid equilibrium line (the melting
point line) slopes backwards rather than forwards.
In the case of water, the melting point gets lower at higher pressures.
Why?
If you have this equilibrium and increase the pressure on it, according to
Le Chatelier's Principle the equilibrium will move to reduce the pressure
again. That means that it will move to the side with the smaller volume.
Liquid water is produced.
To make the liquid water freeze again at this higher pressure, you will
have to reduce the temperature. Higher pressures mean lower melting
(freezing) points.
Now lets put some numbers on the diagram to show the exact positions
of the critical point and triple point for water.
Notice that the triple point for water occurs at a very low pressure. Notice
also that the critical temperature is 374C. It would be impossible to
convert water from a gas to a liquid by compressing it above this
temperature.
The normal melting and boiling points of water are found in exactly the
same way as we have already discussed - by seeing where the 1
atmosphere pressure line crosses the solid-liquid and then the liquidvapour equilibrium lines.
Just one final example of using this diagram (because it appeals to me).
Imagine lowering the pressure on liquid water along the line in the
diagram below.
The phase diagram shows that the water would first freeze to form ice as
it crossed into the solid area. When the pressure fell low enough, the ice
would then sublime to give water vapour. In other words, the change is
from liquid to solid to vapour. I find that satisfyingly bizarre!
The only thing special about this phase diagram is the position of the
triple point which is well above atmospheric pressure. It is impossible to
get any liquid carbon dioxide at pressures less than 5.11 atmospheres.
That means that at 1 atmosphere pressure, carbon dioxide will sublime
at a temperature of -78C.
This is the reason that solid carbon dioxide is often known as "dry ice".
You can't get liquid carbon dioxide under normal conditions - only the
solid or the vapour.
This page deals with Raoult's Law and how it applies to solutions in
which the solute is non-volatile - for example, a solution of salt in water.
A non-volatile solute (the salt, for example) hasn't got any tendency to
form a vapour at the temperature of the solution.
It goes on to explain how the resulting lowering of vapour pressure
affects the boiling point and freezing point of the solution.
Raoult's Law
There are several ways of stating Raoult's Law, and you tend to use
slightly different versions depending on the situation you are talking
about. You can use the simplified definition in the box below in the case
of a single volatile liquid (the solvent) and a non-volatile solute.
Suppose you had a solution containing 10 moles of water and 0.1 moles
of sugar. The total number of moles is therefore 10.1
The mole fraction of the water is:
Now suppose you added enough solute so that the solvent molecules
only occupied 50% of the surface of the solution.
The net effect of this is that when equilibrium is established, there will be
fewer solvent molecules in the vapour phase - it is less likely that they
are going to break away, but there isn't any problem about them
returning.
If there are fewer particles in the vapour at equilibrium, the saturated
vapour pressure is lower.
So, if you added 0.1 moles of sodium chloride, there would actually be
0.2 moles of particles in the solution - and that's the figure you would
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The line separating the liquid and vapour regions is the set of conditions
where liquid and vapour are in equilibrium.
It can be thought of as the effect of pressure on the boiling point of the
water, but it is also the curve showing the effect of temperature on the
saturated vapour pressure of the water. These two ways of looking at the
same line are discussed briefly in a note about half-way down the page
about phase diagrams (follow the last link above).
If you draw the saturated vapour pressure curve for a solution of a nonvolatile solute in water, it will always be lower than the curve for the pure
water.
Note: The curves for the pure water and for the solution are
often drawn parallel to each other. That has got to be wrong!
Suppose you have a solution where the mole fraction of the
water is 0.99 and the vapour pressure of the pure water at
that temperature is 100 kPa. The vapour pressure of the
solution will be 99 kPa - a fall of 1 kPa. At a lower
temperature, where the vapour pressure of the pure water is
10 kPa, the fall will only be 0.1 kPa. For the curves to be
parallel the falls would have to be the same over the whole
temperature range. They aren't!
If you look closely at the last diagram, you will see that the point at which
the liquid-vapour equilibrium curve meets the solid-vapour curve has
moved. That point is the triple point of the system - a unique set of
temperature and pressure conditions at which it is possible to get solid,
liquid and vapour all in equilibrium with each other at the same time.
Since the triple point has solid-liquid equilibrium present (amongst other
equilibria), it is also a melting point of the system - although not the
normal melting point because the pressure isn't 1 atmosphere.
That must mean that the phase diagram needs a new melting point line
(a solid-liquid equilibrium line) passing through the new triple point. That
is shown in the next diagram.
Because of the changes to the phase diagram, you can see that:
We have looked at this with water as the solvent, but using a different
solvent would make no difference to the argument or the conclusions.
The only difference is in the slope of the solid-liquid equilibrium lines. For
most solvents, these slope forwards whereas the water line slopes
backwards. You could prove to yourself that that doesn't affect what we
have been looking at by re-drawing all these diagrams with the slope of
that particular line changed.
You will find it makes no difference whatsoever.
This page explains the relationship between the cooling curves for liquid
mixtures of tin and lead, and the resulting phase diagram. It also offers a
simple introduction to the idea of a eutectic mixture.
Cooling curves
Cooling curves for pure substances
Suppose you have some pure molten lead and allow it to cool down until
it has all solidified, plotting the temperature of the lead against time as
you go. You would end up with a typical cooling curve for a pure
substance.
Throughout the whole experiment, heat is being lost to the surroundings and yet the temperature doesn't fall at all while the lead is freezing. This
is because the freezing process liberates heat at exactly the same rate
that it is being lost to the surroundings.
Energy is released when new bonds form - in this case, the strong
metallic bonds in the solid lead.
If you repeated this process for pure liquid tin, the shape of the graph
would be exactly the same, except that the freezing point would now be
at 232C. (The graph for this is further down the page.)
A sample curve
If you add some tin to the lead, the shape of the cooling curve changes.
The next graph shows what happens if you cool a liquid mixture
containing about 67% lead and 33% tin by mass.
The temperature does stop falling at 183C. Now both tin and lead
are freezing. Once everything has solidified, the temperature
continues to fall.
This particular mixture of lead and tin has a cooling curve which looks
exactly like that of a pure substance rather than a mixture. There is just
the single horizontal part of the graph where everything is freezing.
It's just like the pure lead cooling curve except that tin's freezing point is
lower.
If you add small amounts of lead to the tin, so that you have perhaps
80% tin and 20% lead, you will get a curve like this:
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Notice the lowered freezing point of the tin. Notice also the final freezing
of the whole mixture again takes place at 183C.
As you increase the amount of lead (or decrease the amount of tin same thing!) until there is 62% of tin and 38% of lead, you will again get
the eutectic mixture with the curve we've already looked at.
Notice that at the left-hand side and right-hand sides of the curves you
have the freezing points (melting points) of the pure lead and tin.
Note: The two lines meeting at the eutectic point have been
simplified slightly so that they are drawn as straight lines
rather than slight curves. It doesn't affect the argument in any
way. I haven't been able to find the actual data to plot them
accurately, so the simplification is to avoid giving the
impression that I actually know exactly what the curves look
like!
To finish off the phase diagram, all you have to do is draw a single
horizontal line across at the eutectic temperature. Then you label each
area of the diagram with what you would find under the various different
conditions.
Suppose you have a mixture of 67% lead and 33% tin. That's the mixture
from the first cooling curve plotted above. Suppose it is at a temperature
of 300C.
That corresponds to a set of conditions in the area of the phase diagram
labelled as molten tin and lead.
Now consider what happens if you cool that mixture. Eventually the
temperature will drop to a point where it crosses the line into the next
Now, it is the next bit that needs careful thinking about, because there
are two different ways you can look at it. If you have been taught to do it
one way, then stick with that - otherwise you risk getting very confused!
What would you see in the mixture? To find out, you draw a horizontal tie
line through that point, and then look at the ends of it.
At the left-hand end, you have 100% lead. That represents the solid lead
that has frozen from the mixture. At the right-hand end, you have the
composition of the liquid mixture. This is now much richer in tin than the
whole system is - because obviously a fair bit of solid lead has separated
out.
As the temperature continues to fall, the composition of the liquid mixture
(as shown by the right-hand end of the tie line) will get closer and closer
to the eutectic mixture.
It will finally reach the eutectic composition when the temperature drops
to the eutectic temperature - and the whole lot then freezes.
At a temperature lower than the eutectic temperature, you are obviously
in the solid lead plus solid tin region. That's fairly obvious!
If you cooled a liquid mixture on the right-hand side of the phase diagram
(to the right of the eutectic mixture), everything would work exactly the
same except that solid tin would be formed instead of solid lead. If you
have understood what has gone before, it isn't at all difficult to work out
what happens.
Finally . . . what happens if you cool a liquid mixture which has exactly
the eutectic composition?
It simply stays as a liquid mixture until the temperature falls enough that
it all solidifies. You never get into the awkward areas of the phase
diagram.
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60% tin and 40% lead. This is close to the eutectic composition
(62% tin and 38% lead), giving a low melting point. It will also melt
and freeze cleanly over a very limited temperature range. This is
useful for electrical work.
50% tin and 50% lead. This will melt and freeze over a wider range
of temperatures. When it is molten it will start to freeze at about
220C and finally solidify at the eutectic temperature of 183C.
That means that it stays workable for a useful amount of time.
That's helpful if it is being used for plumbing joints.
Reaction mechanisms
What is a reaction mechanism?
In any chemical change, some bonds are broken and new ones are
made. Quite often, these changes are too complicated to happen in one
simple stage. Instead, the reaction may involve a series of small changes
one after the other.
A reaction mechanism describes the one or more steps involved in the
reaction in a way which makes it clear exactly how the various bonds are
broken and made. The following example comes from organic chemistry.
It doesn't matter in the least if it is unfamiliar to you!
This is a reaction between 2-bromo-2-methylpropane and the hydroxide
ions from sodium hydroxide solution:
The overall reaction replaces the bromine atom in the organic compound
by an OH group.
The first thing that happens is that the carbon-bromine bond in a small
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The reaction is first order with respect to the organic compound, and zero
order with respect to the hydroxide ions. The concentration of the
hydroxide ions isn't affecting the overall rate of the reaction.
If the hydroxide ions were taking part in the slow step of the reaction,
increasing their concentration would speed the reaction up. Since their
concentration doesn't seem to matter, they must be taking part in a later
fast step.
Increasing the concentration of the hydroxide ions will speed up the fast
step, but that won't have a noticeable effect on the overall rate of the
reaction. That is governed by the speed of the slow step.
In a simple case like this, where the slow step of the reaction is the first
step, the rate equation tells you what is taking part in that slow step. In
this case, the reaction is first order with respect to the organic molecule and that's all.
This gives you a starting point for working out a possible mechanism.
Having come up with a mechanism, you would need to find more
evidence to confirm it. For example, in this case you might try to detect
the presence of the positive ion that is formed in the first step.
Example 2
At first sight this reaction seems identical with the last one. A bromine
atom is being replaced by an OH group in an organic compound.
However, the rate equation for this apparently similar reaction turns out
to be quite different. That means that the mechanism must be different.
The reaction this time is first order with respect to both the organic
compound and the hydroxide ions. Both of these must be taking part in
the slow step of the reaction. The reaction must happen by a
straightforward collision between them.
The carbon atom which is hit by the hydroxide ion has a slight positive
charge on it and the bromine a slight negative one because of the
difference in their electronegativities.
As the hydroxide ion approaches, the bromine is pushed off in one
smooth action.
Molecularity of a reaction
You may come across an older term known as the molecularity of a
reaction. This has largely dropped out of UK A' level syllabuses, but if
you meet it, it is important that you understand the difference between
this and the order of a reaction. The terms were sometimes used
carelessly as if they mean the same thing - they don't!
Order of reaction
The important thing to realise is that this is something which can only be
found by doing experiments. It gives you information about which
concentrations affect the rate of the reaction. You cannot look at an
equation for a reaction and deduce what the order of the reaction is
going to be - you have to do some practical work!
Having found the order of the reaction experimentally, you may be able
to make suggestions about the mechanism for the reaction - at least in
simple cases.
Molecularity of a reaction
This starts at the other end! If you know the mechanism for a reaction,
you can write down equations for a series of steps which make it up.
Each of those steps has a molecularity.
The molecularity of a step simply counts the number of species
(molecules, ions, atoms or free radicals) taking part in that step. For
example, going back to the mechanisms we've been looking at:
This step involves a single molecule breaking into ions. Because only
one species is involved in the reaction, it has a molecularity of 1. It could
be described as unimolecular.
The second step of this mechanism, involves two ions reacting together.
Because of the two species involved (one molecule and one ion), this
reaction is also bimolecular.
Unless an overall reaction happens in one step (like this last one), you
can't assign it a molecularity. You have to know the mechanism, and
then each individual step has its own molecularity.
There's nothing the least bit complicated about the term molecularity.
The only confusion is that you may sometimes find it used as if it meant
the same as order. It doesn't!
This page explains how to name some common complex metal ions.
ligand
coded by
(old name)
H2O
aqua
aquo
NH3
ammine
ammino
OH-
hydroxo
hydroxy
Cl-
chloro
F-
fluoro
CN-
cyano
Take care with the code for ammonia as a ligand - it has 2 "m"s in its
name. If you miss one of these out so that you are left with "amine" or
"amino", you are refering to the NH2 group in an organic compound.
This is probably the only point of confusion with these names.
Coding for the number of ligands
The normal prefixes apply if there is more than one ligand.
no of ligands
coded by
di
tri
tetra
penta
hexa
metal
changed to
cobalt
cobaltate
aluminium
aluminate
chromium
chromate
vanadium
vanadate
copper
cuprate
iron
ferrate
So, for example, suppose you bond 4 chloride ions around a Cu2+ ion to
give [CuCl4]2-.
The name shows the 4 (tetra) chlorines (chloro) around a copper in an
overall negative ion (cuprate). The copper has on oxidation state of +2.
This is the tetrachlorocuprate(II) ion.
Similarly, [Al(H2O)2(OH)4]- is called the diaquatetrahydroxoaluminate ion.
Take the name to pieces so that you can see exactly what refers to what.
Don't forget that the two different ligands are named in alphabetical order
- aqua before hydroxo - ignoring the prefixes, di and tetra.
The oxidation state of the aluminium could be shown, but isn't absolutely
necessary because aluminium only has the one oxidation state in its
compounds. The full name is the diaquatetrahydroxoaluminate(III) ion.
This page describes the shapes of some common complex metal ions. It
goes on to look at some simple examples of stereoisomerism (geometric
and optical) in complex ions. If you aren't sure what stereoisomerism is,
you will find a helpful link further down the page.
It doesn't matter what the ligands are. If you have six of them, this is the
shape they will take up. Easy!
The platinum, the two chlorines, and the two nitrogens are all in the same
plane. We will have more to say about cisplatin immediately below.
Geometric isomerism
This occurs in planar complexes like the Pt(NH3)2Cl2 we've just looked
at. There are two completely different ways in which the ammonias and
chloride ions could arrange themselves around the central platinum ion:
The two structures drawn are isomers because there is no way that you
can just twist one to turn it into the other. The complexes are both locked
into their current forms.
The termscis and trans are used in the same way as they are in organic
chemistry. Trans implies "opposite" - notice that the ammonias are
arranged opposite each other in that version, and so are the chlorines.
Cis implies "on the same side" - in this instance, that just means that the
ammonias and the chlorines are next door to each other.
Optical isomerism
You recognise optical isomers because they have no plane of symmetry.
In the organic case, it is fairly easy to recognise the possibiliy of this by
looking for a carbon atom with four different things attached to it. It isn't
qute so easy with the complex ions - either to draw or to visualise!
The examples you are most likely to need occur in octahedral complexes
which contain bidentate ligands - ions like [Ni(NH2CH2CH2NH2)3]2+ or [Cr
(C2O4)3]3-.
Help! If these ions look scarily unfamiliar, you must read the
introductory page on complex ions before you go on. The
shapes of the ions given below will be simplified in a way that
is explained on that page.
Use the BACK button on your browser to return to this page.
If your visual imagination will cope, you may be able to see that this ion
has no plane of symmetry. If you find this difficult to visualise, the only
solution is to make the ion out of a lump of plasticene (or a bit of clay or
dough) and three bits of cardboard cut to shape.
A substance with no plane of symmetry is going to have optical isomers one of which is the mirror image of the other. One of the isomers will
rotate the plane of polarisation of plane polarised light clockwise; the
other rotates it anti-clockwise.
For exam purposes, this doesn't matter in the slightest. As long as you
draw the isomers carefully, with the second one a true reflection of the
first, the two structures will be different.
This page explains how to work out the shapes of molecules and ions
containing only single bonds. If you are interested in the shapes of
molecules and ions containing double bonds, you will find a link at the
bottom of the page.
First you need to work out how many electrons there are around the
central atom:
Write down the number of electrons in the outer level of the central
atom. That will be the same as the Periodic Table group number,
except in the case of the noble gases which form compounds,
when it will be 8.
Add one electron for each bond being formed. (This allows for the
electrons coming from the other atoms.)
Allow for any ion charge. For example, if the ion has a 1- charge,
add one more electron. For a 1+ charge, deduct an electron.
Now work out how many bonding pairs and lone pairs of electrons there
are:
Finally, you have to use this information to work out the shape:
In the diagram, the other electrons on the fluorines have been left out
because they are irrelevant.
Other examples with four electron pairs around the central atom
Ammonia, NH3
Nitrogen is in group 5 and so has 5 outer electrons. Each of the 3
hydrogens is adding another electron to the nitrogen's outer level,
making a total of 8 electrons in 4 pairs. Because the nitrogen is only
forming 3 bonds, one of the pairs must be a lone pair. The electron pairs
arrange themselves in a tetrahedral fashion as in methane.
In this case, an additional factor comes into play. Lone pairs are in
orbitals that are shorter and rounder than the orbitals that the bonding
pairs occupy. Because of this, there is more repulsion between a lone
pair and a bonding pair than there is between two bonding pairs.
That forces the bonding pairs together slightly - reducing the bond angle
from 109.5 to 107. It's not much, but the examiners will expect you to
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know it.
Remember this:
Greatest repulsion
Least repulsion
Be very careful when you describe the shape of ammonia. Although the
electron pair arrangement is tetrahedral, when you describe the shape,
you only take notice of the atoms. Ammonia is pyramidal - like a
pyramid with the three hydrogens at the base and the nitrogen at the top.
Water, H2O
Following the same logic as before, you will find that the oxygen has four
pairs of electrons, two of which are lone pairs. These will again take up a
tetrahedral arrangement. This time the bond angle closes slightly more to
104, because of the repulsion of the two lone pairs.
The shape isn't described as tetrahedral, because we only "see" the
oxygen and the hydrogens - not the lone pairs. Water is described as
bent or V-shaped.
But take care! This is a positive ion. It has a 1+ charge because it has
lost 1 electron. That leaves a total of 8 electrons in the outer level of the
nitrogen. There are therefore 4 pairs, all of which are bonding because of
the four hydrogens.
The ammonium ion has exactly the same shape as methane, because it
has exactly the same electronic arrangement. NH4+ is tetrahedral.
But don't jump to conclusions. There are actually three different ways in
which you could arrange 3 bonding pairs and 2 lone pairs into a trigonal
bipyramid. The right arrangement will be the one with the minimum
amount of repulsion - and you can't decide that without first drawing all
the possibilities.
These are the only possible arrangements. Anything else you might think
of is simply one of these rotated in space.
We need to work out which of these arrangements has the minimum
amount of repulsion between the various electron pairs.
A new rule applies in cases like this:
In this diagram, two lone pairs are at 90 to each other, whereas in the
other two cases they are at more than 90, and so their repulsions can
be ignored. ClF3 certainly won't take up this shape because of the strong
lone pair-lone pair repulsion.
To choose between the other two, you need to count up each sort of
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repulsion.
In the next structure, each lone pair is at 90 to 3 bond pairs, and so
each lone pair is responsible for 3 lone pair-bond pair repulsions.
Because of the two lone pairs there are therefore 6 lone pair-bond pair
repulsions. And that's all. The bond pairs are at an angle of 120 to each
other, and their repulsions can be ignored.
Now consider the final structure.
Each lone pair is at 90 to 2 bond pairs - the ones above and below the
plane. That makes a total of 4 lone pair-bond pair repulsions - compared
with 6 of these relatively strong repulsions in the last structure. The other
fluorine (the one in the plane) is 120 away, and feels negligible repulsion
from the lone pairs.
The bond to the fluorine in the plane is at 90 to the bonds above and
below the plane, so there are a total of 2 bond pair-bond pair repulsions.
The structure with the minimum amount of repulsion is therefore this last
one, because bond pair-bond pair repulsion is less than lone pair-bond
pair repulsion. ClF3 is described as T-shaped.
