Chemical Bonding

Chapter 8
Overview
Lewis Symbols & Octet
Ionic Bonding
Electron Configurations and Ions
Ion Sizes
Covalent Bonding
Multiple Bonds
Bond Polarity
Electronegativity
Lewis Structures
Formal Charge
Resonance Structures
Exceptions to Lewis Rules
Electron Deficient
Expanded Valence
Radicals
Covalent Bond Strengths
Bond Enthalpies
Bond Length
Oxidation Numbers
Lewis Symbols and Octet Rule
Lewis symbols
symbols showing valence electrons for an atom
or ion
for active metals & representative elements
number of valence electron = group number
for representative elements
stability requires 8 electrons -- an octet
like the nobel gases
Lewis Dot Symbols:

Na
C
N
1s
2
2s
2
p
6
3s
1
1s
2
2s
2
2p
2
1s
2
2s
2
2p
3
O
1s
2
2s
2
2p
4
1s
2
2s
2
2p
5






F









Ionic Bonding
Ionic Bond
strong attractive, electrostatic force between
cations and anions
Ions form to achieve noble gas configuration an
octet
ion symbols shown as Lewis symbols
generally forms between metals and non-
metals
overall, the formation of ionic bonds releases
energy, exothermic

Na

Cl





+
Na
Cl






-
+
electropositive
metal
nonmetal with
high electron
affinity
Atoms Ions
both have
octets
Na
(s)
+ Cl
2(g)
NaCl
(s)
DH
f
o
= - 411 kJ/mol
Cl




Cl




Mg
Cl





Cl






Mg





2+
_
_
Atoms Ions
electropositive
metal
nonmetals with
high electron
affinity
all have
octets

Energetics of Ionic Bond Formation
formation of ionic compounds is exothermic
electrostatic attraction E = k Q
1
Q
2

lattice energy d
Q
1
charge of cation, Q
2
charge of anion, d distance
between cation and anion
steps for formation
change Na from solid to gas -- endothermic
dissociate Cl
2(g)
-- endothermic
remove electron from Na -- endothermic
add electron to Cl -- exothermic
combine ions, electrostatic attraction -- very
exothermic
sum of all above is exothermic
Practice Ex. 8.1:
Which would you expect to have the greatest
lattice energy:
AgCl CuO CrN
AgCl Q
1
= +1 Q
2
= -1
CuO Q
1
= +2 Q
2
= -2
CrN Q
1
= +3 Q
2
= -3
CrN because E = k Q
1
Q
2
is largest
d
Problem:
If NaCl has a high lattice E and is very stable,
would you expect NaCl
2
to be even more
stable?
NaCl
2
does not form -- even though the lattice
energy would be higher, the formation of Na
2+

would be so costly, so endothermic, that it
would overwhelm the exothermic lattice
energy
Formation of Ions
Representative Elements
last electron entered in an electron
configuration is the first electron lost in ion
formation
11
Na 1s
2
2s
2
2p
6
3s
1

11
Na
+
1s
2
2s
2
2p
6
3s
0
Transition Metals
the s electrons are always lost first, before any
d electrons are lost
26
Fe [Ar] 4s
2
3d
6

26
Fe
2+
[Ar] 4s
0
3d
6

26
Fe
3+
[Ar] 4s
0
3d
5
Sizes of Ions
Cations smaller than atoms from which
they are derived
removal of one or more electrons will
increase Z
eff
felt by remaining electrons
causes contraction of cation
Anions larger than atoms from which they
are derived
addition of one or more electrons will
decrease Z
eff
felt by outer electrons
causes some repulsion between electrons creating
some expansion of size
Covalent Bonding
A pair of electrons shared between two
atoms
Generally occurs between two non-metals
so that atoms can attain an octet
Releases energy upon formation -- exothermic
Two atoms can share:
one pair of electrons , single bond
two pair of electrons, double bond
three pair of electrons, triple bond
H
H




H H


One Shared Pair of Electrons =
Single Bond
O O









O O









Two Shared Pair of Electrons =
Double Bond
N
N
N N




















Three Shared Pair of Electrons =
Triple Bond
The more electrons, the shorter & stronger the
bond
Bond strength
single < double < triple
Bond length
single > double > triple
N - N N = N NN
1.47 1.24 1.10
163 kJ 418 kJ 941 kJ
Two types of covalent bonds
non-polar
electrons are shared equally
atoms sharing electrons have equal attraction for
them
H H


O O









polar
electrons are not shared equally
atoms sharing electrons have different attractions for
them
H Cl






Cl has a greater attraction for the
electrons
Bond Polarity & Electronegativity
Electronegativity
ability of an atom in a bond to attract the
shared electrons
related to electron affinity & ionization energy
but not the same as
decreases down a group (except for transition
elements)
increases across a row
EN of atom are relative to one another
range from 0.7 to 4.0
Bond Polarity
electrons shared between two atoms with
different EN are shared unequally
unequal sharing creats a separation of charge --
polar bond
greater the DEN of the atoms, the greater the
polarity of the bond
H Cl
d+ d -
H Cl
EN 2.1 EN 3.0
shared electrons spend
more time around Cl
partial (+)
charge
partial (-)
charge
Drawing Lewis Structures
Rules:
write Lewis symbols for each atom in formula
count total no. of electrons
count total no. of unpaired electrons divide by
2 = no. of covalent bonds
arrange atoms (more electropositive in the
center)
place correct no. of covalent bonds
place remaining electrons around atoms so that
all atoms have octets
NH
3
N H H H

8 total electrons 6 upe
-
2 = 3 cov. bonds
N H
H
H

hydrogens are always terminal
CO
2
C O O

16 total electrons 8 upe
-
2 = 4 cov. bonds
= C = O O

more electropositive atom
CO
3
2-
C O O O

24 total electrons 8 upe
-
2 = 4 cov. bonds
C
O
O O




Formal Charge
Bookkeeping method to keep track of
electrons in Lewis structures
Rules
all unshared electrons assigned to the atom on
which they reside
half of all shared electrons are assigned to
each atom in bond
no. valence e
-
on free atom
- no. valence e
-
on bound atom
Formal Charge
NH
3
N H H H

N H
H
H

N 5 e
-

5 e
-

0

H 1 e
-

1 e
-

0

CO
2
C O O

= C = O O

C 4 e
-

4 e
-

0
O 6 e
-

6 e
-

0
CO
3
2-
C O O O

C 4 e
-

4 e
-

0


C
O
O O




0
O 6 e
-

6 e
-

0
0
O 6 e
-

7 e
-

-1
-1 -1
-2
Formal charge must equal any charge on the
structure
prediction of stability
most stable structures have lowest sum of
absolute values of formal charges
O O

= C = O O

- C

0 0 0
0 -1 +1
0 + 0 + 0 = 0
1 + 0 + 1 = 2
preferred structure