IONIC (ELECTROVALENT) BONDING

This page explains what ionic (electrovalent) bonding

is. It starts with a simple picture of the formation of
ions, and then modifies it slightly for A'level purposes.

A simple view of ionic bonding

The importance of noble gas structures

At a simple level (like GCSE) a lot of importance is

attached to the electronic structures of noble gases
like neon or argon which have eight electrons in their
outer energy levels (or two in the case of helium).
These noble gas structures are thought of as being in
some way a "desirable" thing for an atom to have.

You may well have been left with the strong

impression that when other atoms react, they try to
organise things such that their outer levels are either
completely full or completely empty.

Note: The central role given to noble gas

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

Ionic bonding in sodium chloride

Sodium (2,8,1) has 1 electron more than a stable

noble gas structure (2,8). If it gave away that electron
it would become more stable.

Chlorine (2,8,7) has 1 electron short of a stable noble

gas structure (2,8,8). If it could gain an electron from
somewhere it too would become more stable.

The answer is obvious. If a sodium atom gives an

electron to a chlorine atom, both become more stable.

The sodium has lost an electron, so it no longer has

equal numbers of electrons and protons. Because it
has one more proton than electron, it has a charge of
1+. If electrons are lost from an atom, positive ions
are formed.

Positive ions are sometimes called cations.

The chlorine has gained an electron, so it now has

one more electron than proton. It therefore has a
charge of 1-. If electrons are gained by an atom,
negative ions are formed.

A negative ion is sometimes called an anion.

The nature of the bond

The sodium ions and chloride ions are held together

by the strong electrostatic attractions between the
positive and negative charges.

The formula of sodium chloride

You need one sodium atom to provide the extra

electron for one chlorine atom, so they combine
together 1:1. The formula is therefore NaCl.

Some other examples of ionic bonding

magnesium oxide

Again, noble gas structures are formed, and the

magnesium oxide is held together by very strong
attractions between the ions. The ionic bonding is
stronger than in sodium chloride because this time
you have 2+ ions attracting 2- ions. The greater the
charge, the greater the attraction.

The formula of magnesium oxide is MgO.

calcium chloride

This time you need two chlorines to use up the two

outer electrons in the calcium. The formula of calcium
chloride is therefore CaCl2.

potassium oxide

Again, noble gas structures are formed. It takes two

potassiums to supply the electrons the oxygen needs.
The formula of potassium oxide is K2O.
THE A'LEVEL VIEW OF IONIC BONDING

 Electrons are transferred from one atom to

another resulting in the formation of positive and
negative ions.
 The electrostatic attractions between the
positive and negative ions hold the compound
together.

So what's new? At heart - nothing. What needs

modifying is the view that there is something magic
about noble gas structures. There are far more ions
which don't have noble gas structures than there are
which do.

Some common ions which don't have noble gas

structures

You may have come across some of the following ions

in a basic course like GCSE. They are all perfectly
stable , but not one of them has a noble gas structure.

Fe3+ [Ar]3d5
Cu2+ [Ar]3d9
Zn2+ [Ar]3d10
Ag+ [Kr]4d10
[Xe]4f145d106
Pb2+
s2
Noble gases (apart from helium) have an outer
electronic structure ns2np6.

Note: If you aren't happy about writing

electronic structures using of s, p and d
notation, follow this link before you go on.

Return to this page via the menus or by

using the BACK button on your browser.

Apart from some elements at the beginning of a

transition series (scandium forming Sc3+ with an argon
structure, for example), all transition elements and
any metals following a transition series (like tin and
lead in Group 4, for example) will have structures like
those above.

That means that the only elements to form positive

ions with noble gas structures (apart from odd ones
like scandium) are those in groups 1 and 2 of the
Periodic Table and aluminium in group 3 (boron in
group 3 doesn't form ions).

Negative ions are tidier! Those elements in Groups 5,

6 and 7 which form simple negative ions all have
noble gas structures.

