Formal Charge-Resonance Excellent

Chemical
Bonding I:
Lewis Theory
2008, Prentice Hall
Chemistry: A Molecular Approach, 1
st
Ed.
Nivaldo Tro
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Tro, Chemistry: A Molecular Approach 2
Bonding Theories
explain how and why atoms attach together
explain why some combinations of atoms are stable
and others are not
why is water H
2
O, not HO or H
3
O
one of the simplest bonding theories was developed by
G.N. Lewis and is called Lewis Theory
Lewis Theory emphasizes valence electrons to explain
bonding
using Lewis Theory, we can draw models called
Lewis structures that allow us to predict many
properties of molecules
aka Electron Dot Structures
such as molecular shape, size, polarity
Why Do Atoms Bond?
processes are spontaneous if they result in a system
with lower potential energy
chemical bonds form because they lower the potential
energy between the charged particles that compose
atoms
the potential energy between charged particles is
directly proportional to the product of the charges
the potential energy between charged particles is
inversely proportional to the distance between the
charges
Potential Energy Between
Charged Particles
e
0
is a constant
= 8.85 x 10
-12
C
2
/Jm
for charges with the same sign, E
potential
is + and the
magnitude gets less positive as the particles get farther
apart
for charges with the opposite signs, E
potential
is and
the magnitude gets more negative as the particles get
closer together
remember: the more negative the potential energy, the
more stable the system becomes

|
.
|
\
|
-
e
=
r
q q
2 1
0
potential
4
1
E
t
Potential Energy Between
Charged Particles
The repulsion between
like-charged particles
increases as the
particles get closer
together. To bring
them closer requires
the addition of more
energy.
The attraction between
opposite-charged
particles increases as
the particles get closer
together. Bringing
them closer lowers the
potential energy of the
system.
Bonding
a chemical bond forms when the potential
energy of the bonded atoms is less than the
potential energy of the separate atoms
have to consider following interactions:
nucleus-to-nucleus repulsion
electron-to-electron repulsion
nucleus-to-electron attraction
Types of Bonds
Types of Atoms Type of Bond
Bond
Characteristic
metals to
nonmetals
Ionic
electrons
transferred
nonmetals to
nonmetals
Covalent
electrons
shared
metal to
metal
Metallic
electrons
pooled
8
Types of Bonding
Ionic Bonds
when metals bond to nonmetals, some electrons
from the metal atoms are transferred to the
nonmetal atoms
metals have low ionization energy, relatively easy to
remove an electron from
nonmetals have high electron affinities, relatively
good to add electrons to
Covalent Bonds
nonmetals have relatively high ionization energies, so it
is difficult to remove electrons from them
when nonmetals bond together, it is better in terms of
potential energy for the atoms to share valence
electrons
potential energy lowest when the electrons are between the
nuclei
shared electrons hold the atoms together by attracting
nuclei of both atoms
Determining the Number of Valence
Electrons in an Atom
the column number on the Periodic Table will tell you
how many valence electrons a main group atom has
Transition Elements all have 2 valence electrons; Why?
1A/1 2A/2 3A/13 4A/14 5A/15 6A/16 7A/17 8A/10
Li Be B C N O F Ne
1 e
-1
2 e
-1
3 e
-1
4 e
-1
5 e
-1
6 e
-1
7 e
-1
8 e
-1
Lewis Symbols of Atoms
electron dot symbols
use symbol of element to represent nucleus and
inner electrons
use dots around the symbol to represent valence
electrons
pair first two electrons for the s orbital
put one electron on each open side for p electrons
then pair rest of the p electrons
- Li
-
-
Be
-
-
-
B
-
-
-
- C
-
-
-
-
-
N
- -
-
-
-
-

O
- -
-
-
-
-
-

F
- -
-
-
-
-
- -

Ne
Lewis Symbols of Ions
Cations have Lewis symbols without
valence electrons
Lost in the cation formation
Anions have Lewis symbols with 8 valence
electrons
Electrons gained in the formation of the anion
Li Li
+1

