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Structure, properties and shapes of substances

All substances either are simple molecules, or have a giant structure. In this topic we will
consider how the type of bonding and forces between atoms, ions and molecules gives rise
to different physical properties, including the shapes and arrangements of atoms and ions
within substances.
Properties of simple molecules
Many substances, especially organic substances, consist of individual molecules with
strong covalent bonds holding the atoms together within the molecule and weak
intermolecular forces holding one molecule to another. To change the state of such
substances from solid to liquid to gas we have to overcome the forces that hold the
molecules to one another, but we do not break any of the covalent bonds the molecules
are identical regardless of their physical state.
Characteristic
Bonding
Boiling and melting points
Electrical conductivity
Solubility

Simple Molecular Structure


Covalent
Low Reason: only weak intermolecular forces need to be overcome, which
requires relatively little energy.
Not in any state Reason: No ions or free electrons to act as charge carriers
Often dissolve in non-polar solvents (e.g. hydrocarbons)

Properties of giant structures


We need to be able to distinguish between the giant structures (and the types of bonding in
them), and their characteristic properties. To change the state of a giant structure from
solid to liquid to gas, the strong bonds between the atoms or ions in the structure have to
be broken.
Bonding
Boiling and
melting points

Electrical
conductivity

Solubility

Giant Ionic Lattice


Ionic
High
Reason: strong ionic
bonds throughout the
lattice have to be broken,
which requires a lot of
energy.
Solid: No
Molten or in solution: Yes
Reason: Ions in solid are
fixed in lattice, but ions in
solution/liquid are mobile
and can therefore act as
charge carriers

Often dissolve in polar


solvents (e.g. water)

Giant Covalent Lattice


Covalent
High
Reason: strong covalent
bonds throughout the lattice
have to be broken, which
requires a lot of energy.

Giant Metallic Lattice


Metallic
High
Reason: strong metallic
bonds throughout the lattice
have to be broken, which
requires a lot of energy.

Not in any state


Reason: No ions or free
electrons to act as charge
carriers

Yes
Sea of delocalized electrons
are mobile and act as charge
carriers

EXCEPT
Graphite has one delocalized
electron per C atom which is
free to act as charge carrier
Insoluble

Insoluble

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Case Studies in Bonding and Structure


i) Diamond a typical giant covalent lattice
In diamond each carbon atom is covalently bonded to four
other carbon atoms in a tetrahedral arrangement.
Since all four outer shell electrons in carbon are used for
bonding there are no charge carriers in diamond, so it does not
conduct electricity.
Diamond sublimes at an extremely high temperature of
5,530C. This, the extreme strength of the substance, and its
lack of solubility in any solvents are all due to the very strong
covalent bonds throughout the lattice. These must be broken,
requiring a lot of energy, before the structure will melt, break or
dissolve .

The second element in Group 4, silicon, has the same giant


3D structure. Silicon has high melting and boiling points of
1414C and 3265C respectively, for the same reasons as
diamond. It is strong strong and very brittle, and is
a semiconductor, having electrical conductivity somewhere
between that of metals and non-metals.

Silicon

ii) Graphite an unusual giant covalent lattice


In graphite each carbon atom is covalently bonded to three
others forming a hexagonal layer structure with 120 bond
angles. Each layer has further layers above and below.
The one remaining electron in the outer shell of each carbon
atom is not used in bonding. This becomes delocalized and
can move throughout the lattice carrying electrical charge, so
graphite conducts electricity like a metal even though it is not
a metal.

Graphite is a soft substance. The layers are held one to another by weak Van der Waals
forces, which means that the layers can easily slide over each other making graphite
slippery and good for use as a lubricant. Pencils leave their marks on paper because the
graphite 'lead' in the pencil leaves layers of graphite stuck to the paper.

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Graphite has a very high melting point (and boiling point) and is insoluble. To melt or
dissolve graphite would require the layers to be broken down, and this means large
numbers of very strong covalent bonds have to be broken requiring lots of energy.
iii) Graphene
Graphene is a two-dimensional material. Each carbon
atom in graphene is covalently bonded to 3
neighbouring atoms. Each atom has four outer shell
electrons. Three of these are involved in single covalent
bonds to adjacent carbon atoms, and a fourth electron
from each atom is delocalised and free to move
throughout a conjugated network that extends
throughout the lattice. This arrangement means that
carbon-carbon bonds in graphene are extremely strong.
Thanks to this structure, graphene has some unusual properties:
Huge surface area to weight ratio, up to 2630 m 2/g
High electrical conductivity
Exceptionally stiff: Young's modulus about 1 TPa
Strong - fracture strength approximately 130 GPa
The highest thermal conductivity of all known materials
These unique properties mean that graphene could prove valuable in many application
areas. Some examples include:
Transparent conductive films, e.g. for touchscreen displays
Chemical, biological and mechanical sensors, e.g. for detecting nerve agents,
diseases and strain
Additives for composite materials, e.g., for aircraft, car tyres and prosthetics
Inert coatings for protecting materials from harsh environments
The first thorough investigations of graphene properties were reported in 2004, based on
material produced by micromechanical exfoliation, also known as the 'sticky tape' method.
Despite producing high-quality material, this approach is laborious and is only capable of
providing small-area samples. There are now many scalable methods for graphene
production e.g. chemical vapour deposition (CVD) that have been developed for the
industrial production of graphene.
iv) Sodium Chloride a typical giant ionic lattice
Sodium chloride has a regular 3D lattice structure in
which sodium ions and chloride ions alternate. The
electrostatic attraction between the ions is nondirectional so every sodium ion attracts chloride ions
all around it above, below and on each side.
Similarly each chloride ion attracts six sodium ions.