If elements aren't aiming for noble gas structures

when they form ions, what decides how many
electrons are transferred? The answer lies in the
energetics of the process by which the compound is
made.
What determines what the charge is on an ion?

Elements combine to make the compound which is as

stable as possible - the one in which the greatest
amount of energy is evolved in its making. The more
charges a positive ion has, the greater the attraction
towards its accompanying negative ion. The greater
the attraction, the more energy is released when the
ions come together.

That means that elements forming positive ions will

tend to give away as many electrons as possible. But
there's a down-side to this.

Energy is needed to remove electrons from atoms.

This is called ionisation energy. The more electrons
you remove, the greater the total ionisation energy
becomes. Eventually the total ionisation energy
needed becomes so great that the energy released
when the attractions are set up between positive and
negative ions isn't large enough to cover it.

The element forms the ion which makes the

compound most stable - the one in which most energy
is released over-all.

For example, why is calcium chloride CaCl2 rather

than CaCl or CaCl3?

If one mole of CaCl (containing Ca+ ions) is made from

its elements, it is possible to estimate that about 171
kJ of heat is evolved.

However, making CaCl2 (containing Ca2+ ions) releases

more heat. You get 795 kJ. That extra amount of heat
evolved makes the compound more stable, which is
why you get CaCl2 rather than CaCl.

What about CaCl3 (containing Ca3+ ions)? To make one

mole of this, you can estimate that you would have to
put in 1341 kJ. This makes this compound completely
non-viable. Why is so much heat needed to make
CaCl3? It is because the third ionisation energy (the
energy needed to remove the third electron) is
extremely high (4940 kJ mol-1) because the electron is
being removed from the 3-level rather than the 4-level.
Because it is much closer to the nucleus than the first
two electrons removed, it is going to be held much
more strongly.

Note: It would pay you

to read about ionisation
energies if you really
want to understand this.

You could also go to a

standard text book and
investigate Born-Haber
Cycles.
A similar sort of argument applies to the negative ion.
For example, oxygen forms an O2- ion rather than an O-
ion or an O3- ion, because compounds containing the
O2- ion turn out to be the most energetically stable.
CO-ORDINATE (DATIVE COVALENT)
BONDING

This page explains what co-ordinate (also called

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

Important! If you are uncertain about covalent

bonding follow this link before you go on with this
page.

Co-ordinate (dative covalent) bonding

A covalent bond is formed by two atoms sharing a pair

of electrons. The atoms are held together because the
electron pair is attracted by both of the nuclei.

In the formation of a simple covalent bond, each atom

supplies one electron to the bond - but that doesn't
have to be the case. A co-ordinate bond (also called a
dative covalent bond) is a covalent bond (a shared
pair of electrons) in which both electrons come from
the same atom.

For the rest of this page, we shall use the term co-
ordinate bond - but if you prefer to call it a dative
covalent bond, that's not a problem!

The reaction between ammonia and hydrogen chloride

If these colourless gases are allowed to mix, a thick

white smoke of solid ammonium chloride is formed.

NH3 + HCl NH4Cl

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.

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

hydrogen is attached by a dative covalent bond,
because only the hydrogen's nucleus is transferred
from the chlorine to the nitrogen. The hydrogen's
electron is left behind on the chlorine to form a
negative chloride ion.

Once the ammonium ion has been formed it is

impossible to tell any difference between the dative
covalent and the ordinary covalent bonds. Although
the electrons are shown differently in the diagram,
there is no difference between them in reality.

Representing co-ordinate bonds

In simple diagrams, a co-ordinate bond is shown by an

arrow. The arrow points from the atom donating the
lone pair to the atom accepting it.

Dissolving hydrogen chloride in water to make

hydrochloric acid

Something similar happens. A hydrogen ion (H+) is

transferred from the chlorine to one of the lone pairs
on the oxygen atom.

H2O + HCl H3O+ + Cl-

The H3O+ ion is variously called the hydroxonium ion,

the hydronium ion or the oxonium ion.

