Calderside Academy

CfE Higher Chemistry

Unit 1: Chemical Changes &

Structure

Sub-Unit (C): Structure and Bonding

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The Formation of Bonds

• Bonds are electrostatic forces (attractions between positive and

negative charges) which hold atoms together.
• Atoms form bonds to become more stable - by losing, gaining or
sharing electrons.
• The type of bond formed in a substance depends on the elements
involved and their position in the periodic table.

Metallic Bonding

• Metallic bonding occurs between the atoms of metal elements.

• Metals have little attraction for their outer electrons.
• These electrons are given away by the atoms and free to move so
are delocalised.

• The atoms now become positive ions.

• Electrons can move randomly between these partially filled outer
shells creating what is called a ‘sea’ or ‘cloud’ of electrons around
positive metal ions.
• The metallic bond is the electrostatic force between positively
charged ions and delocalised outer electrons.
• The metallic bond is very strong, therefore, metals tend to have
high melting and boiling points.

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Ionic Bonding

• Ionic bonds are formed usually between metal and non-metal

elements with a large difference in electronegativity.
• The non-metal element with the high electronegativity gains the
electrons to form a negative ion:
•
e.g. Cl + e- Cl-

• The metal element with the low electronegativity loses electrons to

form a positive ion:

e.g. Na Na+ + e-

• Both the positive and negative ion will have the same electron
arrangement as a noble gas.
• Ionic bonding is the electrostatic force of attraction between
positively and negatively charged ions.
• The forces of attraction between the oppositely charged ions
results in the formation of a regular structure called an ionic
crystal lattice.
E.g. Sodium chloride

Strong Ionic Bond

• The formula of sodium chloride is Na+Cl- showing that the ratio of

Na+ to Cl- ions in the crystal lattice is 1 to 1.
• The melting and boiling points of ionic compounds tend to be high,
since ionic bonds are very strong and require a lot of energy to be
broken.

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Ionic Lattice Structures
• All ionic compounds are solids at
room temp so have high melting
and boiling points.
• This is because the ionic bonds
holding the lattice together are
strong and a lot of energy is
required to break them.
• The size of the ions will effect
the strength of the ionic bond
and how the ions pack together.
E.g. NaF - m.p 1000oC, NaI - 660oC.
• Ionic compounds conduct electricity when dissolved in water or
when molten as the ions are free to move.
• Electrolysis of an ionic solution or melt causes a chemical change at
the electrodes.
• They do not conduct when solid as the ions are ‘locked in the lattice
and cannot move to carry the current.

Covalent Bonding

• Covalent bonding occurs usually between non-metal elements.

• A covalent bond is the electrostatic force of attraction between
positively charged nuclei and negatively charged outer electrons.

• Covalent substances can be made up of giant covalent network

structures or discrete molecules,

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 • Giant Covalent Network Structures e.g. Silicon dioxide

• Covalent networks have very high melting and boiling points as

many strong covalent bonds need to be broken in order to change
state.
• They can also be very hard.
E.g. Silicon Dioxide or Silicon Carbide (SiC) – carborundum, similar
structure to diamond

Covalent
Tetrahedral Bond = Carbon
shape
= Silicon

The 4 carbon atoms are

available to bond with another 4
silicon atoms resulting in a
covalent network.

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 • It has a high melting point (2700oC)
• SiC is used as an abrasive since it is very hard and tough.
• Covalent network structures are usually non-conductors of
electricity as they have no free moving charged particles.

Small Covalent Molecular Structures e.g. carbon dioxide

• These are made up of separate or “discrete” molecules.

• There are weak forces in between covalent molecules.
• Only these weak forces need to be broken for melting and boiling.
• Therefore, covalent molecular substances usually have low melting
and boiling points as there is little attraction between their
molecules.
E.g. Carbon dioxide CO2: m.pt -57oC

More on Covalent Molecules – Non polar and Polar Bonding

• In non-metal elements, e.g the diatomic elements, there is an

equal sharing of electrons between atoms as they have the same
electronegativity.
• e.g. Fluorine

F – F
4.0 4.0
• This is called pure covalent bonding or non-polar covalent
bonding.

