IB Chemistry 4 Bonding

4.1 Ionic Bonds

Ionic compounds are composed of positive ions (cations) and
negative ions (anions) that are held together because opposite
charges attract.
There is no specific cations connected to a specific anion. It forms
a lattice.
The force that attracts the cations and anions increases with charge
and decreases with distance.

q1q2

d2
We measure the strength of a bond by the energy required to pull
the ions apart.
More highly charged ions will have a stronger ionic bonds (most
important).
Smaller ions will have stronger ionic bonds (considered after
charge).
Ex 1:
Rank the following ionic compounds in order of decreasing bond
strength.
LiCl
NaCl
MgCl2
MgF2
MgO
CaO
The energy to break an ionic bond is the energy required to take
the ions in a compound and pull them apart to individual ions.
This will be an endothermic process (breaking bonds required
energy).
This will be the same as the energy released if individual ions form
an ionic solid (forming bonds in an exothermic process).
The energy of the ionic bonds is called the lattice energy. A
reaction to make a solid from gaseous ions would be very difficult.

IB Chemistry 4 Bonding
According to Hesss Law, we can
find a different set of steps that
have the same overall result, we
can find the energy.
This process is called the BornHaber Cycle. This cycle uses the
enthalpy of formation and a series
of steps to find the lattice energy
Born-Haber Cycle
1. Sublimation energy
2. Bond strength (covalent)
3. Ionization energy
4. Electron affinity
5. Lattice energy
Net reaction: enthalpy of formation.
Ex 2:
Using data from your text (p.362), Data Booklet and The diagram
above, to find the lattice energy for KF.

What are the differences between this Born-Haber cycle

and the one for NaCl?

Problems
9.17, 22, 24, 26, 28, 30, 33

IB Chemistry 4 Bonding

4.2 Lewis Structures

Covalent bonds are formed by molecules sharing electrons.
Usually one electron is donated to the bond from each atom in the
bond.
(If both electrons are from one species it forms a ligand or a
coordinate covalent bond.)
To determine the way electrons are shared we draw Lewis
structures.
Each dot is an electron.
Lines between atoms represent a pair of bonding electrons.
This is a polyatomic ions with a charge of -2: SO42Generally atoms will have an octet about them to become more
stable.
To draw a Lewis Structure with octets:
1. Sum the valence electrons of all atoms. Account for ions.
2. Connect the atoms with single bonds. (Atoms are often
written in order or if there is a central atom with a group of
atoms, the central atom is often written first.)
3. Complete octets for most atoms (H is a duet).
4. If short of electrons form multiple bonds. (sharing 4 or 6
electrons)
Ex 1:
Draw the Lewis structures for:
CH4
H2O

CO2

SO32-

N2

O2

HCN

IB Chemistry 4 Bonding
There can be times when a double bond
can equally be placed at two positions;
the choice of which is arbitrary.
In the Lewis Structure for NO2- the
double bond can be placed with either
oxygen.
The result is half of each. This is a
resonance structure.
Draw the Lewis structure for:
SO3

O3

CH3COO-

There are times when atoms do not form octets.

Boron is small and can form stable compounds with six electrons.
Beryllium can form compounds with four electrons.
These exceptions are included because they have been found to
exist.
There are also compounds that can have more than octets. An
atom that has empty d orbitals can have 10 or 12 electrons
around it. This is only done if it is the only way to place all the
electrons in the Lewis Structure.
Ex 3:
Draw the Lewis Structure for:
a) I3b) XeF4
c) ICl5

Follow Up Problems 10.1, 3, 4, 5

Problems 10.1, 3, 5, 7, 9, 11, 19, 21

IB Chemistry 4 Bonding

4.3 Covalent Bond Energies

Covalent molecules share electrons. The atomic orbitals of the
bonded atoms overlap. The electrons orbit throughout the
molecule, not just in the place that they are drawn in a Lewis
Structure.
Every molecule will have unique bonds between its atoms.
To simplify the bonding model, we assume that all bonds between
similar atoms are similar. We can then use average bonds.
Average bond energies are given in your Data Booklet. This is
defined as the energy required to break the bond per mole.
Stronger bonds are a result of better overlap of atomic orbitals.
Stronger bonds are shorter bonds.
Compare the bond strength and bond length on the chart in your
Data Booklet.
The enthalpy of a reaction can be estimated from the energy
changes in the bonds that are broken and the bonds that are
formed.
This is assuming that the bonds are average covalent bonds.
Example 1:
Calculate the energy for the following reactions:
C2H4 + H2 C2H6

Combustion of acetylene (C2H2).