In an introductory chemistry course (such as GCSE),

whenever you have talked about hydrogen ions (for
example in acids), you have actually been talking
about the hydroxonium ion. A raw hydrogen ion is
simply a proton, and is far too reactive to exist on its
own in a test tube.

If you write the hydrogen ion as H+(aq), the "(aq)"

represents the water molecule that the hydrogen ion
is attached to. When it reacts with something (an
alkali, for example), the hydrogen ion simply becomes
detached from the water molecule again.

Note that once the co-ordinate bond has been set up,
all the hydrogens attached to the oxygen are exactly
equivalent. When a hydrogen ion breaks away again, it
could be any of the three.

The reaction between ammonia and boron trifluoride,

BF3
If you have recently read the page on covalent
bonding, you may remember boron trifluoride as a
compound which doesn't have a noble gas structure
around the boron atom. The boron only has 3 pairs of
electrons in its bonding level, whereas there would be
room for 4 pairs. BF3 is described as being electron
deficient.

The lone pair on the nitrogen of an ammonia molecule

can be used to overcome that deficiency, and a
compound is formed involving a co-ordinate bond.

Using lines to represent the bonds, this could be

drawn more simply as:

The second diagram shows another way that you

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

Aluminium chloride sublimes (turns

straight from a solid to a gas) at about
180°C. If it simply contained ions it would
have a very high melting and boiling point
because of the strong attractions between
the positive and negative ions. The
implication is that it when it sublimes at this
relatively low temperature, it must be covalent. The
dots-and-crosses diagram shows only the outer
electrons.

AlCl3, like BF3, is electron deficient. There is likely to

be a similarity, because aluminium and boron are in
the same group of the Periodic Table, as are fluorine
and chlorine.

Measurements of the relative formula mass of

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

Note: The uninteresting electrons on the chlorines

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

Energy is released when the two co-ordinate bonds

are formed, and so the dimer is more stable than two
separate AlCl3 molecules.

Note: Aluminium chloride is complicated because

of the way it keeps changing its bonding as the
temperature increases. If you are interested in
exploring this in more detail, you could have a look
at the page about the Period 3 chlorides. It isn't
particularly relevant to the present page, though.

If you choose to follow this link, use the BACK

button on your browser to return quickly to this
page later.

The bonding in hydrated metal ions

Water molecules are strongly attracted to ions in

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

Although aluminium chloride is covalent, when it

dissolves in water, ions are produced. Six water
molecules bond to the aluminium to give an ion with
the formula Al(H2O)63+. It's called the
hexaaquaaluminium ion - which translates as six
("hexa") water molecules ("aqua") wrapped around an
aluminium ion.

The bonding in this (and the similar ions

formed by the great majority of other metals)
is co-ordinate (dative covalent) using lone pairs on the
water molecules.

Aluminium is 1s22s22p63s23px1. When it forms an Al3+

ion it loses the 3-level electrons to leave 1s22s22p6.

That means that all the 3-level orbitals are now

empty. The aluminium re-organises (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.

Note: Dotted arrows represent lone pairs coming

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

Two more molecules

Note: It looks as if only one current UK syllabus

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

Carbon monoxide, CO

Carbon monoxide can be thought of as having two

ordinary covalent bonds between the carbon and the
oxygen plus a co-ordinate bond using a lone pair on
the oxygen atom.
Nitric acid, HNO3

In this case, one of the oxygen atoms can be thought

of as attaching to the nitrogen via a co-ordinate bond
using the lone pair on the nitrogen atom.

In fact this structure is misleading because it

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

If you are interested: The bonding is rather similar

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

This page explains what electronegativity is, and how

and why it varies around the Periodic Table. It looks
at the way that electronegativity differences affect
bond type and explains what is meant by polar bonds
and polar molecules.

If you are interested in electronegativity in an organic

chemistry context, you will find a link at the bottom of
this page.

What is electronegativity

Definition

Electronegativity is a measure of the tendency of an

atom to attract a bonding pair of electrons.

The Pauling scale is the most commonly used.

Fluorine (the most electronegative element) is
assigned a value of 4.0, and values range down to
caesium and francium which are the least
electronegative at 0.7.

