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THE PARTICLES OF MATTER (PART III): COVALENT

SUBSTANCES

NON METALS BOND OTHER NON METALS: THE COVALENT BOND

In this case, none of the atoms will give electrons to the other! Instead they share one,
two or three pairs of electrons in order to achieve the complete shell. These “shared
pairs” are no longer located around one of the nuclei but around both and mainly in the
zone between both nuclei. A molecule is formed (see at the beginning of the chapter)

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. The formula of hydrogen gas, formed by hydrogen molecules is H2

Chlorine

Two chlorine atoms could both achieve stable structures by


sharing their single unpaired electron as in the diagram. The
fact that one chlorine atom has been drawn with electrons
marked as crosses and the other as dots is simply to show
where all the electrons come from. 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. The formula of the
molecule is written Cl2. This formula shows not just the relative amount but the actual
number of atoms of different elements in a molecule of the compound

Hydrogen chloride

Now the sharing is between two different non metals. Once again
sharing takes place and a molecule is formed. The hydrogen has a
helium structure, and the chlorine an argon structure. The formula
for this substance is HCl.

Double and triple covalent bonds are formed when two or three pairs of electrons are
shared between the atoms rather than just one pair.

Some Simple Molecules Containing Double Bonds

Oxygen, O2
Two oxygen atoms can both achieve stable structures by sharing two pairs of electrons
as in the diagram.
The double bond is shown conventionally by two lines joining the atoms. Each line
represents one pair of shared electrons.

Carbon dioxide, CO2

Ethene, C2H4
Ethene has a double bond between the two carbon atoms.

Simple examples for the formation of triple bonds are the nitrogen molecule in which
the N atoms share three pairs of electrons, and the ethyne (acetylene) molecule with a
triple C-C share. (try to sketch them both).

The physical properties of molecular substances

Molecules are made of fixed numbers of atoms joined together by covalent bonds, and
can range from the very small (even down to single atoms, as in the noble gases) to the
very large (as in polymers, proteins or even DNA).
The covalent bonds holding the molecules together are very strong, but the forces
among the molecules are weaker than in the other cases as it has been stated. That
is why they are soluble in many solvents and show low melting points (easy to
separate). Physical properties are governed by the intermolecular forces - forces
attracting one molecule to its neighbours.

• Melting and boiling points Molecular substances tend to be gases, liquids or


low melting point solids, because the intermolecular forces of attraction are
comparatively weak. You don't have to break any covalent bonds in order to
melt or boil a molecular substance. The melting or boiling point will depend on
the strength of the intermolecular forces.
• 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.
• Solubility in organic solvents Molecular substances are often soluble in organic
solvents - which are molecular. Both the solute (the substance which is
dissolving) and the solvent are likely to have molecules attracted to each other
by weak intermolecular forces. Although these attractions will be disrupted
when they mix, they are replaced by similar ones between the two different sorts
of molecules.
• Electrical conductivity Molecular substances won't conduct electricity.
INTERMOLECULAR BONDING

Intermolecular attractions are attractions between one molecule and neighbouring


molecules. All molecules experience intermolecular attractions, because as we have
seen at the before, covalent bonds are most of the time polar bonds. The slightly
positive and the slightly negative parts of the molecules attract each other although in
some cases those attractions are very weak. Even in a gas like hydrogen, H 2, if you slow
the molecules down by cooling the gas, the attractions are large enough for the
molecules to stick together eventually to form a liquid and then a solid. These forces
are generally known as van der Waals forces

INTERMOLECULAR BONDING

Consider two water molecules coming close together. The δ+ hydrogen is so strongly
attracted to the lone pair that it is almost as if you were beginning to form a covalent
bond. It doesn't go that far, but the attraction is significantly stronger than an ordinary
dipole-dipole interaction. These relatively powerful intermolecular forces are described
as hydrogen bonds.

The molecules which have this extra bonding are:


Notice that in each of these molecules:

• The hydrogen is attached directly to one of the


most electronegative elements, causing the
hydrogen to acquire a significant amount of positive charge.
• Each of the elements to which the hydrogen is attached is not only significantly
negative, but also has at least one lone pair.

Hydrogen bonds have about a tenth of the strength of an average covalent bond, and are
being constantly broken and reformed in liquid water. If you liken the covalent bond
between the oxygen and hydrogen to a stable marriage, the hydrogen bond has "just
good friends" status. On the same scale, van der Waals attractions represent mere
passing acquaintances!

Hydrogen bonding in Other Compounds

Any molecule which has a hydrogen atom attached directly to an oxygen atom or a
nitrogen is capable of hydrogen bonding. Such molecules will always have higher
boiling points than similarly sized molecules which don't have an -O-H or an -N-H
group. The hydrogen bonding makes the molecules "stickier", and more heat is
necessary to separate them.

Ethanol, CH3CH2-O-H, and methoxymethane,


CH3-O-CH3, both have the same molecular
formula, C2H6O.
However, ethanol has a hydrogen atom attached
directly to an oxygen that has two lone pairs as in a
water molecule. Hydrogen bonding can occur between ethanol molecules.
The chart below shows the dramatic effect that the hydrogen bonding has on the
stickiness of the ethanol molecules:
ethanol (with hydrogen bonding) 78.5°C
methoxymethane (without hydrogen bonding) -24.8°C

When mixed with water, molecules with OH groupings will dissolve far more easily
than other covalent substances do. That is because both molecules can “interchange”
hydrogen bonds. Do you guess why glucose C6H12O6 with 6 OH groups dissolves so
easily in water and hexane C6H14 is almost absolutely insoluble?

