BONDING
Revision: An Overview
1 Periodic Table
2 Types of ELEMENT
Metal Non-Metal
3 Types of BOND
Metallic Ionic Covalent
4 Types of STRUCTURE
Giant Metallic Giant Ionic
Simple Molecular Giant Covalent
IONIC BONDING
Ionic Bonding occurs between metals (which lose electrons
to become positively charged CATIONS) and non-metals
(which gain electrons to become negatively charged
ANIONS).
The formation of an ionic bond is thus an “electron-transfer”
process: in transferring electrons both the metal and the non-
metal achieve stable “full outer shell” arrangements of
electrons.
The oppositely charged ions
are held together by
electrostatic attraction that is
STRONG and
MULTIDIRECTIONAL.
Thus, ionic compounds are
GIANT STRUCTURES and
are crystalline when solid.
Crystals of sodium chloride
Electron “dot-cross” diagrams are a simple but often useful
way of representing many types of bonding. It is conventional
(and less time consuming) to show only the outer shell
electrons:
e.g. the formation of sodium chloride:
(2,8,1) (2,8,7) (2,8) (2,8,8)
sodiu chlorine sodium chloride
m atom ion ion
atom
THE IONIC LATTICE
Many ionic compounds exist as giant ionic crystalline
structures. The shapes of their crystals arise from the way the
ions pack in the lattice.
The type of packing in the lattice depends upon the relative
sizes of the ions involved.
What will affect the size of the ion?
A chloride ion is approximately twice the size of a sodium
ion; sodium chloride, Na+Cl–, packs in a FACE-CENTRED
CUBIC arrangement.
Sodium Chloride
Na+Cl–
The Na+ ion is surrounded by 6 Cl–
ions.
The Cl ion is surrounded by 6 Na+
–
ions.
This is 6:6 coordination.
The ionic radius ratio in Mg2+O2– is also ~1:2, so magnesium
oxide packs in a similar manner.
Note, in Caesium Chloride, the ionic radius ratio is ~1:1, so
Cs+Cl– packs differently and so adopts a different crystal
structure: it forms a SIMPLE CUBIC arrangement.
IONIC RADII
The crystal structures adopted by ionic compounds depend on
the stoichiometry of the compound (i.e. how many of each
type of ion here are) and the ratio of the ionic radii.
So what affects the radii of the ions?
Ions, of course, are not a “fixed size”; their boundaries may
not be certain since the electrons in the ions are found in
orbitals, and the orbital electron density (which says where
the electrons are when they’re in those orbitals) is a
probability plot, and is not absolute.
However, it is intuitive to think that at some point as we move
through the ionic lattice in sodium chloride we pass from a
Na+ ion to a Cl– ion: at some point one ion ends and the next
starts!
The solution to finding “where an ion ends” comes from
“electron density maps”, which can be produced for any
solid using X-ray crystallography.
{In X-ray crystallography, X-rays are fired into the
sample, where they interact with the electrons and are
“scattered”. The pattern of the scattering can be related
to the positions of the electrons in the sample, and hence
a picture of the electron density can be built up.}
These electron density maps show the packing of the ions in
the crystal, with contour lines indicating the density of the
“electron cloud” around these ions. From these images the
ionic radii are estimated, after choosing one ion as the
reference ion.
For example: sodium chloride and calcium fluoride:
Q: do these maps for NaCl and CaF2 suggest that:
i) the ions are discrete entities?
ii) the ions are spherical?
Na+Cl– Ca2+(F–)2
More recently, computer calculations of electron density
maps have been used to elucidate the structures of more
complicated molecules:
This image shows the calculated electron density map of a
molecule of ATP, with the atomic framework shown inside
COVALENT BONDING
Covalent bonds form between non-metal atoms; they are
“shared pairs of electrons” which attract the nuclei of both
atoms and hence hold them together.
The electrons in a hydrogen
molecule spend more time
between the two H nuclei
than elsewhere, and hence
there is a net electrostatic
attraction which pulls the
nuclei together: this is the
covalent bond.
The green lines show
the attractive forces
The diagrams show the electron density maps in an H2
molecule. The electron density is highest at the nuclei, but is
still very high in the region between the two H atoms.
The high electron density in the inter-atom region in H2
corresponds to the sharing of electrons and the formation of
the covalent bond.
Compare these electron density plots with those for ionic
bonds. In covalent bonding the electron density is high
between the atoms, whereas in ionic bonding it dropped to
zero between ions.
Covalent is “sharing” whereas ionic was “transfer”.
Covalent bonds are STRONG and UNI-DIRECTIONAL.
Covalent compounds can be GIANT STRUCTURES or
SIMPLE MOLECULES.
