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THE PARTICLES OF MATTER (PART II): IONIC & METALLIC

SUBSTANCES

INTRODUCTION

The observable physical properties of different substances are related to the interactions
among its particles and these, on turn, depend on the kind of substance we are dealing
with (ionic, metallic, molecular, etc). It can be stated roughly that non metals bond
to each other covalently and to metals ionically, and that metals bond to metals
through a metallic bond; but most cases deserve a further detailed analysis.

THE COMPLETE OUTER SHELL RULE

Let us revise what we’ve studied in the previous unit

Atoms are electrically balanced particles that consist in one positively charged centre
called the nucleus surrounded by a “cloud” of negatively charged particles called the
electrons, to exactly balance the nuclear charge.

Molecules are electrically balanced particles with more than one positive centre
(nucleus). Molecules are sets of bonded atoms that act as a unit.

Ions are atoms (or groups of atoms) with unbalanced charges

The question arises: why should atoms form molecules or ions? The answer to this
question was proposed by Lewis with his “rule of eight” or “complete outer shell rule”.
This rule has a solid theoretical background that goes far beyond the high school syllabi
Nevertheless it is strongly suggested by the simple observation of the following facts.

• Elements belonging to Group I form mono-positive particles, atoms belonging to

Group II di-positive particles.
• To do so, they must get rid of the outer shell’s electrons becoming isoelectronic
with the closest (preceding) noble gas. Isoelectronic means, they have as many
electrons as the noble gas).
• Elements of Groups VI and VII form anions with two and one negative charges
respectively.
• For this purpose they gain electrons (two electrons and one electron
respectively) and they also become isoelectronic with the nearest noble gas in
the Periodic Table.
• This can be extended to other cases as the bonding of nitrogen to three hydrogen
atoms or of carbon to four of them, etc.

This Lewis’ rule or complete outer shell rule, or “the rule of eight” gives a fairly good
explanation to the problem of chemical bond formation and with some modifications
can be generally applied. It states that

Atoms bond to each other giving, taking or sharing electrons in order to complete
their outer shells (to resemble the nearest noble gas’ structure).
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ELECTRONEGATIVITY

The question arises: in what cases do atoms share electrons and in what cases atoms
give and take them? The answer is: according to the difference in electronegativity.
Electronegativity is a measure of the tendency of an atom to attract a bonding pair
of electrons.
Fluorine is the most electronegative element; it is assigned a value of 4.0 and values
range down to caesium and francium which are the least electronegative at 0.7.

Non polar bonds

Consider a bond between two atoms, A and B.

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.
In these cases the electrons are shared evenly between the two atoms.

Polar bonds
What is the situation in case both atoms A and B are different? Suppose B is slightly
more electronegative than A. Then 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 the electrons and
so becomes slightly negative. At the same time, the A end (rather short of electrons)
becomes slightly positive. In the diagram, "δ" (read as "delta") means "slightly" - so δ+
means "slightly positive". This is described as a polar bond. A polar bond is a 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. 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. A give and take bond has been formed .

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 give and take bond?
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.
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Patterns of electronegativity in the Periodic Table

The most electronegative element is fluorine and next comes oxygen. If you
remember that fact, everything becomes easy, because electronegativity must always
increase towards fluorine in the Periodic Table.

ELECTRONEGATIVITY OF THE ELEMENTS

H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.9 1.9 1.6 1.6 1.8 2.0 2.4 2.8

We will consider a bond definitely ionic if the electronegativity difference between

the atoms involved is greater than 2.1.

In the following paragraphs the different classes of chemical bonds will be described ,
we will assume for simplicity that the substances are 100 % “give take” or “sharing”
bonds

METALS BOND TO NON METALS: IONIC BONDS

Most metals have no more than two electrons in their outer shells. On the other hand
most non metals have five or more electrons in the highest level. To resemble the
nearest noble gas, metals give their outer shell’s electrons and non metals take them

Ionic bonding in sodium chloride

Sodium (2,8,1) has 1 electron more than a stable noble gas structure (2,8). If it could
give 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 result is obvious. If a sodium atom gives an electron and a chlorine atom takes it,
both become more stable.
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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 called
cations.

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 called an anion. The sodium ions and chloride ions are held
together by the strong electrostatic attractions between the positive and negative
charges. This is known as an ionic bond. You need one sodium atom to provide the
extra electron for one chlorine atom, so they combine together 1to1. The formula is
therefore NaCl. As you can see, the formula of an ionic compound tells you the
different classes of atoms it is made of and the proportion in which they are combined.
The formula NaCl states that you can find one sodium cation per chlorine in this
substance.

The structure of a typical ionic solids

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

A small bit of a sodium chloride lattice looks like this

shown in the diagram to the right.
If you look at it carefully, you will see that the sodium ions
and chloride ions alternate with each other in each of the
three dimensions. There is no particular cation associated
to any particular anion.
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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 on a chloride ion (that, of course, would
be touched by 6 sodium ions).The pattern repeats
in this way over countless ions.

The physical properties of sodium chloride

• Sodium chloride has a high melting and boiling point. There are strong
electrostatic attractions between the positive and negative ions, and it takes a lot
of heat energy to overcome them. Ionic substances all have high melting and
boiling points. Differences between ionic substances will depend on things like:
• Sodium chloride crystals are brittle: Brittleness is again typical of ionic
substances. Imagine what happens to the crystal if a stress is applied which
shifts the ion layers slightly. Ions of the same charge are brought side-by-side
and so the crystal repels itself to pieces!

• Sodium chloride is soluble in water Many ionic solids are soluble in water -
although not all. It depends on whether there are big enough attractions between
the water molecules and the ions to overcome the attractions between the ions
themselves.
• Sodium chloride is insoluble in organic solvents: This is also typical of ionic
solids. The attractions between the solvent molecules and the ions aren't big
enough to overcome the attractions holding the crystal together.
• The electrical behaviour of sodium chloride Solid sodium
chloride doesn't conduct electricity, because there are no
electrons which are free to move. Molten sodium chloride
undergoes electrolysis, which involves conduction of
electricity because of the movement of the ions. In the process,
sodium and chlorine are produced. Water solutions of sodium
chloride will conduct electricity for the same reasons although
the chemical outcomes in this case will be rather different.

Magnesium, in group II, has to get rid of two electrons to become stable. As chlorine
takes up just one, two chlorine atoms are needed for every magnesium atom. The
formula in that case will be MgCl2. The pattern of the particles in the solid will be
different but the essentials of the ionic bonding still hold.

Writing and Naming Ionic Compounds

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To write formulae of ionic compounds

• Write the symbol of the cation (metal) including its charges
• Then write the symbol of the anion (non metal) including its charges
• Remember that electrons are given or taken to complete the outer shells of both
elements: hence if Ca++ combines with Cl- you must use two Cl- to accept the
two electrons given by calcium
• Count how many atoms of each class you have used and write a subscript below
the atoms that are used more than once. (one Ca++ and two Cl-) Ca++Cl-2
• Wipe out the charges. The formula is CaCl2

To name the compounds

• Name the cation (just the same as the name of the atom)
• In the case of say, iron (Fe), in which there are Fe++ and Fe +++ ions, write in
brackets the roman numeral corresponding to the charge of the ion
• Name the anion changing its ending by “–ide”. The names are chloride, oxide,
sulphide, etc. Na Cl is Sodium chloride, and FeS is iron (II) sulphide etc.
• In Spanish the ending is “-uro” and the anion is named before the cation adding
the preposition “de”. The previous names would be cloruro de sodio and sulfuro
de hierro (II).
• An exception to this is “oxide” that in Spanish turns to be “óxido”
• Names as potassium nitrate do not apply here because the “-ate” ending
indicates that the anion is complex (contains also oxygen).

METALS BOND TO METALS

In this case none of the atoms will keep its outer shell’s electrons. They both are poorly
electronegative. What happens then if the electrons cannot
go away and “nobody likes them”? Atoms in this case pack
tightly forming a compact structure: their outer shells can
be thought as bursting and collapsing into a super-multi-
atom outer shell, a sea of electrons where these particles
move freely as no atom will make any effort to keep them. These free electrons are the
'electronic glue' holding the particles together.