Follow Up Problems 9.2, 3

Problems 9.44, 46, 48, 50, 51

H Dbroken D formed

IB Chemistry 4 Bonding

4.4 VSEPR
The shapes of covalent molecules can be explained
using the VSEPR theory: Valence Shell Electron
Pair Repulsion.
Electron pairs (bonding and non-bonding) will
arrange themselves to maximize the distance
between them so to minimize their potential energy.
The shapes that the atoms adopt depend on the
number of electron pairs around the central atom.
These arrangements allow the electron pairs to be as
far apart as possible.
You need to know the names and angles for these
VSEPR geometries.

In describing a molecules geometry, we only

describe the bonds that are present. Lone pairs must
be accounted for in determining the VSEPR
geometry, but are ignored in the molecular geometry.
Lone pairs repel more than a bonding pair:
They will repel other bonding pairs farther away
from themselves.
If there are two or more lone pairs they will be
arranges far from each other.
Note that bent geometry can result from Triganal
Planer and Tetrahedral geometries.
What are the angles for these molecular bonds?

IB Chemistry 4 Bonding
4.4 VSEPR
Note the position of the lone pairs in the triganol
bipyramidal geometry.
All positions are equal in the octahedral
arrangements.
Example 1:
Give the VSEPR geometry and molecular
geometry (including angles) for:
NH3
XeF4

SeCl4

SO2

O3

I3-

Follow Up Problems 10.6, 7, 8

Problems 10.28, 30, 32, 34, 36, 40, 46

IB Chemistry 4 Bonding

4.5 Bond Hybridization

VSEPR Theory is an empirical theory that lets you
determine what the angles in a molecule or ion should be.
Bond hybridization gives us the explanation of how the
molecules for the bonds in the way that they do.
The s and the p orbitals are combined in ways that
give us the molecular geometries that we find in nature.
Covalent bonds come in two flavours. A sigma bond
()is a bond that forms from atomic orbitals that overlap
directly between the atoms. Single bonds are sigma
bonds. Methane has four sigma bonds.
A molecule that is tetrahedral is combining its s and three p
orbitals to make the four tetrahedral orbitals. These new four
degenerate orbitals are each called an sp3 orbital. Their
geometry is tetrahedral.
Each of these sp3 orbitals is of equal energy. They are higher
energy than an s orbital, but lower than the p orbitals.

Methane has four sigma bonds. Each bond is between an sp3

orbital for the carbon and an s orbital from the hydrogen.

IB Chemistry 4 Bonding
The second type of covalent bond is a pi bond. This bond
forms if a double or triple bond is necessary. In a multiple bond
the first bond is a sigma bond and the second and third bond are pi
bonds. These bonds are outside of the axis between the two atoms

To make a pi bond, an atom must have a p orbital that is not

hybridized. The atom is combining one s orbital and two p
orbitals.

The p orbital is perpendicular to the plane of the sp2 bonds.

IB Chemistry 4 Bonding
Notice that the geometry of the sp2 hybrids is trigonal planer.
This is where the trigonal planer geometry comes from.
Pi bonds are also weaker than sigma bonds. This is why a double
bond is not twice as strong as a single bond.
A bond is stronger if the orbital overlap is greater and if the
electrons can spend more time in the shared orbital.
To make two pi bonds, an atom must have two p orbitals that are
not hybridized. This can occur if an atom is making a triple bond
or two separate double bonds.
To have two p orbitals for pi bonding, there is only one p for
hybridization.

The p orbitals for pi bonding are perpendicular to each other.

10

IB Chemistry 4 Bonding
To determine the p orbitals that are hybridized, subtract any
needed for pi bonds, hybridize the rest.
Example 1: Draw the following molecules indicating the bonding
orbitals:
a) Ammonia (NH3)

b) Oxygen

c) C2H4

d) HCN

e) H2C=C=CH2

11

IB Chemistry 4 Bonding
The last aspect we will examine is bond
delocalization. This allows us to explain
resonance.
In this diagram of NO2, what is the
hybridization of each atom?
Each atom must be able to form a pi bond. The electrons in the
pi bond are actually shared among all of the p orbitals.
Bond delocalization adds stability to molecules. Breaking a
delocalized bond is harder, because it involved more atoms.
Example 2: Draw the bonding for the following molecules:
a) Ozone (O3)

b) NO3

c) Benzene (C6H6 ring)

12

IB Chemistry 4 Bonding
Different types of bonding can be seen in the allotropes of carbon:
diamond, graphite and fullerene (bucky ball).
A diamond has carbon atoms that are sp3 hybridized. Each carbon
is bonded to four other carbons in a three dimensional matrix.
What properties could this give to carbon?

