NORTHERN CARIBBEAN UNIVERSITY

DEPARTMENT OF BIOLOGY AND CHEMISTRY

LECTURE NOTES
GENERAL CHEMISTRY I

Assistant Professor: Dr. Nicole White

5. Molecular Orbital (MO) Theory

This model was developed due to the insufficiencies of the valence bond theory, as it sometimes
lead to an incorrect electronic description. MO theory is a theory of the electronic structure of
molecules in terms of molecular orbitals, which may spread over several atoms or the entire
molecule; in VB theory, we were concerned with atomic orbitals. Here too, as in VB theory,
orbitals overlap; unlike VB theory MO theory involves bonding and antibonding orbitals. Again,
this model is derived from the quantum mechanical wave equation. The need to learn this
equation is not relevant for this course. However, the square of the wave function in said
equation gives the probability of finding an electron in a given region of space.

Orbital- a solution to the Schrödinger wave equation describes a region of space where an
electron is likely to be found.
Atomic orbital – a wave function whose square gives the probability of finding the electron
within a given region of space in an atom.
Molecular orbital – a wave function whose square gives the probability of finding the electron
within a given region in space in a molecule.

In MO theory orbitals can interact 2 ways: additive (electrons are concentrated in areas between
nuclei called bonding orbitals, σ) and subtractive (electrons are concentrated in areas other than
between the two nuclei, σ*). The σ – means that the MO has a cylindrical shape about the bond
and the star (*) tells us that the molecular orbital is antibonding. The orbitals involved in
overlapping must contain 1 electron each and when they overlap these electrons must be in
opposite spin. MOs have specific size, shape and energy level.
The energy associated with the bonding orbital is always lower than the isolated orbitals; hence it
is more stable, while the anitbonding orbital has a higher energy. This higher energy makes the
antibonding orbital unstable as electrons cannot occupy this region and thus do not contribute to
bonding.

To better understand this model let us consider the H2 molecule its MO is shown below.
Electrons are added to molecular orbitals, one at a time, starting with the lowest energy
molecular orbital. Recall the following criteria:

• The aufbau principle, lowest energy MOs fill first, or fill the orbitals from below, IF
there are large orbital energy differences.
• The Pauli exclusion principle, a maximum of two electrons per orbitals and these must
be of opposite spin.
The bonding orbital is denoted as σ1s which tells us that there is a bonding orbital obtained from
the 1s atomic orbital. As is observed from the diagram the energy of the anitbonding orbital
(excited state) is indeed higher than that of the bonding orbital (ground state).

As by now realized, the number of molecular orbitals formed is the same as the number of
atomic orbitals combined.

For helium; both σ1s and σ*1s each have 2 electrons and the stability (decrease in energy) gained
by the bonding MO is cancelled by the antibonding MO energy. This He 2 would be an unstable
molecule – for this reason helium exists as a monatomic gas.

Bond order
This is tells the number of bonds formed between two atoms.
( nb − n a )
bond order =
2
nb − number of bonding electrons
na − number of antibondin g electrons

What is the bond order for H2?

What about He2?
If you have done both calculations you will see that for hydrogen the bond order (BO) is 1. For
helium, the BO is zero (0).

MOs for other diatomic molecules.

The above examples concerned bonding between 1s orbitals which are not the only orbitals
involved in molecular bonding. They also represent homonuclear bonding (molecules composed
of two like nuclei); heteronuclear bonding also occurs between molecules composed of two
different nuclei. For orbitals to interact they must have approximately equal energies and they
will interact to give maximum overlapping – in order to have strong bonds the orbitals must
overlap greatly.

Let us consider the p orbitals. There are 2 ways in which 2p orbitals can interact – 1 set of 2p
orbitals can overlap along their axes, head to head, to give one bonding and one antibonding σ
orbital (σ2p and σ2p*); the other 2 sets then overlap sideways to give two bonding and 2
antibonding π orbitals (π2p and π2p*). The p orbitals are denoted as px, py and pz and when they
overlap they match up – for example, x bonding molecular orbital and a x* antibonding one.
The 2 remaining 2p orbitals interact sideways to give πy and πy* and πx and πx orbitals have the
same energy and are known as degenerate, oriented at 90o. Because they are degenerate filling of
these orbitals must follow Hund’s rule - when there are equal energy or "degenerate"
orbitals, these fill one electron at a time before pairing begins. Or, if two orbitals are not very
different in energy, near-degenerate, or even exactly degenerate, then two electrons will fill both
orbitals with parallel spin.
The order of filling differs depending on the molecule being studied. For O2, F2, and Ne2 the
below diagram is obtained. This leads to less electron charge between the nuclei for the pi
bonding molecular orbital than for the sigma bonding molecular orbital. Less electron character
between the nuclei means less plus-minus attraction, less stabilization, and higher potential
energy for the pi bonding molecular orbital compared to the sigma bonding molecular orbital.
When the interaction is out-of-phase, less overlap leads to less shift of electron charge from
between the nuclei. This leads to more electron charge between the nuclei for the pi antibonding
molecular orbital than for the sigma antibonding molecular orbital. More electron charge
between the nuclei means more plus-minus attraction and lower potential energy for the pi
antibonding molecular orbital compared to the sigma antibonding molecular orbital. The
molecular configuration is written as: σ1s σ1s* σ2s σ2s* σ2p πx πy πx* πy * σ2p*.
For , Li2, B2, C2, and N2 the following MO diagram is obtained.

