Lewis Theory of Bonding

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Chemical bonding is at the heart of understanding chemistry. The Lewis Theory of Bonding essentially combined
observations at the time about chemical bonding together. Not only was it essential in understanding how
elements bonded, it provided a visual representation for them. These Lewis dot structures are a simplistic way of
representing the electrons in molecules. This theory also helped to define formal charge and resonance.
Understanding of electronegativity and electron affinitywill be useful before understanding Lewis Theory of
Bonding.

Introduction

The Lewis Theory used observations from chemists and physicists to form a theory about chemical bonding. This
work was essentially a compilation of the knowledge at the time. It revolved around the importance of valence
electrons in chemical bonding. These are the electrons that are in the outermost shell. For example Na may have
11 electrons, but only one is a valence electron, the one in 3s1. Meanwhile P has 15 electrons, but has five valence
electrons, 3s2 and 3p2. The bonding of an element is based on how they fill their octets i.e. achieve a noble gas
electron configurations.

Lewis went on to explain how certain elements such as Boron did not necessarily follow these same rules. He
explicitly defined two ways electrons were used to form bonds. These were ionic (complete transfer of electron)
and covalent (sharing of electrons) bonding. He added to his covalent bonding theory that atoms can have a
double or triple bonds with other atoms when electrons are shared. A single bond consists of two electrons
sharing between two atoms, double bond consists of four electrons sharing between two atoms, and triple bond
consists of six electrons sharing between two atoms. In both cases Lewis dot structures were used to visualize the
the bonding of the atoms in case of electron sharing or electron transfer.

Basic Lewis Dot Structures

There are two basic types of bonding that form the basis of the Lewis theory and it is important to understood
before one can begin to draw Lewis dot structures.

Ionic Bonding

In ionic bonding one element is much more electronegative then another element. In other words, the
electronegative atom wants an electron much more than the other element; thus, the element with a positive
charge loses electron and the element with the negative charge gains an electron. These two elements then
become attracted to each other because of Coulomb’s Law which states that there is electrostatic interaction
between particles that are electrically charged, in this case the electrons describes the charge of the atom. The
atom that loses electrons is electron deficient; thus, the atomic charge will be positive. The atom that gains
electrons has excess of electrons; thus, the atomic charge will be negative. This attraction between the elements
brings them together to form an ionic bond. An example of an ionic compound is shown below.

Covalent Bonding

In covalent bonding the elements share electrons equally, i.e. both the atoms have an equal share of electrons in
the bond. This sharing of electrons creates a bond that is known as a covalent bond. It is thought that a covalent
bond is equal, but in nature, the bond is never equal. The electronegativity differs between all the elements and
the more electronegative the atom, it has a higher tendency to gain electrons; however, because the bond is
formed by sharing electrons, the atom cannot "possess" an electron. So, the only way for the more electronegative
 atom to take the "advantage" of an electron is by
unequal sharing of electrons. The compounds that
share electrons unequally are called polar
compounds and the process is called polarity. An
example of a polar compound is water (H2O). An
example of a generalized covalent compound is
shown below.

How to Draw Lewis Structure: To begin any Lewis dot structure, begin by counting how many valence electrons are
in all the elements.

CH4 CO2

1 C: 1 * [4 Valence Electrons] (2s22p2) 1 C: 1 * [4 Valence Electrons] (2s22p2)

4 H: 4 * [1 Valence Electron] (1s1) 2 O: 2 * [6 Valence Electrons] (2s22p4)

4+4 = 8 Valence Electrons 4 + 12 = 16 Valence Electrons

Next, arrange the elements in a basic outline, without the electrons or bonds. This is sometimes known as a
skeleton structure. In general the least electronegative element goes in the middle, and hydrogen is almost always
on the outside.

Finally, connect the elements, remembering that

hydrogen only needs 2 electrons and other
elements should have 8. A good strategy is to first
connect them with single bonds and fill in the rest
with electrons. If there are not enough electrons
add in double/triple bonds when necessary.

The essential goal is to always ensure that each element has a full octet and the molecule has all the valence
electrons it should have from its constituents.

Formal Charges

In an atomic bond, either ionic or covalent, atoms gain or lose electrons. The formal charge is the difference
between the original number of valence electrons and the actual number of electrons used in filling the octet. The
actual number of electrons is the addition of the lone pair electrons and one electron from each bond. Only one
electron is counted in a bond because there are two electrons being shared in the bond but only one is being
possessed by each atom.
The following rules are needed to see if a particular Lewis structure can be possibly formed in nature.

Formal charge of 0 --> Really good, possible in nature

Formal charge of -1 or 1 --> Okay, possible in nature

Formal charge < -2 or > 2 --> Not good, impossible in nature

To check if the formal charge for a particular compound is correct, one can check if the total of all formal charges
of the atoms in the compound equal to the charge of that compound. Ane example can be seen in the second
figure of category "Resonace" below.

