Chem 16 General Chemistry 1

04 Chemical Bonding

Dr. Gil C. Claudio

Second Semester 2014-2015
Table of Contents

Contents
1 Basic Concepts of Chemical Bonding

2 The Octet Rule and Electronegativity

3 Lewis Symbols

4 Metallic Bonding

5 Ionic Bonding

6 Covalent Bonding

7 Bond Polarity and Electronegativity

8 Drawing Lewis Structures

9 Formal Charges

10 Resonance Structures

11 Exceptions the the Octet Rule

10

12 Bond Energies and Bond Lengths

11

References
References of these notes
General Chemistry, 10th ed, by Ralph H. Petrucci, F. Geoffrey Herring,
Jeffrey D. Madura, and Carey Bisonnette.

1 Basic Concepts of Chemical Bonding

Lewis Theory: An Overview
The Lewis theory refers to a description of chemical bonding through
Lewis symbols and Lewis structures in accordance with a particular set of
rules.
1. Electrons, especially those of the outermost (valence) electronic shell,
play a fundamental role in chemical bonding.
2. In some cases, electrons are transferred from one atom to another.
Positive and negative ions are formed and attract each other through
electrostatic forces called ionic bonds.
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3. In other cases, one or more pairs of electrons are shared between atoms.
A bond formed by the sharing of electrons between atoms is called a
covalent bond.
4. Electrons are transferred or shared in such a way that each atom acquires
an especially stable electron configuration. Usually this is a noble gas
configuration, one with eight outer-shell electrons, or an octet.

2 The Octet Rule and Electronegativity

Octet Rule
Octet ruleIn forming bonds, main group elements gain, lose, or share
electrons to achieve a stable electron configuration with eight valence electrons.
s2 p6

8 electrons

same electronic configuration as a noble gas, or closed shell

configuration
for example, for Ne, shell 2 is full (2s2 2p6 ) and shell 3 is empty, all
electrons paired.
open shells, which has unpaired electrons, are less stable than
closed shells
Chemical Bonds and Electronegativity
Bonds are electrostatic forces of attraction between atoms.
Start with 2 concepts
Octet rule atoms acquire a special stability when orbitals are completely
filled
Electronegativity difference between the two bonded atoms.
Electronegativity: Pauling Scale

en.wikipedia.org/wiki/Electronegativity

3 Lewis Symbols
Lewis Symbol
In the Lewis symbol of an element, valence electrons are represented by
dots placed around the chemical symbol of the element.
2

s2p6

s2p5

s2p4

s2p3

s2p2

s2p1

s2

s1

Lewis Symbols of Main Group Elements

He

Li

Be

Ne

Na

Mg

Al

Si

Cl

Ar

Ca

Ga

Ge

As

Se

Br

Kr

Rb

Sr

In

Sn

Sb

Te

Xe

Cs

Ba

Tl

Pb

Bi

Po

At

Ra

Fr

Ra

Lewis Structure
A Lewis structure is a combination of Lewis symbols that depicts the
transfer or sharing of electrons in a chemical bond.

4 Metallic Bonding
Metallic Bonding
Metallic bondingan idealized type of bonding based on the attraction
between metal ions and a delocalized sea of their valence electron.
In general, metal atoms are relatively large and have a small number of
outer electrons that are shielded from the nuclear charge by filled inner
levels.
Thus they lose their electrons comparatively easily (low IE) but do not
gain them very readily (small or positive EA).
Thus metal atoms are in a pool of evenly distributed sea of electrons that
flow among the metal ions and attracts them together. The electrons in
metallic bonding are delocalized and move freely throughout the piece
of metal.

5 Ionic Bonding
Ionic Bond
Ionic bond a bond formed on the basis of electrostatic forces that exist
between oppositely charged ions. The ions are formed from atoms by a transfer
of one or more electrons.
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 Ionic bonds exist between atoms that have a high EN difference.

Given sodium chloride, NaCl. Their ENs are 0.9 and 3.0, respectively
Because of the big difference in electronegativity, Na will tend to give one
electron and Cl will accept the electron.
Because of the octet rule, Na will only give one electron and Cl will only
accept one electron. Doing so, both follow a noble gas configuration
Na+ [Ne] and Cl [Ar]
Ions
Ions are electrically charged atom or group of atoms (poly-atomic ion)
Ions can be positively charged (cations) or negatively charged (anions)
atoms that lose electron(s) become cations
atoms that gain electron(s) become anions
Binary and Ternary Ionic Compounds
Binary ionic compounds consist of monatomic cations and monatomic
anions.
e.g., NaCl, MgCl2
Ternary ionic compounds consist of monatomic and polyatomic ions.
e.g., K2 SO4
Bonding between atoms within the polyatomic ions is covalent.
Ionic Size
Cations are smaller than their parent atom.
The outermost electron(s) vacates its (their) orbital, resulting an a
decrease of electron-electron repulsion and a greater effective inward pull
of the nucleus.
while Li+ is 0.68 A.