What happens if two atoms of equal electronegativity

bond together?

Consider a bond between two atoms, A and B. Each

atom may be forming other bonds as well as the one
shown - but these are irrelevant to the argument.

If the atoms are equally electronegative, both have

the same tendency to attract the bonding pair of
electrons, and so it will be found on average half way
between the two atoms. To get a bond like this, A and
B would usually have to be the same atom. You will
find this sort of bond in, for example, H2 or Cl2
molecules.

Note: It's important to realise that this is an

average picture. The electrons are actually in a
molecular orbital, and are moving around all the
time within that orbital.

This sort of bond could be thought of as being a

"pure" covalent bond - where the electrons are shared
evenly between the two atoms.

What happens if B is slightly more electronegative

than A?

B will attract the electron pair rather more than A

does.

That means that the B end of the bond has more than
its fair share of electron density and so becomes
slightly negative. At the same time, the A end (rather
short of electrons) becomes slightly positive. In the
diagram, " " (read as "delta") means "slightly" - so +
means "slightly positive".

Defining polar bonds

This is described as a polar bond. A polar bond is a

covalent bond in which there is a separation of charge
between one end and the other - in other words in
which one end is slightly positive and the other
slightly negative. Examples include most covalent
bonds. The hydrogen-chlorine bond in HCl or the
hydrogen-oxygen bonds in water are typical.

What happens if B is a lot more electronegative than

A?

In this case, the electron pair is dragged right over to

B's end of the bond. To all intents and purposes, A has
lost control of its electron, and B has complete
control over both electrons. Ions have been formed.

A "spectrum" of bonds

The implication of all this is that there is no clear-cut

division between covalent and ionic bonds. In a pure
covalent bond, the electrons are held on average
exactly half way between the atoms. In a polar bond,
the electrons have been dragged slightly towards one
end.

How far does this dragging have to go before the bond

counts as ionic? There is no real answer to that. You
normally think of sodium chloride as being a typically
ionic solid, but even here the sodium hasn't
completely lost control of its electron. Because of the
properties of sodium chloride, however, we tend to
count it as if it were purely ionic.

Note: Don't worry too much about the exact cut-

off point between polar covalent bonds and ionic
bonds. At A'level, examples will tend to avoid the
grey areas - they will be obviously covalent or
obviously ionic. You will, however, be expected
to realise that those grey areas exist.
Lithium iodide, on the other hand, would be described
as being "ionic with some covalent character". In this
case, the pair of electrons hasn't moved entirely over
to the iodine end of the bond. Lithium iodide, for
example, dissolves in organic solvents like ethanol -
not something which ionic substances normally do.

Summary

 No electronegativity difference between two

atoms leads to a pure non-polar covalent bond.
 A small electronegativity difference leads to a
polar covalent bond.
 A large electronegativity difference leads to an
ionic bond.

Polar bonds and polar molecules

In a simple molecule like HCl, if the bond is polar, so

also is the whole molecule. What about more
complicated molecules?

In CCl4, each bond is polar.

Note: Ordinary lines represent bonds in the

plane of the screen or paper. Dotted lines
represent bonds going away from you into the
screen or paper. Wedged lines represent bonds
coming out of the screen or paper towards you.

The molecule as a whole, however, isn't polar - in the

sense that it doesn't have an end (or a side) which is
slightly negative and one which is slightly positive.
The whole of the outside of the molecule is somewhat
negative, but there is no overall separation of charge
from top to bottom, or from left to right.

By contrast, CHCl3 is polar.

The hydrogen at the top of the molecule is less

electronegative than carbon and so is slightly
positive. This means that the molecule now has a
slightly positive "top" and a slightly negative
"bottom", and so is overall a polar molecule.

A polar molecule will need to be "lop-sided" in some

way.

Patterns of electronegativity in the Periodic

Table

The most electronegative element is fluorine. If you

remember that fact, everything becomes easy,
because electronegativity must always increase
towards fluorine in the Periodic Table.