There are two possible structures, but in one of them the lone pairs
would be at 90. Instead, they go opposite each other. XeF4 is described
as square planar.
ClF4Chlorine is in group 7 and so has 7 outer electrons. Plus the 4 from the
four fluorines. Plus one because it has a 1- charge. That gives a total of
12 electrons in 6 pairs - 4 bond pairs and 2 lone pairs. The shape will be
identical with that of XeF4.
This page explains how to work out the shapes of molecules and ions
containing double bonds. It assumes that you have just read the page on
shapes of molecules and ions containing only single bonds.
The carbon originally had 4 electrons in its outer level (group 4). Each
oxygen contributes 2 electrons - 1 for each bond. That means there are a
total of 8 electrons around the carbon, in 4 pairs. Because there are 4
bonds, these are all bond pairs.
Each double bond uses 2 bond pairs - which are then thought of as a
single unit. Those two double bond units will try to get as far apart as
possible, and so the molecule is linear. The structure we've drawn above
does in fact represent the shape of the molecule.
Because the lone pair isn't counted when you describe the shape, SO2 is
described as bent or V-shaped. In this case, our original structure
misrepresented the shape.
Like the sulphate ion, the negative charges are again found on two of the
oxygen atoms.
Beyond A'level: Again, this is a simplification. All the carbonoxygen bonds are identical, and the two negative charges are
spread over the three oxygens. The ion is again delocalised.
The carbon has 4 outer electrons, and the four bonds to the oxygens add
another 4 - making 8 in total. Once again, you don't need to add any
electrons for the negative charges because those charges aren't on the
carbon.
There are 4 pairs of electrons, and the carbon is forming 4 bonds - so
there aren't any lone pairs to worry about. Two of the pairs of electrons
make up a single unit - the double bond. The double bond unit and the
two single bonds arrange themselves as far apart as possible in a
trigonal planar arrangement.
The nitrate ion, NO3The nitrate ion is distinctly awkward and there isn't any simple way of
working out its shape. The problem is that it contains a co-ordinate
(dative covalent) bond.
The nitrate ion comes from nitric acid, so we'll start from the structure of
that.
Look carefully at the bonding around the nitrogen. You will see that one
of the bonds is formed entirely from the lone pair on the nitrogen. That's
the co-ordinate bond.
The nitrate ion is formed by the loss of the hydrogen ion, and so its
structure is:
Around the central nitrogen there are 4 pairs of shared electrons, and no
remaining lone pair. The original lone pair has now become a bonding
pair. Two of those pairs make up a double bond. The double bond unit
and the two single bonds arrange themselves as far apart as possible in
a trigonal planar arrangement - exactly the same as the carbonate ion.
This page is going to take a simple look at the origin of colour in complex
ions - in particular, why so many transition metal ions are coloured. Be
aware that this is only an introduction to what can grow into an extremely
complicated topic.
Working out what colour you will see isn't easy if you try to do it by
imagining "mixing up" the remaining colours. You wouldn't have thought
that all the other colours apart from some red would look cyan, for example.
Sometimes what you actually see is quite unexpected. Mixing different
wavelengths of light doesn't give you the same result as mixing paints or
other pigments.
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You can, however, sometimes get some estimate of the colour you would
see using the idea of complementary colours.
Complementary colours
If you arrange some colours in a circle, you get a "colour wheel". The
diagram shows one possible version of this. An internet search (see below)
will throw up many different versions!
Colours directly opposite each other on the colour wheel are said to be
complementary colours. Blue and yellow are complementary colours; red
and cyan are complementary; and so are green and magenta.
Mixing together two complementary colours of light will give you white light.
What this all means is that if a particular colour is absorbed from white
light, what your eye detects by mixing up all the other wavelengths of light
is its complementary colour. Copper(II) sulphate solution is pale blue
(cyan) because it absorbs light in the red region of the spectrum. Cyan is
the complementary colour of red.
This shortened version of the Periodic Table shows the first row of the d
block, where the 3d orbitals are being filled.
The usual definition of a transition metal is one which forms one or more
stable ions which have incompletely filled d orbitals.
Zinc with the electronic structure [Ar] 3d104s2 doesn't count as a transition
metal whichever definition you use. In the metal, it has a full 3d level.
When it forms an ion, the 4s electrons are lost - again leaving a completely
full 3d level.
At the other end of the row, scandium ( [Ar] 3d14s2 ) doesn't really counts
as a transition metal either. Although there is a partially filled d level in the
metal, when it forms its ion, it loses all three outer electrons.
The Sc3+ ion doesn't count as a transition metal ion because its 3d level is
empty.
The corresponding transition metal ions are coloured. Some, like the
hexaaquamanganese(II) ion (not shown) and the hexaaquairon(II) ion, are
quite faintly coloured - but they are coloured.
So . . . what causes transition metal ions to absorb wavelengths from
visible light (causing colour) whereas non-transition metal ions don't? And
why does the colour vary so much from ion to ion?
Note: If you aren't sure about the shapes of complex ions, you
might find it useful to follow this link before you go on. You only
need to read the beginning of that page.
If you don't know what a ligand is, you should read the
introduction to complex ions as a matter of urgency!
Use the BACK button on your browser to return to this page.
When the ligands bond with the transition metal ion, there is repulsion
between the electrons in the ligands and the electrons in the d orbitals of
the metal ion. That raises the energy of the d orbitals.
However, because of the way the d orbitals are arranged in space, it
doesn't raise all their energies by the same amount. Instead, it splits them
into two groups.
The diagram shows the arrangement of the d electrons in a Cu2+ ion
before and after six water molecules bond with it.
orbitals are always split into 2 groups in this way - 2 with a higher energy
than the other 3.
The size of the energy gap between them (shown by the blue arrows on
the diagram) varies with the nature of the transition metal ion, its oxidation
state (whether it is 3+ or 2+, for example), and the nature of the ligands.
When white light is passed through a solution of this ion, some of the
energy in the light is used to promote an electron from the lower set of
orbitals into a space in the upper set.
Each wavelength of light has a particular energy associated with it. Red
light has the lowest energy in the visible region. Violet light has the
greatest energy.
Suppose that the energy gap in the d orbitals of the complex ion
corresponded to the energy of yellow light.
The yellow light would be absorbed because its energy would be used in
promoting the electron. That leaves the other colours.
Your eye would see the light passing through as a dark blue, because blue
is the complementary colour of yellow.
Tetrahedral complexes
Simple tetrahedral complexes have four ligands arranged around the
central metal ion. Again the ligands have an effect on the energy of the d
electrons in the metal ion. This time, of course, the ligands are arranged
differently in space relative to the shapes of the d orbitals.
The net effect is that when the d orbitals split into two groups, three of
them have a greater energy, and the other two a lesser energy (the
opposite of the arrangement in an octahedral complex).
Apart from this difference of detail, the explanation for the origin of colour
shift away from the red end of the spectrum towards orange, yellow and so
on.
There is a fairly clear-cut case in copper(II) chemistry.
If you add an excess of ammonia solution to hexaaquacopper(II) ions in
solution, the pale blue (cyan) colour is replaced by a dark inky blue as
some of the water molecules in the complex ion are replaced by ammonia.
The first complex must be absorbing red light in order to give the
complementary colour cyan. The second one must be absorbing in the
yellow region in order to give the complementary colour dark blue.
Yellow light has a higher energy than red light. You need that higher
energy because ammonia causes more splitting of the d orbitals than
water does.
It isn't often as simple to see as this, though! Trying to sort out what is
being absorbed when you have murky colours not on the simple colour
wheel further up the page is much more of a problem.
The diagrams show some approximate colours of some ions based on
chromium(III).
It is obvious that changing the ligand is changing the colour, but trying to
explain the colours in terms of our simple theory isn't easy.
The 2+ ion is almost the same colour as the hexaaquacopper(II) ion, and
the 3+ ion is the hard-to-describe violet-blue-gey colour.
Notice the change in the co-ordination of the cobalt. Chloride ions are
bigger than water molecules, and there isn't room to fit six of them
around the central cobalt ion.
This reaction can be easily reversed by adding water to the solution.
Adding water to the right-hand side of the equilibrium has the effect of
moving the position of equilibrium to the left. The pink colour of the
hexaaquacobalt(II) ion is produced again (only paler, of course, because
it is more dilute).
The reaction taking place is reversible, and you get a mixture of colours
due to both of the complex ions.
Adding water to the green solution, replaces the chloride ions as ligands
by water molecules again, and the solution returns to blue.
Note: You will find full details of the reactions involved in the
formation of the precipitates described on a separate page
about the reaction of ammonia with metal aqua ions.
That page also describes the quite complex reasons why the
precipitate dissolves again.
Notice that the four ammonias all lie in one plane, with the water
molecules above and below.
What you see in a test tube is:
The colour of the deep blue complex is so strong that this reaction is
used as a sensitve test for copper(II) ions in solution. Even if you try to
reverse the change by adding large amounts of water to the equilibrium,
the strength of the deep blue (even highly diluted) always masks the pale
blue of the aqua ion.
This page describes and explains the reactions between complex ions of
the type [M(H2O)6]n+ and ammonia solution.
Adding ammonia again tips the equilibrium to the right - either by reacting
with the hydrogen ions, or by reacting directly with the complex on the
left-hand side.
When this happens, the new complex formed no longer has a charge this is a "neutral complex". It is insoluble in water - and so a precipitate is
formed.
This precipitate is often written without including the remaining water
ligands. In other words we write it as M(OH)2. A precipitate of the metal
hydroxide has been formed.
Summarising what has happened
If you did the same reaction with a 3+ ion, the only difference is that you
would have to remove a total of 3 hydrogen ions in order to get to the
neutral complex. That would give the overall equation:
Note: The final solution rapidly darkens in air to a deep redbrown. This is due to oxidation from hexaamminecobalt(II) to
hexaamminecobalt(III) ions.
This oxidation is described in more detail on the page about
cobalt chemistry.
Use the BACK button on your browser to return quickly to this
page.
hexaaquacopper(II)
hexaaquairon(II)
Iron is very easily oxidised under alkaline conditions. Oxygen in the air
oxidises the iron(II) hydroxide precipitate to iron(III) hydroxide especially
around the top of the tube. The darkening of the precipitate comes from
the same effect. This is NOT a ligand exchange reaction.
hexaaquamanganese(II)
I have shown the original solution as very pale pink (the palest I can
produce!), but in fact it is virtually colourless. The pale brown precipitate
is oxidised to darker brown manganese(III) oxide in contact with oxygen
from the air. Again, this isn't a ligand exchange reaction.
hexaaquanickel(II)
hexaaquazinc
Note: I have shown the final zinc ion as [Zn(NH3)4]2+, but I'm
not certain about this. Some sources (although a minority)
show it as [Zn(NH3)4(H2O)2]2+. I don't know which is right!
3+ ions
hexaaquaaluminium
hexaaquairon(III)
hexaaqua ions. The only real difference lies in the colour of the cobalt
precipitate.
Notice that the hexaaqua ion appears in both of these. There is now an
interaction between the two equilibria:
This page explains why complex ions of the type [M(H2O)6]n+ are acidic.
Each of the six water molecules are attached to the central iron(III) ion
via a co-ordinate bond using one of the lone pairs on the oxygen.
We'll choose one of these water molecules at random (it doesn't make
any difference which one!), and look at the bonding in a bit more detail showing all the bonds around the oxygen.
Imagine for the moment that the 3+ charge is located entirely on the iron.
When the lone pairs on the oxygens form co-ordinate bonds with the
iron, there is obviously a movement of electrons towards the iron.
That has an effect on the electrons in the O-H bonds. These electrons, in
turn, get pulled towards the oxygen even more than usual. That leaves
the hydrogen nuclei more exposed than normal.
The overall effect is that each of the hydrogen atoms is more positive
than it is in ordinary water molecules. The 3+ charge is no longer located
entirely on the iron but spread out over the whole ion - much of it on the
hydrogen atoms.
The effect of dissolving this ion in water
The theory
The hydrogen atoms attached to the water ligands are sufficiently
positive that they can be pulled off in a reaction involving water
molecules in the solution.
The first stage of this process is:
However, if you write it like this, remember that the hydrogen ion isn't just
falling off the complex ion. It is being pulled off by a water molecule in the
solution. Whenever you write "H+(aq)" what you really mean is a
hydroxonium ion, H3O+.
The hexaaquairon(III) ion is quite strongly acidic giving solutions with
pH's around 1.5, depending on concentration. You can get further loss of
hydrogen ions as well, from a second and a third water molecule.
Losing a second hydrogen ion:
This time you end up with a complex with no charge on it. This is
described as a neutral complex. Because it has no charge, it doesn't
dissolve in water to any extent, and a precipitate is formed.
In practice
What do you actually get in solution if you dissolve an iron(III) salt in
water? In fact you get a mixture of all the complexes that you have seen
in the equations above. These reactions are all equilibria, so everything
will be present. The proportions depend on how concentrated the
solution is.
The colour of the solution is very variable and depends in part on the
concentration of the solution. Dilute solutions containing iron(III) ions can
be pale yellow. More concentrated ones are much more orange, and
may even produce some orange precipitate.
None of these colours represents the true colour of the [Fe(H2O)6]3+ ion which is a very pale lilac colour! That colour is only really easy to see in
solids containing the ion.
Looking at the equilibrium showing the loss of the first hydrogen ion:
The colour of the new complex ion on the right-hand side is so strong
that it completely masks the colour of the hexaaqua ion.
In concentrated solutions, the equilibrium position will be even further to
the right-hand side (Le Chatelier's Principle), and so the colour darkens.
You will also get significant loss of other hydrogen ions leading to some
formation of the neutral complex - and so you get some precipitate.
You can move the position of this equilibrium by adding extra hydrogen
ions from a concentrated acid - for example, by adding concentrated
nitric acid to a solution of iron(III) nitrate.
The new hydrogen ions push the position of the equilibrium to the left so
that you can see the colour of the hexaaqua ion. This is slightly easier to
follow if you write the simplified version of the equilibrium.
Warning! If you like your chemistry all tidy and simple, don't
read any further. I have got to the point that most text books
get to at this level. In fact, as I will show below, it is quite
difficult to show this effect of ionic radius in any simple ions.
There are too many exceptions.
Note: It isn't necessary for this topic, but if you need to know
more about pKa, you can find it by following this link.
Use the BACK button on your browser to return quickly to this
page.
Ionic radius
A real problem arises here! Almost every data source that you refer to
quotes different values for ionic radii. This is because the radius of a
metal ion varies depending on what negative ion it is associated with. We
are interested in what happens when the metal ion is bonded to water
molecules, so haven't got simple ions at all! Whatever values we take are
unlikely to represent the real situation.
In the graphs which follow I have taken values for ionic radii from two
common sources so that you can see what a lot of difference it makes to
the argument.
The graphs
If it is true that the smaller the ionic radius, the stronger the acidity of the
hexaaqua ion, you would expect some sort of regular increase in pKa
(showing weaker acids) as ionic radius increases.
The following graphs plot pKa against ionic radii for the 2+ ions of the
elements in the first transition series from vanadium to copper.
The first graph plots pKa against ionic radii taken from Chemistry Data
Book by Stark and Wallace.
You can see that there is a trend for several of the ions, but it is
completely broken by vanadium and chromium.
The second graph uses ionic radii taken from the Nuffield Advanced
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In this case, the pattern is much more confused. Which is right? I don't
know!!
A final comment
During the couple of weeks I spent trying to understand this, I failed
completely. The only conclusion I came to is that there probably is a
relationship between ionic radius and acid strength, but that it is nothing
like as simple and straightforward as most books at this level pretend.
The problem is that there are other more important effects operating as
well (quite apart from differences in charge) and these can completely
swamp the effect of the changes in ionic radius. You have to look in far
more detail at the bonding in the hexaaqua ions and the product ions.
This is all just too difficult to understand at this level. In fact, to be honest,
I did wonder while I was researching this whether anyone really
understood all of this! There is, of course, no reason why they should - it
is nonsense to think that we can explain everything in chemistry at the
present moment.
To Main Menu . . .
This page describes and explains the reactions between complex ions of
the type [M(H2O)6]n+ and hydroxide ions from, for example, sodium
hydroxide solution.
It assumes that you know why these ions are acidic, and are happy
about the equilibria involved.
Notice that this isn't a ligand exchange reaction. The hydroxide ion has
removed a hydrogen ion from one of the ligand water molecules. The
reaction has also become virtually one-way.
The second stage of the reaction
Whichever of the above reactions happens, you end up with [M(H2O)5
(OH)]+ ions in solution. These are also acidic, and can lose hydrogen
ions from another of the water ligands.
Taking the easier version of the equilibrium:
Adding hydroxide ions again tips the equilibrium to the right - either by
reacting with the hydrogen ions, or by reacting directly with the complex
on the left-hand side.
When this happens, the new complex formed no longer has a charge we describe it as a "neutral complex". In all the cases we are looking at,
this neutral complex is insoluble in water - and so a precipitate is formed.
This precipitate is often written without including the remaining water
ligands. In other words we write it as M(OH)2. A precipitate of the metal
hydroxide has been formed.
Going further
There is no logical reason why the removal of hydrogen ions from the
complex should stop at this point. Further hydrogen ions can be removed
by hydroxide ions to produce anionic complexes - complexes carrying
negative charges.
Whether this actually happens in the test tube to any extent varies from
metal to metal.
Note: It would be absurd to sit and learn all this! All you
need to do is to understand that one hydrogen ion gets
removed at a time. When you have a neutral complex, it will
form a precipitate. That is equally true of the 2+ or 3+ cases.
Just be careful with the charges on the complexes.
Remember that for every hydrogen ion you remove, you will
lose a positive charge (or will gain one more negative charge).
When you come to looking at individual metals, you will, of
course, have to remember where the sequence usually stops.
Note: I don't know the reason for the change in colour. One
reliable source quotes it vaguely as a change in coordination
of the metal ion. Another suggests that the blue precipitate
involves a chloride ion (from the cobalt(II) chloride solution if
that's what you used) as a ligand. You are unlikely to need to
worry about this at this level. Remember the colour changes!
hexaaquacopper(II)
hexaaquairon(II)
Iron is very easily oxidised under alkaline conditions. Oxygen in the air
oxidises the iron(II) hydroxide precipitate to iron(III) hydroxide especially
around the top of the tube. The darkening of the precipitate comes from
the same effect.
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hexaaquamanganese(II)
I have shown the original solution as very pale pink (the palest I can
produce!), but in fact it is virtually colourless. The pale brown precipitate
is oxidised to darker brown manganese(III) oxide in contact with oxygen
from the air.
hexaaquanickel(II)
hexaaquazinc
3+ ions
hexaaquaaluminium
This looks exactly the same in the test tube as the corresponding zinc
reaction above - but beware the different formulae of the precipitate and
the final solution.
hexaaquachromium(III)
hexaaquairon(III)
Note: The original colour of the iron(III) ion is very variable from a pale yellow to a darkish orange-brown. None of these
colours is actually the colour of the true hexaaquairon(III) ion.
This is explored in more detail on the page about the acidity
of the hexaaqua ions.
If you add an acid (dilute sulphuric acid, for example), the hydrogen ions
get put back on one at a time.
You already know the colours of the significant stages (the beginning, the
end, and the neutral complex). It isn't a separate bit of learning!
You can apply this to any case. If you know the colours as you remove
hydrogen ions, you automatically know them as you put the hydrogen
ions back on again.
It also doesn't matter where you start from either - whether, for example,
you add acid to an ionic complex like [Cr(OH)6]3-, or a neutral one like [Fe
(H2O)4(OH)2].
You will know that the [Fe(H2O)4(OH)2] is a dirty green precipitate. When
you add the hydrogen ions back to it, it will revert to the very pale green
solution of the [Fe(H2O)6]2+ ion. None of this is a new bit of learning - you
just have to re-arrange what you already know!
Amphoteric hydroxides
An amphoteric substance has both acidic and basic properties. In other
words, it will react with both bases and acids. Some of the metal
hydroxides we've been looking at are doing exactly that.
Chromium(III) hydroxide as an amphoteric hydroxide
"Chromium(III) hydroxide" is a simple way of naming the neutral complex
[Cr(H2O)3(OH)3]. You have seen that it reacts with bases (hydroxide
ions) to give [Cr(OH)6]3-. It also reacts with acids (hydrogen ions) to give
[Cr(H2O)6]3+.
This is a good example of amphoteric behaviour.
Other examples of amphoteric hydroxides are zinc hydroxide and
aluminium hydroxide.
Copper(II) hydroxide as a basic oxide
Quite a lot of metal hydroxides won't react any further with hydroxide ions
if you use sodium hydroxide solution at the sort of concentrations
normally used in the lab. That means that they don't have any significant
acidic nature.