Resonance

Draw a Lewis dot structure for [SCN]-. Is it one of the ones below?

All of these molecules look different, but

they fulfill the simple rules of Lewis dot
structures. They all fulfill the octet rule and use 16 electrons (15 valence electrons +1 from the -). This
demonstrates that in certain cases, molecules can have the same elements but it can be arranged differently by
the Lewis dot theory. The different Lewis structures are called resonance structures. It is important to recognize
resonance structures but one also has to consider the natural chance of each one occurring in nature. One
method is to look at the formal charges as shown below.

One can immediately see

that it is extremely unlikely
for the middle one to occur because of the formal charge of -2 to one of the atom i.e. Nitrogen atom. The formal
charge means that nitrogen will take more electrons and so sulfur will become positive. By comparing the two
formal charges on the terminal atoms, one can see that, in either case, sulfur has a charge of 0 or -1. This is same
for Nitrogen. Now understanding the concept of electronegativity and electron affinity, which atom is more likely
to have a negative charge? To answer that question we must look at electron affinities. Nitrogen has a higher
electron affinity, and thus is more likely to have a negative charge. The first structure is most common, whereas
the middle structure is least probable structure for SCN-.
Pauli Exclusion Principle

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The Pauli Exclusion Principle states that, in an atom or molecule, no two electrons can have
the same four electronic quantum numbers. As an orbital can contain a maximum of only two electrons,
the two electrons must have opposing spins. This means if one is assigned an up-spin ( +1/2), the other
must be down-spin (-1/2).

Electrons in the same orbital have the same first three quantum numbers,
e.g., n=1n=1, l=0l=0, ml=0ml=0 for the 1s subshell. Only two electrons can have these numbers, so that
their spin moments must be either ms=−1/2ms=−1/2 or ms=+1/2ms=+1/2. If the 1s orbital contains only
one electron, we have one msms value and the electron configuration is written as 1s1 (corresponding
to hydrogen). If it is fully occupied, we have two msms values, and the electron configuration is
1s2 (corresponding to helium). Visually these two cases can be represented as

As you can see, the 1s subshell can hold only two electrons and when filled the electrons have opposite
spins.

Aufbau Principle

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Aufbau comes from the German word "Aufbauen" which means "to build". In essence when writing
electron configurations we are building up electron orbitals as we proceed from atom to atom. As we
write the electron configuration for an atom, we will fill the orbitals in order of increasing atomic
number. The Aufbau principle originates from the Pauli’s exclusion principle which says that no
two fermions (e.g., electrons) in an atom can have the same set of quantum numbers, hence they have
to "pile up" or "build up" into higher energy levels. How the electrons build up is a topic of electron
configurations.

Example

If we follow the pattern across a period from B (Z=5) to Ne (Z=10) the number of electrons increase and
the subshells are filled. Here we are focusing on the p subshell in which as we move towards Ne, the p
subshell becomes filled.

B (Z=5) configuration: 1s2 2s2 2p1

C (Z=6) configuration: 1s2 2s2 2p2

N (Z=7) configuration: 1s2 2s2 2p3

O (Z=8) configuration: 1s2 2s2 2p4

F (Z=9) configuration: 1s2 2s2 2p5

Ne (Z=10) configuration: 1s2 2s2 2p6

The Aufbau principle states that, hypothetically, electrons orbiting one or more atoms fill the lowest
available energy levels before filling higher levels (e.g., 1s before 2s). In this way, the electrons of
an atom, molecule, or ion harmonize into the most stable electron configuration possible.

The details of this "building-up" tendency are described mathematically by atomic orbital functions.
Electron behavior is elaborated by other principles of atomic physics, such as Hund's ruleand the Pauli
exclusion principle. Hund's rule asserts that even if multiple orbitals of the same energy are available,
electrons fill unoccupied orbitals first, before reusing orbitals occupied by other electrons. But,
according to the Pauli exclusion principle, in order for electrons to occupy the same orbital, they must
have different spins (−1/2 and 1/2).

A version of the Aufbau principle known as the nuclear shell model is used to predict the configuration
of protons and neutrons in an atomic nucleus.[1]

RULES OF ELECTRONIC CONFIGURATION

HUND'S RULE OF MAXIMUM
MULTIPLICITY
According to Hund's rule of maximum multiplicity:
1. The electrons tend to avoid being in the same orbital.Thus as the electrons are
successively added, a maximum number of electrons will try occupy orbitals singly.
.
2. When all the orbitals are singly occupied only then the pairing of electrons commences.
.
3. In the ground state, the electrons occupying the orbitals singly will have their spin
parallel.
.

Hund's rule indicates that the electronic arrangement is more stable than

.
EXPLANATION
N (Z = 7) :
CORRECT AND STABLE ELECTRONIC CONFIGURATION = 1s2, 2s2, 2px1, 2py1, 2pz1
WRONG AND UNSTABLE ELECTRONIC CONFIGURATION = 1s 2, 2s2, 2px2, 2py1, 2pz0
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