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Chemistry 445

Inorganic Chemistry
Lecture 1.

Lewis Dot Structures


VSEPR

G. N. Lewis
was probably
the best chemist
who never won
the Nobel Prize

Gilbert Newton Lewis (1875-1946)

Lewis Dot Structures (revision)


Lewis dot structures present a simple approach to bonding that
allows us to rationalize much molecular structure. The idea is that
atoms share electrons in the valence shell to form the chemical
bond, with one pair of electrons per bond. Note that each H-atom
has two electrons, which is the structure of He, the next inert gas.
Electron pair = single bond
Valence electrons

H-atom

H-atom

(Each H-atom has one valence electron)

H 2 molecule

Lewis Dot Structures (contd.):


Two shared pairs of electrons
= double bond

O-atom

O-atom

O 2 molecule

Periodic table

3
Oxygen has six valence electrons

The octet rule


Electrons are shared in forming bonds such that atoms have the
same number of electrons in their valence shells as the nearest
noble gas, including the electrons shared with the atom to which
they are bonded.

O-atom

O-atom

O 2 molecule

Each oxygen atom in the O2 molecule now has eight


valence electrons, including those it shares with the
other oxygen atom = number of electrons (8 = octet)
in the nearest inert gas = neon.

8.1 Chemical Bonds, Lewis Symbols, and


the Octet rule.
Chemical bonding involves mainly the attempt to
achieve the rare gas number of valence electrons,
i.e. an octet. This can be achieved in several
ways.
Ionic bond: Electrons are mainly the property of
one of the two atoms forming the bond.
Covalent bond: Electrons are shared so that each
atom has a noble gas electronic configuration.
Metallic bonds. Electrons are lost into the
conduction band.

8.2 Ionic Bonding.


This occurs between metallic elements from
the left-hand side of the periodic table and
non-metallic elements from the right hand
side of the periodic table.

Note that Na gives up its lone valence


electron to Cl, so that they both end up with
an octet of electrons.

8.3 Covalent bonding.


Here the two atoms share the electrons
to achieve a covalent bond.

two pairs of electrons equally shared


between the two oxygen atoms

Multiple Bonds and bond order:


The sharing of a single pair of electrons
consititutes a single bond. Sharing of two
pairs of electrons constitutes a double bond,
and sharing three pairs of electrons
constitutes a triple bond.

.. ..

H:H
Single bond

:O::O:
double bond

:N:::N:
triple bond

Bond order: a single bond has bond order =


1, a double bond has bond order = 2, and a
triple bond has a bond order = 3. Fractional
bond orders such as 1 or 1 are also
possible, as discussed below.

Some more examples of Lewis dot structures:


The N2 molecule:

N-atom

N-atom

triple bond

N 2 molecule

Periodic table
1

Examples of Lewis dot diagrams:


Methane, CH4:
One shared
pair of electrons
= single bond

Carbon has four


valence electrons (red)

H
H

H
Hydrogens
achieve two
electrons like He

Carbon achieves
octet of electrons

single line
= single bond

Examples of Lewis dot diagrams:


Carbon dioxide: (CO2)
Carbon has four
valence electrons (red)

oxygens have six


valence electrons (black)

O=C=O
Carbon and both oxygens
achieve an octet of electrons

double line =
double bond

two shared
pairs of electrons
= double bond

Examples of Lewis dot diagrams:


Sulfur dioxide: (SO2)

double
bond?

single
bond?

O=S-O
(or O-S=O ?)
SO2 is an example where a
actual structure is average
of the two (bond order = 1) :
molecule can be written in
two ways and actual structure
is the average of the two. This
is called RESONANCE (see later)

Slightly different Lewis dot


representations:
One can also represent molecules/ions with a
combination of dots and lines for bonds,
remembering that each line represents a shared
pair of electrons, e.g. the phosphate anion:

8.6 Resonance structures: Ozone (O3)


bond order = 1

..

..

double arrow
= resonance

The ozone molecule can


be written with two
equivalent Lewis dot
structures. In such a
situation the actual
structure is the average
of these two structures,
with the two O-O bond
lengths equal.

O
=
O
O
O
O-O bonds = 2.78

O
O

The ozone molecule

Resonance structures the nitrite anion: (NO2-)


In drawing up a Lewis dot diagram, if we are dealing with
an anion, we must put in an extra electron for each
negative charge on the anion:
negative charge
on anion
One extra electron
in Lewis dot
N
diagram because
O
Bond order
O
of single negative
= 1
charge on anion

..

..
N

..
N

Two resonance structures

N
O

average structure

The nitrate anion:


..

B.O. = 2

O
N

average bond
order (B.O.)=
2 + 1 + 1 = 1
3

B.O. = 1

Number of canonical structures

O
N

O
N

B.O. = 1

to work out bond order,


pick the same bond in
each structure and
average the bond order
for that bond

Resonance in benzene.
H
C
H

C
C

H
C

C
H

H
H

C
C

C
H

or

C
C
H

There are two


canonical structures
for benzene, which
means that the C to C
bonds have a bond
order of (2+1)/2 = 1.5.
The benzene ring has
a very high stability
due to this resonance,
which is called
aromaticity.

Short-hand versions for the benzene ring

8.7. Exceptions to the octet rule.


BF3. This can be written as F2B=F with three
resonance structures. To complete its octet, BF3
readily reacts with e.g. H2O to form BF3.H2O. The
actual structure of BF3 appears not to involve a
double bond and does not obey the octet rule:
Possible resonance
structure for BF3,
but is not important
as this would
involve the very
electronegative
F donating es to B

Best representation of
BF3 with B
having only
6 electrons
in its valence
shell

Exceptions to the octet rule: free radicals


There are some molecules that do not obey the octet
rule because they have an odd number of electrons.
Such molecules are very reactive, because they do
not achieve an inert gas structure, and are known as
free radicals. Examples of free radicals are chlorine
dioxide, nitric oxide, nitrogen dioxide, and the
superoxide radical:
odd electrons

nitric oxide

chlorine dioxide

Exceptions to the Octet rule: Heavier atoms (P, As, S,


Se, Cl, Br, I) may attain more than an octet of
electrons:
Example: PF5.
In PF5, the P atom has ten electrons in its valence
shell, which occurs commonly for heavier non-metal
atoms:
leave off F
F
electrons not
shared with P

F
P has
10 valence
electrons

F
F

PF5

Many phosphorus compounds do obey the


octet rule:

PF3 and [PO4]3- :

three blue electrons are


from charge on anion

Some compounds greatly exceed an


octet of electrons:

IF7
XeF6
(both I and Xe have 14 valence es)
(Think about [XeF8]2-)