"Copper(II) hydroxide" is what we would normally call the neutral
complex [Cu(H2O)4(OH)2]. This doesn't dissolve in sodium hydroxide
solution at any concentration normally used in the lab. It doesn't show
any acidic character.
On the other hand, it will react with acids - replacing the lost hydrogen
ions on the water ligands. Because it is accepting hydrogen ions, it is
acting as a base.
Hydroxides like this (which react with acids, but not bases) are not
amphoteric - they are just simple bases.
cobalt
COBALT
This page looks at some aspects of cobalt chemistry required for UK A'
level exams. These are mainly summarised from elsewhere on the site,
with links available to more detailed explanations.
cobalt
Note: I don't know the reason for the change in colour. One
reliable source quotes it vaguely as a change in coordination
of the metal ion. Another suggests that the blue precipitate
involves a chloride ion (from the cobalt(II) chloride solution if
that's what you used) as a ligand. You are unlikely to need to
worry about this at this level.
You will find the reactions between hexaaqua ions and
hydroxide ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
cobalt
cobalt
cobalt
cobalt
cobalt
Note: Only one of the UK A' level Exam Boards wants this,
and this is the simplification that they make. In fact, the
precipitate is better described as a basic carbonate with a
formula of the type xCoCO3,yCo(OH)2,zH2O.
You will find the reactions between hexaaqua ions and
carbonate ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
If you add water to the blue solution, it returns to the pink colour.
cobalt
Writing ionic equations for redox reactions done under alkaline conditions
electrons
water
Writing ionic equations for redox reactions done under alkaline conditions
The whole process is fairly automatic, and provided you take care, there
isn't much to go wrong.
How is this different under alkaline conditions?
The problem is that the water and the hydroxide ions that you add to
balance the equations under alkaline conditions contain both hydrogen
and oxygen.
To balance the oxygens, you could in principle add either H2O or OH- to
the equation. The same thing is true for balancing the hydrogens. How do
you know what to start with?
Four examples
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Writing ionic equations for redox reactions done under alkaline conditions
Everything balances apart from the charges. Add an electron to the righthand side to give both sides an overall charge of 2+.
The hydrogen peroxide half-equation isn't very difficult either, except that
you aren't told what is formed and so have to make a guess. It would
balance very nicely if you ended up with 2 hydroxide ions on the righthand side.
This is a good example of a case where it is fairly obvious where to put
hydroxide ions.
You would then just have to add 2 electrons to the left-hand side to
balance the charges.
Writing ionic equations for redox reactions done under alkaline conditions
Combining the half-reactions to make the ionic equation for the reaction
What we have so far is:
You obviously need another hydroxide ion on the left-hand side. This is
even more straightforward than the previous example.
Writing ionic equations for redox reactions done under alkaline conditions
The half-equation for the oxygen isn't so easy. You don't know what is
being formed.
It isn't at all obvious whether you need to balance the oxygens by adding
water molecules or hydroxide ions to the right-hand side. OK - treat it as if
it were being done under acidic conditions, and the problem disappears!
In this case, you can only balance the oxygens by adding water
molecules to the right-hand side.
Now you have got a perfectly balanced half-equation. The problem is, of
course, that it only applies under acidic conditions. We should have
alkaline conditions - with hydroxide ions present not hydrogen ions.
So . . . get rid of the hydrogen ions! Add enough hydroxide ions to both
sides of the equation so that you can neutralise all the hydrogen ions.
Because it is now a balanced equation, you must add the same number
to both sides to maintain the balance.
The hydrogen ions and hydroxide ions on the left-hand side would turn
into 4 water molecules:
Finally, there are water molecules on both sides of the equation. Cancel
out any which aren't changed.
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Writing ionic equations for redox reactions done under alkaline conditions
This has all been a bit tedious - although you haven't actually had to think
very much! Don't forget to re-check that everything balances now that you
have finished.
Combining the half-reactions to make the ionic equation for the reaction
From here on it's all back to the usual routine. We've worked out the two
half-equations:
The iron equation will have to happen 4 times to supply enough electrons
to the oxygen.
Notice that the hydroxide ions on each side cancel out. (Perhaps to your
surprise - certainly to mine when I worked this out!)
Writing ionic equations for redox reactions done under alkaline conditions
So what is happening to the hydroxide ions to turn them into oxygen gas?
It isn't actually very difficult to work out the half-equation directly, but
suppose you want to avoid thinking and go through a standard routine:
Write down what you know, balancing the oxygens in the process:
Now get rid of the hydrogen ions by adding enough hydroxide ions to
both sides of the equation:
Writing ionic equations for redox reactions done under alkaline conditions
Combining the half-reactions to make the ionic equation for the reaction
What we have so far is:
The manganese reaction will have to happen four times in order to use up
the four electrons produced by the hydroxide equation. Putting this
together, you get:
The chemistry may be unfamiliar, but working out the equation isn't too
hard!
So this time we just need to put together the half-equation for the
chromium ions. What we know is:
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Writing ionic equations for redox reactions done under alkaline conditions
It isn't the least bit obvious where to put hydroxide ions or water
molecules, so treat it as if it were being done under acidic conditions.
That way, you start by balancing the oxygens by adding water molecules.
To get 6 oxygens on each side, you need two waters on the right-hand
side:
Combining the half-reactions to make the ionic equation for the reaction
The two half-equations are:
If you multiply one equation by 3 and the other by 2, that transfers a total
of 6 electrons.
Writing ionic equations for redox reactions done under alkaline conditions
Finally, tidy up the hydroxide ions that occur on both sides to leave the
overall ionic equation:
This page describes and explains the reactions between complex ions of
the type [M(H2O)6]n+ and carbonate ions from, for example, sodium
carbonate solution.
You can also usefully write the complete change as an overall reaction.
Note: Only one of the UK A' level Exam Boards wants this,
and this is the simplification that they make. In fact, the
precipitates are better described as basic carbonates with a
formula of the type xMCO3,yM(OH)2,zH2O.
Starting from a colourless solution, you get a white precipitate - but with
bubbles of gas as well. The precipitate is identical to the one you get if
you add small amounts of either sodium hydroxide or ammonia solutions
to a solution of the hexaaquaaluminium ions.
hexaaquachromium(III)
Again, the precipitate is just the same as if you had added small amounts
of either sodium hydroxide or ammonia solution.
hexaaquairon(III)
. . . and again, exactly the same precipitate as if you had added any
other base.
Summary
In each case you get a precipitate of the neutral complex - the metal
hydroxide. This is exactly the same precipitate that you get if you add
small amounts of either sodium hydroxide solution or ammonia solution
to solutions of these ions. Bubbles of carbon dioxide are also given off.
2+ ions
hexaaquacobalt(II)
Again, there isn't any carbon dioxide - just a precipitate of the "copper(II)
carbonate".
hexaaquairon(II)
Summary
Hexaaqua ions with a 2+ charge aren't sufficiently acidic to liberate
carbon dioxide from carbonate ions. Instead you get a precipitate which
you can think of as being the metal carbonate.
Understanding Chemistry
The elements in the Periodic Table which correspond to the d levels filling
are called d block elements. The first row of these is shown in the
shortened form of the Periodic Table below.
Sc
[Ar] 3d14s2
Ti
[Ar] 3d24s2
[Ar] 3d34s2
Cr
[Ar] 3d54s1
Mn
[Ar] 3d54s2
Fe
[Ar] 3d64s2
Co
[Ar] 3d74s2
Ni
[Ar] 3d84s2
Cu
[Ar] 3d104s1
Zn
[Ar] 3d104s2
You will notice that the pattern of filling isn't entirely tidy! It is broken at
both chromium and copper.
Transition metals
Not all d block elements count as transition metals! There are
discrepancies between the various UK A' level syllabuses, but the majority
use the definition:
A transition metal is one which forms one or more stable ions which
have incompletely filled d orbitals.
On the basis of this definition, scandium and zinc don't count as transition
metals - even though they are members of the d block.
Scandium has the electronic structure [Ar] 3d14s2. When it forms ions, it
always loses the 3 outer electrons and ends up with an argon structure.
The Sc3+ ion has no d electrons and so doesn't meet the definition.
Zinc has the electronic structure [Ar] 3d104s2. When it forms ions, it always
loses the two 4s electrons to give a 2+ ion with the electronic structure [Ar]
3d10. The zinc ion has full d levels and doesn't meet the definition either.
By contrast, copper, [Ar] 3d104s1, forms two ions. In the Cu+ ion the
electronic structure is [Ar] 3d10. However, the more common Cu2+ ion has
the structure [Ar] 3d9.
Copper is definitely a transition metal because the Cu2+ ion has an
incomplete d level.
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Remember this:
When d-block elements form ions, the 4s electrons are lost first.
Co
[Ar] 3d74s2
Co2+
[Ar] 3d7
[Ar] 3d34s2
V3+
[Ar] 3d2
Note: If you aren't sure about oxidation states, you really need
to follow this link before you go on.
Use the BACK button on your browser to return quickly to this
page.
+2
in Mn2+
+3
in Mn2O3
+4
in MnO2
+6
in MnO42-
+7
in MnO4-
Other examples
You will find the above examples and others looked at in detail if you
explore the chemistry of individual metals from the transition metal menu.
There is a link to this menu at the bottom of the page.
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The amount of energy needed to ionise the metal (the sum of the
various ionisation energies)
The amount of energy released when the compound forms. This will
either be lattice enthalpy if you are thinking about solids, or the
hydration enthalpies of the ions if you are thinking about solutions.
The more highly charged the ion, the more electrons you have to remove
and the more ionisation energy you will have to provide.
But off-setting this, the more highly charged the ion, the more energy is
released either as lattice enthalpy or the hydration enthalpy of the metal
ion.
Note: What I am talking about here in a general way are BornHaber cycles. These aren't covered anywhere on this site, but
if you want to explore them in more detail, you may be
interested in my chemistry calculations book.
Fe
[Ar] 3d64s2
Fe2+
[Ar] 3d6
Fe3+
[Ar] 3d5
The 4s orbital and the 3d orbitals have very similar energies. There isn't a
huge jump in the amount of energy you need to remove the third electron
compared with the first and second.
The figures for the first three ionisation energies (in kJ mol-1) for iron
compared with those of calcium are:
metal
1st IE
2nd IE
3rd IE
Ca
590
1150
4940
Fe
762
1560
2960
What all these have got in common is active lone pairs of electrons in the
outer energy level. These are used to form co-ordinate bonds with the
metal ion.
Some examples of complex ions formed by transition metals
[Fe(H2O)6]2+
[Co(NH3)6]2+
[Cr(OH)6]3[CuCl4]2Other metals also form complex ions - it isn't something that only transition
metals do. Transition metals do, however, form a very wide range of
complex ions.
You will find these and others discussed if you follow links to individual
metals from the transition metal menu (link at the bottom of the page).
Alternatively, you could explore the complex ions menu (follow the link in
the help box which has just disappeared off the top of the screen).
The origin of colour in the transition metal ions
When white light passes through a solution of one of these ions, or is
reflected off it, some colours in the light are absorbed. The colour you see
is how your eye perceives what is left.
Attaching ligands to a metal ion has an effect on the energies of the d
orbitals. Light is absorbed as electrons move between one d orbital and
another. This is explained in detail on another page.
Catalytic activity
Transition metals and their compounds are often good catalysts. A few of
the more obvious cases are mentioned below, but you will find catalysis
explored in detail elsewhere on the site (follow the link after the examples).
Transition metals and their compounds function as catalysts either
because of their ability to change oxidation state or, in the case of the
metals, to adsorb other substances on to their surface and activate them in
the process. All this is expored in the main catalysis section.
Iron ions in the reaction between persulphate ions and iodide ions
Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful
oxidising agents. Iodide ions are very easily oxidised to iodine. And yet the
reaction between them in solution in water is very slow.
The reaction is catalysed by the presence of either iron(II) or iron(III) ions.
vanadium
VANADIUM
vanadium
Although the catalyst has been temporarily changed during the reaction,
at the end it is chemically the same as it started.
Note: If you want more detail about the Contact Process, you
will find a full description of the conditions used and the
reasons for them by following this link.
If you want to find out more about catalysis, this link will take
you to an introductory page about catalysts with further links
to other catalysis pages if you want them.
Use the BACK button on your browser (or the History file of
Go menu) if you want to return to this page later.
vanadium
vanadium
It is important to notice that the green colour you see isn't actually another
oxidation state. it is just a mixture of the original yellow of the +5 state and
the blue of the +4.
Be very careful with the formulae of the two vanadium ions - they are very
easy to confuse!
vanadium
Note: Just like the VO2+ ion, the VO2+ ion will have water
molecules attached to it as well - [VO(H2O)5]2+. We usually
use the simpler form.
The reason for the inverted commas around the vanadium(III) ion is that
this is almost certainly a simplification. The exact nature of the complex
ion will depend on which acid you use in the reduction process. The
simplification is probably reasonable at this level.
vanadium
If it is allowed to stand for a long time, the solution eventually turns blue
as the air oxidises it back to the vanadium(IV) state - VO2+ ions.
Adding nitric acid (a reasonably powerful oxidising agent) to the original
vanadium(II) solution also produces blue VO2+ ions. The vanadium(II) is
again oxidised back to vanadium(IV).
vanadium
vanadium
So . . . if you mix together zinc and VO2+ ions in the presence of acid to
provide the H+ ions:
That converts the two equilibria into two one-way reactions. You can write
these down and combine them to give the ionic equation for the reaction if
you want to.
vanadium
Remember that for the vanadium reactions to move to the right (which is
what we want), their E values must be more positive than whatever you
are reacting them with.
In other words, for the reactions to work, zinc must always have the more
negative value - and that's the case.
vanadium
Zinc can reduce the vanadium through each of these steps to give the
vanadium(II) ion.
Using other reducing agents
Suppose you replaced zinc as the reducing agent by tin. How far would
the set of reductions go this time?
Here are the E values again:
In order for each reduction to happen, the vanadium reaction has to have
the more positive E value because we want it to go to the right. That
means that the tin must have the more negative value.
In the first vanadium equation (from +5 to +4), the tin value is more
negative. That works OK.
In the second vanadium equation (from +4 to +3), the tin value is again
the more negative. That works as well.
But in the final vanadium reaction (from +3 to +2), tin no longer has the
more negative E value. Tin won't reduce vanadium(III) to vanadium(II).
vanadium
The reaction with the more negative E value goes to the left; the reaction
with the more positive (or less negative) one to the right.
That means that the vanadium(II) ions will be oxidised to vanadium(III)
vanadium
In order for the vanadium equilibrium to move to the left, it would have to
have the more negative E value. It hasn't got the more negative E value
and so the reaction doesn't happen.
Oxidation by nitric acid
In a similar sort of way, you can work out how far nitric acid will oxidise
the vanadium(II).
Here's the first step:
The vanadium reaction has the more negative E value and so will move
to the left; the nitric acid reaction moves to the right.
Nitric acid will oxidise vanadium(II) to vanadium(III).
The second stage involves these E values:
The nitric acid again has the more positive E value and so moves to the
right. The more negative (less positive) vanadium reaction moves to the
left.
vanadium
No, it won't! For the vanadium reaction to move to the left to form the
dioxovanadium(V) ion, it would have to have the more negative (less
positive) E value. It hasn't got a less positive value, and so the reaction
doesn't happen.
vanadium
You can work out the effect of any other oxidising agent on the lower
oxidation states of vanadium in exactly the same way. But don't assume
that because the E values show that a reaction is possible, it will
necessarily happen.
chromium
CHROMIUM
This page looks at some aspects of chromium chemistry required for UK A' level
exams. It includes: reactions of chromium(III) ions in solution (summarised from
elsewhere on the site); the interconversion of the various oxidation states of
chromium; the chromate(VI)-dichromate(VI) equilibrium; and the use of dichromate
(VI) ions as an oxidising agent (including titrations).
The first part of this page is a summary of the reactions of chromium(III) ions in
solution. You will find links to other pages where these reactions are discussed in
more detail.
Note: If you aren't happy about complex ions (including the way they
are bonded and named), it would pay you to follow this link and explore
the first couple of pages in the complex ions menu before you go on.
Use the BACK button on your browser to return to this page.
chromium
However, if you write it like this, remember that the hydrogen ion isn't just falling
off the complex ion. It is being pulled off by a water molecule in the solution.
Whenever you write "H+(aq)" what you really mean is a hydroxonium ion, H3O+.
Note: You will find the full reasons for the acidity of hexaaqua ions if
you follow this link. You only need to read the beginning of that page
which concentrates on explaining the acidity of the hexaaquairon(III)
ion. What is said applies equally to the chromium-containing ion.
Use the BACK button on your browser to return to this page.
chromium
One of the water molecules is replaced by a sulphate ion. Notice the change in
the charge on the ion. Two of the positive charges are cancelled by the presence
of the two negative charges on the sulphate ion.
Replacement of the water by chloride ions
In the presence of chloride ions (for example with chromium(III) chloride), the
most commonly observed colour is green. This happens when two of the water
molecules are replaced by chloride ions to give the tetraaquadichlorochromium(III)
ion - [Cr(H2O)4Cl2]+.
Once again, notice that replacing water molecules by chloride ions changes the
charge on the ion.
chromium
Note: The colour coding is to show that this isn't a ligand exchange
reaction. The oxygens which were originally attached to the chromium
are still attached in the neutral complex.
But the process doesn't stop there. More hydrogen ions are removed to give ions
like [Cr(H2O)2(OH)4]- and [Cr(OH)6]3-.
For example:
chromium
Note: You will find the reactions between hexaaqua ions and
hydroxide ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
chromium
Note: You might wonder why this second equation is given starting
from the original hexaaqua ion rather than the neutral complex.
Explaining why the precipitate redissolves is quite complicated. You
will find the explanation in full (although by reference to the
corresponding copper case) on the page about the reactions between
hexaaqua ions and ammonia solution.
Use the BACK button on your browser to return to this page.
chromium
between the hydrogen ions and carbonate ions. The more usually quoted
equation shows the formation of carbon dioxide.
Apart from the carbon dioxide, there is nothing new in this reaction:
Note: You will find the reactions between hexaaqua ions and
carbonate ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
chromium
Note: Although it is still a complex ion, you don't write square brackets
around the chromate(VI) ion - any more than you would around a
sulphate or carbonate ion.
If you want to know how to work out this equation , follow this link.
Use the BACK button on your browser to return to this page.
chromium
chromium
If you add extra hydrogen ions to this, the equilibrium shifts to the right. This is
consistent with Le Chatelier's Principle.
If you add hydroxide ions, these react with the hydrogen ions. The equilibrium tips
to the left to replace them.
chromium
The reason for the inverted commas around the chromium(III) ion is that this is a
simplification. The exact nature of the complex ion will depend on which acid you
use in the reduction process. This has already been discussed towards the top of
the page.
chromium
Note: If you don't know how to work out equations like this, you can
find out how to do it on the page about writing ionic equations for redox
reactions.
Use the BACK button on your browser to return to this page.
For example, with ethanol (a primary alcohol), you can get either ethanal (an
aldehyde) or ethanoic acid (a carboxylic acid) depending on the conditions.
If the alcohol is in excess, and you distil off the aldehyde as soon as it is
formed, you get ethanal as the main product.
chromium
If the oxidising agent is in excess, and you don't allow the product to
escape - for example, by heating the mixture under reflux (heating the flask
with a condenser placed vertically in the neck) - you get ethanoic acid.
The oxygen written in square brackets just means "oxygen from an oxidising
agent".
Note: These are not a proper substitute for real equations. Only use
them if your examiners are happy with them. Check your syllabus and
look at past papers and mark schemes.
If you don't have these things, UK A' level students can find out how to
get hold of them by going to the syllabuses page.
chromium
In practice
There are advantages and disadvantages in using potassium dichromate(VI).
Advantages
Disadvantage
chromium
You can see that the reacting proportions are 1 mole of dichromate(VI) ions to 6
moles of iron(II) ions.
Once you have established that, the titration calculation is going to be just like any
other one.
Note: If you aren't very good at doing titration calculations, you might
be interested in my chemistry calculations book.
chromium
manganese
MANGANESE
manganese
I have shown the original solution as very pale pink (the palest I can
produce!), but in fact it is virtually colourless. The pale brown precipitate
is oxidised to darker brown manganese(III) oxide in contact with oxygen
from the air.
Note: You will find the reactions between hexaaqua ions and
hydroxide ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
manganese
Again, I have shown the original solution as the palest pink I can
produce, but in fact it is virtually colourless. The pale brown precipitate is
oxidised to darker brown manganese(III) oxide in contact with oxygen
from the air.