Simple covalent molecules are often conveniently represented
by electron dot-cross diagrams:
e.g. Ammonia, NH3:
Electron pairs that form bonds are called BONDING
PAIRS.
Electron pairs not involved in bonding are called
LONE PAIRS (or NON-BONDING PAIRS).
One pair of shared electrons forms a SINGLE bond.
Two pairs of shared electrons forms a DOUBLE
bond.
Three pairs of shared electrons forms a TRIPLE
bond.
Hydrogen: Oxygen:
single bond double bond
DATIVE COVALENT BONDS
Covalent bonds usually involve shared electrons
originating from both atoms. In a DATIVE covalent
bond, both of the bonding electrons come from the
same atom!
e.g. in Carbon monoxide, CO:
Dative covalent bonds can be represented by an “arrow”:
this points from the atom which is giving both of the
electrons.
e.g. in Carbon monoxide:
e.g. in the ammonium ion, :
BONDING EXECISE: Drawing dot-cross diagrams
Give electronic structures for the following species.
Show only outer-shell electrons. Use dots and crosses to
distinguish between electrons from different atoms.
Draw covalent bonds ( , and for a dative bond)
where appropriate in the smaller box.
The first two have been done as examples.
sodium chloride methane
Na+Cl–
sodium hydride calcium oxide
carbon dioxide ammonia
ammonium ion nitric acid
nitrate ion sulphuric acid
sulphate ion nitrogen
GIANT COVALENT STRUCTURES
Some covalent molecules cannot be easily drawn as
dot-cross diagrams because they are large molecules that
effectively extend infinitely through space.
CARBON
Carbon forms two giant covalent structures, diamond
and graphite.
In DIAMOND, each carbon atom forms FOUR strong
covalent bonds with its neighbours in a 3-Dimensional
lattice.
Like most giant covalent structures, diamond does not
conduct electricity.
Pure diamond is colourless.
The colours in the diamonds
above are due to impurities,
e.g. Chromium impurities
give it a red colour.
Silicon dioxide (SiO2) has a similar
giant covalent structure.
It is the same but with the C–C unit
replaced by a Si–O–Si unit.
In GRAPHITE, each carbon atom forms THREE strong
covalent bonds with its neighbours in a 2-Dimensional
layer made up of hexagons. The 4th electron from each
carbon atom is free to move in the space between the
layers: these electrons form weak attractive forces
between the layers which hold them together, but which
also allow the layers to slide over one another (because
the forces are weak).
The presence of the mobile electrons explains why
graphite has an unusual property for a non-metal: it
conducts electricity (because the electrons can move
between the layers and carry the charge).
There is another (strange) form of Carbon: Buckminster
Fullerene, C60. It is a simple molecule (because it is a
finite size) but it has a relatively large number of atoms,
60.
It is like a warped section of graphite, with some of the
hexagons replaced by pentagons, and then curved round
on itself. It is shaped like a football.
Other versions of this molecule form tubes (“Bucky
Tubes”) which have special properties:
o They are stronger than steel (weight for weight)
o Some conduct electricity
Some people believe these could be used to tether a
space station to the earth!
METALLIC BONDING
When they undergo ionic bonding, metals lose electrons to
form stable ions with full outer-shell configurations.
In the pure metals themselves,
the situation is similar.
However, instead of these
electrons being transferred to
non-metal atoms, they just
form a “sea” of electrons
surrounding the positive metal
ions. These spherical metal
ions arrange themselves in a
regular 3-Dimensional
structure.
The negative electrons can
move around the positive ions,
and hence are called
“delocalised”. They act as the
“glue” holding the positive ions
together.
Because these electrons can move even when the metal itself
is a solid (i.e. when the ions cannot move), if a voltage is
applied across the
metal then the
electrons move
together in a
certain direction
and a current
flows: this is
electronic
conductivity.
BONDS OF INTERMEDIATE CHARACTER
Bonding is rarely completely ionic or completely covalent.
These are extremes, and most bonding lies somewhere in
between.
IONIC CRYSTALS
There is in fact not complete transfer of “electron density”
from metal to non-metal in ionic crystals, and there is
increasingly less ionic character when DISTORTION OF
THE ANION (or POLARISATION) occurs.
Consider NaCl v. AlCl3
The small, highly charged Al3+ ion attracts the
electrons in the Cl– ion towards it, and hence the
spherical anion becomes distorted and more “pear-
dropped” in shape. This effect is greater for small
cations as they can get closer to the anion.
The Na+ ion does not have a high enough charge and
so now the Cl– ion remains undistorted.
So what causes the traces of “covalency” in an ionic lattice?
How might ELECTRONEGATIVITY values assist us in
determining ionic or covalent character?