- -
-
-
-
-
-

F
1

F
- -
-
-
-
-
- -
(
(

What We Know
the noble gases are the least reactive group
of elements
the alkali metals are the most reactive
metals and their atoms almost always lose 1
electron when they react
the halogens are the most reactive group of
nonmetals and in a lot of reactions they gain
1 electron
Stable Electron Arrangements
And Ion Charge
Metals form cations by losing
enough electrons to get the
same electron configuration
as the previous noble gas
Nonmetals form anions by
gaining enough electrons to
get the same electron
configuration as the next
noble gas
The noble gas electron
configuration must be very
stable
Atom Atoms
Electron
Config
Ion Ions
Electron
Config
Na [Ne]3s
1
Na
+1
[Ne]
Mg [Ne]3s
2
Mg
+2
[Ne]
Al [Ne]3s
2
3p
1
Al
+3
[Ne]
O [He]2s
2
2p
4
O
-2
[Ne]
F [He]2s
2
2p
5
F
-1
[Ne]

Octet Rule
when atoms bond, they tend to gain, lose, or share electrons to
result in 8 valence electrons
ns
2
np
6
noble gas configuration
many exceptions
H, Li, Be, B attain an electron configuration like He
He = 2 valence electrons
Li loses its one valence electron
H shares or gains one electron
though it commonly loses its one electron to become H
+

Be loses 2 electrons to become Be
2+

though it commonly shares its two electrons in covalent bonds, resulting in 4
valence electrons
B loses 3 electrons to become B
3+
though it commonly shares its three electrons in covalent bonds, resulting in 6
valence electrons
expanded octets for elements in Period 3 or below
using empty valence d orbitals
Lewis Theory
the basis of Lewis Theory is that there are
certain electron arrangements in the atom that
are more stable
octet rule
bonding occurs so atoms attain a more stable
electron configuration
more stable = lower potential energy
no attempt to quantify the energy as the calculation
is extremely complex
Covalent Bonding:
Bonding and Lone Pair Electrons
Covalent bonding results when atoms share pairs
of electrons to achieve an octet
Electrons that are shared by atoms are called
bonding pairs
Electrons that are not shared by atoms but belong
to a particular atom are called lone pairs
aka nonbonding pairs
Lone Pairs Bonding Pairs
O S O

Single Covalent Bonds
two atoms share a pair of electrons
2 electrons
one atom may have more than one single bond
F

H
H
O

H

H

O

F
F
Double Covalent Bond
two atoms sharing two pairs of electrons
4 electrons
O O

O O

Triple Covalent Bond
two atoms sharing 3 pairs of electrons
6 electrons
N

N

N
N N

Covalent Bonding
Predictions from Lewis Theory
Lewis theory allows us to predict the formulas of
molecules
Lewis theory predicts that some combinations should be
stable, while others should not
because the stable combinations result in octets
Lewis theory predicts in covalent bonding that the
attractions between atoms are directional
the shared electrons are most stable between the bonding atoms
resulting in molecules rather than an array
Covalent Bonding
Model vs. Reality
molecular compounds have low melting points and
boiling points
MP generally < 300C
molecular compounds are found in all 3 states at room
temperature
melting and boiling involve breaking the attractions
between the molecules, but not the bonds between
the atoms
the covalent bonds are strong
the attractions between the molecules are generally weak
the polarity of the covalent bonds influences the strength of
the intermolecular attractions
Intermolecular Attractions vs. Bonding
Ionic Bonding
Model vs. Reality
some molecular solids are brittle and hard, but
many are soft and waxy
the kind and strength of the intermolecular
attractions varies based on many factors
the covalent bonds are not broken, however, the
polarity of the bonds has influence on these
attractive forces
Ionic Bonding
Model vs. Reality
molecular compounds do not conduct electricity in the
liquid state
molecular acids conduct electricity when dissolved in
water, but not in the solid state
in molecular solids, there are no charged particles
around to allow the material to conduct
when dissolved in water, molecular acids are ionized,
and have the ability to move through the structure and
therefore conduct electricity
Bond Polarity
covalent bonding between unlike atoms results in
unequal sharing of the electrons
one atom pulls the electrons in the bond closer to its side
one end of the bond has larger electron density than the
other
the result is a polar covalent bond
bond polarity
the end with the larger electron density gets a partial
negative charge
the end that is electron deficient gets a partial positive
charge
HF
H F