There is no observable difference in appearance between this reaction
and the last one.
Note: You will find the reactions between hexaaqua ions and
ammonia solution discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
manganese
manganese
In the case of the ethyl side chain, you will also get carbon dioxide. With
longer side chains, you will get all sorts of mixtures of other products but in each case, the main product will be benzoic acid.
manganese
Background
Potassium manganate(VII) solution is used to find the concentration of all
sorts of reducing agents. It is always used in acidic solution.
For example, it oxidises
manganese
manganese
iron
IRON
This page looks at some aspects of iron chemistry required for UK A'
level exams (summarised from elsewhere on the site). You will find links
to pages where full details and explanations are given.
iron
For the sake of argument, we'll take the catalyst to be iron(II) ions. The
reaction happens in two stages.
If you use iron(III) ions, the second of these reactions happens first.
This is a good example of the use of transition metal compounds as
catalysts because of their ability to change oxidation state.
iron
They are both acidic, but the iron(III) ion is more strongly acidic.
iron
Iron is very easily oxidised under alkaline conditions. Oxygen in the air
oxidises the iron(II) hydroxide precipitate to iron(III) hydroxide especially
around the top of the tube. The darkening of the precipitate comes from
the same effect.
In the iron(III) case:
iron
Note: You will find the reactions between hexaaqua ions and
hydroxide ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
iron
The appearance is just the same as in when you add sodium hydroxide
solution. The precipitate again changes colour as the iron(II) hydroxide
complex is oxidised by the air to iron(III) hydroxide.
In the iron(III) case:
The reaction looks just the same as when you add sodium hydroxide
solution.
Note: You will find the reactions between hexaaqua ions and
ammonia solution discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
iron
Note: Only one of the UK A' level Exam Boards wants this,
and this is the simplification that they make. In fact, the
precipitate is better described as a basic carbonate with a
formula of the type xFeCO3,yFe(OH)2,zH2O.
iron
Apart from the carbon dioxide, there is nothing new in this reaction:
Note: You will find the reactions between hexaaqua ions and
carbonate ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
iron
iron
iron
You can see that the reacting proportions are 1 mole of dichromate(VI)
ions to 6 moles of iron(II) ions.
Once you have established that, the titration calculation is again going to
be just like any other one.
iron
copper
COPPER
This page looks at some aspects of copper chemistry required for UK A'
level exams. The chemistry of copper(II) is mainly summarised from
elsewhere on the site, with links available to more detailed explanations.
The page also covers some simple copper(I) chemistry.
copper
Note: You will find the reactions between hexaaqua ions and
hydroxide ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
copper
copper
Note: Only one of the UK A' level Exam Boards wants this,
and this is the simplification that they make. In fact, the
precipitate is better described as a basic carbonate with a
formula of the type xCuCO3,yCu(OH)2,zH2O.
You will find the reactions between hexaaqua ions and
carbonate ions discussed in detail if you follow this link.
Use the BACK button on your browser to return to this page.
copper
copper
Note: If you need to, you can find out more about oxidation
states by following this link.
Use the BACK button on your browser to return to this page.
copper
You can find the amount of iodine liberated by titration with sodium
thiosulphate solution.
copper
copper
But in the presence of excess chloride ions from the HCl, this reacts to
give a stable, soluble copper(I) complex.
You can get the white precipitate of copper(I) chloride (mentioned above)
by adding water to this solution. This reverses the last reaction by
stripping off the extra chloride ion.
copper
This page explains what is meant by a stability constant for a complex ion,
and goes on to look at how its size is governed in part by the entropy
change during a ligand exchange reaction.
In fact, the water molecules get replaced one at a time, and so this is
made up of a series of part-reactions:
Although this can look a bit daunting at first sight, all that is happening is
that first you have one, then two, then three, then four water molecules in
total replaced by ammonias.
Individual stability constants
Let's take a closer look at the first of these equilibria:
Like any other equilibrium, this one has an equilibrium constant, Kc except that in this case, we call it a stability constant. Because this is the
first water molecule to be replaced, we call it K1.
There are two points of possible confusion here - one minor, one more
important!
With that out of the way, let's go back to where we were - but introduce a
value for K1:
The value of the equilibrium constant is fairly large, suggesting that there
is a strong tendency to form the ion containing an ammonia molecule.
A high value of a stability constant shows that the ion is easily formed.
Each of the other equilibria above also has its own stability constant, K2,
K3 and K4. For example, K2 is given by:
The ion with two ammonias is even more stable than the ion with one
ammonia.
You could keep plugging away at this and come up with the following table
of stability constants:
ion
Kn
log Kn
[Cu(NH3)(H2O)5]2+
K1
1.78 x 104
4.25
[Cu(NH3)2(H2O)4]2+
K2
4.07 x 103
3.61
[Cu(NH3)3(H2O)3]2+
K3
9.55 x 102
2.98
[Cu(NH3)4(H2O)2]2+
K4
1.74 x 102
2.24
You will often find these values quoted as log K1 or whatever. All this does
is tidy the numbers up so that you can see the patterns more easily.
The ions keep on getting more stable as you replace up to 4 water
molecules, but notice that the equilibrium constants are gradually getting
less big as you replace more and more waters. This is common with
individual stability constants.
Overall stability constants
The overall stability constant is simply the equilibrium constant for the total
reaction:
You can see that overall this is a very large equilibrium constant, implying
a high tendency for the ammonias to replace the waters. The "log" value is
13.1.
This overall value is found by multiplying together all the individual values
of K1, K2 and so on. To find out why that works, you will need a big bit of
paper and some patience!
Write down expressions for all the individual values (the first two are done
for you above), and then multiply those expressions together. You will find
that all the terms for the intermediate ions cancel out to leave you with the
expression for the overall stability constant.
Summary
Whether you are looking at the replacement of individual water molecules
or an overall reaction producing the final complex ion, a stability constant
is simply the equilibrium constant for the reaction you are looking at.
The larger the value of the stability constant, the further the reaction lies to
the right. That implies that complex ions with large stability constants are
more stable than ones with smaller ones.
Stability constants tend to be very large numbers. In order to simplify the
numbers a "log" scale is often used. Because of the way this works, a
difference of 1 in the log value comes from a 10 times difference in the
stability constant. A difference of 2 comes from a 100 (in other words, 102)
times difference in stability constant - and so on.
Compare what happens if you replace two water molecules around a [Cu
(H2O)6]2+ ion with either 2 ammonia molecules or one molecule of 1,2diaminoethane.
ion
log K
[Cu(NH3)2(H2O)4]2+
7.86
[Cu(H2O)4(en)]2+
10.6
The enthalpy changes of the two reactions are fairly similar. You might
expect this because in each case you are breaking two bonds between
copper and oxygen atoms and replacing them by two bonds between
copper and nitrogen atoms.
If the enthalpy changes are similar, what causes the difference in the
extent to which the two reactions happen?
You need to think about the entropy change during each reaction.
Entropy is most easily thought of as a measure of disorder. Any change
which increases the amount of disorder increases the tendency of a
reaction to happen.
If you look again at the two equiilbria, you might notice that the 1,2diaminoethane equilibrium does lead to an increase in the disorder of the
system (an increase in its entropy). There are only two species on the lefthand side of the equation, but three on the right.
You can obviously get more disorder out of three species than out of only
two.
Compare that with the other equilibrium. In this case, there is no change in
the total number of species before and after reaction, and so no useful
contribution to an increase in entropy.
In the case of the complex with EDTA, the increase in entropy is very
pronounced.
Here, we are increasing the number of species present from two on the
left-hand side to seven on the right. You can get a major amount of
increase in disorder by making this change.
Reversing this last change is going to be far more difficult in entropy
terms. You would have to move from a highly disordered state to a much
more ordered one. That isn't so likely to happen, and so the copper-EDTA
complex is very stable.
Summary
Complexes involving multidentate ligands are more stable than those with
only unidentate ligands in them.
The underlying reason for this is that each multidentate ligand displaces
more than one water molecule. This leads to an increase in the number of
species present in the system, and therefore an increase in entropy.
The Facts
Beryllium
Beryllium has no reaction with water or steam even at red heat.
Magnesium
Magnesium burns in steam to produce magnesium oxide and hydrogen.
Very clean magnesium has a very slight reaction with cold water. The
reaction soon stops because the magnesium hydroxide formed is almost
insoluble in water and forms a barrier on the magnesium preventing
further reaction.
The hydroxides aren't very soluble, but they get more soluble as you go
down the Group. The calcium hydroxide formed shows up mainly as a
white precipitate (although some does dissolve). You get less precipitate
as you go down the Group because more of the hydroxide dissolves in
the water.
Summary of the trend in reactivity
The Group 2 metals become more reactive towards water as you go
down the Group.
If you calculate the enthalpy change for the possible reactions between
beryllium or magnesium and steam, you come up with these answers:
Notice that both possible reactions are strongly exothermic, giving out
almost identical amounts of heat. However, only the magnesium reaction
actually happens. The explanation for the different reactivities must lie
somewhere else.
Similarly, if you calculate the enthalpy changes for the reactions between
calcium, strontium or barium and cold water, you again find that the
amount of heat evolved in each case is almost exactly the same - in this
case, about -430 kJ mol-1.
The reason for the increase in reactivity must again lie elsewhere.
Looking at the activation energies for the reactions
The activation energy for a reaction is the minimum amount of energy
which is needed in order for the reaction to take place. It doesn't matter
how exothermic the reaction would be once it got started - if there is a
high activation energy barrier, the reaction will take place very slowly, if
at all.
When Group 2 metals react to form oxides or hydroxides, metal ions are
formed.
The formation of the ions from the original metal involves various stages
all of which require the input of energy - contributing to the activation
energy of the reaction. These stages involve the input of:
After this, there will be a number of steps which give out heat again leading to the formation of the products, and overall exothermic reactions.
The graph shows the effect of these important energy-absorbing stages
as you go down Group 2.
Notice that the ionisation energies dominate this - particularly the second
ionisation energies. Ionisation energies fall as you go down the Group.
Because it gets easier to form the ions, the reactions will happen more
quickly.
The Facts
The reactions with oxygen
Formation of simple oxides
On the whole, the metals burn in oxygen to form a simple metal oxide.
Beryllium is reluctant to burn unless it is in the form of dust or powder.
Beryllium has a very strong (but very thin) layer of beryllium oxide on its
surface, and this prevents any new oxygen getting at the underlying
beryllium to react with it.
"X" in the equation can represent any of the metals in the Group.
It is almost impossible to find any trend in the way the metals react with
oxygen. It would be quite untrue to say that they burn more vigorously as
you go down the Group.
To be able to make any sensible comparison, you would have to have
pieces of metal which were all equally free of oxide coating, with exactly
the same surface area and shape, exactly the same flow of oxygen
around them, and heated to exactly the same extent to get them started.
It can't be done!
What they metals look like when they burn is a bit problematical!
Formation of peroxides
Strontium and barium will also react with oxygen to form strontium or
barium peroxide.
Strontium forms this if it is heated in oxygen under high pressures, but
barium forms barium peroxide just on normal heating in oxygen. Mixtures
of barium oxide and barium peroxide will be produced.
The familiar white ash you get when you burn magnesium ribbon in air is
a mixture of magnesium oxide and magnesium nitride (despite what you
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might have been told when you were first learning Chemistry!).
The Explanations
Trying to pick out patterns in the way the metals burn
There are no simple patterns. It would be tempting to say that the
reactions get more vigorous as you go down the Group, but it isn't true.
The overall amount of heat evolved when one mole of oxide is produced
from the metal and oxygen shows no simple pattern:
In this case, though, the effect of the fall in the activation energy is
masked by other factors - for example, the presence of existing oxide
layers on the metals, and the impossibility of controlling precisely how
much heat you are supplying to the metal in order to get it to start
burning.
The covalent bond between the two oxygen atoms is relatively weak.
Now imagine bringing a small 2+ ion close to the peroxide ion. Electrons
in the peroxide ion will be strongly attracted towards the positive ion. This
is then well on the way to forming a simple oxide ion if the right-hand
oxygen atom (as drawn below) breaks off.
We say that the positive ion polarises the negative ion. This works best
if the positive ion is small and highly charged - if it has a high charge
density.
Ions of the metals at the top of the Group have such a high charge
density (because they are so small) that any peroxide ion near them falls
to pieces to give an oxide and oxygen. As you go down the Group and
the positive ions get bigger, they don't have so much effect on the
peroxide ion.
Barium peroxide can form because the barium ion is so large that it
doesn't have such a devastating effect on the peroxide ions as the
metals further up the Group.
Energy is evolved when the ions come together to produce the crystal
lattice. This energy is known as lattice energy or lattice enthalpy.
The size of the lattice energy depends on the attractions between the
ions. The lattice energy is greatest if the ions are small and highly
charged - the ions will be close together with very strong attractions. In
the whole of Group 2, the attractions between the 2+ metal ions and the
3- nitride ions are big enough to produce very high lattice energies.
When the crystal lattices form, so much energy is released that it more
than compensates for the energy needed to produce the various ions in
the first place. The excess energy evolved makes the overall process
exothermic.
This is in contrast to what happens in Group 1 of the Periodic Table
(lithium, sodium, potassium, rubidium and caesium). Their ions only carry
one positive charge, and so the lattice energies of their nitrides will be
much less.
Lithium is the only metal in Group 1 to form a nitride. Lithium has by far
the smallest ion in the Group, and so lithium nitride has the largest lattice
energy of any possible Group 1 nitride. Only in lithium's case is enough
energy released to compensate for the energy needed to ionise the
metal and the nitrogen - and so produce an exothermic reaction overall.
In all the other cases in Group 1, the overall reaction would be
endothermic. Those reactions don't happen, and the nitrides of sodium
and the rest aren't formed.
Solubility of the hydroxides, sulphates and carbonates of the Group 2 elements in water
This page looks at the solubility in water of the hydroxides, sulphates and
carbonates of the Group 2 elements - beryllium, magnesium, calcium,
strontium and barium. Although it describes the trends, there isn't any
attempt to explain them on this page - for reasons discussed later.
You will find that there aren't any figures given for any of the solubilities.
There are major discrepancies between the figures given by two
common A'level Data Books (Nuffield Advanced Science Book of Data,
and Chemistry Data Book by Stark and Wallace). There are also
important inconsistencies within the books (one set of figures doesn't
agree with those which can be calculated from another set). I haven't
been able to find data which I am sure is correct, and therefore prefer not
to give any.
The Facts
Solubility of the hydroxides
This is a trend which holds for the whole Group, and applies whichever
set of data you choose.
Some examples may help you to remember the trend:
Magnesium hydroxide appears to be insoluble in water. However, if you
shake it with water, filter it and test the pH of the solution, you find that it
is slightly alkaline. This shows that there are more hydroxide ions in the
solution than there were in the original water. Some magnesium
hydroxide must have dissolved.
Calcium hydroxide solution is used as "lime water". 1 litre of pure water
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Solubility of the hydroxides, sulphates and carbonates of the Group 2 elements in water
The simple trend is true provided you include hydrated beryllium sulphate
in it, but not if the beryllium sulphate is anhydrous.
The Nuffield Data Book quotes anyhydrous beryllium sulphate, BeSO4,
as insoluble (I haven't been able to confirm this from any other source),
whereas the hydrated form, BeSO4.4H2O is soluble. (The Data Books
agree on this - giving a figure of about 39 g dissolving in 100 g of water
at room temperature.)
Figures for magnesium sulphate and calcium sulphate also vary
depending on whether the salt is hydrated or not, but nothing like so
dramatically.
Two common examples may help you to remember the trend:
You are probably familiar with the reaction between magnesium and
dilute sulphuric acid to give lots of hydrogen and a colourless solution of
magnesium sulphate. Notice that you get a solution, not a precipitate.
The magnesium sulphate is obviously soluble.
You may also remember that barium sulphate is formed as a white
precipitate during the test for sulphate ions in solution. The ready
formation of a precipitate shows that the barium sulphate must be pretty
insoluble. In fact, 1 litre of water will only dissolve about 2 mg of barium
sulphate at room temperature.
Solubility of the carbonates
Solubility of the hydroxides, sulphates and carbonates of the Group 2 elements in water
What - no explanations?
Before I started to write this page, I thought I understood the trends in
solubility patterns including the explanations for them. The more I have
dug around to try to find reliable data, and the more time I have spent
thinking about it, the less I'm sure that it is possible to come up with any
simple explanation of the solubility patterns.
Solubility of the hydroxides, sulphates and carbonates of the Group 2 elements in water
This page looks at the usual explanations for the solubility patterns in the
hydroxides, sulphates and carbonates of Group 2. It goes on to look at
my misgivings about these. This page is probably best avoided unless
your syllabus specifically asks for these explanations!
each other.
A sample calculation to make this clear
Here is an example of the sort of calculations you might do to work out
the enthalpy change of solution for sodium chloride and potassium
chloride.
You can see that the enthalpy of solution changes from NaCl to KCl
because the lattice enthalpy and hydration enthalpy of the positive ion fall
by different amounts.
If the hydration enthalpy falls faster than the lattice enthalpy (as in
this case), the net effect is that the overall change becomes more
endothermic (or less exothermic in other possible cases where the
total enthalpy change turns out to be negative).
If the lattice enthalpy falls faster than the hydration enthalpy, the
opposite happens - the change will become less endothermic (or
more exothermic).
For small negative ions like hydroxide, the lattice enthalpy falls
faster than the hydration enthalpy of the positive ions. That means
that the enthalpy of solution will become less positive (or more
negative).
For large negative ions like sulphate or carbonate, the hydration
enthalpy of the positive ions falls faster than the lattice enthalpy. In
this case, the enthalpy of solution will become more positive (or
less negative).
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including the distance between the negative and positive ions. Where
you have a big negative ion, this inter-ionic distance is largely controlled
by the size of that negative ion. Changes in the size of the positive ion
don't make as great a percentage difference to the inter-ionic distance as
they would if the negative ion was small.
With sulphates, for example, the percentage increase in the inter-ionic
distance as you go from magnesium to calcium sulphate isn't as great as
it would be with a smaller negative ion like hydroxide.
Since the percentage increase in inter-ionic distance isn't very great, the
change in the lattice enthalpy won't be very great either.
The relationship between enthalpy of solution and solubility
The assumption is made that the more endothermic (or less exothermic)
the enthalpy of solution is, the less soluble the compound.
So sulphates and carbonates become less soluble as you go down the
Group; hydroxides become more soluble.
Calculated value
(kJ mol-1)
NaCl
+1
+3.9
KCl
+15
+17.2
RbCl
+10
+16.7
CsCl
+5
+17.9
The discrepancies are enough to disrupt any pattern (such as there is!).
The reasons for the discrepancies lie in the way the numbers are
calculated. These are very small numbers worked out from much larger
ones. Small uncertainties in those large numbers will cause large swings
in the answers.
For example, if each of the numbers in the calculations we did earlier on
this page was out by just 5 kJ, each answer could vary by +/- 15 kJ completely disrupting the patterns!
You can't therefore reliably use the data available to calculate the trends
you want with sufficient accuracy to make sense.
Enthalpy of
solution
(kJ mol-1)
Solubility
(mol /100 g of water)
NaCl
+3.9
0.615
KCl
+17.2
0.481
RbCl
+16.7
0.781
CsCl
+17.9
1.13
MgCO3
-25.3
CaCO3
-12.3
SrCO3
-3.4
BaCO3
+4.2
Sodium chloride and the other Group 1 chlorides dissolve despite the
fact that their enthalpies of solution are positive, and yet magnesium
carbonate (and most of the other Group 2 carbonates) are very sparingly
soluble, but have exothermic enthalpies of solution. You might have
expected exactly the opposite to happen.
However if you ignore the comparison with the Group 1 chlorides, you
could argue that the figures get progressively less exothermic, and at
barium carbonate become endothermic. That would seem to support the
decrease in solubility as you go down the Group quite nicely.
Unfortunately, if you look at the solubility data, the trend is broken at the
bottom of the Group. Barium carbonate is more soluble than strontium
carbonate! Although figures from my two data sources differ in detail,
they agree on this.
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This happens because the water molecules become more ordered when
the compound dissolves in them. Instead of milling around pretty much at
random, they become attracted to the ions present and arranged around
them.
This is particularly effective if the ions are small and highly charged - and
so the effect is greatest for the positive ions at the top of the Group, and
gets less as you go down. It is also much more important in Group 2 than
in Group 1 where the ions only carry one positive charge.
That means that you have two entropy effects to consider. There is the
increase in disorder as the crystal lattice breaks up, but a corresponding
increase in order in the water - which varies depending on the sizes and
charges of the ions present.
What a nightmare!