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The formula NaCl does not indicate that sodium and chloride ions "go around in pairs", but
that there is a ratio of one sodium ion for every chloride ion in the lattice it is an empirical
formula.
Because the electrostatic attractions between the oppositely-charged ions run throughout
the lattice, sodium chloride is hard and brittle. These attractions are strong, and must be
overcome before the lattice can be broken down to form a liquid, which requires a lot of
energy. Sodium chloride thus has a high melting and boiling point.
Sodium chloride dissolves in polar solvents such as water. The energy needed to break
down the lattice so the ions can be in solution is offset by the energy released when bonds
are formed between the ions and the water molecules.
Once in solution (or melted), the sodium and chloride ions are free to move around. They
are charge carriers, so in these states sodium chloride is able to conduct electricity. When
solid the ions are locked in place in the lattice and although they are charged, they are
unable to move and carry the electrical charge. This means that solid sodium chloride does
not conduct electricity.
v) Iodine a simple molecular lattice
Iodine has a simple molecular structure. Iodine atoms
are bonded in pairs by covalent bonds, so the formula
is I2.
In the solid state, the weak intermolecular forces
between the iodine molecules hold them together in a
3D lattice structure. This is a simple molecular lattice.
There are no delocalized electrons in iodine, and no
ions, so there are no charge carriers and iodine cannot
conduct electricity.
Iodine has the unusual property that when heated it
goes directly from being solid to being a gas. This
property is called sublimation. It does this at a low
temperature (114C) because only weak intermolecular forces hold the iodine molecules
together and these take little energy to overcome. Iodine vapour still consists of I 2
molecules no bonds have been broken in turning iodine into a gas.
Being non-polar iodine dissolves readily in most non-polar organic solvents such as hexane
or trichloromethane. It is almost completely insoluble in water because to dissolve in water
the hydrogen bonds between the water molecules have to be broken, and there are no new
bonds formed between iodine and the water so the energy cannot be offset by any
released energy.

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vi) Water and Ice


In water there are two lone pairs on the - O atom, and two
+ H atoms so each water molecule can form two hydrogen
bonds making networks and lattices of water molecules are
possible.
Ice consists water molecules held in a 3D lattice by a
network of hydrogen bonds. The two lone pairs on the
oxygen atom in each water molecule form hydrogen bonds
to the hydrogen atoms of two other water molecules forming
a 3D network of hydrogen bonds.
The hydrogen bonds do not take anywhere as much energy
to overcome as covalent bonds would, so the temperature required to break down the
simple molecular lattice in ice is much lower than the temperature required to melt giant
covalent lattices.
Water has a number of unusual properties which arise from the hydrogen bonding between
water molecules:
- anomalously high boiling point and melting point compared to similar simple
molecules without hydrogen bonding
- ice floats (solids are usually more dense than same substance in liquid state)
- surface tension (needles float, pond skaters walk on it)
The strength of the hydrogen bonds which need to be overcome in ice before it can be
melted give rise to the unusually high melting point. In the liquid state water molecules
collect in hydrogen-bonded groups (clumps). These must be broken up and separated
before water can be boiled and water vapour formed. The energy required to do this gives
rise to the unusually high boiling point.
In ice, each hydrogen atom is covalently bonded to one oxygen atom and hydrogen bonded
to another. The hydrogen bonds (0.159nm) are LONGER than the covalent bonds
(0.096nm), which spaces out the molecules in the ice lattice, making them typically further
apart than in water ice has a more open structure than water, so has a lower density
(which is unusual for a solid). This is why ice floats, and why it expands when it freezes.
At the surface, the water molecules form a 2-D network of hydrogen bonded water
molecules this is the origin of surface tension, explaining why a water droplet can stand
up on a flat surface it is difficult to penetrate the surface because that requires breaking
the network of hydrogen bonds. Also explains why pond-skaters can walk on water.