o+ o
- -
-
-
- -
F H

EN 2.1 EN 4.0
Electronegativity
measure of the pull an atom has on bonding
electrons
increases across period (left to right) and
decreases down group (top to bottom)
fluorine is the most electronegative element
francium is the least electronegative element
the larger the difference in electronegativity,
the more polar the bond
negative end toward more electronegative atom
Electronegativity Scale
31
Electronegativity and Bond Polarity
If difference in electronegativity between bonded atoms
is 0, the bond is pure covalent
equal sharing
is 0.1 to 0.4, the bond is nonpolar covalent
0.5 to 1.9, the bond is polar covalent
larger than or equal to 2.0, the bond is ionic
100%
0 0.4 2.0 4.0
4% 51%
Percent Ionic Character
Electronegativity Difference
Bond Polarity
EN
Cl
= 3.0
3.0 - 3.0 = 0
Pure Covalent
EN
Cl
= 3.0
EN
H
= 2.1
3.0 2.1 = 0.9
Polar Covalent
EN
Cl
= 3.0
EN
Na
= 0.9
3.0 0.9 = 2.1
Ionic
Bond Dipole Moments
the dipole moment is a quantitative way of describing the
polarity of a bond
a dipole is a material with positively and negatively charged ends
measured
dipole moment, , is a measure of bond polarity
it is directly proportional to the size of the partial charges and
directly proportional to the distance between them
= (q)(r)
not Coulombs Law
measured in Debyes, D
the percent ionic character is the percentage of a bonds
measured dipole moment to what it would be if full ions
Dipole Moments
Water a Polar Molecule
stream of
water
attracted
to a
charged
glass rod
stream of
hexane
not
attracted
to a
charged
glass rod
Example 9.3(c) - Determine whether an N-O
bond is ionic, covalent, or polar covalent.
Determine the electronegativity of each element
N = 3.0; O = 3.5
Subtract the electronegativities, large minus small
(3.5) - (3.0) = 0.5
If the difference is 2.0 or larger, then the bond is
ionic; otherwise its covalent
difference (0.5) is less than 2.0, therefore covalent
If the difference is 0.5 to 1.9, then the bond is
polar covalent; otherwise its covalent
difference (0.5) is 0.5 to 1.9, therefore polar covalent
Lewis Structures
of Molecules
shows pattern of valence electron distribution in
the molecule
useful for understanding the bonding in many
compounds
allows us to predict shapes of molecules
allows us to predict properties of molecules and
how they will interact together
Lewis Structures
use common bonding patterns
C = 4 bonds & 0 lone pairs, N = 3 bonds & 1 lone pair,
O= 2 bonds & 2 lone pairs, H and halogen = 1 bond, Be
= 2 bonds & 0 lone pairs, B = 3 bonds & 0 lone pairs
often Lewis structures with line bonds have the lone
pairs left off
their presence is assumed from common bonding patterns
structures which result in bonding patterns
different from common have formal charges
B
C
N O F
Writing Lewis Structures of Molecules
HNO
3

1) Write skeletal structure
H always terminal
in oxyacid, H outside attached to Os
make least electronegative atom central
N is central
2) Count valence electrons
sum the valence electrons for each
atom
add 1 electron for each charge
subtract 1 electron for each + charge
O N O H
O
N = 5
H = 1
O
3
= 36 = 18
Total = 24 e
-