To explain this properly, you need to think about the way lattice enthalpy
changes as you go down the Group, the way that hydration enthalpies
change, and the way that entropy changes. The way those changes
happen will vary from one type of compound to another.
Can we explain everything now?
No - at least not easily! For example, although it might be possible to
account for the lack of pattern in the solubilities of the Group 1 chlorides
(and also the bromides) by a mathematical application of these effects,
trying to do it in general terms defeats me completely!
MgCO3
-25.3
CaCO3
-12.3
SrCO3
-3.4
BaCO3
+4.2
But the entropy change will also be varying as you go down the Group.
At the top, where you have small 2+ ions, the overall entropy change in
the system must be negative - the system as a whole becomes more
ordered when the compound dissolves because of the way the water
molecules become organised around the positive ions. That negative
entropy change is going to be enough to wipe out the effect of the
exothermic enthalpy of solution.
Towards the bottom of the Group, this effect changes. The bigger ions
have less organising effect on the water molecules. The entropy change
is becoming less negative (or perhaps even at this stage, positive).
That's going to tend to make the compounds more soluble.
The overall effect is a complex balance between the way the enthalpy of
solution varies and the way the entropy change of solution alters. At
barium carbonate, the effect of increasing entropy must be enough to
make it more soluble than strontium carbonate.
This page looks at the effect of heat on the carbonates and nitrates of the
Group 2 elements - beryllium, magnesium, calcium, strontium and
barium. It describes and explains how the thermal stability of the
compounds changes as you go down the Group.
The Facts
The effect of heat on the Group 2 carbonates
All the carbonates in this Group undergo thermal decomposition to give
the metal oxide and carbon dioxide. Thermal decomposition is the term
given to splitting up a compound by heating it.
If "X" represents any one of the elements:
As you go down the Group, the nitrates also have to be heated more
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The nitrates also become more stable to heat as you go down the
Group.
Summary
Both carbonates and nitrates become more thermally stable as you go
down the Group. The ones lower down have to be heated more strongly
than those at the top before they will decompose.
Explanations
This page offers two different ways of looking at the problem. You need
to find out which of these your examiners are likely to expect from you so
that you don't get involved in more difficult things than you actually need.
You should look at your syllabus, and past exam papers - together with
their mark schemes
Detailed explanations are given for the carbonates because the diagrams
are easier to draw, and their equations are also easier. Exactly the same
arguments apply to the nitrates.
space. Its charge density will be lower, and it will cause less distortion to
nearby negative ions.
The structure of the carbonate ion
If you worked out the structure of a carbonate ion using "dots-andcrosses" or some similar method, you would probably come up with:
This shows two single carbon-oxygen bonds and one double one, with
two of the oxygens each carrying a negative charge. Unfortunately, in
real carbonate ions all the bonds are identical, and the charges are
spread out over the whole ion - although concentrated on the oxygen
atoms. We say that the charges are delocalised.
This is a rather more complicated version of the bonding you might have
come across in benzene or in ions like ethanoate. For the purposes of
this topic, you don't need to understand how this bonding has come
about.
If this is heated, the carbon dioxide breaks free to leave the metal oxide.
How much you need to heat the carbonate before that happens depends
on how polarised the ion was. if it is highly polarised, you need less heat
than if it is only slightly polarised.
The smaller the positive ion is, the higher the charge density, and the
greater effect it will have on the carbonate ion. As the positive ions get
bigger as you go down the Group, they have less effect on the carbonate
ions near them. To compensate for that, you have to heat the compound
more in order to persuade the carbon dioxide to break free and leave the
metal oxide.
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In other words, as you go down the Group, the carbonates become more
thermally stable.
What about the nitrates?
The argument is exactly the same here. The small positive ions at the top
of the Group polarise the nitrate ions more than the larger positive ions at
the bottom. Drawing diagrams to show this happening is much more
difficult because the process has interactions involving more than one
nitrate ion. You wouldn't be expected to attempt to draw this in an exam.
MgCO3
+117
CaCO3
+178
SrCO3
+235
BaCO3
+267
You can see that the reactions become more endothermic as you go
down the Group. That's entirely what you would expect as the
carbonates become more thermally stable. You have to supply
increasing amounts of heat energy to make them decompose.
Explaining the enthalpy changes
Here's where things start to get difficult! If you aren't familiar with Hess's
Law cycles (or with Born-Haber cycles) and with lattice enthalpies (lattice
energies), you aren't going to understand the next bit. Don't waste your
time looking at it.
Note: If you should know about these cycles, but don't really
understand them, you might be interested in my book on
A'level calculations. What you need to know and be able to
do is covered in a lot of detail.
You can apply Hess's Law to this, and find two routes which will have an
equal enthalpy change because they start and end in the same places.
For reasons we will look at shortly, the lattice enthalpies of both the
oxides and carbonates fall as you go down the Group. But they don't fall
at the same rate.
The oxide lattice enthalpy falls faster than the carbonate one. If you think
carefully about what happens to the value of the overall enthalpy change
of the decomposition reaction, you will see that it gradually becomes
more positive as you go down the Group.
The lattice enthalpies of both carbonates and oxides fall as you go down
the Group because the positive ions are getting bigger. The inter-ionic
distances are increasing and so the attractions become weaker.
0.065
Ca2+
0.099
O2-
0.140
CO32-
The lattice enthalpies fall at different rates because of the different sizes
of the two negative ions - oxide and carbonate. The oxide ion is relatively
small for a negative ion (0.140 nm), whereas the carbonate ion is large
(no figure available).
In the oxides, when you go from magnesium oxide to calcium oxide, for
example, the inter-ionic distance increases from 0.205 nm (0.140 +
0.065) to 0.239 nm (0.140 + 0.099) - an increase of about 17%.
In the carbonates, the inter-ionic distance is dominated by the much
larger carbonate ion. Although the inter-ionic distance will increase by the
same amount as you go from magnesium carbonate to calcium
carbonate, as a percentage of the total distance the increase will be
much less.
Some made-up figures show this clearly.
I can't find a value for the radius of a carbonate ion, and so can't use real
figures. For the sake of argument, suppose that the carbonate ion radius
was 0.3 nm. The inter-ionic distances in the two cases we are talking
about would increase from 0.365 nm to 0.399 nm - an increase of only
about 9%.
The rates at which the two lattice energies fall as you go down the Group
depends on the percentage change as you go from one compound to the
next. On that basis, the oxide lattice enthalpies are bound to fall faster
than those of the carbonates.
What about the nitrates?
The nitrate ion is bigger than an oxide ion, and so its radius tends to
dominate the inter-ionic distance. The lattice enthalpy of the oxide will
again fall faster than the nitrate. if you constructed a cycle like that further
up the page, the same arguments would apply.
But the hydrated beryllium ions (called tetraaquaberyllium ions) are quite
strongly acidic. The small beryllium ion at the centre attracts the
electrons in the bonds towards itself, and that makes the hydrogen atoms
in the water even more positive than they usually are. If the solution is
hot and concentrated (as it is likely to be if you add water to solid
beryllium chloride - a very exothermic reaction), chloride ions can remove
one or more of these hydrogen ions to produce hydrogen chloride gas.
All the other ionic chlorides in Group 2 dissolve in water without any
obvious reaction.
In the solid, the BeCl2 molecules polymerise to make long chains. They
do this by forming coordinate bonds (dative covalent bonds) between
lone pairs on chlorine atoms and adjacent beryllium atoms. The diagram
shows a simple dimer - the start of the polymerisation process.
You can see from the last diagram that the beryllium atoms are still
electron deficient. The process continues. The next diagram shows the
coordinate bonds in the conventional way using arrows. The arrow goes
from the atom which is supplying the pair of electrons to the atom with
the empty orbital.
Make sure that you fully understand how this diagram relates to the
dimer shown in the previous diagram.
Each water molecule, of course, has two lone pairs of electrons. Only
one of them is shown to avoid cluttering the diagram.
Notice that once four water molecules have bonded in this way, there
isn't any more space available at the bonding level. All the empty orbitals
from the original beryllium ion are being used.
The water molecules arrange themselves to get as far apart as possible which is pointing towards the corners of a tetrahedron. The ion therefore
has a tetrahedral shape.
The hydration of magnesium
You might think that magnesium would behave just the same, but at the
3-level there are 3d orbitals available as well as 3s and 3p.
When the magnesium ion is formed, it leaves empty 3s, 3p and 3d
orbitals. When that ion is hydrated, it uses the 3s orbital, all three of the
3p orbitals and two of the 3d orbitals. These are reorganised to leave a
total of six empty orbitals which are then used for bonding.
Why does magnesium stop at attaching six waters? Why doesn't it use
the remaining 3d orbitals as well? You can't physically fit more than six
water molecules around the magnesium - they take up too much room.
What about the other ions in Group 2?
As the ions get bigger, there is less tendency for them to form proper
coordinate bonds with water molecules. The ions become so big that
they aren't sufficiently attractive to the lone pairs on the water molecules
to form formal bonds - instead the water molecules tend to cluster more
loosely around the positive ions.
Where they do form coordinate bonds with the water, however, they will
be 6-coordinated just like the magnesium.
This contains the complex ion, [Be(OH)4]2-. The name describes this ion.
Tetra means four; hydroxo refers to the OH groups; beryllate shows that
the beryllium is present in a negative ion. The "ate" ending always shows
that the ion is negative.
A simple explanation of what is happening
You need to think about where the beryllium hydroxide came from in the
first place. It would probably have been made by adding sodium
hydroxide solution to a solution of a beryllium salt like beryllium sulphate.
Remember that beryllium ions in solution exist as the hydrated ion, [Be
(H2O)4]2+. The beryllium has such a strongly polarising effect on the
water molecules that hydrogen ions are very easily removed from them.
The sodium hydroxide solution contains hydroxide ions which are
powerful bases. If you add just the right amount of sodium hydroxide
solution, you get a precipitate of what is normally called "beryllium
hydroxide" - but which is a shade more complicated than that!
Note: This has been simplified to bring it into line with the
sort of treatment you will meet for the acid-base behaviour of
transition metal hydroxides. In particular, the structure of
beryllium hydroxide is probably even more complicated than
has been suggested above!
amines as bases
AMINES AS BASES
amines as bases
If the acid was hydrochloric acid, for example, you would end up with a
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amines as bases
. . . but if you do it this way, you must include the state symbols. If you
write H+ on its own, it implies an unattached hydrogen ion - a proton.
Such things don't exist on their own in solution in water.
If the reaction is happening in the gas state, the ammonia accepts a
proton directly from the hydrogen chloride:
Or:
amines as bases
The presence of the hydroxide ions from this reaction makes the solution
alkaline.
The corresponding reaction with amines
The amine still contains the nitrogen lone pair, and does exactly the
same thing.
amines as bases
amines as bases
amines as bases
As the amines get bigger and more bulky, the formula of the final product
may change - simply because it is impossible to fit four large amine
molecules and two water molecules around the copper atom.
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amines as bases
Phenylamine as a base
Amines are bases because the lone pair of electrons on the nitrogen atom
can accept a hydrogen ion - in other words, for exactly the same reason
that ammonia is a base.
With phenylamine, the only difference is that it is a much weaker base than
ammonia or an amine like ethylamine - for reasons that we will explore
later.
The lone pair on the nitrogen touches the delocalised ring electrons . . .
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 electron density around the nitrogen is nothing like it is in, say, an
ammonia molecule.
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 - means that phenylamine is a very
weak base indeed.
idea to check your syllabus before you get too bogged down.
Follow this link if you are a UK A level student and haven't got
a copy of your syllabus.
Use the BACK button (or HISTORY file or GO menu) on your
browser to return to this page when you have done all this.
With ethanoic anhydride, heat is needed. In this case, the products are a
mixture of N-phenylethanamide and phenylammonium ethanoate.
If you stop and think about it, this is obviously the same molecule as in the
equation above, but it stresses the phenylamine part of it much more.
Looking at it this way, notice that one of the hydrogens of the -NH2 group
has been replaced by an acyl group - an alkyl group attached to a carbonoxygen double bond.
You can say that the phenylamine has been acylated or has undergone
acylation.
Because of the nature of this particular acyl group, it is also described as
ethanoylation. The hydrogen is being replaced by an ethanoyl group,
CH3CO-.
Important: You should read the first half of the page about
amines as nucleophiles to give you explanations about amines
in general - and possibly also the further link on that page back
to reactions of halogenoalkanes for even more detail.
Again, take your time over this. It isn't easy, particularly if you
have to go beyond the formation of the secondary amine.
Use the BACK button on your browser to return to this page
when you have done that.
The reaction wouldn't stop there. You will get further reactions to produce
a tertiary amine and its salt, and eventually a quaternary ammonium
compound. If you want to explore this further, refer to the last link just up
the page, and trace the sequence of equations through using phenylamine
rather than ethylamine.
HYDROLYSING AMIDES
This page describes the hydrolysis of amides under both acidic and
alkaline conditions. It also describes the use of alkaline hydrolysis in
testing for amides.
Amides Menu
Understanding Chemistry
AMIDES MENU
Background . . .
An introduction to amides including their physical properties.
Preparation of amides . . .
Their preparation from carboxylic acids, acyl chlorides and acid
anhydrides.
The hydrolysis of amides . . .
The hydrolysis of amides using acids or alkalis (including the test
for an amide).
Other reactions of amides . . .
The lack of base character in amides, the dehydration of amides to
make nitriles, and the Hofmann degradation of amides to make
primary amines with one less carbon atom.
Polyamides . . .
A summary of the chemistry of simple polyamides like nylon and
Kevlar, including their formation, structure, hydrolysis and uses.
Amides Menu
Go to Main Menu . . .
an introduction to amides
INTRODUCING AMIDES
This page explains what amides are and looks at their simple physical
properties such as solubility and melting points.
HCONH2
methanamide
CH3CONH2
ethanamide
CH3CH2CONH2
propanamide
Notice that in each case, the name is derived from the acid by replacing
an introduction to amides
Physical properties
Melting points
Methanamide is a liquid at room temperature (melting point: 3C), but the
other amides are solid.
For example, ethanamide forms colourless deliquescent crystals with a
melting point of 82C. A deliquescent substance is one which picks up
water from the atmosphere and dissolves in it. Ethanamide crystals
nearly always look wet.
an introduction to amides
The melting points of the amides are high for the size of the molecules
because they can form hydrogen bonds. The hydrogen atoms in the NH2 group are sufficiently positive to form a hydrogen bond with a lone
pair on the oxygen atom of another molecule.
As you can see, there is the potential for lots of hydrogen bonds to be
formed. Each molecule has two slightly positive hydrogen atoms and two
lone pairs on the oxygen atom.
These hydrogen bonds need a reasonable amount of energy to break,
and so the melting points of the amides are quite high.
an introduction to amides
Solubility in water
The small amides are soluble in water because they have the ability to
hydrogen bond with the water molecules.
It needs energy to break the hydrogen bonds between amide molecules
and between water molecules before they can mix - but enough energy
is released again when the new hydrogen bonds are set up to allow this
to happen.
MAKING AMIDES
This page describes the preparation of amides from carboxylic acids, acyl
chlorides (acid chlorides) and acid anhydrides.
When the reaction is complete, the mixture is heated and the ammonium
salt dehydrates producing ethanamide.
The presence of the excess ethanoic acid helps to prevent this from
happening by moving the position of equilibrium to the left.
Then the hydrogen chloride produced reacts with excess ammonia to give
ammonium chloride.
. . . and you can combine all this together to give one overall equation:
Note: If you are want the mechanism for this reaction, you will
find it by following this link to another part of the site dealing
with nucleophilic addition-elimination reactions.
You can find more about the reactions of acyl chlorides with
nitrogen compounds by following this link. This will also give
you information about the preparation of N-substituted amides
by the reaction between acyl chlorides and primary amines.
Use the BACK button on your browser to return to this page.
Then the ethanoic acid produced reacts with excess ammonia to give
ammonium ethanoate.
. . . and you can combine all this together to give one overall equation:
You need to follow this through really carefully, because the two products
of the reaction overall can look confusingly similar.
This page explains the reason for the lack of basic character in amides,
and describes their dehydration to give nitriles, and their reaction with
bromine and sodium hydroxide solution to form primary amines with one
less carbon atom (the Hofmann degradation).
Note: The reasons that these are bases and the differences
between them (because there are slight differences) are
explored in some detail on a page about organic bases. It
would be useful to read this page before you go on because
it is relevant to what is coming next.
If you follow this link, use the BACK button on your browser
to return to this page.
For example, if you dissolve these compounds in water, the nitrogen lone
pair takes a hydrogen ion from a water molecule - and equilibria like
these are set up:
Notice that the reactions are reversible. In both cases the positions of
equilibrium lie well to the left. These compounds are weak bases
because they don't hang on to the incoming hydrogen ion very well.
Both ammonia and the amines are alkaline in solution because of the
presence of the hydroxide ions, and both of them turn red litmus blue.
The result of this is that the nitrogen lone pair becomes delocalised - in
other words it is no longer found located on the nitrogen atom, but the
electrons from it are spread out over the whole of that part of the
molecule.
This has two effects which prevent the lone pair accepting hydrogen ions
and acting as a base:
If you started with ethanamide, you would get methylamine. The full
equation for the reaction is:
POLYAMIDES
This page looks at the structures, formation, hydrolysis and uses of the
polyamides, nylon and Kevlar.
Nylon
In nylon, the repeating units contain chains of carbon atoms. (That is
different from Kevlar, where the repeating units contain benzene rings see below.) There are various different types of nylon depending on the
nature of those chains.
Nylon-6,6
Nylon-6,6 is made from two monomers each of which contain 6 carbon
atoms - hence its name.
One of the monomers is a 6 carbon acid with a -COOH group at each
end - hexanedioic acid.
When these two compounds polymerise, the amine and acid groups
combine, each time with the loss of a molecule of water. This is known
as condensation polymerisation.
Condensation polymerisation is the formation of a polymer involving the
loss of a small molecule. In this case, the molecule is water, but in other
cases different small molecules might be lost.
The diagram shows the loss of water between two of the monomers:
This keeps on happening, and so you get a chain which looks like this:
Nylon-6
If you are doing UK A level, you are unlikely to need the structure of
nylon-6. I am including it to show that it is possible to get a polyamide
from a single monomer.
Nylon-6 is made from a monomer called caprolactam.
Notice that this already contains an amide link. When this molecule
polymerises, the ring opens, and the molecules join up in a continuous
chain.
Kevlar
Kevlar is similar in structure to nylon-6,6 except that instead of the amide
links joining chains of carbon atoms together, they join benzene rings.
The two monomers are benzene-1,4-dicarboxylic acid and 1,4diaminobenzene.
If you line these up and remove water between the -COOH and -NH2
groups in the same way as we did with nylon-6,6, you get the structure of
Kevlar:
Making nylon-6,6
Making nylon-6,6 industrially
Nylon-6,6 is made by polymerising hexanedioic acid and 1,6diaminohexane exactly as shown further up the page.
Because the acid is acidic and the amine is basic, they first react
together to form a salt. That is then converted into nylon-6,6 by heating it
under pressure at 350C.
If you compare the next diagram with the diagram further up the page for
the formation of nylon-6,6, you will see that the only difference is that
molecules of HCl are lost rather than molecules of water.
In the lab, this reaction is the basis for the nylon rope trick.
You make a solution of the hexanedioyl dichloride in an organic solvent,
and a solution of 1,6-diaminohexane in water. You carefully float one
solution on top of the other in a small beaker, taking care to get as little
mixing as possible.
Nylon-6,6 forms at the boundary between the two solutions. If you pick
up the boundary layer with a pair of tweezers, you can pull out an
amazingly long tube of nylon from the beaker.
Hydrolysis of polyamides
Simple amides are easily hydrolysed by reaction with dilute acids or
alkalis.
Polyamides are fairly readily attacked by strong acids, but are much
more resistant to alkaline hydrolysis. Hydrolysis is faster at higher
temperatures. Hydrolysis by water alone is so slow as to be completely
unimportant. Kevlar is rather more resistant to hydrolysis than nylon is.
If you spill something like dilute sulphuric acid on a fabric made from
nylon, the amide linkages are broken. The long chains break and you
can eventually end up with the original monomers - hexanedioic acid and
1,6-diaminohexane.
Because you produce small molecules rather than the original polymer,
the fibres are destroyed, and you end up with a hole!
Uses of polyamides
Nylon
Apart from obvious uses in textiles for clothing and carpets, a lot of nylon
is used to make tyre cords - the inner structure of a vehicle tyre
underneath the rubber.
The fibres are also used in ropes, and nylon can be cast into solid
shapes for cogs and bearings in machines, for example.
Kevlar
Kevlar is a very strong material - about five times as strong as steel,
weight for weight. It is used in bulletproof vests, in composites for boat
construction, in lightweight mountaineering ropes, and for lightweight skis
and racquets - amongst many other things.
amines as nucleophiles
AMINES AS NUCLEOPHILES
amines as nucleophiles
In the first stage of the reaction, you get the salt of a secondary amine
formed. For example if you started with ethylamine and bromoethane,
you would get diethylammonium bromide
amines as nucleophiles
This time there isn't any hydrogen left on the nitrogen to be removed. The
reaction stops here.
Note: You will find this reaction explored in the page about
the reactions between halogenoalkanes and ammonia although in that case starting from bromoethane and
ammonia. It would be useful to read that in order to compare
the ammonia reactions with the amine reactions. The only
real difference is that the hydrogen ions are removed by an
amine in the case we are currently looking at rather than
ammonia on the other page.
You will find a further link to the mechanisms for these
reactions on that page. If you follow that link it will take you to
quite a number of pages exploring these reactions. You will
need to spend some time on these if you really want to
understand this. However, understanding the reactions in
terms of their mechanisms means that you can work out what
happens if you need to rather than trying to remember all this
(a fairly pointless and soul-destroying exercise!).
Use the BACK button (or HISTORY file or GO menu) on your
browser to return to this page.
amines as nucleophiles
amines as nucleophiles
This page looks at the reactions of nitrous acid with aliphatic amines
(those where the amine group isn't attached directly to a benzene ring).
Nitrous acid is properly called nitric(III) acid, but that name isn't
commonly used.
Reactions between nitrous acid and aromatic amines like phenylamine
(where the -NH2 group is attached directly to a benzene ring) are dealt
with elsewhere.
Because nitrous acid is a weak acid, the position of equilibrium lies well
the right.
. . . but the propan-1-ol will be only one product among many - including
propan-2-ol, propene, 1-chloropropane, 2-chloropropane and others.
The nitrogen, however, is given off in quantities exactly as suggested by
the equation. By measuring the amount of nitrogen produced, you could
use this reaction to work out the amount of amine present in the solution.
Note: The reason for the complexity lies in how the reaction
happens. In the first instance, you get a diazonium ion
formed - for example, CH3CH2CH2N2+. Unless the -N2+
group is attached directly to a benzene ring, these ions are
very unstable and fall apart immediately to give nitrogen gas
and a carbocation (carbonium ion) - in this example,
CH3CH2CH2+.
It is rearrangements and reactions of this ion which lead to
the mess of products.
With aromatic amines like phenylamine (aniline) the
diazonium ion formed is much more stable. If you are
interested in reactions of diazonium ions (but only in the
context of amines like phenylamine), follow this link.
Use the BACK button on your browser if you want to return to
this page later.
All that has happened is that the amine has formed an ion by reacting
with the acid present. With trimethylamine, for example, you would get a
trimethylammonium ion, (CH3)3NH+.
Because nitrous acid is a weak acid, the position of equilibrium lies well
the right.
Phenylamine reacts with nitrous acid differently depending on the
temperature.
Note: I've drawn the diazonium ion with the -N2+ group at
the side for two reasons. First, because it is easier to show
that the benzene ring and the two nitrogen atoms lie in a
straight line. Secondly, because that's the way I shall need to
draw it in some of its reactions to make certain structures
clear.
Notice that the chloride ions from the acid aren't involved in this in any
way. If you use hydrochloric acid, the solution will contain
benzenediazonium chloride. If you used a different acid, you would just
get a different salt - a sulphate or hydrogensulphate, for example, if you
used sulphuric acid.
The reactions of a diazonium salt are always done with a freshly
prepared solution made in this way. The solutions don't keep. Diazonium
salts are very unstable and tend to be explosive as solids.
In this set of reactions of the diazonium ion, the -N2+ group is replaced by
something else. The nitrogen is released as nitrogen gas.
Substitution by an -OH group
To get this reaction, all you need to do is warm the benzenediazonium
chloride solution. The diazonium ion reacts with the water in the solution
and phenol is formed - either in solution or as a black oily liquid
(depending on how much is formed). Nitrogen gas is evolved.
This is the same reaction that you get if you react phenylamine with
nitrous acid in the warm. The diazonium ion is formed first and then
immediately reacts with the water in the solution to give phenol.
Modifying the groups present in the molecule can have an effect on the
light absorbed, and so on the colour you see. You can take advantage of
this in indicators.
Methyl orange is an azo dye which exists in two forms in equilibrium with
each other:
As the hydrogen ion is lost or gained there is a shift in the exact nature of
the delocalisation in the molecule, and that causes a shift in the
wavelength of light absorbed. Obviously that means that you see a
different colour.
When you add acid to methyl orange, the equilibrium is shifted to give
more of the red form. Methyl orange is red in acidic solutions (in fact
solutions of pH less than 3.1).
If you add an alkali, hydrogen ions are removed and the equilibrium shifts
to give more of the yellow form. Methyl orange is yellow at pH's greater
than 4.4.
In between, at some point there will be equal amounts of the red and
yellow forms and so methyl orange looks orange.
Note: You can find out much more about indicators in the
physical chemistry part of this site.
hydrogenation of alkenes
hydrogenation of alkenes
Margarine manufacture
Some margarine is made by hydrogenating carbon-carbon double bonds
in animal or vegetable fats and oils. You can recognise the presence of
this in foods because the ingredients list will include words showing that
it contains "hydrogenated vegetable oils" or "hydrogenated fats".
The impression is sometimes given that all margarine is made by
hydrogenation - that's simply not true.
Animal and vegetable fats and oils
These are similar molecules, differing in their melting points. If the
compound is a solid at room temperature, you usually call it a fat. If it is a
liquid, it is often described as an oil.
Their melting points are largely determined by the presence of carboncarbon double bonds in the molecule. The higher the number of carboncarbon double bonds, the lower the melting point.
If there aren't any carbon-carbon double bonds, the substance is said to
be saturated. A typical saturated fat might have the structure:
hydrogenation of alkenes
If there are two or more carbon-carbon double bonds in each chain, then
it is said to be polyunsaturated.
For example:
For simplicity, in all these diagrams, all three hydrocarbon chains in each
molecule are the same. That doesn't have to be the case - you can have
a mixture of types of chain in the same molecule.
Making margarine
Vegetable oils often contain high proportions of polyunsaturated and
mono-unsaturated fats (oils), and as a result are liquids at room
temperature. That makes them messy to spread on your bread or toast,
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hydrogenation of alkenes
hydrogenation of alkenes
hydrogenation of alkenes
Note: If you don't know what this means, you will find more
about it towards the bottom of the introductory page about
esters. If you don't understand what cis and trans isomers
are, you won't make any sense of what comes next!
Use the BACK button on your browser to return to this page.
Note: As I said earlier, ideas about this change all the time.
It would be worth doing a Google search on trans fatty
acids. The US Food and Drugs Administration (FDA) has a
useful up-to-date fact sheet about them, and the Google
search will find it for you amongst a lot of other information.
hydrogenation of alkenes
What happens if you add the hydrogen to the carbon atom at the righthand end of the double bond, and the chlorine to the left-hand end? You
would still have the same product.
The chlorine would be on a carbon atom next to the end of the chain you would simply have drawn the molecule flipped over in space.
That would be different of the alkene was unsymmetrical - that's why we
have to look at them separately.
Conditions
The alkenes react with gaseous hydrogen halides at room temperature. If
the alkene is also a gas, you can simply mix the gases. If the alkene is a
liquid, you can bubble the hydrogen halide through the liquid.
Alkenes will also react with concentrated solutions of the gases in water.
A solution of hydrogen chloride in water is, of course, hydrochloric acid.
A solution of hydrogen bromide in water is hydrobromic acid - and so on.
There are, however, problems with this. The water will also get involved
in the reaction and you end up with a mixture of products.
Reaction rates
Variation of rates when you change the halogen
Reaction rates increase in the order HF - HCl - HBr - HI. Hydrogen
fluoride reacts much more slowly than the other three, and is normally
ignored in talking about these reactions.
When the hydrogen halides react with alkenes, the hydrogen-halogen
bond has to be broken. The bond strength falls as you go from HF to HI,
and the hydrogen-fluorine bond is particularly strong. Because it is
difficult to break the bond between the hydrogen and the fluorine, the
addition of HF is bound to be slow.
Variation of rates when you change the alkene
This applies to unsymmetrical alkenes as well as to symmetrical ones.
For simplicity the examples given below are all symmetrical ones- but
they don't have to be.
Reaction rates increase as the alkene gets more complicated - in the
sense of the number of alkyl groups (such as methyl groups) attached to
the carbon atoms at either end of the double bond.
For example:
There are two ways of looking at the reasons for this - both of which
need you to know about the mechanism for the reactions.
Note: If you should know about the mechanism, but are a bit
uncertain about it, then you should spend some time
exploring the electrophilic addition mechanisms menu before
you go on, and then come back to this page later. You should
look at the addition of hydrogen halides to unsymmetrical
alkenes as well as symmetrical ones.
This will take you some time. Use the BACK button (or, more
efficiently, the HISTORY file or GO menu) on your browser to
return to this page.
If you don't need to know about the mechanisms, skip over
the next bit!
Alkenes react because the electrons in the pi bond attract things with any
degree of positive charge. Anything which increases the electron density
around the double bond will help this.
Alkyl groups have a tendency to "push" electrons away from themselves
towards the double bond. The more alkyl groups you have, the more
negative the area around the double bonds becomes.
The more negatively charged that region becomes, the more it will attract
molecules like hydrogen chloride.
Note: If you aren't sure about pi bonds, you will find a simple
mention of them in the introductory page on alkenes
You will find more about the electron pushing effect of alkyl
groups on a page about carbocations in the mechanism
section of this site. That is also important reading if you are to
understand the next bit.
Use the BACK button on your browser to return to this page
later.
The stability of the intermediate ions governs the activation energy for
the reaction. As you go towards the more complicated alkenes, the
activation energy for the reaction falls. That means that the reactions
become faster.
That is exactly the same as the way the other hydrogen halides add.
Making propan-2-ol
More complicated alkyl hydrogensulphates react with water in exactly the
same way. For example:
Notice that the position of the -OH group is determined by where the
HSO4 group was attached. You get propan-2-ol rather than propan-1-ol
because of the way the sulphuric acid originally added across the double
bond in propene.
Using these reactions
These reactions were originally used as a way of manufacturing alcohols
from alkenes in the petrochemical industry. These days, alcohols like
ethanol or propan-2-ol tend to be manufactured by direct hydration of the
alkene because it is cheaper and easier.
This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between sulphuric acid 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 mechanism for the reaction between ethene and sulphuric acid
Sulphuric acid as an electrophile
The hydrogen atoms are attached to very electronegative oxygen atoms
which means that the hydrogens will have a slight positive charge while
the oxygens will be slightly negative. In the mechanism, we just focus on
one of the hydrogen to oxygen bonds, because the other one is too far
from the carbon-carbon double bond to be involved in any way.
The mechanism
Look carefully at the structure of the product so that you can see how it
relates to the various formulae given earlier (CH3CH2OSO2OH etc).
Having worked out the structure of the product, you could then write a
simple equation for the reaction if you wanted to.
This page guides you through the mechanism for the electrophilic
addition of sulphuric acid to symmetrical alkenes like ethene or
cyclohexene. Unsymmetrical alkenes are covered separately, and you
will find a link at the bottom of the page.
When the sulphuric acid reacts, the whole of the shaded part of the
molecule remains as a complete unit. What happens to that unit is
exactly the same as happens to the bromine in the reaction involving HBr.
When you write the mechanisms involving sulphuric acid, keep that
shaded part unchanged throughout - apart from where you would change
the bromine. For example, you will need to put a lone pair and a negative
charge on the oxygen atom in the middle of the mechanism. That's
exactly what you had to do with the bromine in the HBr case.
The mechanism
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: There are other lone pairs around the oxygen atom as
well, but we are only showing one of them for clarity.
the pi bond breaks and the pair of electrons is used to form a bond
with the hydrogen atom;
the electrons in the hydrogen-oxygen bond are pushed on to the
oxygen atom giving it a full negative charge;
the lower carbon atom in the original C=C bond becomes
positively charged because the electron it originally supplied to the
pi bond has been moved away to form the new bond.
In the second stage, the lone pair on the negatively charged oxygen is
attracted towards the positively charge carbon and forms a bond with it.
To Main Menu . . .
This page gives you the facts and a simple, uncluttered mechanism for
the electrophilic addition reactions between sulphuric acid and
unsymmetrical alkenes like propene. If you want the mechanism
explained to you in detail, there is a link at the bottom of the page.
To Main Menu . . .
This page guides you through the mechanism for the electrophilic
addition of sulphuric acid to unsymmetrical alkenes like propene.
The electron movements continue until a new bond is made between one
of the carbon atoms and the hydrogen. The oxygen now has both
electrons from the H-O bond, and so becomes negatively charged.
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:
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.
Because the secondary ion is more energetically stable, it will form more
easily and so the reaction needs less activation energy - and so happens
faster.
Once the ions have been formed, the lone pair on the negative oxygen is
strongly attracted towards the positive carbon atom. It moves towards it
and forms a bond.
Manufacturing ethanol
Ethanol is manufactured by reacting ethene with steam. The reaction is
reversible.
Only 5% of the ethene is converted into ethanol at each pass through the
reactor. By removing the ethanol from the equilibrium mixture and
recycling the ethene, it is possible to achieve an overall 95% conversion.
A flow scheme for the reaction looks like this:
This page looks at the manufacture of epoxyethane from ethene, and then
at some of the products that are made from epoxyethane.
Pressure:
about 15 atmospheres
Catalyst:
silver
The overlap between the atomic orbitals in forming the carbon-carbon and
carbon-oxygen bonds is less good than it is normally, and there is
considerable repulsion between the bonding pairs. The system becomes
more stable if the ring is broken.
When epoxyethane reacts a carbon-oxygen bond is always broken and the
ring opens up.
Uses of epoxyethane
Manufacture of ethane-1,2-diol (ethylene glycol)
Acid catalysed hydrolysis of epoxyethane
Epoxyethane reacts with water in the presence of an acid catalyst (very
dilute sulphuric acid) at a temperature of about 60C. Ethane-1,2-diol is
produced.
A large excess of water is used to try to prevent the product from reacting
with the original epoxyethane. Ethane-1,2-diol is an alcohol (because it
contains simple -OH groups), and alcohols react with epoxyethane (see
below).
Even in the presence of a large excess of water, this reaction happens as
well:
The product is still an alcohol, and similar reactions can also lead to quite
long chains.
Uses of ethane-1,2-diol
Ethane-1,2-diol is used as an antifreeze in car engines. It is added to the
cooling water to prevent it from freezing under very cold conditions.
Ethane-1,2-diol is also used in the manufacture of polyesters such as poly
(ethylene terephthalate). You may have come across this as a fibre used to
make clothes (perhaps under the brand name Terylene), or as a clear
material used to make plastic drinks bottles (PET).
The product from this reaction is again an alcohol, and can go on to react
with even more epoxyethane! What you get eventually is a chain with a
structure:
To Main Menu . . .
Phenol Menu
Understanding Chemistry
PHENOL MENU
Background . . .
An introduction to phenol and its physical properties.
The acidity of phenol . . .
Including its reaction with sodium and sodium hydroxide, and its
lack of reaction with carbonates and hydrogencarbonates.
Ring reactions of phenol . . .
The reactions of phenol with bromine and with nitric acid.
Making an azo dye from phenol . . .
The coupling reaction of phenol with benzenediazonium chloride
solution to make an azo dye. The reaction you want is one of
several on the page that this will take you to. (That page is in a
different part of the site - use the BACK button on your browser if
you need to come back here again.)
Other reactions of phenol . . .
The combustion of phenol, its esterification, and its reaction with
iron(III) chloride solution (ferric chloride solution).
Phenol Menu
Go to Main Menu . . .
an introduction to phenol
INTRODUCING PHENOL
This page looks at the structure and physical properties of phenol (very
old name: carbolic acid). Phenol is the simplest member of a family of
compounds in which an -OH group is attached directly to a benzene ring.
Phenol itself is the only one of the family that you are likely to need to
know about for UK A level purposes.
. . . but to understand phenol properly, you need to dig a bit deeper than
this.
an introduction to phenol
The donation of the oxygen'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. That is explored in another page in
this phenol section.
It also helps to make the -OH group's hydrogen a lot more acidic than it
is in alcohols. That will also be explored elsewhere in this section.
Physical properties
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an introduction to phenol
40 - 43
182
C6H5CH3
-95.0
111
an introduction to phenol
The reason for the higher values for phenol is in part due to permanent
dipole-dipole attractions due to the electronegativity of the oxygen - but is
mainly due to hydrogen bonding.
Hydrogen bonds can form between a lone pair on an oxygen on one
molecule and the hydrogen on the -OH group of one of its neighbours.
Solubility in water
Phenol is moderately soluble in water - about 8 g of phenol will dissolve
in 100 g of water.
If you try to dissolve more than this, you get two layers of liquid. The top
layer is a solution of phenol in water, and the bottom one a solution of
water in phenol. The solubility behaviour of phenol and water is
complicated, and beyond UK A level.
Phenol is somewhat soluble in water because of its ability to form
hydrogen bonds with the water.
This page explains why phenol is a weak acid and looks at its reactions
(or in some cases, lack of reaction) with bases and with sodium metal.
Phenol is a very weak acid and the position of equilibrium lies well to the
left.
Phenol can lose a hydrogen ion because the phenoxide ion formed is
stabilised to some extent. The negative charge on the oxygen atom is
delocalised around the ring. The more stable the ion is, the more likely it
is to form.
One of the lone pairs on the oxygen atom overlaps with the delocalised
electrons on the benzene ring.
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.
Spreading the charge around makes the ion more stable than it would be
if all the charge remained on the oxygen.
However . . . oxygen is the most electronegative element in the ion and
the delocalised electrons will be drawn towards it. That means that there
will still be a lot of charge around the oxygen which will tend to attract the
hydrogen ion back again.
That's why phenol is only a very weak acid.
In this reaction, the hydrogen ion has been removed by the strongly
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This page looks at the way the reactions of the benzene ring in phenol
are modified by the presence of the attached -OH group. It covers the
reactions of phenol with bromine water and with nitric acid.
One of the lone pairs on the oxygen atom in the -OH group overlaps with
the delocalised ring electron system . . .
The donation of the oxygen's lone pair into the ring system increases the
electron density around the ring.
A benzene ring undergoes substitution reactions in which the ring
electrons are attacked by positive ions or the slightly positive parts of
molecules. In other words, it undergoes electrophilic substitution. If you
increase the electron density around the ring, it becomes even more
attractive to incoming electrophiles. That's what happens in phenol.
Note: If you aren't sure what any of these terms mean, you
could find out by following this link to a page introducing
electrophilic substitution.
If you choose to follow this link, use the BACK button (or the
HISTORY file or GO menu) on your browser to return to this
page later.
Specific examples
Reaction with bromine water
If bromine water is added to a solution of phenol in water, the bromine
water is decolourised and a white precipitate is formed which smells of
antiseptic.
The precipitate is 2,4,6-tribromophenol. (The smell is similar to the
antiseptic TCP: 2,4,6-trichlorophenol.)
Notice the multiple substitution around the ring - into all the activated
positions. (The 6- position is, of course, just the same as the 2- position.
Both are next door to the -OH group.)
Combustion of phenol
Phenol burns in a plentiful supply of oxygen to give carbon dioxide and
water.
Esterification of phenol
You will probably remember that you can make esters from alcohols by
reacting them with carboxylic acids. You might expect phenol to be similar.
hydroxide solution.
The phenoxide ion reacts more rapidly with benzoyl chloride than the
original phenol does, but even so you have to shake it with benzoyl
chloride for about 15 minutes. Solid phenyl benzoate is formed.
This reaction isn't important itself, but a very similar reaction is involved in
the manufacture of aspirin (covered in detail on another page - link below).
This page deals briefly with the combustion of alkanes and cycloalkanes.
In fact, there is very little difference between the two.
Complete combustion
Complete combustion (given sufficient oxygen) of any hydrocarbon
produces carbon dioxide and water.
Equations
It is quite important that you can write properly balanced equations for
these reactions, because they often come up as a part of
thermochemistry calculations. Don't try to learn the equations - there are
far too many possibilities. Work them out as you need them.
Some are easier than others. For example, with alkanes, the ones with
an even number of carbon atoms are marginally harder than those with
an odd number!
For example, with propane (C3H8), you can balance the carbons and
hydrogens as you write the equation down. Your first draft would be:
With butane (C4H10), you can again balance the carbons and hydrogens
as you write the equation down.