Note: This simplification ignores the noble

gases. Historically this is because they were
believed not to form bonds - and if they don't form
bonds, they can't have an electronegativity value.
Even now that we know that some of them do
form bonds, data sources still don't quote
electronegativity values for them.
Trends in electronegativity across a period

As you go across a period the electronegativity

increases. The chart shows electronegativities from
sodium to chlorine - you have to ignore argon. It
doesn't have an electronegativity, because it doesn't
form bonds.

Trends in electronegativity down a group

As you go down a group, electronegativity decreases.

(If it increases up to fluorine, it must decrease as you
go down.) The chart shows the patterns of
electronegativity in Groups 1 and 7.
Explaining the patterns in electronegativity

The attraction that a bonding pair of electrons feels

for a particular nucleus depends on:

 the number of protons in the nucleus;

 the distance from the nucleus;
 the amount of screening by inner electrons.

Note: If you aren't happy about the concept of

screening or shielding, it would pay you to read
the page on ionisation energies before you go on.
The factors influencing ionisation energies are
just the same as those influencing
electronegativities.

Use the BACK button on your browser to return

to this page.

Why does electronegativity increase across a period?

Consider sodium at the beginning of period 3 and

chlorine at the end (ignoring the noble gas, argon).
Think of sodium chloride as if it were covalently
bonded.

Both sodium and chlorine have their bonding

electrons in the 3-level. The electron pair is screened
from both nuclei by the 1s, 2s and 2p electrons, but
the chlorine nucleus has 6 more protons in it. It is no
wonder the electron pair gets dragged so far towards
the chlorine that ions are formed.
Electronegativity increases across a period because
the number of charges on the nucleus increases. That
attracts the bonding pair of electrons more strongly.

Why does electronegativity fall as you go down a

group?

Think of hydrogen fluoride and hydrogen chloride.

The bonding pair is shielded from the fluorine's

nucleus only by the 1s2 electrons. In the chlorine case
it is shielded by all the 1s22s22p6 electrons.

In each case there is a net pull from the centre of the

fluorine or chlorine of +7. But fluorine has the bonding
pair in the 2-level rather than the 3-level as it is in
chlorine. If it is closer to the nucleus, the attraction is
greater.

As you go down a group, electronegativity decreases

because the bonding pair of electrons is increasingly
distant from the attraction of the nucleus.

Diagonal relationships in the Periodic Table

What is a diagonal relationship?

At the beginning of periods 2 and 3 of the Periodic

Table, there are several cases where an element at
the top of one group has some similarities with an
element in the next group.

Three examples are shown in the diagram below.

Notice that the similarities occur in elements which
are diagonal to each other - not side-by-side.

For example, boron is a non-metal with some

properties rather like silicon. Unlike the rest of Group
2, beryllium has some properties resembling
aluminium. And lithium has some properties which
differ from the other elements in Group 1, and in some
ways resembles magnesium.

There is said to be a diagonal relationship between

these elements.

There are several reasons for this, but each depends

on the way atomic properties like electronegativity
vary around the Periodic Table.

So we will have a quick look at this with regard to

electronegativity - which is probably the simplest to
explain.

Explaining the diagonal relationship with regard to

electronegativity

Electronegativity increases across the Periodic Table.

So, for example, the electronegativities of beryllium
and boron are:

B 1.
e 5
2.
B
0
Electronegativity falls as you go down the Periodic
Table. So, for example, the electronegativities of
boron and aluminium are:

2.
B
0
A 1.
l 5
So, comparing Be and Al, you find the values are (by
chance) exactly the same.

The increase from Group 2 to Group 3 is offset by the

fall as you go down Group 3 from boron to aluminium.

Something similar happens from lithium (1.0) to

magnesium (1.2), and from boron (2.0) to silicon (1.8).

In these cases, the electronegativities aren't exactly

the same, but are very close.

Similar electronegativities between the members of

these diagonal pairs means that they are likely to
form similar types of bonds, and that will affect their
chemistry. You may well come across examples of
this later on in your course.