HNO
3
3) Attach central atom to the surrounding atoms with
pairs of electrons and subtract from the total
O N O H
O

|
Electrons
Start 24
Used 8
Left 16
HNO
3
4) Complete octets, outside-in
H is already complete with 2
1 bond
and re-count electrons
- - - -
- - - -
- -
|
:
: :
O N O H
O
N = 5
H = 1
O
3
= 36 = 18
Total = 24 e
-

Electrons
Start 24
Used 8
Left 16
Electrons
Start 16
Used 16
Left 0
HNO
3
5) If all octets complete, give extra
electrons to central atom.
elements with d orbitals can have
more than 8 electrons
Period 3 and below
6) If central atom does not have
octet, bring in electrons from
outside atoms to share
follow common bonding patterns
if possible
- -
- - - -
- -
= :
: :
O N O H
|
O
Practice - Lewis Structures
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
Practice - Lewis Structures
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
:O::C::O:
O P
O
O
O
H H
H
F Se
O
F
O S
O
O
O N O
16 e
-

26 e
-

18 e
-

26 e
-

32 e
-

14 e
-

H P P H
H H

Formal Charge
during bonding, atoms may wind up with more
or less electrons in order to fulfill octets - this
results in atoms having a formal charge
FC = valence e
-
- nonbonding e
-
- bonding e
-

left O FC = 6 - 4 - (4) = 0
S FC = 6 - 2 - (6) = +1
right O FC = 6 - 6 - (2) = -1
sum of all the formal charges in a molecule = 0
in an ion, total equals the charge

O S O

Writing Lewis Formulas of
Molecules (contd)
7) Assign formal charges to the atoms
a) formal charge = valence e
-
- lone pair e
-
- bonding e
-

b) follow the common bonding patterns
- -
-
-
-
-
- -
- -
-
-
- - - - - -
O S O
H
|
H O C C H
|| |
O H
- -
- -
-
-
- -

0
+1 -1
all 0
Common Bonding Patterns
B
C
N O
C
+
N
+
O
+
C
-
N
-
O
-
B
-
F
F
+
-
F
Practice - Assign Formal Charges
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
O P
O
O
O
H H
H
F Se
O
F
O S
O
O
O N O
H P P H
H H

Practice - Assign Formal Charges
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
O P
O
O
O
H H
H
F Se
O
F
O S
O
O
O N O
H P P H
H H

all 0
-1
P = +1
rest 0
S = +1

Se = +1

-1
-1
all 0
-1
-1
-1
Resonance
when there is more than one Lewis structure for a
molecule that differ only in the position of the
electrons, they are called resonance structures
the actual molecule is a combination of the
resonance forms a resonance hybrid
it does not resonate between the two forms,
though we often draw it that way
look for multiple bonds or lone pairs

O S O O S O

Resonance
Ozone Layer
Rules of Resonance Structures
Resonance structures must have the same connectivity
only electron positions can change
Resonance structures must have the same number of
electrons
Second row elements have a maximum of 8 electrons
bonding and nonbonding
third row can have expanded octet
Formal charges must total same
Better structures have fewer formal charges
Better structures have smaller formal charges
Better structures have formal charge on more
electronegative atom
O N
O
O
Drawing Resonance Structures

1. draw first Lewis structure that
maximizes octets
2. assign formal charges
3. move electron pairs from atoms
with (-) formal charge toward
atoms with (+) formal charge
4. if (+) fc atom 2
nd
row, only move
in electrons if you can move out
electron pairs from multiple
bond
5. if (+) fc atom 3
rd
row or below,
keep bringing in electron pairs to
reduce the formal charge, even if
get expanded octet.

-1
-1
+1
O N
O
O
-1
-1 +1
Exceptions to the Octet Rule
expanded octets
elements with empty d orbitals can have more
than 8 electrons
odd number electron species e.g., NO
will have 1 unpaired electron
free-radical
very reactive
incomplete octets
B, Al
Drawing Resonance Structures
1. draw first Lewis structure that
maximizes octets
2. assign formal charges
3. move electron pairs from atoms
with (-) formal charge toward
atoms with (+) formal charge
4. if (+) fc atom 2
nd
row, only move
in electrons if you can move out
electron pairs from multiple bond
5. if (+) fc atom 3
rd
row or below,
keep bringing in electron pairs to
reduce the formal charge, even if
get expanded octet.