Counting the oxygens leads to a slight problem - with 13 on the righthand side. The simple trick is to allow yourself to have "six-and-a-half"
O2 molecules on the left.
Trends
The hydrocarbons become harder to ignite as the molecules get bigger.
This is because the bigger molecules don't vaporise so easily - the
reaction is much better if the oxygen and the hydrocarbon are well mixed
as gases. If the liquid isn't very volatile, only those molecules on the
surface can react with the oxygen.
Bigger molecules have greater Van der Waals attractions which makes it
more difficult for them to break away from their neighbours and turn to a
gas.
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.
Provided the combustion is complete, all the hydrocarbons will burn with
a blue flame. However, combustion tends to be less complete as the
number of carbon atoms in the molecules rises. That means that the
bigger the hydrocarbon, the more likely you are to get a yellow, smoky
flame.
Incomplete combustion
Incomplete combustion (where there isn't enough oxygen present) can
lead to the formation of carbon or carbon monoxide.
As a simple way of thinking about it, the hydrogen in the hydrocarbon
gets the first chance at the oxygen, and the carbon gets whatever is left
over!
The presence of glowing carbon particles in a flame turns it yellow, and
black carbon is often visible in the smoke. Carbon monoxide is produced
as a colourless poisonous gas.
Why carbon monoxide is poisonous
Oxygen is carried around the blood by haemoglobin (US: hemoglobin).
Unfortunately carbon monoxide binds to exactly the same site on the
haemoglobin that oxygen does.
The difference is that carbon monoxide binds irreversibly - making that
particular molecule of haemoglobin useless for carrying oxygen. If you
breath in enough carbon monoxide you will die from a sort of internal
suffocation.
Alkanes
The reaction between alkanes and fluorine
This reaction is explosive even in the cold and dark, and you tend to get
carbon and hydrogen fluoride produced. It is of no particular interest. For
example:
Note: I can't discover the truth about this! Some sources say
that it doesn't react; others say that it reacts very slowly. I
have found it impossible to find all the data I need to estimate
whether there might be a temperature at which the reaction
becomes feasible. The information needed depends too
much on what assumptions you make about the physical
states of the reactants and products - for example, whether
the iodine is present as a solid, a gas or a solution.
If you have any hard information, could you contact me via
the address on the about this site page.
If chance was the only factor, you would expect to get 3 times as much of
the isomer with the chlorine on the end. There are 6 hydrogens that
could get replaced on the end carbon atoms compared with only 2 in the
middle.
In fact, you get about the same amount of each of the two isomers.
If you use bromine instead of chlorine, the great majority of the product is
where the bromine is attached to the centre carbon atom.
The reasons for this are beyond UK A level chemistry.
Cycloalkanes
The reactions of the cycloalkanes are generally just the same as the
alkanes, with the exception of the very small ones - particularly
cyclopropane.
The extra reactivity of cyclopropane
In the presence of UV light, cyclopropane will undergo substitution
reactions with chlorine or bromine just like a non-cyclic alkane. However,
it also has the ability to react in the dark.
In the absence of UV light, cyclopropane can undergo addition
reactions in which the ring is broken. For example, with bromine,
cyclopropane gives 1,3-dibromopropane.
This can still happen in the presence of light - but you will get substitution
reactions as well.
The ring is broken because cyclopropane suffers badly from ring strain.
The bond angles in the ring are 60 rather than the normal value of about
109.5 when the carbon makes four single bonds.
The overlap between the atomic orbitals in forming the carbon-carbon
bonds is less good than it is normally, and there is considerable repulsion
between the bonding pairs. The system becomes more stable if the ring
is broken.
To Main Menu . . .
CH4 + Br2
CH3Br + HBr
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.
Chain initiation
The chain is initiated (started) by UV light breaking a bromine molecule
into free radicals.
Br2
2Br
CH3
+ Br2
+ HBr
CH3Br + Br
Br2
+
CH3 +
CH3
CH3Br
CH3CH3
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Because we want to stress the fact that the bromine atoms have single
unpaired electrons, then we call them bromine free radicals - or more
usually just bromine 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 bromine molecule would be shown as:
Br2
2Br
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 bromine 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 bromine
radicals are likely to hit, and what could happen as a result of that
collision.
At the moment the mixture contains
Br2
Br-Br +
The bromine 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 bromine, and so one electron is left behind on the carbon
atom. A new free radical is formed - this time a methyl radical, CH3 .
CH4 + Br
CH3
+ HBr
CH3
Br
+
CH3Br
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 bromine
molecule (something that's quite likely to occur), the following change
can happen:
CH3
+ Br2
CH3Br + Br
2Br
CH3
+ Br2
+ HBr
CH3Br + Br
Br2
+
CH3 +
CH3
CH3Br
CH3CH3
The facts
When a mixture of methane and bromine is exposed to ultraviolet light typically sunlight - a substitution reaction occurs and the organic product
is bromomethane.
CH4 + Br2
CH3Br + HBr
However, the reaction doesn't stop there, and all the hydrogens in the
methane can in turn be replaced by bromine atoms. That means that you
could get any of bromomethane, dibromomethane, tribromomethane or
tetrabromomethane.
CH4 + Br2
CH3Br + HBr
CH3Br + Br2
CH2Br2 + HBr
CH2Br2 + Br2
CHBr3 + HBr
CHBr3 + Br2
CBr4 + HBr
You might think that you could control which product you got by the
proportions of methane and bromine you used, but it isn't as simple as
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that. If you use enough bromine you will eventually get CBr4, but any
other proportions will always lead to a mixture of products.
The mechanisms
The formation of multiple substitution products like di-, tri- and
tetrabromomethane can be explained in just the same sort of way as the
formation of the original bromomethane. You just have to look at the
likely collisions as the reaction progresses.
Making dibromomethane
You will remember that the over-all equation for the first stage of the
reaction is
CH4 + Br2
CH3Br + HBr
CH2Br + HBr
CH2Br2 + Br
CHBr2 + HBr
CHBr3 + Br
As the amount of tribromomethane builds up, then you will get these
steps giving tetrabromomethane:
CHBr3 + Br
CBr3 + Br2
CBr3 + HBr
CBr4 + Br
This is why you will always get a mixture of products whatever the
reaction proportions of methane and bromine you use. The whole
process is simply governed by chance. Having produced some
bromomethane there is no way that you can prevent it from being hit by
bromine radicals, and similarly for dibromomethane and
tribromomethane.
Trying to produce mainly one product
If you wanted tetrabromomethane, you could of course get it by using a
large excess of bromine, so that eventually all the hydrogens would be
replaced.
If you wanted mainly bromomethane, you could favour this by using a
huge excess of methane so that the chances were always greater of a
bromine 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 dibromomethane or
tribromomethane.
To Main Menu . . .
You may remember that one of the chain termination steps produces
ethane, CH3CH3.
CH3 +
CH3
CH3CH3
If bromine radicals hit that, you are going to get bromoethane and
dibromoethane 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!
CRACKING ALKANES
This page describes what cracking is, and the differences between
catalytic cracking and thermal cracking used in the petrochemical
industry.
Cracking
What is cracking?
Cracking is the name given to breaking up large hydrocarbon molecules
into smaller and more useful bits. This is achieved by using high
pressures and temperatures without a catalyst, or lower temperatures
and pressures in the presence of a catalyst.
The source of the large hydrocarbon molecules is often the naphtha
fraction or the gas oil fraction from the fractional distillation of crude oil
(petroleum). These fractions are obtained from the distillation process as
liquids, but are re-vaporised before cracking.
There isn't any single unique reaction happening in the cracker. The
hydrocarbon molecules are broken up in a fairly random way to produce
mixtures of smaller hydrocarbons, some of which have carbon-carbon
double bonds. One possible reaction involving the hydrocarbon C15H32
might be:
Or, showing more clearly what happens to the various atoms and bonds:
This is only one way in which this particular molecule might break up.
The ethene and propene are important materials for making plastics or
producing other organic chemicals. The octane is one of the molecules
found in petrol (gasoline).
Catalytic cracking
Modern cracking uses zeolites as the catalyst. These are complex
aluminosilicates, and are large lattices of aluminium, silicon and oxygen
atoms carrying a negative charge. They are, of course, associated with
positive ions such as sodium ions. You may have come across a zeolite
if you know about ion exchange resins used in water softeners.
The alkane is brought into contact with the catalyst at a temperature of
about 500C and moderately low pressures.
The zeolites used in catalytic cracking are chosen to give high
percentages of hydrocarbons with between 5 and 10 carbon atoms particularly useful for petrol (gasoline). It also produces high proportions
of branched alkanes and aromatic hydrocarbons like benzene.
For UK A level purposes, you aren't expected to know how the catalyst
works, but you may be expected to know that it involves an ionic
intermediate.
The zeolite catalyst has sites which can remove a hydrogen from an
alkane together with the two electrons which bound it to the carbon. That
leaves the carbon atom with a positive charge. Ions like this are called
carbonium ions (or carbocations). Reorganisation of these leads to the
various products of the reaction.
Thermal cracking
In thermal cracking, high temperatures (typically in the range of 450C to
750C) and pressures (up to about 70 atmospheres) are used to break
the large hydrocarbons into smaller ones. Thermal cracking gives
mixtures of products containing high proportions of hydrocarbons with
double bonds - alkenes.
This page explains how aldehydes and ketones are made in the lab by
the oxidation of primary and secondary alcohols.
If at least one of these groups is a hydrogen atom, then you will get an
aldehyde. If they are both alkyl groups then you get a ketone.
If you now think about where they are coming from, you will get an
aldehyde if your starting molecule looks like this:
In other words, if you start from a primary alcohol, you will get an
aldehyde.
You will get a ketone if your starting molecule looks like this:
Making aldehydes
Aldehydes are made by oxidising primary alcohols. There is, however, a
problem.
The aldehyde produced can be oxidised further to a carboxylic acid by
the acidified potassium dichromate(VI) solution used as the oxidising
agent. In order to stop at the aldehyde, you have to prevent this from
happening.
use an excess of the alcohol. That means that there isn't enough
oxidising agent present to carry out the second stage and oxidise
the aldehyde formed to a carboxylic acid.
distil off the aldehyde as soon as it forms. Removing the aldehyde
as soon as it is formed means that it doesn't stay in the mixture to
be oxidised further.
If you used ethanol as a typical primary alcohol, you would produce the
aldehyde ethanal, CH3CHO.
The full equation for this reaction is fairly complicated, and you need to
understand about electron-half-equations in order to work it out.
Secondary alcohols
Secondary alcohols are oxidised to ketones. There is no further reaction
which might complicate things. For example, if you heat the secondary
alcohol propan-2-ol with sodium or potassium dichromate(VI) solution
acidified with dilute sulphuric acid, you get propanone formed.
Playing around with the reaction conditions makes no difference
whatsoever to the product.
Using the simple version of the equation:
This page looks at the reaction of aldehydes and ketones with Grignard
reagents to produce potentially quite complicated alcohols. It is mainly a
duplication of the information on these same reactions from a page on
Grignard reagents in the section on properties of halogenoalkanes.
Any reactions using the Grignard reagent are carried out with the mixture
produced from this reaction. You can't separate it out in any way.
Assuming that you are starting with CH3CH2MgBr and using the general
equation above, the alcohol you get always has the form:
Since both R groups are hydrogen atoms, the final product will be:
A primary alcohol is formed. A primary alcohol has only one alkyl group
attached to the carbon atom with the -OH group on it.
You could obviously get a different primary alcohol if you started from a
different Grignard reagent.
Again, think about how that relates to the general case. The alcohol
formed is:
So this time the final product has one CH3 group and one hydrogen
attached:
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A secondary alcohol has two alkyl groups (the same or different) attached
to the carbon with the -OH group on it.
You could change the nature of the final secondary alcohol by either:
This time when you replace the R groups in the general formula for the
alcohol produced you get a tertiary alcohol.
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This page explains what second, third, (etc) ionisation energy means,
and then looks at patterns in successive ionisation energies for selected
elements. It assumes that you understand about first ionisation energy.
suddenly breaking in to an inner level. You can use this to work out
which group of the Periodic Table an element is in from its successive
ionisation energies.
Magnesium (1s22s22p63s2) is in group 2 of the Periodic Table and has
successive ionisation energies:
Here the big jump occurs after the second ionisation energy. It means
that there are 2 electrons which are relatively easy to remove (the 3s2
electrons), while the third one is much more difficult (because it comes
from an inner level - closer to the nucleus and with less screening).
Silicon (1s22s22p63s23px13py1) is in group 4 of the Periodic Table and
has successive ionisation energies:
Here the big jump comes after the fourth electron has been removed.
The first 4 electrons are coming from the 3-level orbitals; the fifth from
the 2-level.
The lesson from all this:
Count the easy electrons - those up to (but not including) the big jump.
That is the same as the group number.
Another example:
Decide which group an atom is in if it has successive ionisation energies:
The ionisation energies are going up one or two thousand at a time for
the first five. Then there is a huge jump of about 15000. There are 5
relatively easy electrons - so the element is in group 5.
If you put a ruler on the first and second points to establish the trend,
you'll find that the third, fourth and fifth points lie above the value you
would expect. That is because the first two electrons are coming from
pairs in the 3p levels and are therefore rather easier to remove than if
they were unpaired.
Again, if you put a ruler on the 3rd, 4th and 5th points to establish their
trend, you'll find that the 6th and 7th points lie well above the values you
would expect from a continuation of the trend. That is because the 6th
and 7th electrons are coming from the 3s level - slightly closer to the
nucleus and slightly less well screened.
The massive jump as you break into the inner level at the 8th electron is
fairly obvious!
Understanding Chemistry
Go to Main Menu . . .
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Understanding Chemistry
How the M+2 (and possibly M+4) peak arises, and its use in
showing the presence of chlorine or bromine in a compound.
You can apply exactly the same principle to atomic sized particles.
Acceleration
The positive ions are repelled away from the very positive ionisation
chamber and pass through three slits, the final one of which is at 0 volts.
The middle slit carries some intermediate voltage. All the ions are
accelerated into a finely focused beam.
Deflection
the mass of the ion. Lighter ions are deflected more than heavier
ones.
the charge on the ion. Ions with 2 (or more) positive charges are
deflected more than ones with only 1 positive charge.
These two factors are combined into the mass/charge ratio. Mass/
charge ratio is given the symbol m/z (or sometimes m/e).
For example, if an ion had a mass of 28 and a charge of 1+, its mass/
charge ratio would be 28. An ion with a mass of 56 and a charge of 2+
would also have a mass/charge ratio of 28.
In the last diagram, ion stream A is most deflected - it will contain ions
with the smallest mass/charge ratio. Ion stream C is the least deflected it contains ions with the greatest mass/charge ratio.
It makes it simpler to talk about this if we assume that the charge on all
the ions is 1+. Most of the ions passing through the mass spectrometer
will have a charge of 1+, so that the mass/charge ratio will be the same
as the mass of the ion.
Assuming 1+ ions, stream A has the lightest ions, stream B the next
lightest and stream C the heaviest. Lighter ions are going to be more
deflected than heavy ones.
Detection
Only ion stream B makes it right through the machine to the ion detector.
The other ions collide with the walls where they will pick up electrons and
be neutralised. Eventually, they get removed from the mass
spectrometer by the vacuum pump.
When an ion hits the metal box, its charge is neutralised by an electron
jumping from the metal on to the ion (right hand diagram). That leaves a
space amongst the electrons in the metal, and the electrons in the wire
shuffle along to fill it.
A flow of electrons in the wire is detected as an electric current which can
be amplified and recorded. The more ions arriving, the greater the
current.
Detecting the other ions
How might the other ions be detected - those in streams A and C which
have been lost in the machine?
Remember that stream A was most deflected - it has the smallest value
of m/z (the lightest ions if the charge is 1+). To bring them on to the
detector, you would need to deflect them less - by using a smaller
magnetic field (a smaller sideways force).
To bring those with a larger m/z value (the heavier ions if the charge is
+1) on to the detector you would have to deflect them more by using a
larger magnetic field.
If you vary the magnetic field, you can bring each ion stream in turn on to
the detector to produce a current which is proportional to the number of
ions arriving. The mass of each ion being detected is related to the size
of the magnetic field used to bring it on to the detector. The machine can
be calibrated to record current (which is a measure of the number of
ions) against m/z directly. The mass is measured on the 12C scale.
You may find diagrams in which the vertical axis is labelled as either
"relative abundance" or "relative intensity". Whichever is used, it means
the same thing. The vertical scale is related to the current received by
the chart recorder - and so to the number of ions arriving at the detector:
the greater the current, the more abundant the ion.
As you will see from the diagram, the commonest ion has a mass/charge
ratio of 98. Other ions have mass/charge ratios of 92, 94, 95, 96, 97 and
100.
That means that molybdenum consists of 7 different isotopes. Assuming
that the ions all have a charge of 1+, that means that the masses of the 7
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isotopes on the carbon-12 scale are 92, 94, 95, 96, 97, 98 and 100.
This page looks at the information you can get from the mass spectrum
of an element. It shows how you can find out the masses and relative
abundances of the various isotopes of the element and use that
information to calculate the relative atomic mass of the element.
It also looks at the problems thrown up by elements with diatomic
molecules - like chlorine, Cl2.
23
100
The 5 peaks in the mass spectrum shows that there are 5 isotopes of
zirconium - with relative isotopic masses of 90, 91, 92, 94 and 96 on the
12C scale.
The abundance of the isotopes
This time, the relative abundances are given as percentages. Again you
can find these relative abundances by measuring the lines on the stick
diagram.
In this case, the 5 isotopes (with their relative percentage abundances)
are:
zirconium-90
zirconium-91
zirconium-92
zirconium-94
zirconium-96
51.5
11.2
17.1
17.4
2.8
This page looks at how fragmentation patterns are formed when organic
molecules are fed into a mass spectrometer, and how you can get
information from the mass spectrum.
The uncharged free radical won't produce a line on the mass spectrum.
Only charged particles will be accelerated, deflected and detected by the
mass spectrometer. These uncharged particles will simply get lost in the
machine - eventually, they get removed by the vacuum pump.
The ion, X+, will travel through the mass spectrometer just like any other
positive ion - and will produce a line on the stick diagram.
All sorts of fragmentations of the original molecular ion are possible - and
that means that you will get a whole host of lines in the mass spectrum.
For example, the mass spectrum of pentane looks like this:
Note: All the mass spectra on this page have been drawn
using data from the Spectral Data Base System for Organic
Compounds (SDBS) at the National Institute of Materials and
Chemical Research in Japan.
They have been simplified by omitting all the minor lines with
peak heights of 2% or less of the base peak (the tallest peak).
It's important to realise that the pattern of lines in the mass spectrum of
an organic compound tells you something quite different from the pattern
of lines in the mass spectrum of an element. With an element, each line
represents a different isotope of that element. With a compound, each
line represents a different fragment produced when the molecular ion
breaks up.
The tallest line in the stick diagram (in this case at m/z = 43) is called the
base peak. This is usually given an arbitrary height of 100, and the
height of everything else is measured relative to this. The base peak is
the tallest peak because it represents the commonest fragment ion to be
formed - either because there are several ways in which it could be
produced during fragmentation of the parent ion, or because it is a
particularly stable ion.
How many carbon atoms are there in this ion? There can't be 5 because
5 x 12 = 60. What about 4? 4 x 12 = 48. That leaves 9 to make up a total
of 57. How about C4H9+ then?
C4H9+ would be [CH3CH2CH2CH2]+, and this would be produced by the
following fragmentation:
The methyl radical produced will simply get lost in the machine.
The line at m/z = 43 can be worked out similarly. If you play around with
the numbers, you will find that this corresponds to a break producing a 3carbon ion:
The other lines in the mass spectrum are more difficult to explain. For
example, lines with m/z values 1 or 2 less than one of the easy lines are
often due to loss of one or more hydrogen atoms during the
fragmentation process. You are very unlikely to have to explain any but
the most obvious cases in an A'level exam.
This time the base peak (the tallest peak - and so the commonest
fragment ion) is at m/z = 57. But this isn't produced by the same ion as
the same m/z value peak in pentane.
If you remember, the m/z = 57 peak in pentane was produced by
[CH3CH2CH2CH2]+. If you look at the structure of pentan-3-one, it's
impossible to get that particular fragment from it.
Work along the molecule mentally chopping bits off until you come up
with something that adds up to 57. With a small amount of patience,
you'll eventually find [CH3CH2CO]+ - which is produced by this
fragmentation:
You would get exactly the same products whichever side of the CO
group you split the molecular ion.
The m/z = 29 peak is produced by the ethyl ion - which once again could
be formed by splitting the molecular ion either side of the CO group.
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.
