3B: Covalent Bonding

3.10 understand that covalent bonding is the strong electrostatic

attraction between two nuclei and the shared pair of electrons between
them, based on the evidence:
A covalent bond is the strong electrostatic attraction
between the two positive nuclei and the shared electrons in
the bond.
Both of electron density maps and physical properties serve as evidence for the existence of covalent
bonding.

(i) the physical properties of giant atomic structures

GIANT covalent structures are ALL high melting point solids because a lot of
energy is needed to break the STRONG covalent bonds. Strong covalent bonds can
exist throughout most, or all of, the structure
(ii)electron density maps for simple molecules
3.11 be able to draw dot-and-cross diagrams to show electrons in covalent substances, including:

i molecules with single, double and triple bonds

single bond
 DOUBLE BOND

Triple bond
ii species with dative covalent (coordinate) bonds, including Al2Cl6 and the ammonium ion

EG NO.1:
EG NO.2:

EG NO.3:

Eg no.4
3.12 be able to describe the different structures formed by giant lattices of carbon atoms, including
graphite, diamond and graphene, and discuss the applications of each.

GIANT COVALENT LATTICES Giant covalent lattices are sometimes called network covalent lattices. They
consist of a giant network of atoms linked to each other by covalent bonds. Four of the most common
giant covalent substances are:

• diamond

• graphite

• graphene

• silicon(IV) oxide (not discussed below)

 A large structure where large numbers of atoms or ions are held in a lattice by
strong bondsThis is the defintion for "gaint covalent structure" or
"macromolecules"

GIANT COVALENT STRUCTURES

This page decribes the structures of giant covalent substances like diamond,
graphite and silicon dioxide (silicon(IV) oxide), and relates those structures to
the physical properties of the substances.

The structure of diamond

The giant covalent structure of diamond

Carbon has an electronic arrangement of 2,4. In diamond, each carbon

shares electrons with four other carbon atoms - forming four single bonds.
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.

Note: We quoted the electronic structure of carbon as 2,4. That simple view is perfectly
adequate to explain the bonding in diamond. If you are interested in a more modern view,
you could read the page on bonding in methane and ethane in the organic section of this
site. In the case of diamond, each carbon is bonded to 4 other carbons rather than
hydrogens, but that makes no essential difference.

How to draw the structure of diamond

Don't try to be too clever by trying to draw too much of the structure! Learn to
draw the diagram given above. Do it in the following stages:

Practise until you can do a reasonable free-hand sketch in about 30 seconds.

The physical properties of diamond

Diamond
  has a very high melting point (almost 4000°C). Very strong carbon-
carbon 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
attractions which could occur between solvent molecules and carbon
atoms which could outweigh the attractions between the covalently
bound carbon atoms.

The structure of graphite

The giant covalent structure of graphite

Graphite has a layer structure which is quite difficult to draw convincingly in

three dimensions. The diagram below shows the arrangement of the atoms in
each layer, and the way the layers are spaced.

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 bonding in graphite

Each carbon atom uses three of its electrons to form simple bonds to its three
close neighbours. That leaves a fourth electron in the bonding level. These
"spare" electrons in each carbon atom become delocalised over the whole of
the sheet of atoms in one layer. They are no longer associated directly with
any particular atom or pair of atoms, but are free to wander throughout the
whole sheet.

If you are interested (beyond A'level): The bonding in graphite is like a vastly extended
version of the bonding in benzene. Each carbon atom undergoes sp2 hybridisation, and
then the unhybridised p orbitals on each carbon atom overlap sideways to give a massive
pi system above and below the plane of the sheet of atoms.

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 forcesfollow this link before you go on. Use
the BACK button on your browser to return to this page.
The physical properties of graphite

Graphite

 has a high melting point, similar to that of diamond. In order to melt

graphite, it isn't enough to loosen one sheet from another. You have to
break the covalent bonding throughout the whole structure.
 has a soft, slippery feel, and is used in pencils and as a dry lubricant
for things like locks. You can think of graphite rather like a pack of
cards - each card is strong, but the cards will slide over each other, or
even fall off the pack altogether. When you use a pencil, sheets are
rubbed off and stick to the paper.
 has a lower density than diamond. This is because of the relatively
large amount of space that is "wasted" between the sheets.
 is insoluble in water and organic solvents - for the same reason that
diamond is insoluble. Attractions between solvent molecules and
carbon atoms will never be strong enough to overcome the strong
covalent bonds in graphite.
 conducts electricity. The delocalised electrons are free to move
throughout the sheets. If a piece of graphite is connected into a circuit,
electrons can fall off one end of the sheet and be replaced with new
ones at the other end.

Note: The logic of this is that a piece of graphite ought only to conduct electricity in 2-
dimensions because electrons can only move around in the sheets - and not from one
sheet to its neighbours.

In practice, a real piece of graphite isn't a perfect crystal, but a host of small crystals stuck
together at all sorts of angles. Electrons will be able to find a route through the large piece
of graphite in all directions by moving from one small crystal to the next.
The structure of silicon dioxide, SiO2

Silicon dioxide is also known as silicon(IV) oxide.

The giant covalent structure of silicon dioxide

There are three different crystal forms of silicon dioxide. The easiest one to
remember and draw is based on the diamond structure.

Crystalline silicon has the same structure as diamond. To turn it into silicon
dioxide, all you need to do is to modify the silicon structure by including some
oxygen atoms.

Notice that each silicon atom is bridged to its neighbours by an oxygen atom.
Don't forget that this is just a tiny part of a giant structure extending on all 3
dimensions.

Note: If you want to be fussy, the Si-O-Si bond angles are wrong in this diagram. In reality
the "bridge" from one silicon atom to its neighbour isn't in a straight line, but via a "V"
shape (similar to the shape around the oxygen atom in a water molecule). It's extremely
difficult to draw that convincingly and tidily in a diagram involving this number of atoms.
The simplification is perfectly acceptable.

The physical properties of silicon dioxide

Silicon dioxide

 has a high melting point - varying depending on what the particular

structure is (remember that the structure given is only one of three
possible structures), but around 1700°C. Very strong silicon-oxygen
 covalent bonds have to be broken throughout the structure before
melting occurs.
 is hard. This is due to the need to break the very strong covalent
bonds.
 doesn't conduct electricity. There aren't any delocalised electrons. 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
attractions which could occur between solvent molecules and the
silicon or oxygen atoms which could overcome the covalent bonds in
the giant structure.

 GRAPHENE: Graphene is pure carbon in the form of a very thin sheet, one atom thick (fi
g C). The carbon atoms are bonded in exactly the same way as in graphite and it can,
therefore, be described as a one-atom thick layer of graphite

iodine, I2

Iodine is a dark grey crystalline solid with a purple vapour. M.Pt:

114°C. B.Pt: 184°C. It is very, very slightly soluble in water, but
dissolves freely in organic solvents.

Iodine is therefore a low melting point solid. The crystallinity

suggests a regular packing of the molecules.
The structure is described as face centred cubic - it is a cube
of iodine molecules with another molecule at the centre of each
face.

The orientation of the iodine molecules within this structure is

quite difficult to draw (let alone remember!). If your syllabus and
past exam papers suggests that you need to remember it, look
carefully at the next sequence of diagrams showing the layers.

Note: If you are studying a UK-based

syllabus and haven't got a copy of
your syllabus or copies of recent past
papers, follow this link to find out how to
get them.

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 -80°C. The ice

you are familiar with has a different, hexagonal structure. It is
called "ice".

GRAPHITE Graphite has a layered structure as shown in fi g B. Each carbon

atom is bonded to three others by sigma bonds, forming interlocking
hexagonal rings. The fourth electron on each carbon atom is in a p-orbital.
The carbon atoms are close enough for the p-orbitals to overlap with one
another to produce a cloud of delocalised electrons, both above and below
the plane of the rings. We will compare this with the structure of benzene in
Topic 18 (Book 2: IAL).
 ADDITIONAL READING: Graphite can be used as a solid lubricant since the
layers slide easily over one another. Although there are only relatively weak
London forces of attraction between the layers (see Topic 7), this does not
account for its lubricating properties. Graphite is fi ve times less able to act
as a lubricant at high altitude, and eight times less in a vacuum. Its
lubricating properties are as a result of adsorbed gases on the surface of the
carbon atoms. Graphite’s inability to act as an effective lubricant in a
vacuum is the reason why it is not used as a lubricant in spacecraft. Either
molybdenum disulfi de (MoS2) or hexagonal boron nitride (BN) can be used
instead. Graphite is a fairly good conductor of electricity. The delocalised
electrons between the layers are free to flow under the infl uence of an
applied potential difference. An interesting feature of graphite is that it can
only conduct electricity parallel to its layers. The delocalised electrons are
not free to move from one layer to the next. Compare this with a metal,
which is able to conduct electricity in all directions throughout the structure.
Graphite has a high melting temperature for the same reason as diamond

 In diamond All bond angles are 109.5°

 Diamond is extremely hard because of the very strong C—C
bonding throughout the structure. It also has a very high
melting temperature because a great number of strong C—C
bonds have to be broken in order to melt it. This requires a
large amount of heat energy.

3.13 understand the meaning of the term ‘electronegativity’ as applied to atoms in a covalent bond

Electronegativity: The ability of an atom to attract a bonding pair of electrons in a

covalent bond.
Polar covalent bond: A type of covalent bond between two atoms where the
bonding electrons are unequally distributed; because of this, one atom carries a
slight negative charge & the other a slight positive charge.

 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.
 Covalent bonds that are nonpolar are sometimes called ‘normal’ covalent bonds or ‘pure’
covalent bonds. This is to distinguish them from polar covalent bonds. Both types of bond are
formed by the overlap of atomic orbitals. In both cases the overlapping area contains two
electrons per bond formed
3.14 know that ionic and covalent bonding are the extremes of a continuum of bonding type
and be able to explain this in terms of electronegativity differences, leading to bond polarity in
bonds and molecules, and to ionic bonding if the electronegativity is large enough.

3.15 be able to distinguish between polar bonds and polar molecules and predict whether or not a given
molecule is likely to be polar.

 Oxygen is the 2nd most electronegative element.

 If the electronegativity difference is more than 0.5 then the molecule is
polar.
 If the electronegativity difference is LESS than 0.5 then the molecule is
NON-POLAR.
 In order, to have a polar molecule there should be NET DIPOLE MOMENT.
 Eg: C-O carbon to oxygen this molecule is polar

but CO2 carbon dioxide molecule is NON-POLAR because there is no net

dipole moment. Since, both oxygen atoms cancel out each other .

Eg 2 : H-O is polar because the electronegativity difference is 1.4

2.1-3.5 3.5-2.1+1.4

And H2O the shape of h2O is not like carbon dioxide that’s why both hydroge don’t cancel out each
other so therefore the molecule as a whole Is POLAR too.

H H

Further suggested practical

Determine the effect of an electrostatic force on jets of liquids (water, ethanol and
cyclohexane) and use the results to determine whether the molecules are polar or
non-polar
1. Rub a glass or polythene rod with a cloth to build up electrostatic forces
2. Hold the charged rod next to the stream of liquid from a burette
3. If the liquid is deflected, it is polar (eg. water, hexene), if not, it is non-polar (eg. hexane)