Li is 1.23 A
while Na+ is 0.98 A.

Na is 1.57 A
Anions are larger than their parent atoms.
The increase in electrons increases the electron-electron repulsion and
thus the electrons are more spread out in space.
while F is 1.33 A.

F is 0.64 A
while Cl is 1.81 A.

Cl is 0.99 A
Exercise
Write the Lewis structures for the following compounds:
1. BaO
2. MgCl2
3. aluminum oxide

Lattice Energy
Lattice energy is the quantity of energy released in the formation of one
mole of a crystalline ionic solid from its separated gaseous ions.
Li+ (g) + F (g) LiF(s)

0 = lattice energy = -1050 kJ

HLiF

The lattice energy is an important indication of the strength of ionic

interactions and is a major factor in influencing melting points, hardness,
and solubilities of ionic compounds.
Lattice energies can be calculated through a Born-Haber cycle, which
is a series of steps from elements to ionic compounds for which all the
enthalpies are known except the lattice energy.
Born-Haber Cycle for LiF
Given that all the other energies are experimentally available
Li(s)
1
2 F2 (g)
Li(g)
F(g)
Li+ (g) + F (g)
Li(s) + 12 F2 (g)

Li(g)
F(g)
Li+ (g)
F (g)
LiF(s)
LiF(s)

H 0 = atomization = 161 kJ
H 0 = 21 bond energy = 79.5 kJ
H 0 = IE1 = 520 kJ
H 0 = EA = -328 kJ
0 = lattice energy = ?
HLiF
0 = formation = -617 kJ
HLiF

0 = -1050 kJ/mol.
The lattice energy is computed as HLiF

6 Covalent Bonding
Covalent Bond
A covalent bond is a bond formed between two or more atoms by a sharing
of electrons
Covalent bonds exist between atoms with high EN values.
Both would want to keep their electrons and are not willing to give up
their electrons. The only way they can get each others electrons and attain
stability through the octet rule is by sharing electrons.

Examples: Cl2 has zero EN difference, carbon tetrachloride CCl4 .

Bond Pair and Lone Pair
A bond pair is a pair of electrons involved in covalent bond formation.
A lone pair is a pair of electrons found in the valence shell of an atom
and not involved in bond formation.

H + O + H

HOH

0.0
covalent

1.65
partly covalent
partly ionic

3.3
most ionic

Covalent Bonds
The sharing of a single pair of electrons between bonded atoms produces
a single covalent bond.
In a double covalent bond, two pairs of electrons are shared between
bonded atoms. The bond is represented by a double-dash sign. E.g.,
CO2 .
In a triple covalent bond, three pairs of electrons are shared between the
bonded atoms. It is represented by a triple-dash sign. E.g., HCN
In a coordinate covalent bond, electrons shared between two atoms are
contributed by just one of the atoms. As a result, the bonded atoms
exhibit formal charges. E.g., NH4+ .

7 Bond Polarity and Electronegativity

Transition Between Ionic and Covalent Bonds
Those with EN difference (EN) of zero are considered pure covalent.
Equal sharing of electrons. E.g., Cl2 , H2 .
The maximum possible EN occurs in CsF (or FrF). Considered as
purely ionic. Complete transfer of electrons.
All the rest are partly covalent and partly ionic
The greater the EN, the more polar the bond. This will have great
relevance to polarity of molecules, and in turn to the phases of matter.
Polar Covalent Bond
In a polar covalent bond a separation exists between the centers of positive
and negative charge in the bond.
The unequal sharing of the electrons leads to a partial negative charge
() on the more nonmetallic element, and a corresponding partial
positive charge (+) on the more metallic element.
Electrostatic Potential Map
An electrostatic potential map depicts the electron charge distribution in a
molecule. The color red is used to represent the region with the most negative
charge, and blue represents the most positive charge.
H2 and HF