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Shapes of Molecules
There are a variety of basic shapes and bond angles:
LINEAR

NON-LINEAR (BENT)
e.g. 104.5 in H2O

TRIGONAL PLANAR

PYRAMIDAL

e.g. 107 in NH3

TRIGONAL BIPYRAMIDAL

TETRAHEDRAL

OCTAHEDRAL

The shapes of real molecules are determined by the outer shell electrons of the atoms
which are bonded together. A dot-cross diagram is the essential starting point for working
out shape. What we need to know is how many lone pairs and how many bonding pairs
surround the central atom in each molecule.
Valence Shell Electron Pair Repulsion theory (VSEPR)
The shapes of molecules are caused by the mutual repulsion electron pairs (bonding pairs
and lone pairs). As a result of this repulsion the bonds and lone pairs arrange themselves
as far apart as possible.
Lone pairs repel more strongly than bonding pairs, so a lone pair will push bonding pairs
away from itself, closing the bond angle between bonding pairs by about 2.5 per lone pair.
To determine the shape of a molecule, we have to work out the spatial arrangement of the
lone pairs and bonding pairs and the bond angles (angles between the bonding pairs).
Then we match the positions of the atoms to the various shapes, above.
We will find that particular shapes correspond to particular numbers of lone pairs and
bonding pairs.

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BeCl2
Central Be atom:

bonds = 2
lone pairs = 0

The two bonding pairs repel as far as possible from one another, giving a bond angle of
180. The lone pairs on Cl have no effect on the shape. The molecule is LINEAR.

CO2

Central C atom:

bonds 2 (doubles)
lone pairs = 0

The fact that the bonds are double has no effect on shape the two double bonds repel
each other as far as possible. The bond angle is 180and the molecule is LINEAR.
For the purpose of working out shapes (only) we dont consider double or triple bonds any
differently than single bonds.

BF3

Central B atom:

bonds = 3
lone pairs = 0

There are 3 bonds arranging themselves as far away as


possible. This leads to 120 bond angles in a planar
molecule. The shape is TRIGONAL PLANAR.

CH4

Central C atom:

bonds = 4
lone pairs = 0

There are 4 bonds arranging themselves as far


away as possible. This leads to a 109.5 bond angle
and a TETRAHEDAL shape.

PF5

Central P atom:

bonds = 5
lone pairs = 0

There are 5 bonds arranging themselves as far


apart as possible. Three lie in a plane, with 120
bond angles and the other two are at 90 to this
plane. The shape is TRIGONAL BIPYRAMIDAL

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SF6

Central S atom:

bonds = 6
lone pairs = 0

There are 6 bonds arranging themselves as far apart


as possible. Each lies at 90 to the others.
The shape is OCTAHEDRAL.

NF3

Central N atom:

bonds = 3
lone pairs = 1

There are four bonds/lone pairs repelling each other, so the arrangement around the
central N atom is tetrahedral but the lone pair repels the bonding pairs more than the
bonding pairs repel each other so the bond angle between the N-F bonds is reduced from
109.5 to 107 degrees. The positions of the atoms match the PYRAMIDAL shape.

H2S

Central S atom:

bonds = 2
lone pairs = 2

There are four bonds/lone pairs repelling each other, so the arrangement around the
central S atom is tetrahedral but the two lone pairs reduce the bond angle by 2.5 each, so
the H-S bond angle is 104.5. The positions of the atoms match the NON-LINEAR or
BENT shape.
NH4+

Central N atom:

bonds = 4
lone pairs =0

It doesnt matter that its an ion shapes work just the same. It doesnt matter that one bond
is dative. Covalent and dative bonds are identical once they are formed. The central N has
four bonds and no lone pairs, so the shape is TETRAHEDRAL and the bond angle 109.5.

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Check your understanding:


Predict the shapes and bond angles in:
i)
sulphur dichloride (SCl2)
ii)
silane (SiH4)
iii)
carbon disulphide (CS2)
iv)

sulphur trioxide

v)

ozone

Shapes of more complicated molecules


Most molecules don't consist of one central atom with a few other atoms bonded to it. In a
larger molecule, we need to consider each atom that has more than one other atom
bonded to it. While we can't specify the overall shape of the molecule we can specify the
shape around at each of these atoms but considering lone pairs and bonding pairs in the
usual way.
For example, consider the aldehyde, ethanal:

CH3CHO

We could draw a dot-cross diagram for this molecule, or just


consider the valence shell electrons of the bonded atoms, to
determine that the C of the CH3 has four bonding pairs and no
lone pairs. The shape around this carbon is therefore
tetrahedral and the bond angles will be 109.5. The other
carbon, in the CHO group, has three bonding pairs (one of which is a double bond, but for
shapes we treat these the same as single bonds) and no lone pairs. The shape around this
carbon is therefore trigonal planar and the bond angles will be 120.

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Answers to 'Check your Understanding' questions simple molecules


Predict the shapes of:
i)
sulphur dichloride (SCl2)
ii)
silane (SiH4)
iii)
carbon disulphide (CS2)
iv)
sulphur trioxide (SO3)
v)
ozone (O3)

non linear
tetrahedral
linear
trigonal planar
non-linear

104.5
109.5
180
120
117.5

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