Look first at the very strong peak at m/z = 43. This is caused by a
different ion than the corresponding peak in the pentane mass spectrum.
This peak in 2-methylbutane is caused by:
You would get the same ion, of course, if the left-hand CH3 group broke
off instead of the bottom one as we've drawn it.
In these two spectra, this is probably the most dramatic example of the
extra stability of a secondary carbocation.
CH3COCH2CH2CH3
pentan-3-one
CH3CH2COCH2CH3
[CH3CO]+
[COCH2CH2CH3]+
[CH3CH2CO]+
Understanding Chemistry
Background . . .
An explanation of how an infra-red spectrum arises.
The fingerprint region . . .
How an infra-red spectrum can be used to identify a compound.
Identifying the presence of particular groups . . .
How you can use an infra-red spectrum to identify a few easily
recognised groups in an organic compound.
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This page describes what an infra-red spectrum is and how it arises from
bond vibrations within organic molecules.
The energy involved in this vibration depends on things like the length of
the bond and the mass of the atoms at either end. That means that each
different bond will vibrate in a different way, involving different amounts
of energy.
Bonds are vibrating all the time, but if you shine exactly the right amount
of energy on a bond, you can kick it into a higher state of vibration. The
amount of energy it needs to do this will vary from bond to bond, and so
each different bond will absorb a different frequency (and hence energy)
of infra-red radiation.
Bond bending
As well as stretching, bonds can also bend.
Again, bonds will be vibrating like this all the time and, again, if you shine
exactly the right amount of energy on the bond, you can kick it into a
higher state of vibration. Since the energies involved with the bending will
be different for each kind of bond, each different bond will absorb a
different frequency of infra-red radiation in order to make this jump from
one state to a higher one.
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In the diagram, three sample absorptions are picked out to show you the
bond vibrations which produced them. Notice that bond stretching and
bending produce different troughs in the spectrum.
Note: If you aren't sure what the fingerprint region is, follow
this link before you go on.
The possible absorption due to the C-O single bond is queried because it
lies in the fingerprint region. You couldn't be sure that this trough wasn't
caused by something else.
This time the O-H absorption is missing completely. Don't confuse it with
the C-H trough fractionally less than 3000 cm-1. The presence of the
C=O double bond is seen at about 1740 cm-1.
The C-O single bond is the absorption at about 1240 cm-1. Whether or
not you could pick that out would depend on the detail given by the table
of data which you get in your exam, because C-O single bonds vary
anywhere between 1000 and 1300 cm-1 depending on what sort of
compound they are in. Some tables of data fine it down, so that they will
tell you that an absorption from 1230 - 1250 is the C-O bond in an
ethanoate.
You will find that this is very similar to the infra-red spectrum for ethyl
ethanoate, an ester. Again, there is no trough due to the O-H bond, and
again there is a marked absorption at about 1700 cm-1 due to the C=O.
Confusingly, there are also absorptions which look as if they might be
due to C-O single bonds - which, of course, aren't present in propanone.
This reinforces the care you have to take in trying to identify any
absorptions in the fingerprint region.
Aldehydes will have similar infra-red spectra to ketones.
This is interesting because it contains two different sorts of O-H bond the one in the acid and the simple "alcohol" type in the chain attached to
the -COOH group.
The O-H bond in the acid group absorbs between 2500 and 3300, the
one in the chain between 3230 and 3550 cm-1. Taken together, that
gives this immense trough covering the whole range from 2500 to 3550
cm-1. Lost in that trough as well will be absorptions due to the C-H bonds.
Notice also the presence of the strong C=O absorption at about 1730 cm1.
Primary amines contain the -NH2 group, and so have N-H bonds. These
absorb somewhere between 3100 and 3500 cm-1. That double trough
(typical of primary amines) can be seen clearly on the spectrum to the
left of the C-H absorptions.
This page explains what the fingerprint region of an infra-red spectrum is,
and how it can be used to identify an organic molecule.
The region to the right-hand side of the diagram (from about 1500 to 500
cm-1) usually contains a very complicated series of absorptions. These
are mainly due to all manner of bending vibrations within the molecule.
This is called the fingerprint region.
It is much more difficult to pick out individual bonds in this region than it
is in the "cleaner" region at higher wavenumbers. The importance of the
fingerprint region is that each different compound produces a different
pattern of troughs in this part of the spectrum.
Understanding Chemistry
Background . . .
An explanation of how an NMR spectrum arises, and the meaning
of the term "chemical shift".
Low resolution NMR spectra . . .
How a low resolution NMR spectrum is used to identify where the
hydrogen atoms in a molecule are. Read this before you go on to
high resolution spectra.
High resolution NMR spectra . . .
Looks at the additional information which you can get from a high
resolution NMR spectrum.
Integrator traces . . .
How to find the ratio of the numbers of differently placed hydrogen
atoms from an integrator trace.
This page describes what a proton NMR spectrum is and how it how it
tells you useful things about the hydrogen atoms in organic molecules.
Again, the alignment where it is opposed to the field is less stable (at a
higher energy). It is possible to make it flip from the more stable
alignment to the less stable one by supplying exactly the right amount of
energy.
The energy needed to make this flip depends on the strength of the
external magnetic field used, but is usually in the range of energies found
in radio waves - at frequencies of about 60 - 100 MHz. (BBC Radio 4 is
found between 92 - 95 MHz!)
It's possible to detect this interaction between the radio waves of just the
right frequency and the proton as it flips from one orientation to the other
as a peak on a graph. This flipping of the proton from one magnetic
alignment to the other by the radio waves is known as the resonance
condition.
Suppose you were using a radio frequency of 90 MHz, and you adjusted
the size of the magnetic field so that an isolated proton was in the
resonance condition.
If you replaced the isolated proton with one that was attached to
something, it wouldn't be feeling the full effect of the external field any
more and so would stop resonating (flipping from one magnetic
alignment to the other). The resonance condition depends on having
exactly the right combination of external magnetic field and radio
frequency.
How would you bring it back into the resonance condition again? You
would have to increase the external magnetic field slightly to compensate
for the effect of the electrons.
Now suppose that you attached the hydrogen to something more
electronegative. The electrons in the bond would be further away from
the hydrogen nucleus, and so would have less effect on the magnetic
field around the hydrogen.
To bring the hydrogen back into resonance you would again have to
increase the external magnetic field slightly to compensate for the effect
of the electrons - but not as much as when the hydrogen was attached to
the X atom.
Summary
For a given radio frequency (say, 90 MHz) each hydrogen atom will need
a slightly different magnetic field applied to it to bring it into the
resonance condition depending on what exactly it is attached to - in other
words the magnetic field needed is a useful guide to the hydrogen atom's
environment in the molecule.
The peaks
There are two peaks because there are two different environments for
the hydrogens - in the CH3 group and attached to the oxygen in the
COOH group. They are in different places in the spectrum because they
need slightly different external magnetic fields to bring them in to
resonance at a particular radio frequency.
The sizes of the two peaks gives important information about the
numbers of hydrogen atoms in each environment. It isn't the height of the
peaks that matters, but the ratio of the areas under the peaks. If you
could measure the areas under the peaks in the diagram above, you
would find that they were in the ratio of 3 (for the larger peak) to 1 (for the
smaller one).
That shows a ratio of 3:1 in the number of hydrogen atoms in the two
environments - which is exactly what you would expect for CH3COOH.
You will find that some NMR spectra show the peak due to TMS (at
zero), and others leave it out. Essentially, if you have to analyse a
spectrum which has a peak at zero, you can ignore it because that's the
TMS peak.
TMS is chosen as the standard for several reasons. The most important
are:
This page describes how you interpret simple low resolution nuclear
magnetic resonance (NMR) spectra. It assumes that you have already
read the background page on NMR so that you understand what an NMR
spectrum looks like and the use of the term "chemical shift".
The numbers against the peaks represent the relative areas under each
peak. That information is extremely important in interpreting the spectra.
Notice that there are three peaks showing three different environments
for the hydrogens. That eliminates methyl ethanoate as a possibility
because that would only give two peaks - due to the two differently
situated CH3 group hydrogens.
Does the ratio of the areas under the peaks help? Not in this case - both
the other compounds would have three peaks in the ratio of 1:2:3.
Now you need to look at the chemical shifts:
Comparing these with the actual spectrum means that the substance
was propanoic acid, CH3CH2COOH.
Example 2
How would you use low resolution NMR to distinguish between the
isomers propanone and propanal?
The propanone would only give one peak in its NMR spectrum because
both CH3 groups are in an identical environment - both are attached to COCH3.
The propanal would give three peaks with the areas underneath in the
ratio 3:2:1.
You could refer to the chemical shift table above to decide where the
peaks are likely to be found, but it isn't really necessary.
Example 3
How many peaks would there be in the low resolution NMR spectrum of
the following compound, and what would be the ratio of the areas under
the peaks?
All the CH3 groups are exactly equivalent so would only produce 1 peak.
There would also be peaks for the hydrogens in the CH2 group and the
COOH group.
There would be three peaks in total with areas in the ratio 9:2:1.
This page describes how you use an integrator trace (or integration
trace) to find the ratio of the numbers of hydrogen atoms in different
environments in an organic compound.
This page describes how you interpret simple high resolution nuclear
magnetic resonance (NMR) spectra. It assumes that you have already
read the background page on NMR so that you understand what an NMR
spectrum looks like and the use of the term "chemical shift". It also
assumes that you know how to interpret simple low resolution spectra.
1 peak
2 peaks in the cluster
3 peaks in the cluster
4 peaks in the cluster
a singlet
a doublet
a triplet
a quartet
You can get exactly the same information from a high resolution
spectrum as from a low resolution one - you simply treat each cluster of
peaks as if it were a single one in a low resolution spectrum.
But in addition, the amount of splitting of the peaks gives you important
extra information.
quartet
Note: You probably won't need to know the origin of the n+1
rule, but if you are interested there is a page on the reasons
for splitting which you could look at.
Assume that you know that the compound above has the molecular
formula C4H8O2.
Treating this as a low resolution spectrum to start with, there are three
clusters of peaks and so three different environments for the hydrogens.
The hydrogens in those three environments are in the ratio 2:3:3. Since
there are 8 hydrogens altogether, this represents a CH2 group and two
CH3 groups.
What about the splitting?
The CH2 group at about 4.1 ppm is a quartet. That tells you that it is next
door to a carbon with three hydrogens attached - a CH3 group.
The CH3 group at about 1.3 ppm is a triplet. That must be next door to a
CH2 group.
This combination of these two clusters of peaks - one a quartet and the
other a triplet - is typical of an ethyl group, CH3CH2. It is very common.
Get to recognise it!
Finally, the CH3 group at about 2.0 ppm is a singlet. That means that the
carbon next door doesn't have any hydrogens attached.
So what is this compound? You would also use chemical shift data to
help to identify the environment each group was in, and eventually you
would come up with:
Note: You now know how to get the information you need
from NMR spectra, but it often isn't easy to fit all that
information together into a final formula. You simply need to
practise! Go through all the examples in past papers from
your Exam Board. How complicated they are will vary
markedly from Board to Board. Some of the compounds you
will come across may be very unfamiliar. Don't forget to use
the information in chemical shift tables - if your examiners
include some obscure group, it's almost certain you will need
to use it. Take all the hints that are going!
The Nuffield Data Book quotes 2.0 - 4.0, but the Nuffield text book
shows a peak at about 5.4.
The OCR Data Sheet for use in their exams quotes 3.5 - 5.5.
A reliable degree level organic chemistry text book quotes1.0 - 5.0,
but then shows an NMR spectrum for ethanol with a peak at about
6.1.
The SDBS database (used throughout this site) gives the -OH
peak in ethanol at about 2.6.
The problem seems to be that the position of the -OH peak varies
dramatically depending on the conditions - for example, what solvent is
used, the concentration, and the purity of the alcohol - especially on
whether or not it is totally dry.
Help! Do you need to worry about this? Not really - you can
assume that in an exam question, any NMR spectrum will be
consistent with the chemical shift data you are given.
The reason for the loss of the peak lies in the interaction between the
deuterium oxide and the alcohol. All alcohols, such as ethanol, are very,
very slightly acidic. The hydrogen on the -OH group transfers to one of
the lone pairs on the oxygen of the water molecule. The fact that here
we've got "heavy water" makes no difference to that.
The negative ion formed is most likely to bump into a simple deuterium
oxide molecule to regenerate the alcohol - except that now the -OH
group has turned into an -OD group.
These four hydrogens are all exactly equivalent. You would get a single
peak with no splitting at all.
You only have to change the molecule very slightly for this no longer to
be true.
Because the molecule now contains different atoms at each end, the
hydrogens are no longer all in the same environment. This compound
would give two separate peaks on a low resolution NMR spectrum. The
high resolution spectrum would show that both peaks subdivided into
triplets - because each is next door to a differently placed CH2 group.
This page describes the reason that you get clusters of peaks in a high
resolution NMR spectrum in place of simple peaks in the low resolution
spectrum. The effect is known as spin-spin coupling or spin-spin
splitting.
Spin-spin coupling
The origin of a doublet
Consider what the high resolution NMR spectrum of the compound
CH2Cl-CHCl2 would look like.
The two arrangements in the centre of the diagram produce the same
field (exactly the same as the external field). So . . . there are three
possible magnetic fields that the CH hydrogen could feel, and so there
are three peaks close together - a triplet.
The areas under the peaks are in the ratio of 1:2:1 because that
represents the chances of these various magnetic fields occurring.
All the arrangements in the second line produce the same field. All the
alignments in the third line also produce the same field, but this time a bit
smaller. There are four different possible fields, with the chances of them
arising in the ratio 1:3:3:1.
So a CH3 group produces a quartet in the spectrum of the hydrogens of
the next door group, with the peak sizes in the ratio 1:3:3:1.
This page explains how to find the relative formula mass (relative
molecular mass) of an organic compound from its mass spectrum. It also
shows how high resolution mass spectra can be used to find the
molecular formula for a compound.
Note: This mass spectrum has been drawn using data from
the Spectral Data Base System for Organic Compounds
(SDBS) at the National Institute of Materials and Chemical
Research in Japan.
It has been simplified by omitting all the minor lines with peak
heights of 2% or less of the base peak (the tallest peak).
Because the largest m/z value is 72, that represents the largest ion going
through the mass spectrometer - and you can reasonably assume that
this is the molecular ion. The relative formula mass of the compound is
therefore 72.
Note: This assumes that the charge on the ion is 1+. That's
always the case when you are interpreting these mass
spectra.
Finding the relative formula mass (relative molecular mass) from a mass
spectrum is therefore trivial. Look for the peak with the highest value for
m/z, and that value is the relative formula mass of the compound.
There are, however, complications which arise because of the possibility
of different isotopes (either of carbon or of chlorine or bromine) in the
molecular ion. These cases are dealt with on separate pages.
12C
12
14N
14
16O
16
1.0078
12.0000
14N
14.0031
16O
15.9949
The carbon value is 12.0000, of course, because all the other masses
are measured on the carbon-12 scale which is based on the carbon-12
isotope having a mass of exactly 12.
44.0624
CH3CHO
44.0261
You can easily check that by adding up numbers from the table of
accurate relative isotopic masses above.
A possible exam question
A gas was known to contain only elements from the following list:
1H
1.0078
12C
12.0000
14N
14.0031
16O
15.9949
The gas had a molecular ion peak at m/z = 28.0312 in a high resolution
mass spectrometer. What was the gas?
After a bit of playing around, you might reasonably come up with 3 gases
which had relative formula masses of approximately 28 and which
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contained the elements from the list. They are N2, CO and C2H4.
Working out their accurate relative formula masses gives:
N2
28.0062
CO
C2H4
27.9949
28.0312
This page explains how the M+1 peak in a mass spectrum can be used
to estimate the number of carbon atoms in an organic compound.
In A'level questions, the M+1 peak is often left out to avoid confusion particularly if you were being asked to find the relative formula mass of
the compound from the molecular ion peak.
The carbon-13 isotope
The M+1 peak is caused by the presence of the 13C isotope in the
molecule. 13C is a stable isotope of carbon - don't confuse it with the 14C
isotope which is radioactive. Carbon-13 makes up 1.11% of all carbon
atoms.
If you had a simple compound like methane, CH4, approximately 1 in
every 100 of these molecules will contain carbon-13 rather than the more
common carbon-12. That means that 1 in every 100 of the molecules will
have a mass of 17 (13 + 4) rather than 16 (12 + 4).
The mass spectrum will therefore have a line corresponding to the
molecular ion [13CH4]+ as well as [12CH4]+.
The line at m/z = 17 will be much smaller than the line at m/z = 16
because the carbon-13 isotope is much less common. Statistically you
will have a ratio of approximately 1 of the heavier ions to every 99 of the
lighter ones. That's why the M+1 peak is much smaller than the M+ peak.
This page explains how the M+2 peak in a mass spectrum arises from
the presence of chlorine or bromine atoms in an organic compound. It
also deals briefly with the origin of the M+4 peak in compounds
containing two chlorine atoms.
Note: All the mass spectra on this page have been drawn
using data from the Spectral Data Base System for Organic
Compounds (SDBS) at the National Institute of Materials and
Chemical Research in Japan.
With one exception, they have been simplified by omitting all
the minor lines with peak heights of 2% or less of the base
peak (the tallest peak).
The molecular ion peaks (M+ and M+2) each contain one chlorine atom but the chlorine can be either of the two chlorine isotopes, 35Cl and 37Cl.
The molecular ion containing the 35Cl isotope has a relative formula
mass of 78. The one containing 37Cl has a relative formula mass of 80 hence the two lines at m/z = 78 and m/z = 80.
Notice that the peak heights are in the ratio of 3 : 1. That reflects the fact
that chlorine contains 3 times as much of the 35Cl isotope as the 37Cl
one. That means that there will be 3 times more molecules containing the
lighter isotope than the heavier one.
So . . . if you look at the molecular ion region, and find two peaks
separated by 2 m/z units and with a ratio of 3 : 1 in the peak heights, that
tells you that the molecule contains 1 chlorine atom.
You might also have noticed the same pattern at m/z = 63 and m/z = 65
in the mass spectrum above. That pattern is due to fragment ions also
containing one chlorine atom - which could either be 35Cl or 37Cl. The
fragmentation that produced those ions was:
The lines in the molecular ion region (at m/z values of 98, 100 ands 102)
arise because of the various combinations of chlorine isotopes that are
possible. The carbons and hydrogens add up to 28 - so the various
possible molecular ions could be:
28 + 35 + 35 = 98
28 + 35 + 37 = 100
28 + 37 + 37 = 102
If you have the necessary maths, you could show that the chances of
these arrangements occurring are in the ratio of 9:6:1 - and this is the
ratio of the peak heights. If you don't know the right bit of maths, just
learn this ratio!
So . . . if you have 3 lines in the molecular ion region (M+, M+2 and M+4)
with gaps of 2 m/z units between them, and with peak heights in the ratio
of 9:6:1, the compound contains 2 chlorine atoms.
The carbons and hydrogens add up to 29. The M+ and M+2 peaks are
therefore at m/z values given by:
29 + 79 = 108
29 + 81 = 110
So . . . if you have two lines in the molecular ion region with a gap of 2 m/
z units between them and with almost equal heights, this shows the
presence of a bromine atom in the molecule.
Understanding Chemistry
You can get almost all the books on this page directly from Amazon.co.
uk, and you will find links to the Amazon site where appropriate. You can,
of course, also buy the books from normal bookshops.
The suggestions are mainly suitable for UK A level chemistry courses. If
you want to make life as easy as possible for yourself, I think there is a
lot to be said for using books designed especially to cover your particular
syllabus. The content is then exactly what you need - and no more.
The alternative is to use a short revision guide for all the facts, and to get
your explanations in detail from a website like this one.
There are lots of these around. Of the ones I have looked at, the books in
the Letts series seem to me to be the easiest and most logical to find
your way around - with clear coding to show what is needed for each
syllabus.
AQA
Textbooks
Collins and Heinemann both publish textbooks written specifically for the
AQA AS and A2 syllabuses.
Revision books
The same publishers both produce a set of revision notes.
The Collins Student Support Materials provide one booklet for each
module.
The Heinemann material comes in two books - one for AS and one for
A2.
Edexcel
Nelson Advanced Science produces 4 books to cover each of the theory
units in the AS and A2 syllabuses, and an overall revision guide.
Textbooks
Revision books
OCR
Textbooks
There are two textbooks for the OCR syllabus in the Cambridge
Advanced Science series.
The OCR A2 syllabus has an options section. The following books in the
Cambridge Advanced Science series cover these options:
Biochemistry
Environmental Chemistry
Transition Elements
Revision books
Go to Main Menu . . .