The molecular configuration is written as: σ1s σ1s* σ2s σ2s* πx πy σ2p πx* πy* σ2p*. As should be
noted, there is a lower shell of electrons that is not represented in the orbital diagram, which is
because they are filled both their boding and antibonding orbitals and so they are not considered
because the stability gained by the bonding orbitals is cancelled by the instability caused by the
antibonding orbital. These inner shells are denoted as KK – inner shells of 2 atoms.

What is the difference between nonbonding and antibonding?

A molecule can be determined as paramagnetic (substances with unpaired electrons and are
attracted by magnetic fields) or diamagnetic (substances whose electrons are all spin paired and
are weakly repelled or not attracted by magnetic fields) from their molecular orbital.
Which of the following diatomic molecules are diamagnetic and which are paramagnetic:
O2, N2 and F2.

6. Chemical Reactions

In a chemical reaction there is a rearrangement of the atoms present in the reacting substances to
give new chemical combinations present in the substances formed by the reaction.

2HCl(aq) + Zn(s) → H2(g) + ZnCl2(aq)

It is also important that you know the correct state symbols to place behind each species in your
reaction. The state symbols id basically an indication of the state of the substances in the
reaction: (s) – solid, (l) – liquid, (g) – gas, (aq) aqueous. An aqueous solution means that the
substance was dissolved in water.

There are, in essence, 3 main types of chemical reactions and as students of chemistry it is
important that you are able to distinguish one type from another.
• Precipitation/ exchange
• Neutralization
• Reduction-oxidation (redox)

Precipitation/Exchange reaction: a precipitate is an insoluble solid compound formed during a

chemical reaction in solution. In order to know whether or not a precipitate will occur, the
solubilities of the potential products must be known. In this type of reaction ions will exchange
‘partners’ as it were.

2AgNO3(aq) + Na2CO3(aq) → Ag2CO3(s) + 2NaNO3(aq)

Neutralization reaction: which occurs in acid-base reactions, the H+ ion in the acid reacts with
the OH- ion in the base causing the formation of water. Generally, the product of this reaction is
some ionic salt and water.

2HCl(aq) + Ca(OH) 2 (aq) →CaCl 2 (aq) + 2H 2 O(l)

acid base salt
Reduction-oxidation reactions: this type is further divided into combination/synthesis,
decomposition, displacement and combustion reactions.
• Combination/synthesis – is a reaction in which two substances combine to form a more
complicated substance and has the general form - A + B → AB
2Na(s) + Cl2(g) → 2NaCl(s)
In the above, sodium is oxidized and chlorine was reduced.

• Decomposition - A decomposition reaction is the opposite of a synthesis reaction; a

complex molecule breaks down to make simpler ones – AB → A + B.
∆
2 HgO ( s ) 
→ 2 Hg (l ) + O2 ( g )

In the above, mercury is reduced and oxygen is oxidized.

• Displacement – a reaction in which an element reacts with a compound, displacing an

element from it.
Cu(s) + 2AgNO3(aq) → Cu(NO3)2(aq) + 2Ag(s)
In the above, copper is oxidized and silver is reduced.

• Combustion - A combustion reaction is when oxygen combines with another compound

to form water and carbon dioxide. These reactions are exothermic, meaning they produce
heat.
2C4H10(g) + 13O2(g) → 8CO2(g) + 10H2O(g)

Balancing equations
When balancing a chemical reaction it is important to remember the law of conservation of mass
– no mass is lost or gained during a chemical reaction. In other words the reactants and products
must be in the same proportions. In balancing an equation it is good to take note of the
following:
• Never touch subscripts when balancing equations since that will change the
composition and therefore the substance itself.
• Make an element inventory. How are you going to know if the equation is balanced if
you don't actually make a list of how many of each atom you have? You won't. You have
to make an inventory of how many atoms of each element you have, and then you have to
keep it current throughout the whole problem.
• Check to be sure that you have included all sources of a particular element that you are
balancing on a particular side since there may be two or more compounds that contain the
same element on a given side of an equation.

Example:
Let us balance the following equation.

Make an inventory of the elements noting how much of each you have on either side. The
numbers should be the same as shown below.