GIANT COVALENT STRUCTURES

The so called gigantic covalent structures in which millions of millions of atoms are
bonded covalently deserve a separate paragraph. We don’t have a regular molecule in
this case but a giant structure. In fact the atoms form just one super-particle (if we
allow the term particle to be applied in this case) and dissolving or melting it would
require the breaking down of millions of chemical bonds.

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.

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 giant covalent structure of graphite


Graphite has a layer structure which is quite difficult to draw convincingly in three
dimensions. The diagrams below show 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.

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 free to wander throughout the whole sheet.
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.

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.
• 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.

Simple examples for the formation of triple bonds are the nitrogen molecule in which
the N atoms share three pairs of electrons, and the ethyne (acetylene) molecule with a
triple C-C share.

The chart next page sums up what has been previously explained
NB: SUBSTANCES SHOWING BOTH COVALENT AND IONIC BONDS
BEHAVE AS IONIC SUBSTANCES

Class Formed by Structure Melting Solubility Conducts Example


(scheme) point electricity
Soluble en
solvents
Covalent Molecules <300º C And not in Never Oil, petrol
water
(generally)
Macromolecules
Covalent Insoluble in Only Graphite, quartz
(macro) >1500º C any liquid graphite
conducts

THE SHAPE OF MOLECULES

The electron pair repulsion theory

The shape of a molecule or ion is governed by the arrangement of the outer shell’s
electron pairs around the central atom. All you need to do is to work out how many
electron pairs there are at the bonding level, and then arrange them to produce the
minimum amount of repulsion between them. You have to include both bonding pairs
and lone pairs.

How to work out the number of electron pairs

You can do this by drawing dots-and-crosses pictures.


 First you need to work out how many groups there are bonded around the central
atom.
 Now work out how many lone (non bonding) pairs of electrons there are. These
pairs will count as a group. If there are multiple bonds, the second or third
pairs of electrons forming the bond will not count
 Finally, work out the shape. Arrange the groups and lone electron pairs in space
to minimise repulsions. How this is done will become clear in the examples
which follow.
 Lone pairs being more “free to move” occupy more space and will push other
groups backwards so that the angle between them and other groups is slightly
wider.

Four electron pairs around the central atom

There are lots of examples of this. The simplest is methane, CH4.


Carbon is in group 4, and so has 4 outer electrons. It is forming 4
bonds to hydrogen atoms, adding another 4 electrons - 8 altogether,
in 4 pairs. Because it is forming 4 bonds, these must all be bonding pairs. Four electron
pairs arrange themselves in space in what is called a tetrahedral arrangement. A
tetrahedron is a regular triangularly-based pyramid. The carbon atom would be at the
centre and the hydrogen atoms at the four corners. All the bond angles are 109.5°.

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
hydrogen atoms is adding another electron to the nitrogen's outer
level, making a total of 8 electrons in 4 pairs. The electron pairs
arrange themselves in a tetrahedral fashion as in methane. But
because the nitrogen is only forming 3 bonds, one of the pairs
must be a lone pair. lone pairs occupy more space and will push other groups
backwards so that the angle between them and other groups is slightly wider.

Remember this:
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 hydrogen atoms 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.

THE SHAPE OF MOLECULES WITH THREE GROUPS AROUND THE


CENTRAL ATOM

The simple cases of this would be BF3 or BCl3.


Boron is in group 3, so starts off with 3 electrons. It is forming 3 bonds,
adding another 3 electrons. There is no charge, so the total is 6
electrons - in 3 pairs.
Because it is forming 3 bonds there can be no lone pairs. The 3 pairs arrange themselves
as far apart as possible. They all lie in one plane at 120° to each other. The arrangement
is called trigonal planar.

In the diagram, the other electrons on the fluorines have been left out because they are
irrelevant.

THE SHAPE OF MOLECULES WITH TWO GROUPS AROUND THE


CENTRAL ATOM

Two groups around the central atom

As we have already seen in carbon dioxide C atom forms two double bonds. As the
bonding pairs to the oxygen atoms will try to be as far as possible
from each other, they arrange themselves at 180° to each other. The molecule is
described as being linear.
HCN (hydrogen cyanide) belongs to this group
PROBLEMS

1- Carbon dioxide is a compound in which carbon forms double bonds to oxygen


(shares two pairs of electrons). Write the cross and dot diagram for carbon
dioxide. (Cross and dot : see the diagrams of Cl2, HCl and H2)

2- Write a cross-and-dot diagram for the ammonia molecule NH3

3- Silicon is an element that melts at 1.410 °C and a poor conductor.


a- What can you say about its structure? Explain
b- What can you predict about its solubility both in water and in organic
solvents? Explain.

4- The chart shows some properties of tour substances A, B, C and D.

Substance Melting Electric Solubility in Solubility in


point conductivity water solvents
Solid Melted
A 961 °C Good Good insoluble insoluble
B 1610 °C Poor Poor insoluble insoluble
C 776 °C Poor Good very soluble insoluble
D 37 °C Poor Poor insoluble soluble
Using the information in the text (see chart) decide which of them is:
a- Eicosane?
b- Silver?
c- Quartz?
d- Potassium chloride?
e- Should eicosane’s formula be C20H42 or rather SrO?

5- Explain the following facts


a- Graphite conducts electricity but diamond does not.
b- You can write with a graphite pencil.
c- Glucose C6H12O6 melts at 146 ºC and NaCl at 801
d- H2O is a liquid (boils at 100 ºC) and H2S is a gas (boils at -61 ºC)

6- The following table shows the melting point (in K) of the elements of the 3rd
period. Explain the trend.

7- Which factors affect the solubility of molecular substances in water?

8- Which of each pair can be predicted to have a higher solubility in water?


a- CH3-CH2-O-CH2-CH3 or CH3-CH2-CH2-CH2-OH

b- CH3-CH2-CH2-CH2-CH3 or CH3-CH2-O-CH2-CH3