en.wikipedia.org/wiki/File: Hydrogen-fluoride-elpot-transparent-3D-balls.png

8 Drawing Lewis Structures

Some Reminders
All the valence electrons of the atoms in a Lewis structure must appear
in the structure.
Usually, all the electrons in a Lewis structure are paired.
Usually, each atom acquires an outer-shell octet of electrons. Hydrogen,
however, is limited to two outer-shell electrons.
Sometimes, multiple covalent bonds (double or triple bonds) are needed.
Multiple covalent bonds are formed most readily by C, N, O, P, and S
atoms.
Skeletal Structures
In writing a Lewis structure, first designate the skeletal structure, where
all the atoms in the structure arranged in the order in which they are bonded
to one another.
A central atom is bonded to two or more atoms.
A terminal atom is bonded to just one other atom.
Some other reminders
Hydrogen atoms are always terminal atoms.
Central atoms are generally those with the lowest electronegativity.
Carbon atoms are always central atoms.
Except for the very large number of chain-like organic molecules,
molecules and polyatomic ions generally have compact, symmetrical
structures.
Drawing Lewis Structures
1. Sum the valence electrons from all atoms.
2. Write the symbols for the atoms to show which atoms are attached to
which, and connect them with a single bond.
3. Complete the octets of the atoms bonded to the central atom.
4. Place any leftover electrons on the central atom, even if doing so results
in more than octet.
5. If there are not enough electrons to give the central atom an octet, try
multiple bonds. Use one or more of the unshared pairs of electrons on
the atoms bonded to the central atom to form double or triple bonds.
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Exercises
Draw the Lewis structures for the following molecules or ions:
1. C2 N2 , cyanogen, a poisonous gas used as a fumigant and rocket
propellant.
2. NO2+ , nitronium ion.
3. NF3 , nitrogen trifluoride
4. CH3 OH, methanol
5. C2 H4 , ethylene

9 Formal Charges
Formal Charges
Formal charge is the number of outershell (valence) electrons in an isolated
atom minus the number of electrons assigned to that atom in a Lewis structure.
Count lone-pair electrons as belonging entirely to the atom on which they
are found.
Divide bond-pair electrons equally between the bonded atoms.
Formal Charges and Lewis Structures
The following are general rules that can help to determine the plausibility
of a Lewis structure based on its formal charges.
The sum of the formal charges in a Lewis structure must equal zero for
a neutral molecule and must equal the magnitude of the charge for a
polyatomic ion.
Where formal charges are required, they should be as small as possible.
Negative formal charges usually appear on the most electronegative
atoms; positive formal charges, on the least electronegative atoms.
Structures having formal charges of the same sign on adjacent atoms are
unlikely.
Some Examples (1)

H
H

C H
H
CH4

H
Cl C Cl
H
CH2 Cl2

H
C C
H

H
8

C 2 H4

C N
HCN

N N
N2

Cl P Cl
Cl
PCl3
Some Examples (2)

C O
CO2

CO

H
C O
H
CH2 O

Br
O
BrO3

O
O

O
O3

3O
O

P
O

PO43
9

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Resonance Structures

Resonance
Resonance occurs when two or more plausible Lewis structures can be
written for a species. The true structure is a composite or hybrid of these
different contributing structures.
The possible Lewis structures are the resonance structures (or resonance
forms).
The actual molecule is a resonance hybrid, something like an average of
the resonance forms.
The need for resonance structures is the result of electron-pair
delocalization
Resonance Structures of O3

O
O

O
O

Exercises
Write the resonance structures and formal charges of the following species.
Choose which structure is more probable.
1. O3 , ozone
2. NO3 , nitrite ion
3. N3 , azide ion
4. NCO , cyanate ion
5. CH3 COO , acetate ion
6. SO2 , sulfur dioxide

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Exceptions the the Octet Rule

Odd-Electron Species
Free radicals are highly reactive molecular fragments containing unpaired
electrons.
These molecules have an odd number of valence electrons.
Most of them have a central atom from an odd-numbered group, such as
N and Cl.
The presence of an unpaired electron causes odd-electron species to be
paramagnetic.
e.g., NO, NO2
Others are transitory species (e.g., found in flames). Examples are the
methyl radical and hydroxyl radical.

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Incomplete Octets
Gaseous compounds containing Be and B as the central atom are often
electron deficient (> 8 in the central Be or B atom).
e.g., BeCl2 and BF3
possible resonance structures with higher formal charges
Electron-deficient molecules often attain an octet in reactions by forming
additional bonds.
e.g., BF3 + NH3 BF3 NH3
Expanded Valence Shells
Expanded valence shell is a term used to describe Lewis structures in which
certain atoms in the third or higher period of the periodic table appear to
require 10 or 12 electrons in their valence shells.
e.g., SF6 , a remarkably inert gas used as an insulator in electrical
equipment.
e.g., PCl5 , a fuming yellow-white solid used in the manufacture of
lacquers and films.
e.g., H2 SO4 , SO42 , SO3 , and SO2
S and P can accommodate a maximum of 12 electrons, and I as many
as 14. These atoms expand their valence shells to form more bonds and
minimize formal charge.