O S
O
O
O
H H
-1
-1
+2
O S
O
O
O
H H
0
0
0
Practice - Identify Structures with Better or
Equal Resonance Forms and Draw Them
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
O P
O
O
O
H H
H
F Se
O
F
O S
O
O
O N O
H P P H
H H

all 0
-1
P = +1
S = +1

Se = +1

-1
-1
all 0
-1
-1
-1
Practice - Identify Structures with Better or
Equal Resonance Forms and Draw Them
CO
2

SeOF
2

NO
2
-1
H
3
PO
4

SO
3
-2

P
2
H
4
O P
O
O
O
H H
H
O P
O
O
O
H H
H
F Se
O
F
F Se
O
F
O S
O
O
O S
O
O
O S
O
O
O S
O
O
O N O

O N O

H P P H
H H

none
-1
-1
-1
+1
all 0
+1
all 0
-1
none
S = 0
in all
res. forms
Bond Energies
chemical reactions involve breaking bonds in reactant
molecules and making new bond to create the products
the AH
reaction
can be calculated by comparing the cost
of breaking old bonds to the profit from making new
bonds
the amount of energy it takes to break one mole of a
bond in a compound is called the bond energy
in the gas state
homolytically each atom gets bonding electrons
Trends in Bond Energies
the more electrons two atoms share, the stronger
the covalent bond
CC (837 kJ) > C=C (611 kJ) > CC (347 kJ)
CN (891 kJ) > C=N (615 kJ) > CN (305 kJ)
the shorter the covalent bond, the stronger the
bond
BrF (237 kJ) > BrCl (218 kJ) > BrBr (193 kJ)
bonds get weaker down the column
Using Bond Energies to Estimate AH
rxn

the actual bond energy depends on the surrounding
atoms and other factors
we often use average bond energies to estimate the
AH
rxn
works best when all reactants and products in gas state
bond breaking is endothermic, AH(breaking) = +
bond making is exothermic, AH(making) =
AH
rxn
= (AH(bonds broken)) + (AH(bonds formed))

63
Using Bond Energies to Estimate AH
rxn

AH
rxn
NaCl
65
Estimate the Enthalpy of the Following Reaction
H H
+
O O
H O O H
Estimate the Enthalpy of the Following Reaction
H
2
(g) + O
2
(g) H
2
O
2
(g)
reaction involves breaking 1mol H-H and 1 mol O=O
and making 2 mol H-O and 1 mol O-O
bonds broken (energy cost)
(+436 kJ) + (+498 kJ) = +934 kJ
bonds made (energy release)
2(464 kJ) + (142 kJ) = -1070
AH
rxn
= (+934 kJ) + (-1070. kJ) = -136 kJ
(Appendix AH
f
= -136.3 kJ/mol)
Bond Lengths
the distance between the nuclei of
bonded atoms is called the bond
length
because the actual bond length
depends on the other atoms around
the bond we often use the average
bond length
averaged for similar bonds from
many compounds
Trends in Bond Lengths
the more electrons two atoms share, the shorter the
covalent bond
CC (120 pm) < C=C (134 pm) < CC (154 pm)
CN (116 pm) < C=N (128 pm) < CN (147 pm)
decreases from left to right across period
CC (154 pm) > CN (147 pm) > CO (143 pm)
increases down the column
FF (144 pm) > ClCl (198 pm) > BrBr (228 pm)
in general, as bonds get longer, they also get weaker
Bond Lengths

Formal Charge-Resonance Excellent

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Chemical

Tro, Chemistry: A Molecular Approach 14

Tro, Chemistry: A Molecular Approach 22

Drawing Resonance Structures

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