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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.
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
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.
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
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.