Bonding and Structure PDF
Bonding and Structure PDF
Bonding and Structure PDF
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Topic 3A: Ionic Bonding
Physical evidence
Ionic substances are brittle and they are unable to conduct electricity in solid form. However,
when ionic substances are molten or aqueous the ions are free to move and so can conduct
electricity in these states. These properties, in comparison to metals which are malleable and
conduct electricity when solid, can be explained by the model of oppositely charged ions in a
giant ionic lattice.
Electron density maps therefore allow chemists to work out the type of bonding present, and
also the distance between ions in an ionic lattice.
Ion migration
In electrolysis, ions are free to move and ions move to the oppositely charged electrode -
where they gain or lose electrons to form atoms. This ion migration can be explained by the
electrostatic attraction that results between oppositely charged species.
Ionic bonding
Ionic bonding occurs between a metal and a non-metal. Electrons are transferred from the
metal to the non-metal to achieve full outer shells, according to the octet rule. The octet rule
states that atoms will often react to form a full outer shell containing 8 electrons.
When the electrons are transferred, it creates charged particles called ions. Oppositely
charged ions attract through strong electrostatic forces to form a giant ionic lattice.
Positive ions are formed when an atom loses at least one electron.
Negative ions are formed when an atom gains at least one electron.
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Example:
Sodium chloride is an ionic compound formed from Na+ and Cl- ions. Sodium loses an
electron and chlorine gains an electron to produce ions with a full outer electron shell.
The ions are then attracted to one another, forming an ionic lattice:
Larger ions that have a greater ionic radius will have a weaker attraction to the oppositely
charged ion because the attractive forces have to act over a greater distance.
The red dot clearly shows the transferred electron from sodium to chloride to produce
two ions with full outer electron shells.
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Ionic radii
Down a group
As you move down a group, the number of electron shells increases, and therefore the ionic
radius increases.
Across a period
Groups 1 and 2: The atoms in these groups lose electrons to form positive ions. As you go
across the period, the magnitude of the positive charge increases for the same amount of
electron shielding. This means there is a greater electrostatic attraction which pulls the outer
electrons more tightly in towards the nucleus, decreasing the ionic radius.
The ions formed are said to be isoelectronic as they have the same electronic configuration
(but lose different numbers of electrons to form this configuration).
Example: Ne, Na+ and Mg2+ all have the following electron configuration: 1s22s22p6.
Groups 6, 7 and 8: The atoms in these groups gain electrons to form negative ions. As you go
across the period the additional proton makes less of a difference, so the only change is a
slight decrease in ionic radius.
Example: N3-, O2- and F- all have the following electron configuration: 1s22s22p4.
Polarisation
In ionic bonds, polarisation refers to the distortion of the electron cloud. In the perfect ionic
model, ions are spherical with no distortion. In reality, the positive ion will attract some of the
negative ion’s electron cloud towards itself.
The polarising power of a cation and the polarisability of an anion depends on the radius and
charge of the ions.
● A highly charged cation will have a strong electrostatic attraction with an anion which
will distort the anion’s electron cloud. If a cation has a smaller radius, there will generally
be a greater concentration of charge in a small area, causing a distortion of the electron
cloud. Therefore, the cation’s polarising power increases with an increase in charge
and decrease in radius.
● The more negatively charged an anion is, the greater the electron cloud. The larger the
electron cloud, the more easily it is distorted. Also, a larger radius means the outer
electrons are held more loosely, allowing them to be more easily distorted.
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Therefore, the anion’s polarisability increases as the radius increases and charge
becomes more negative.
Physical evidence
Giant covalent structures have high melting and boiling points due to strong covalent
bonds. They have no free ions or electrons (except graphite and graphene) so generally cannot
conduct electricity.
Simple covalent molecules have low melting and boiling points because, although the
covalent bonds are strong, the intermolecular forces between molecules are weak.
The properties of these covalent structures can all be explained by the model of covalent
bonding.
Covalent bonding
Covalent bonds form between two non-metals. There is a strong electrostatic attraction
between the two nuclei and the shared electrons between them. Electrons are shared between
the two outer shells in order to form a full outer shell. Multiple electron pairs can be shared to
produce multiple covalent bonds.
The shared electron pairs can be represented using dot and cross diagrams. The overlap
includes a covalent bond. The number of electrons within the overlap tells you the nature of
the covalent bond:
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Example: Dot and cross diagram of chlorine, Cl2
Double and triple bonds can also be shown on dot and cross diagrams with the multiple electron
pairs being displayed in the shared segment between the two atoms.
The length of a covalent bond is strongly linked to its strength. Shorter bonds tend to be
stronger as the atoms are held closer together so the forces of attraction are greater,
requiring more energy to be overcome. Double and triple bonds are shorter than single covalent
bonds, explaining why they are so much stronger.
Dative Bonding
Dative or coordinate bonds form when both of the electrons in the shared pair are supplied
from a single atom. It is indicated using an arrow from the lone electron pair.
Example:
Ammonia (NH3) has a lone electron pair that can form a dative bond
with a H+ ion to produce an ammonium ion (NH4+).
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Since both electrons come from the same atom in a dative covalent bond, in
dot and cross diagrams both electrons in that bond will have the same
shape.
In other words, they will both be dots or both be crosses.
Macromolecular covalent substances are covalently bonded into a giant lattice structure.
Each atom has multiple covalent bonds which are very strong, giving the substance a very
high melting point.
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Graphite is another macromolecular structure made up of carbon atoms. However, in graphite,
each carbon atom is bonded to three others in flat hexagonal sheets. This means there is one
delocalised electron per carbon atom. These electrons can move freely, allowing graphite to
conduct electricity. Graphite can therefore be used in an electrode. The intermolecular
forces between layers of graphite are weak and can easily slide over each other, meaning
graphite can be used as a lubricant.
Graphene consists of single, 2D sheets of graphite that are just one atom thick. These
sheets are formed of hexagonal carbon rings that create a very strong, rigid material that is
extremely lightweight. Delocalised electrons move through each layer allowing it to conduct
electricity, making graphene a useful material in electronics.
Bond Polarity
The negative charge around a covalent bond is not spread evenly around the orbitals of the
bonded atoms.
Electronegativity
Every atom has electronegativity, which is defined as:
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The power of an atom to attract the electron pair in a covalent bond towards itself.
This ‘power’ is different for every atom depending on its size and nuclear charge.
Electronegativity increases along a period, as atomic radius decreases and decreases down
a group, as shielding increases.
Ionic and covalent bonding are the extremes in a continuous scale of bonding as shown
below. If the electronegativity between two atoms is great enough, an ionic bond will form
between them.
Example:
This bond polarity can be permanent or induced depending on the molecule and how it
interacts with things around it.
Permanent Dipole
If the two atoms that are bonded have sufficiently different electronegativities, a polar bond
forms. The more electronegative atom draws more of the negative charge towards itself and
away from the other atom, producing a ∂- region and a ∂+ region. This produces a permanent
dipole.
Example:
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Polar molecules with a permanent dipole can align to form a lattice of molecules similar to an
ionic lattice.
Polarisability of ions
Where electronegativity difference is large enough the electrons will not be shared between
atoms but will instead spend most of their time localised around one of the atoms only - forming
ions. A cation is able to distort the shape of the electron cloud on a nearby anion. The extent
by which the electron cloud is distorted is known as polarisability.
Smaller cations with a greater charge are the most polarising. Anions with a larger ionic
radius can have their electron clouds distorted more easily.
A polar bond results from a large difference in electronegativity between two atoms forming a
covalent bond. Tables of electronegativity can be used to workout if a bond will be polar or not.
If the difference in electronegativity between two bonding atoms is between 0.4 and 1.7, the
bond will be a polar covalent bond. If the difference in electronegativity is greater than that, the
bond will be ionic.
Since electronegativity is a periodic trend, elements that are close together on the periodic
table will not form polar bonds.
Polar molecules
Polar molecules arise when there is an overall difference in polarity across the molecule,
due to the arrangement of polar bonds and the geometry of the molecule. Polar molecules must
have polar bonds, however a molecule with polar bonds may not necessarily be a polar
molecule.
Example:
CO2 - the C=O bonds in CO2 are polar, however the molecule is linear so the dipoles created by
each polar bond cancel out.
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H2O - the O-H bonds in water are polar and the geometry of the molecule is bent, so overall
there is a polarity and the molecule is polar.
Molecule Shapes
The shape of a molecule can be determined by considering the type and quantity of electron
pairs:
1. Find the number of electron pairs.
2. Determine how many of the pairs are bonding
pairs and how many are lone pairs.
3. Bonding pairs indicate the basic shape and lone
pairs indicate any additional repulsion.
Molecules may also be described in terms of their bond lengths and bond angles.
● Bond length - the average distance between two nuclei in a covalent bond.
● Bond angle - the angle between two covalent bonds from the same atom.
Linear 2 0 180
Cl - Be - Cl
O=C=O
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V - Shaped 2 2 104.5
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Trigonal Bipyramidal 5 0 180 and 120
Octahedral 6 0 90
Example:
The greater the charge on the positive ion, the stronger the attractive force since more
electrons are released into the ‘sea’.
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Ions that are larger in size, such as barium, produce a weaker attraction due to their greater
atomic radius.
Metals are also malleable because the uniform layers of positive ions are able to slide over one
another. The delocalised electrons prevent fragmentation as they can move around the lattice.
Example:
The electrostatic forces of attraction between the positive ions and delocalised electrons are
very strong and therefore require a lot of energy to overcome. This means metallic substances
have high melting points and are nearly always solid at room temperature. Mercury is the
only metal which is liquid at room temperature.
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