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 • Polar covalent bonding is similar to pure covalent bonding but is
formed in compounds between different non-metal elements as
they have different electronegativities.
• In polar covalent bonds there is an uneven share of electrons.
• The atom which has the higher electronegativity has a stronger
attraction for the electrons. This atom is given the
symbol (delta negative), which means slightly negative.
The atom which has the weaker attraction for the electrons is
given the symbol (delta positive), which means slightly positive.
2.2
e.g. Hydrogen Fluoride Water 3.5

δ+
H - Fδ- 2.2
2.2 4.0

Ethanol Propanone
3.5

3.5 2.2 2.5

Bonding Continuum – looking at Ionic, Polar Covalent and Pure

Covalent

• The greater the difference in electronegativity between two

elements, the less likely they are to share electrons, i.e. form
covalent bonds.
• This means that the smaller the difference in electronegativity,
the more likely a compound will be covalent and conversely, the
greater the difference in electronegativity, the more likely a
compound will be ionic.

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• Pure Covalent • Polar Covalent • Ionic
• Same • Small difference • Large difference
electronegativity in in
• Electrons equally electronegativity electronegativity
shared • Electrons shared • Electrons
• Atoms have no unequally completely
charges • Atoms have transferred from
partial charges metal to non-
metal
• Full ionic charges

More on Polar Molecules and Permanent Dipoles

• A polar molecule is one which has permanently charged ends

(permanent dipole).
• Not all substances with polar covalent bonds will be ‘polar
molecules’.
• If there is a symmetrical arrangement of polar bonds, the polarity
cancels out over the molecule as a whole.
• The polarity of the bonds and the shape of the molecule has to be
taken into account
e.g. Carbon dioxide: CO2 – this has a linear shape

• There is no overall positive and negative end to the molecule, so

carbon dioxide would be described as a non-polar molecule.

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 Tetrachloromethane: CCl4– this has a tetrahedral shape

• There is no overall positive and negative end to the molecule, so

tetrachloromethane would be described as a non-polar molecule.
• If the bonds are not symmetrical, the molecule has an overall
polarity and is said to have a permanent dipole, i.e. each end has a
different charge.
• i.e The spatial arrangement of polar covalent bonds can result in a
molecule being polar.
e.g Water H2O

Chloromethane CH3Cl

Slightly negative end

Slightly positive end

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Summary of Non-Polar / Polar Molecules

Polar
molecule

Since there is
an overall +ve
and –ve end.

Non Polar
Molecule

Since there
aren’t any
polar bonds.

Non – Polar
Since the
polar bonds
cancel out –
there is no
+ve and –ve
end

Bonding Between Covalent Molecules

• There are attractive forces between non-polar covalent and

polar covalent molecules which can affect their properties.
• These attractions between molecules are called Van der Waals or
intermolecular forces (or bonds).

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There are 3 types of Van der Waals forces:

1. London Dispersion Forces

2. Dipole-dipole Attractions (permanent dipole-permanent
dipole)
3. Hydrogen Bonds are a special type of dipole-dipole
attraction which is particularly strong.

1. London Dispersion Forces

• This is the weakest form of intermolecular bonding and it exists

between all atoms and covalent molecules.
• London Dispersion forces are caused by uneven distributions of
electrons in atoms or molecules

• This results in a slightly negative ( ) and slightly positive

charge on either side of the atom or molecule.
• A temporary dipole has been established.
• This charge can then induce an opposite charge in a neighbouring
atom or molecule called an induced dipole.
• The oppositely charged ends of the atom/molecule attract each
other creating London Dispersion Forces.

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 • The relative strength of the force depends on the size of the
atoms or molecules and the number of electrons there are in the
atom or molecule.
• London Dispersion forces increase with increasing atomic and
molecular size because of the increasing numbers of electrons
within the atom or molecule.

Strength of London Dispersion forces and

Electrons
Electrons and BPs M S
o T
10 electrons r R
e O
-164 oC
N
G
18 electrons e E
l R
- 89 oC e
c F
26 electrons t O
r
- 42 oC o R
n C
34 electrons s E
- 1 oC S

10 of 43 © Boardworks Ltd 2009

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2. Permanent Dipole-Permanent Dipole Attractions

• A polar molecule is one which has permanently charged ends

(permanent dipole).
• Polar-Polar attractions (permanent dipole-permanent dipole) are
the intermolecular force of attraction between the oppositely
charged ends of the polar molecules.