Metallic bonding

The electrons can move freely within this “sea” and so, each electron becomes detached
from its parent atom. The electrons are said to be delocalised. The metal is held
together by the strong forces of attraction between the positive nuclei and the
delocalised electrons.
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This is sometimes described as "an array of positive ions in a sea of electrons".

If you are going to use this view, beware! Is a metal made up of atoms or ions? It is
made of atoms.

Each positive centre in the diagram represents all the rest of the atom apart from the
outer electron, but that electron hasn't been lost - it may no longer have an attachment to
a particular atom, but it's still there in the structure. Sodium metal is therefore written as
Na and not Na+.

The structure of metals

Metals are giant structures of atoms held together by metallic bonds. "Giant" implies
that large but variable numbers of atoms are involved - depending on the size of the bit
of metal.

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.

Some metals (notably those in Group 1 of the

Periodic Table) are packed less efficiently,
having only 8 touching neighbours.

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. The
grain boundaries are also known as dislocations.

The physical properties of metals

• Melting points and boiling points Metals tend to have high melting and boiling
points because of the strength of the metallic bond. The strength of the bond
varies from metal to metal and depends on the number of electrons which each
atom delocalises into the sea of electrons, and on the packing.

• Electrical conductivity Metals conduct electricity. The delocalised

electrons are free to move throughout the structure in 3-dimensions. They can
cross grain boundaries. Liquid metals also conduct electricity.
• 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.
• Malleability and ductility Metals are described as malleable (can be
beaten into sheets) and ductile
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(can be pulled out into wires). This is because of the ability of the atoms to roll
over each other into new positions without breaking the metallic bond. of the
easy-rolling layers of atoms in the “lubricating” sea of electrons”. Bearings in a
ball bearing roll in a similar way.

• Hardness: This rolling of layers of atoms over each other is hindered by grain
boundaries because the rows of atoms don't line up properly. It follows that the
more grain boundaries there are (the smaller the individual crystal grains), the
harder the metal becomes. Offsetting this, because the grain boundaries are areas
where the atoms aren't in such good contact with each other, metals tend to
fracture at grain boundaries. Increasing the number of grain boundaries not only
makes the metal harder, but also makes it more brittle. You can break up the
regular arrangement of the atoms by inserting atoms of a slightly different size
into the structure. Alloys such as brass (a mixture of copper and zinc) are harder
than the original metals because the irregularity in the structure helps to stop
rows of atoms from slipping over each other.

The below sums up what has been previously explained

Class Formed by Structure Melting Solubility Conducts Example

(scheme) point electricity
Insoluble in
Metalli Cations / any liquid Always Copper, iron
c electrons Variable (except for
reaction)
Soluble in
water and Not in
Ionic Cations / anions not in solid state Salt, sodium
>400º C solvents Conduct if bicarbonate
(generally) molten or
dissolved

PROBLEMS

1- Name one difference between an atom and an ion and one difference between an
atom and a molecule.
2- Bronze is not an element but an alloy formed by copper and tin. (metals). How
does tin bond to copper atoms in the alloy?
3- Using the electronegativity table classify the following substances as ionic or
covalent: NaCl Na2O CO2 NH3 BaCl2 Al F3 Ca3N2.

4- Write the following bonds in order of increasing polarity: C – O C – Cl C –

H O- H N – H S – O

5- Why are the noble gases not shown in the electronegativity table?

6- Write the formula for the following substances:

lithium hydride calcium sulphide sodium oxide magnesium fluoride
aluminium oxide
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7- Write the name of the following substances:

K2O MgS AlCl3 FeCl3 NaP

8- Explain why KF has a formula but not a molecule.

9- Explain the following

a- Brass is harder than copper.
b- Heating treatments makes metals softer.
c- Potassium chloride solution conducts electricity
d- Calcium oxide is brittle