Graphite is made of carbon atoms that are sp2 hybridized. They are
like benzene rings that continue in large layers. The electrons are
delocalized between the layers of carbon atoms. Properties?

If a graphite layer is curled into a ball, it forms a fullerene

(bukminsterfullerene).
Properties?

Follow Up Problems 11.2

Problems 11.7, 9, 11, 20, 21, 23, 40, 42, 50, 58

13

IB Chemistry 4 Bonding

4.6 Intermolecular Bonding

The strength of bonding between separate molecules can be seen
through boiling points, melting points, and other physical
properties.
Stronger intermolecular bonds generate higher boiling points and
higher melting points.
Ionic compounds do not have discreet molecules. They form a
lattice. To melt this lattice, the ions must be separated by breaking
the ionic bonds.
Are those ionic bonds intermolecular bonds, or intramolecular
bonds? They are both. (Bonding intermolecular forces)
Regardless, these bonds are hard to break, and ionic compounds
usually have very high melting points.
For covalent compounds, intermolecular bonds fall into three
categories
(Non-bonding intermolecular forces or Van Der
Walls Forces):
Dipole-dipole forces are an attraction between molecules that have
a permanent dipole (positive and negative end).
Hydrogen bonds (special type of dipole).
Dispersion forces, or London Forces, or London Dispersion
Forces, that involve temporary dipoles.
The first step is to determine if a molecule has a dipole (a positive
and a negative end). This is done by:
1) Identifying polar bonds by comparing the electronegativity
of the bonded atoms.
2) Finding lone pairs of electrons.
3) Determining if symmetry in the molecule balances out the
positive and negative parts of the molecule.

Example 1:
Determine if the following have a dipole:
CH4
NH3

H2O

CO2

Cl2

SO2

14

IB Chemistry 4 Bonding
Dipole bonding attracts molecules together. The stronger the
bonding, the higher the temperature must be before the substance
will boil or melt.
Solid

Liquid

Hydrogen bonding is a dipole that is formed with HN, HO, H

F bonds. The small size of these atoms produces a very strong
dipole bond.
London Dispersion Forces are due to a temporary dipole that forms
when the electrons are temporarily unbalanced. This produces a
weak, short lived dipole attraction. (These are erroneously called
van der Walls forces which is really a larger category.)
The temporary dipoles are stronger in larger atoms. Larger atoms
have a greater chance for electron imbalances.
The total force due to Dispersion Forces will also be greater in
larger (longer) molecules. There are more places for attraction to
occur.
The temporary dipoles occur in molecules with permanent dipoles,
but they are most important in non-polar molecules.
To determine the strength of the inter-molecular bonding:
1) Determine if there is Hydrogen bonding.
2) Determine if there is a dipole.
3) Determine the extent of the Dispersion forces.
These are in priority order.
See Table 12.2, p. 437 for relative strengths.

15

IB Chemistry 4 Bonding

Example 2:
Explain the following trends:
B.P of noble gasses
B.P. of halogens

Predict the strength of the inter molecular bonding for:

CO2, SO3, O2, CH4, H2CO

Example 3:
Explain the trends in the graph below.

Follow Up Problems 10.9, 12.2, 3

Problems 10.52, 55, 57, 12.5, 32, 34, 37, 39, 41, 43, 45(polarizability is ease of
forming dispersion forces), 47, 49, 51, 53

16

IB Chemistry 4 Bonding

4.6 Metallic Bonding

Bonding in metals is different than ionic or covalent solids.
Generally, metals are:
Malleable
Ductile
Electrically conductive
Thermally conductive
Can these be explained by ionic or covalent bonding?
Metallic bonding is modeled as
positive ions with a sea of
electrons among the cations.
How does this explain metallic
properties.
To melt a metal, the cations must
be pulled from the electrons. This
should be harder for metals that
form cations with a greater charge.
Larger cations should also have lower forces and lower melting
points.
Check this model with the melting points of some first and second
row metals.
Check with other metal properties.

17

IB Chemistry 4 Bonding

18

IB Chemistry 4 Bonding
Some compounds can form large, covalently bonded molecules,
macro-molecules.
Diamond is an example of a network covalent solid. Melting a
diamond involves breaking the covalent bonds between
carbon atoms.
Are these inter- or
intra-molecular bonds?

Silicon dioxide also forms a network covalent solid.

Be able to explain trends in m.p. and b.p. for metals.

Explain how the metallic bonding model explains the properties of
metals.

19