“Electronegativity” is the ability of an atom to attract the
bonding electrons in a covalent bond. The elements have the
values:
“Polarisation” may occur between cations of high charge
density (small size and high charge) and anions of low charge
density (large size and low charge), e.g. Al3+ and I–, Be2+ and
Cl–.
The difference in electronegativity can be used as a measure
of the “degree of ionicity” or “ionic character”:
Electronegativity
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6
Difference
Percentage ionic
0.5 1 2 4 6 9 12 15 19 22 26 30 34 39 43 47
character
Electronegativity
1.7 1.8 1.9 2.0 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.0 3.1 3.2
difference
Percentage ionic
51 55 59 63 67 70 74 76 79 82 84 86 88 89 91 92
Character
POLAR BONDS
A large difference in electronegativity between two
covalently bonded atoms results in a polar bond: this has a
“separation of charge” resulting in one end of the bond
being negatively charged and the other being positively
charged.
The larger the difference in electronegativity the more polar
the bond (and the greater the ionic character).
e.g.
water hydrogen fluoride
and
equal “pull” on unequal pull on
Polarity makes bonds electron density electron density
more reactive: = POLARITY
e.g. Nitrogen is a very unreactive gas, but carbon monoxide is
a reactive gas.
Both have the same arrangement of electrons (they are
“isoelectronic”).
Both have triple bonds, but only CO is polar.
INTERMOLECULAR FORCES
Intermolecular forces exist between molecules. They
attract species together that are not bonded to each other.
These forces are due to uneven charge distributions in the
molecules.
PERMANENT DIPOLE-PERMANENT DIPOLE
INTERACTIONS
Consider CHCl3: it has a permanent dipole
electrons are more
attracted to chlorine
as it is more
electronegative, so
there is a separation
of charge.
The different molecules attract each other due to
favourable dipole-dipole interactions (the positive end
of one dipole attracts the negative end of another: they
always line up this way so these forces are always
attractive).
These intermolecular forces are present in all dipolar
compounds.
PERMANENT DIPOLE-INDUCED DIPOLE
INTERACTIONS
Is CHCl3 attracted to CCl4?
o CHCl3 has a dipole but CCl4 does not (as it is
symmetrical so there is no separation of
charge)
o The CCl4 molecule may, however, form an
instantaneous dipole, because the electrons in it
move around.
e.g.
Electrons move around within
the molecules, and so have an
unsymmetrical distribution at
any instant in time.
So … the attraction between CHCl3 and CCl4 is between
a permanent dipole and an instantaneously induced
dipole.
INSTANTANEOUS DIPOLE-INDUCED DIPOLE
INTERACTIONS
Why do Noble gases liquefy and freeze?
o There must be attractive forces between the
atoms that hold them together.
These forces are due to the instantaneous fluctuations
of the electron clouds.
The electrons in the first atom instantaneously
move to the right, causing that side to become
negatively charged.
In turn, this negative charge repels the
electrons in the next atom, causing the nearest
side of that atom to have fewer electrons than
usual and hence become positively charged.
The negative side of the first atom then
attracts the positive side of the next atom.
These attractive forces exist in ALL molecules, even
those that are NON-POLAR.
These instantaneous dipole-induced dipole forces are
also known as London Dispersion forces and more
commonly van der Waals’ forces.
HYDROGEN BONDING
Why are the boiling points of NH3, H2O and HF
anomalously high compared to the other hydrides?
There must be extra inter-molecular forces that are
stronger than the usual dipole-dipole interactions.
These forces are known as HYDROGEN BONDS.
What is a hydrogen bond?
N, O and F are very electronegative: when bonded to H
they draw the electrons in the bond close towards them,
e.g.
The H atom has no inner shell electrons, and when the
bonding electrons are pulled away from it, an almost
“bare” nucleus is left which is readily available for
dipole-dipole attractions.
The H atom is also very small, and so it can place itself
in between two of the larger electronegative atoms, and
be very close to both. It then exerts an attractive force
on both, and so pulls them closer together.
A hydrogen bond is therefore:
an extra-strong intermolecular, permanent dipole-
permanent dipole attraction.
A hydrogen bond requires:
o A hydrogen atom attached to a highly
electronegative atom (N, O, or F)
o A lone pair of electrons on the adjacent
electronegative atom (N, O, or F)
See the diagrams below …
Hydrogen Bonding
The electron density maps show the similarity between the
bonding pair of electrons (on O1) and the lone pair (on O2). The
lone pair of electrons (shown in pink, from O2) is very close to
the H (which is itself covalently bonded to O1), and hence there is
a strong interaction of H with both O atoms.
O1–H is a covalent bond and O2–H is a Hydrogen bond.
e.g. water:
