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Simple

Bonding Theory
M.A.M.

Introduction
A modern era in understanding chemical bonding happened with the
recognition of the importance of electron sharing
between two atoms. This was followed by theory
driven by large accumulating empirical evidence
evolving rapidly toward the belief that electron pairs
play a key role in chemical bonding. With the
formulation of the electron-pair bond and the octet
rule, Gilbert N. Lewis (1916) and Irving Langmuir
Irving Langmuir
(1920) have climaxed this evolution.
The early notions of Lewis and Langmuir were
Gilbert N. Lewis
founded largely on chemical facts derived from compounds of the main
groups, particularly those containing light elements. In such compounds, the separations in
energy levels are usually very large compared to inter-electronic repulsion energies, and
excitation or ionization energies are high. These factors, coupled with the tendency of
atoms to use as many of their valence shell orbitals as possible in bonding, leads to stable
molecules where all electrons tend to be paired and the number of pairs in the valence shell
equals the number of valence orbitals; hence, the close association between molecular
stability and the closed shell or noble gas configuration. It is quite evident, however, that
cases where the number of electrons is other than twice the number of available valence
orbitals give serious problems to theories that attribute a special role to electron pairs in
bonding.

Because the electron-pair view of bonding works so well for much of main group
elements, it has been retained and developed as a useful empirical formulation by chemists
whose interests lie in that area. In the early days when very few detailed structures of
molecules were known, the chief preoccupation was the reconciliation of the octet rule,
which required that each atom have a shell of eight valence electrons with known linkage
patterns.

One extremely important aspect of this simple view of bonding was the
systemization it brought to one of the most fundamental chemical reactions: the acid-base
reaction. Lewis generalized the idea of acids and bases as classes of molecules or ions,
which formed bonds by either accepting or donating a pair of electrons. The tendency was
to view this kind of sharing as qualitatively different from the situation wherein each atom
contributed one electron to the bonding pair. Now however, we already know this
conception to be false and that the electrons in a molecule carry no record of their atomic
origins.

By the 1950s, significant number of molecular structures had been determined in
detail, and since then the trickle of structure determinations has become a deluge. This
knowledge of molecular structure brought a lot of pressure on theory to satisfactorily
explain the fine details of structure. An early advance was made by Sidgwick and Powell

(1940), who concluded from analysis of the molecular structures known at the time that
molecules or ions with only single bonds adopt structures that allow the valence electron
pairs to be as far away as possible from the other. A set of simple postulates, which
together constitute the Valence Shell Electron-Pair Repulsion (VSEPR) Theory, were
proposed by Nyholm and Gillespie (1957) to resolve many
outstanding stereochemical questions.

Science satisfies two basic human tendencies: the
desire to understand the fundamental workings of the
universe and the desire to put it to practical use. There are
times when fundamentally inadequate but simple theories
are of much greater practical use than theories that are
more fundamentally correct but very complex that they are
Ronald J. Gillespie (left) and Ronald inaccessible to most people. Similarly, an insignificant
S. Nyholm (right)
exception at the practical level may prove more important
to theoretical progress than all the generally obeyed rules;
so it is with the localized electron-pair bond, beloved by practical chemists. It allows
systemization and manipulation of a vast amount of chemical information and is therefore
justifiable in terms of its usefulness.

Lewis Electron-Dot Diagrams
Lewis Electron-Dot Diagrams got its name from the American Chemist Gilbert Newton
Lewis, whom has a substantial contribution to the understanding of chemical bonding and
thermodynamics in the early twentieth century. G. N. Lewis used dots to represent the
valence electrons in his teaching of chemical bonding. He eventually published his theory of
chemical bonding in 1916.
Lewis dot structures are useful in explaining the chemical bonding in molecules or
ions. In Lewis diagrams, bonds between two atoms exist when they share one or more
pairs of electrons. Furthermore, some molecules have nonbonding pairs, also called lone
pairs, of electrons on atoms. These electrons contribute to the shape and reactivity of the
molecule but do not directly bond the atoms together.
Although Lewis diagrams are overly simplified, it provides a good starting point for
analyzing bonding in molecules. These diagrams are used to represent
paired and unpaired valence electrons in an atom. Figure 1 is an example
Figure 1
the Lewis diagrams for hydrogen, helium, and carbon, where the symbol
represents the element while the dots represent the electrons in the outer shell.
The Lewis structure is used to represent the covalent bonding of a molecule or ion.
Covalent bonds are a type of chemical bonding formed by the sharing of electrons in the
valence shells of the atoms. Covalent bonds are stronger than the electrostatic interactions
of ionic bonds. Most Lewis structures are based on the concept, called the octet rule, that
eight valence electrons, corresponding to s and p electrons outside the noble gas core,
form a particularly stable arrangement, as in the noble gases with s2p6 configuration;
hydrogen is an exception for it is stable with two valence electrons. Furthermore, some
molecules require more than eight electrons around a given central atom, and some
molecules require fewer than eight electrons.

Lewis dot symbols of the first two periods


are given here to illustrate this point (figure 2). In
fact, the entire group (column) of elements has the
same Lewis dot symbols, because they have the
same number of valence electrons.


For simple molecules, the most effective
way to get the correct Lewis structure is to write
the Lewis diagrams for all the atoms involved in
Figure 2
the bonding and adding up the total number of
valence electrons that are available for bonding.
An example is oxygen, which has 6 electrons in the outer
shell the pattern of two lone pairs and two singles. If the
electrons are not placed correctly, one could think that
oxygen has three lone pairs, which would not leave any
unshared electrons to form chemical bonds. An
Figure 3
illustration is provided in figure 3. After adding the four
unshared electrons around element symbol, form electron pairs using the remaining two
outer shell electrons.

One good example of a molecule that follows the octet rule is water.
Water has the chemical formula of H2O, which means there are two
Figure 4
hydrogen atoms and one oxygen atom. The Lewis structure of each of these
atoms is illustrated in figure 4. It can be seen that there are eight valence electrons, six from
oxygen and one from each of the hydrogen atoms. With few exceptions, hydrogen atoms
are always placed on the outside of the molecule, and in this case the central atom would be
oxygen. Each of the two unpaired electrons of the oxygen atom will
form a bond with one of the unpaired electrons of the hydrogen
atoms. The bonds formed by the shared electron pairs can be
represented by either two closely places dots between two element
Figure 5
symbols (figure 5) or more commonly by a straight line between Figure 6
element symbols (figure 6).

When several dot structures are reasonable for a molecule or ion, they all contribute
to the molecular or ionic structure making it more stable. The representation of a
molecular or ionic structure by several structures is called resonance. The more stable the
dot structure is, the more it contributes to the electronic structure of the molecule or ion.

When it is impossible to draw a structure consistent with the octet rule because
additional valence electrons remain to be assigned after the octet rule is satisfied on all
atoms, it is necessary to increase the number of electrons around the central atom. The
increased number of electrons is often described as an expanded shell or an expanded
electron count. The term used to describe central atoms that have electron counts greater
than the atoms usual requirement is hypervalent.

The apparent electron charge of each atom in a molecule, based on the electron-dot
structure, formal charge, helps assess resonance structures and molecular topology. They
are presented as a simplified method of describing structures, just as the Bohr model is a
simple method of describing electron configurations in atoms. The number of valence
electrons available in a free atom of an element minus the total for that atom in the

moleculedetermined by counting lone pairs as two electrons and bonding pairs as one
electron assigned to each atomis the formal charge on the atom:



In addition, the charge on a molecule or ion is equal to sum of all formal charges. However,
it is essential to remember that formal charge is only a tool for assessing Lewis structures,
not a measure of any actual charge on the atoms.



Valence Shell Electron-Pair Repulsion

There is no direct relationship between the formula of a compound and the shape of its
molecules. The shapes of these molecules can be predicted from their Lewis structures,
however, with a model developed about 30 years ago known as the Valence Shell Electron-
Pair Repulsion (VSEPR) Theory.
The VSEPR theory proposes that the geometric arrangement of terminal atoms, or
groups of atoms about a central atom in a covalent compound, or charged ion, is
determined solely by the repulsions between electron pairs present in the valence shell of
the central atom. It is based on the premise that groups of electrons surrounding a central
atom repel each other, and that to minimize the overall energy of the molecule, these
groups of electrons try to get as far apart as possible. Groups of electrons can refer to
electrons that participate in a bond (single, double, or triple) to another atom, or to non-
bonding electrons (e.g. lone pair electrons).
The ideal electronic symmetry of a molecule consisting of a central atom
surrounded by a number of substituents (bonded atoms and non-bonding electrons) is
characteristic of the total number of substituents, and is determined solely by geometric
considerations -- the substituents are arranged so as to maximize the distances amongst
them. VSEPR is useful for predicting the shape of a molecule when there are between 2 and
6 substituents around the central atom (the case of one substituent is not discussed
because it is trivial -- the only possible shape for such a molecule is linear). That means that
there are only five unique electronic geometries to remember. Molecular geometries are
really just special cases of the parent electronic geometry -- this will hopefully be evident
from the models shown on the pages linked to this one.
Since the molecular geometry is determined by how many bonding and non-
bonding electron groups surround the central atom, the first thing one needs to do is count
how many of each there are. There is a notation that simplifies this bookkeeping: ABxEy, the
A represents the central atom, B represents the electron groups that form bonds to other
atoms, and E represents the non-bonding electron groups. The subscripts x and y
indicate how many of each kind are present.


The following is a table with general formula and shapes:


The VSEPR model considers double and triple bonds to have slightly greater
repulsive effects than single bonds because of the repulsive effect of p electrons that
increase the electron density between the bonded atoms beyond that present in an s bond.
For example, the H3CCCH3 angle in (CH3)2C=CH2 is smaller, and the H3CC=CH2 angle is
larger than the trigonal 120.
By the VSEPR approach, trends in many bond angles can be explained by
electronegativity. As the electronegativity of the halogen increases, the halogen exerts a
stronger pull on electron pairs it shares with the central atom. This effect reduces the
concentration of electrons near the central atom, decreasing somewhat the repulsion
between the bonding pairs near the central atom, and allows the lone pair to have more
impact in compressing the halogencentral atomhalogen angles. If the central atom
remains the same, molecules that have a larger difference in electronegativity values
between their central and outer atoms have smaller bond angles. The atom with larger
electronegativity draws the shared electrons toward itself and away from the central atom,
reducing the repulsive effect of these electrons. The net effect is that an increase in bonding
pairbonding pair repulsions near the central atom increases the bond angles. In these
situations the molecule with the most electronegative central atom has the largest bond
angles.
The most electronegative atoms are consequently also the smallest. For example,
the smallest halogen, fluorine, is also the most electronegative. Thus, it could be predicted
that the trends in bond angles is also based on the atomic size, with the smallest atoms
capable of being crowded together most closely. It is important to also consider situations
in which size and electronegativity might have opposite effects, where a smaller outer
group is less electronegative than a larger group attached to a central atom.


Molecular Polarity

When atoms with different electronegativities are bonded, the resulting molecule has polar
bonds, with the electrons of the bond concentrated, perhaps very slightly, on the more
electronegative atom; the greater the difference in electronegativity, the more polar the
bond. As a result, the bonds are dipolar, with relatively positive and negative ends. This
polarity can cause specific interactions between molecules, depending on the overall
molecular structure.


Hydrogen Bonding

The high boiling points of ammonia, water, and hydrogen fluoride are caused by hydrogen
bonds, in which hydrogen atoms bonded to nitrogen, oxygen, or fluorine also form weaker
bonds to a lone pair of electrons on another nitrogen, oxygen, or fluorine. Bonds between
hydrogen and these strongly electronegative atoms are very polar, with a partial positive
charge on the hydrogen. This partially positive hydrogen is strongly attracted to the
partially negative nitrogen, oxygen or fluorine of neighboring molecules.

The attractions among these molecules were considered in the past as primarily
electrostatic in nature, but an alternative molecular orbital approach gives a more

complete description of this phenomenon. The strongly positive hydrogen and the strongly
negative lone pairs tend to line up and hold the molecules together, regardless of the
detailed explanation of the forces involved in hydrogen bonding.

The definition of what atoms can participate in hydrogen bonds has expanded
dramatically beyond the traditional atoms of N, O, and F. Other atoms with high
electronegativity, such as chlorine, can also enable formation of hydrogen bonds in polar
molecules such as chloroform.

In general, boiling points rise with increasing molecular weight, both because the
additional mass requires higher temperature for rapid movement of the molecules and
because the larger number of electrons in the heavier molecules provides larger London
forces. The difference in temperature between the actual boiling point of water and the
extrapolation of the line connecting the boiling points of the heavier analogous compounds
is almost 200 C. Ammonia and hydrogen fluoride have similar but smaller differences from
the extrapolated values for their families. Water has a much larger effect, because each
molecule can have as many as four hydrogen bonds (two through the lone pairs and two
through the hydrogen atoms). Hydrogen fluoride can average no more than two hydro- gen
bonds, because hydrogen fluoride has only one hydrogen.


Self-Assessment Questions

Objective Type

1. What is the correct ABxEy designation of the molecule XeF2Cl2?

a. AB4E2 b. AB2E2 c. AB2E4 d. AB4E4

Answer: a. AB4E2

2. What should the C-C-C bond angle be in the following structure?


a. 60 b. 90 c. 109 d. 120 e. 180

Answer: e. 180

3. Which of the following statements is FALSE about the VSEPR theory?

a. The geometry of the electron groups is determined by minimizing their
repulsions.
b. The geometry of a molecule is determined by the number of electron groups on
the central atom.
c. Bond angles can vary from the idealized angles because lone pairs of electrons
take up less space than bonding groups.
d. Each of the following counts as a single electron group: a lone pair, a single bond,
a double bond, a triple bond, and a single electron.
e. The number of electron groups can be determined from the Lewis structure of
the molecule.


Answer: c.

4. What is the molecular shape of C2H2?

a. Trigonal Bipyramidal

b. Linear

c. Trigonal planar

d. Octahedral

e. Tetrahedral

Answer: b. linear

5. Which one is a good Lewis structure for chlorate?


Answer: a.


Problem Solving

1. Draw the best Lewis Dot Structure for each of the following species.

a) BeF2
b) BCl3
c) CCl4

Answer:

2. Give the name of the electronic arrangement and molecular geometry for each of the
species in question no. 1.

Answer:
a. Linear
b. Trigonal Planar
c. Tetrahedral

3. Consider the following resonance structures of indigo for questions i, ii, and iii.

i.
ii.
iii.

Which one of the resonance structures cant exist?


Which is the best structure?
Which two are completely equivalent resonance structures?

Answer:
i. a; ii. B; iii. c. & e.

4. Answer the following questions for bromine pentafluoride, BrF5.

i. What is its Lewis structure?

ii. What is its VSEPR number?

iii. What is its electron geometry?

Iv. What is its molecular shape?

Answer:

i.

ii. 6 5 1

iii. Octahedral

iv. Square Pyramidal


5. Answer the following questions for tellurium tetrafluoride, TeF4.

i. What is its Lewis structure?

ii. What is its VSEPR number?

iii. What is its electron geometry?

Iv. What is its molecular shape?

Answer:

i.

ii. 5 4 1
iii. Trigonal Bipyramidal
iv. See-Saw




References
Miessler, G. (2014). Inorganic Chemistry. New Jersey: Pearson Education, Inc.
Lewis, Gilbert Newton. The Atom and the Molecule. New York: Chemical Catalog, 1923.
Lewis
Diagrams
and
Structures.
(2002)
Retrieved
from:
http://www.shodor.org/unchem/basic/lewis/
Lewis
Dot
Structures.
Retrieved
from:
http://www.science.uwaterloo.ca/~cchieh/cact/c120/dotstruc.html
Butler, I. (1989). Inorganic Chemistry: Principles and Applications. California: The
Benjamin/Cummings Publishing Company, Inc.