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Bond Energies and Bond Lengths

Bond Order and Bond Length

Bond order is one-half the difference between the numbers of electrons in
bonding and in antibonding molecular orbitals in a covalent bond.
A single bond has a bond order of 1; a double bond, 2; and a triple bond,
3.
Bond length (bond distance) is the distance between the centers of two atoms
joined by a covalent bond.
A double bond between atoms is shorter than a single bond, and a triple
bond is shorter still.
Some Average Bond Lengths
Bond
HH
HC
HN
HO
HS
HF
HCl
HBr
HI

Bond
Length, pm
74.14
110
100
97
132
91.7
127.4
141.4
160.9

Bond
CC
CC
C
C
CN
CN
C
N
CO
CO
CCl

Bond
Length, pm
154
134
120
147
128
116
143
120
178

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Bond
NN
NN
N
N
NO
NO
OO
OO
FF
ClCl
BrBr
II

Bond
Length, pm
145
123
109.8
136
120
145
121
143
199
228
266

Bond Lengths
The length of the covalent bond between two atoms can be approximated
as the sum of the covalent radii of the two atoms.
For resonance structures, the bond length can be approximated as the
average of the individual resonance structures
Estimating Bond Lengths
PHMB 10e, Example 10-14, p 434
Provide the best estimate you can of these bond lengths for
1. the nitrogen-to-hydrogen bonds in NH3
2. the bromine-to-chlorine bond in BrCl
3. the carbon-to-oxygen bond in CO32
ANSWERS
1. 100 pm (the measured bond length is 101.7 pm)
2. 214 pm (the measured bond length is 213.8 pm)
3. 129 pm
Bond-Dissociation Energy
Bond-dissociation energy, D, is the quantity of energy required to break
one mole of covalent bonds in a gaseous species, usually expressed in kJ/mol.
Some Average Bond Energies
bond
HH
HC
HN
HO
HS
HF
HCl
HBr
HI

kJ/mol
436
414
389
464
368
565
431
364
297

bond
CC
CC
C
C
CN
CN
C
N
CO
CO
CCl

kJ/mol
347
611
837
305
615
891
360
736
339

bond
NN
NN
N
N
NO
NO
OO
OO
FF
ClCl
BrBr
II

kJ/mol
163
418
946
222
590
142
498
159
243
193
151

BDE for Diatomic Molecules

bond breakage

H2 (g)

2 H(g)
H = D(HH) = +435.93 kJ/mol

bond formation

2 H(g)

H2 (g)
H = D(HH) = -435.93 kJ/mol

BDE for Polyatomic Molecules

An average bond energy is the average of bond-dissociation energies for a
number of different species containing a particular covalent bond.
HOH(g)
OH(g)

H(g) + OH(g)
H(g) + O(g)

H = D(HOH) = +498.8 kJ/mol

H = D(OH) = +428.0 kJ/mol

The average bond energy for OH is 464 kJ/mol.

For methanol CH3 OH, D(HOCH3 ) = 436.8 kJ/mol.
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Higher Bond Order Bond Energies

Bond energies of higher order bonds are greater than those of lower bond
orders.
Double bonds have higher bond energies than do single bonds between
the same atoms, but they are not twice as large.
Triple bonds are stronger still, but their bond energies are not three times
as large as single bonds between the same atoms.
Enthalpy of Reactions (1)
Enthalpy of reactions involving gases can be approximated from bond
energies

Hrxn

H (bond breakage) + H (bond formation)

BE(reactants) + BE(products)

The process is
gaseous reactants gaseous atoms gaseous products
Enthalpy of Reactions (2)
We can base the calculation of H just on the net number and types of
bonds broken and formed.
The use of enthalpy of formation data is more accurate than using bond
energy data in predicting the enthalpy of a reaction.
However, if enthalpy of formation data is lacking, the use of bond energy
data can be used.
from Bond Energies
Calculating Hrxn
PHMB 10e, Example 10-15, p 436
The reaction of methane CH4 and chlorine produces a mixture of products
called chloromethanes. One of these is monochloromethane CH3 Cl used in the
reaction
preparation of silicones. Calculate for the Hrxn

CH4 (g) + Cl2 (g) CH3 Cl(g) + HCl(g)

ANSWER: -113 kJ
Endothermic/Exothermic from BDE
Another way to use bond energies is in predicting whether a reaction will
be endothermic or exothermic. In general,
weak bonds
(reactants)

strong bonds
(products)

H < 0 exothermic

strong bonds
(reactants)

weak bonds
(products)

H > 0 endothermic

and

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