• These forces of attraction between polar molecules are in addition

to London Dispersion Forces. i.e. polar molecules will also have
London Dispersion Forces because the electrons will move around
creating temporary dipoles.
• However, permanent dipole-permanent dipole forces are stronger,
so they are the more significant force between polar molecules.

Effect of permanent dipole-permanent dipole attractions

• The effect of permanent dipole-permanent dipole forces can be

seen if a non-polar and polar molecule are compared.
• To make it a fair comparison, they should have the same molecular
mass.

• E.g. Propanone and Butane

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 Propanone Butane
Formula Mass 58 58
Structure
H O H H H H H
H C C C H H C C C C H
H H H H H
H

Type of molecule Polar Non-polar

Intermolecular London + London
forces permanent dipole-
permanent dipole

Boiling Point 56oC 0oC

• Polar molecules have higher boiling points than non-polar molecules

of a similar mass due to the permanent dipole-permanent dipole
interactions.
• Permanent dipole-permanent dipole interactions are stronger than
London Dispersion forces.

3. Hydrogen Bonding

• Hydrogen bonds are permanent dipole-permanent dipole

interactions found between molecules which contain highly polar
bonds.
• They are usually found in molecules where hydrogen is bonded to
very electronegative atoms like fluorine, oxygen or nitrogen (+
chlorine).

e.g. Water – where hydrogen is bonded to oxygen

Hydrogen bond
( in between the
water molecules)

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 • Other examples of compounds which would have hydrogen bonding
in between the molecules include:
 Ammonia: NH3 (hydrogen is bonded to nitrogen)
 Alkanoic acids (hydrogen is bonded to oxygen)
 Alkanols (hydrogen is bonded to oxygen)
 Hydrogen fluoride (hydrogen is bonded to fluorine)
• Hydrogen bonds are stronger than permanent dipole-permanent
dipole attractions and London Dispersion Forces but are weaker
than covalent bonds.

Effects of Hydrogen Bonding

• When Hydrogen bonds are present, the compound will have a much
higher melting point (m.pt) and boiling point (b.pt) than other
compounds of similar molecular size.

E.g. Ethanol (has hydrogen bonding) Ether ( does not

have hydrogen bonding)

B.P. = 79oC B.P. = 35oC

• Alcohols will always have higher melting and boiling points than
similar mass alkanes, since the alcohol will have hydrogen bonding.
• Water has a much higher b.p. than similar compounds containing
hydrogen
• Hydrogen bonding explains why water, HF and NH3 have a b.p.
higher than expected.
• E.g. HF b.p. 19 oC
• Whereas: HBr –68 oC and HI –35 oC
• See the graph on next page

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Other effects of Hydrogen Bonding

Viscosity
1.Substance diethyl ether ethanol water glycerol
2.Molecular mass 74 46 18 92
3.Structural
Formula

4. No of –OH groups 0 1 2 3

• Viscosity is not only related to molecular mass but also to

Hydrogen bonding.
• The –OH groups allow hydrogen bonding between the molecules
and this increases the viscosity.

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Miscibility

• Miscible liquids mix thoroughly without any visible boundary

between them, e.g. ethanol and water would be described as
miscible but water and oil are immiscible as the oil forms a visible
layer on water.
• Hydrogen bonding aids miscibility (ethanol and water both contain
hydrogen bonds).
• NB very strongly polar liquids (without Hydrogen bonding) can also
be miscible with water.

Hydrogen Bonding and the Properties of Water

Hydrogen Bonds

• Each water molecule is surrounded by 4 hydrogen bonds

• Water has a high surface tension.
• The molecules on the surface have hydrogen bonds pulling the
surface molecules closer together.
• Why do pipes burst when water freezes and why does ice float
on water?
• As matter is cooled, it normally contracts and becomes more
dense.
• However, as water freezes it expands (at
about 4oC) because the strong hydrogen
bonds between the molecules force them
into an open lattice structure.
• This makes the solid ice less dense (takes
more space) than the liquid so ice floats on
water and pipes burst when water freezes.

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Summary of Bonding and Properties in Compounds
• By considering the polarity and number of electrons present in
molecules, it is possible to make predictions of the strength of the
intermolecular forces.
Melting and Boiling Points
• Compounds with polar molecules may have slightly higher m.pts
and b.pts than non-polar molecules due to permanent dipole-
permanent dipole attractions.
e.g. Iodine chloride Bromine
I - Cl Br – Br
o
b.pt 97 C b.pt 59oC

• When hydrogen bonds are present, the compounds will have a much
higher m.pt and b.pt than other compounds of similar molecular
size as more energy is required to separate the molecules. (see
earlier note on hydrogen bonding – ethanol and ether)

Solubility and Solutions

• Ionic lattices and polar covalent molecular compounds tend to be:
 Soluble in water and other polar solvents, due to the
attraction between the opposite charges.
 Insoluble in non-polar solvents, as there is no attraction
between the ions and the solvent molecules.
e.g. when ionic compounds dissolve in water the lattice is broken
Water δ- δ-
molecule
δ+ δ+ δ+ δ+
Ionic
+ - + - + - lattice

δ+ δ-
δ+
δ+ δ+
Hydrated δ+
δ+ δ- + δ-
δ+ - δ+
δ- ions δ-
δ+ δ + δ-
δ+ δ+
-ve ions attracted to +ve
+ve ions attracted to –ve
ends of water molecule
ends of water molecule
up and the ions are surrounded by water molecules

• Non-polar covalent substances tend to be:

 Soluble in non-polar solvents like carbon tetrachloride or hexane.
 Insoluble in water and other polar solvents as there are no
charged ends to be attracted.

Like dissolves in like

Page 18 of 24
 Summary of Bonding and Properties in Compounds Table

Bonding Structure Type Electro Melting and Solubility Conductivity

of negativi boiling pts.
eleme ty
nts differen
ce
Ionic Closely packed ions Metals Large High melting and Generally NO when solid
with positive ions and boiling points due soluble in due to ions
having a strong non to the strong polar being unable to
attraction for the metals attraction between solvents move.
negative ions in a 3D usually closely packed such as YES when
lattice structure. . positive and water molten or
e.g. sodium chloride negative ions. dissolved
because ions
can move.
Covalent Giant network lattice Non- High melting and insoluble NO
network
structure with atoms metals boiling points due
inter-linked to each to the strong
other in 3 dimensions covalent bonds
by strong covalent between atoms
bonds. e.g. silicon having to be
dioxide, broken.
silicon carbide.
Covalent Individual(discrete) Non- Small or Low melting and Insoluble in
discrete
NO
molecular
molecules with weak metals no boiling points due water but
non- London Dispersion difference to only weak soluble in
polar forces between the London Dispersion non-polar
molecules. Molecules forces between liquids such
tend to be molecules having as pentane
symmetrical. to be broken. or white
spirit
Covalent Individual(discrete) Non- Moderate Low melting and Soluble in NO
discrete difference
molecular molecules with weak metals boiling points(but water and
polar London Dispersion (0.5 to higher than other polar
forces and dipole to 1.3) expected- liquids e.g.
dipole attractions anomolous) due to ethanol
between the the dipole to
molecules. Molecules dipole attractions
tend to be non- or hydrogen bonds
symmetrical. If between
hydrogen is involved in molecules having
the dipoles then to be broken.
hydrogen bonding is
present as well as the
other van der Waals’s
forces.

Page 19 of 24
Bonding and Properties of Elements 1-20

Monatomic Elements - Noble Gases

Bonding
• All consist of single, unbonded atoms.
• Only have London Dispersion forces between the atoms.

Properties
• Low densities, m.pts and b.pt.s
• B.pts increase as the size of the atom increases.
• This happens because the London Dispersion forces increase due
to more electrons being present in the atom or molecule.

b.p / oC

Covalent Molecular Elements (in 1-20)

• All consist of discrete molecules of
varying size.
• Fairly low m.pts, b.pts and
C
densities.
• Non-conductors of electricity.
• Diatomic elements – H2, N2 , O2 , F2 ,
Cl2

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 • As the size of the halogen atom increases, the number of
electrons increases, so does the strength of the London
dispersion forces.

200
160
120
80
40
0
--40
b.p./oC --80
--120
-160
0

F Cl Br I
Phosphorus – P4 is a solid covalent molecule

Sulphur - S8 is a solid covalent molecule

• Phosphorus and sulphur have higher m.pts. because there are

stronger London Dispersion forces between larger molecules.
• This means they are solid at room temperature.

Page 21 of 24
 Fullerenes (Carbon)

• Buckminster fullerene C60 (Bucky Balls) discovered in the 1980’s

Nanotubes

• Due to the large molecules , fullerenes have stronger dispersion

forces between their molecules than smaller
molecules.
NB – they are molecules not covalent networks

Covalent Network Elements (in 1-20)

• Giant network structures containing millions

of atoms.
• E.g. Carbon exists in 2 main forms…

Diamond

4 bonds per carbon atom –

tetrahedral structure.
Non-conductor of electricity
as no free electrons.

• Hardest natural substance as

many strong bonds to break so used
for drills, cutting tools, etc.

Page 22 of 24
 Graphite

• 3 bonds per carbon atom – layered

structure with London dispersion forces
between the layers

• Conductor of electricity due to

delocalised electrons between the layers – used
in electrodes.

• Very soft – the layers break away easily due to weak

dispersion forces so good as a lubricant and for drawing
(pencils).

Metallic elements (Revision of Nat 5)

• All have metallic lattice structure
• Solids (except Hg) with high densities, m.pts and
b.pts due to the closely packed lattice structure
with lots of bonds to break.
• M.pts are relatively low compared to the B.Pts as
when a metal is molten the metallic bond is still
present.
• B.pts are much higher as you need to break the metallic bonds
throughout the metal lattice.

Positive nucleus (core)

Delocalised electrons

Metal b.p.’s are dependent on

(i) How many electrons are in the outer shell
(ii) How many electron shells there are.

• In a period, the greater the number of electrons in the outer shell

the stronger the metallic bond.
• So the melting point of Al>Mg>Na
• Conductors of electricity when solid or liquid due to delocalised
outer electrons which are free to move.

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 Summary - Bonding, Structure and Properties of the Elements in the
Periodic Table.

Area Bonding Structure Type of Conductivity Melting and boiling

elements pts.
A Metallic Closely packed atoms Metals Can conduct when High melting and
with positive nuclei solid or liquid due to boiling points due to
having a strong Li, Be, de-localised the strong attraction
attraction for the Na, Mg, electrons being able between closely
electrons of Al, K, Ca to move from atom to packed nuclei and
neighbouring atoms. The atom. electrons of
electrons are de- surrounding atoms
localised and can move
from atom to atom.
B Covalent Giant network lattice Non- Non-conductors but High melting and
network structure with atoms metals the exception is boiling points due to
inter-linked to each carbon in the form of the strong covalent
other in 3 dimensions. B, C graphite with a 2D bonds between
However carbon in the (diamond lattice structure and atoms having to be
form of graphite has a 2- and delocalised broken.
dimensional structure, graphite), electrons between
Si layers.
C Covalent Individual(discrete) Non- Non-conductors. Low melting and
discrete molecules. The elements metals boiling points due to
molecular ending in –gen and only weak London
-ine are diatomic H2, N2, Dispersion forces
molecules O2, F2, between molecules
Phosphorus is A Cl2, Br2, having to be broken.
tetraatomic molecule(4 P4, S8
atoms) and sulphur is an
octatomic molecule (8 [and
atoms). C60(fullere
Carbon can exist as a ne)]
large molecule called
Fullerene (C60)
Monatomic Single atoms NOT Non- Non-conductors but Very low melting
D
gases bonded to any other metals emit different colours and boiling points
atoms by strong bonds. (Noble when electricity is due to only weak
Very weak London gases) passed through them. London dispersion
dispersion forces exist. forces between
He, Ne, atoms having to be
Ar, Kr broken.

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