Beirut Arab University

Faculty of Science
Chemistry Department

PRINCIPLES OF CHEMISTRY
(CHEM 241)

(Fall 2017-2018)
 Chapter 8

Bonding
General concepts
8.1 Types of Chemical Bonds
A Chemical Bond

• Forces that hold groups of atoms together and

make them function as a unit.

• A bond will form if the energy of the aggregate is

lower than that of the separated atoms.
8.1 Types of Chemical Bonds
Key Ideas in Bonding

• Ionic Bonding – electrons are transferred

• Covalent Bonding – electrons are shared equally

• What about intermediate cases?

 Polar covalent bond or polar bond

8.1 Types of Chemical Bonds
Valence electrons are the outer shell electrons of an atom. The
valence electrons are the electrons that participate in chemical
bonding.

Group e- configuration # of valence e-

1A ns1 1
2A ns2 2
3A ns2np1 3
4A ns2np2 4
5A ns2np3 5
6A ns2np4 6
7A ns2np5 7
8.1 Types of Chemical Bonds
8.1 Types of Chemical Bonds
The Ionic Bond
electrons are transferred from one atom to another

Li + F Li+ F -
1s22s1 1s22s22p5 1s2 1s22s22p6
[He] [Ne]

Li Li+ + e-

e- + F F -

Li+ + F - Li+ F -
 8.1 Types of Chemical Bonds
Electrostatic (Lattice) Energy
Lattice energy (E) is the energy required to completely separate one
mole of a solid ionic compound into gaseous ions.
k is proportionality constant
Q+ is the charge on the cation
Q+Q-
E=k Q- is the charge on the anion
r
r is the distance between the ions
cmpd lattice energy
MgF2 2957 Q = +2,-1
Lattice energy (E) increases as
MgO 3938 Q = +2,-2
Q increases and/or
LiF 1036
as r decreases. r F < r Cl
LiCl 853
8.1 Types of Chemical Bonds
Born-Haber Cycle for Determining Lattice Energy

DHooverall = DHo1 + DHo2 + DHo3 + DH4o + DH5o

 Born-Haber Cycle

Formation of an Ionic Solid

1.Sublimation of the solid metal.

• M(s)  M(g) [endothermic]
2. Ionization of the metal atoms.
• M(g)  M+(g) + e [endothermic]
3. Dissociation of the nonmetal.
• 1/2X2(g)  X(g) [endothermic]

4. Formation of X ions in the gas phase.

• X(g) + e  X(g) [exothermic]
5. Formation of the solid MX.
• M+(g) + X(g)  MX(s)
[quite exothermic]
8.1 Types of Chemical Bonds
8.1 Types of Chemical Bonds
A covalent bond is a chemical bond in which two or more electrons
are shared by two atoms.

The Interaction of
Two Hydrogen
Atoms
8.1 Types of Chemical Bonds

• The Interaction of Two Hydrogen Atoms

 8.1 Types of Chemical Bonds

F + F F F
7e- 7e- 8e- 8e-

Lewis structure of F2

single covalent bond lone pairs F F lone pairs

single covalent bond

lone pairs F F lone pairs
Lewis structure of water single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond – two atoms share two pairs of electrons

O C O or O C O
8e- 8e- 8e- double bonds

Triple bond – two atoms share three pairs of electrons

N N or N N
8e- 8e-
triple bond
 Lengths of Covalent Bonds
Bond
Bond Length
Type
(pm)
C-C 154
CC 133
CC 120
C-N 143
CN 138
CN 116
Bond Lengths
Triple bond < Double Bond < Single Bond
8.1 Types of Chemical Bonds
Polar covalent bond or polar bond is a covalent bond with
greater electron density around one of the two atoms

• Unequal sharing of electrons between atoms in a molecule.

• Results in a charge separation in the bond (partial positive and

partial negative charge).

electron poor electron rich

e- poor e- rich
region region
H F H F
d+ d-
8.2 Electronegativity

Electronegativity is the ability of an atom to attract toward

itself the electrons in a chemical bond.

• The ability of an atom in a molecule to attract shared

electrons to itself.

• For a molecule HX, the relative electronegativities of the H

and X atoms are determined by comparing the measured
H–X bond energy with the “expected” H–X bond energy.
8.2 Electronegativity

• On the periodic table, electronegativity generally increases

across a period and decreases down a group.
• The range of electronegativity values is from 4.0 for fluorine
(the most electronegative) to 0.7 for cesium and francium (the
least electronegative).
8.2 Electronegativity

The Relationship Between Electronegativity and Bond Type

 Classification of bonds by difference in electronegativity

Difference Bond Type

0 Covalent
2 Ionic
0 < and <2 Polar Covalent

Increasing difference in electronegativity

Covalent Polar Covalent Ionic

share e- partial transfer of e- transfer e-

 Classify the following bonds as ionic, polar covalent, or
covalent: The bond in CsCl; the bond in H2S; and the NN
bond in H2NNH2.

Cs – 0.7 Cl – 3.0 3.0 – 0.7 = 2.3 Ionic

H – 2.1 S – 2.5 2.5 – 2.1 = 0.4 Polar Covalent

N – 3.0 N – 3.0 3.0 – 3.0 = 0 Covalent

8.3 Bond Polarity and Dipole Moments
Dipole Moment
• Property of a molecule whose charge distribution can be
represented by a center of positive charge and a center of
negative charge.
• Use an arrow to represent a dipole moment.
 Point to the negative charge center with the tail of the
arrow indicating the positive center of charge.
8.3 Bond Polarity and Dipole Moments

No Net Dipole Moment (Dipoles Cancel)

8.4 Ions: Electron Configurations and Sizes

Stable Compounds
• Atoms in stable compounds usually have a noble gas
electron configuration.
8.4 Ions: Electron Configurations and Sizes

Electron Configurations in Stable Compounds

• When two nonmetals react to form a covalent bond, they share

electrons in a way that completes the valence electron
configurations of both atoms.

• When a nonmetal and a representative-group metal react to

form a binary ionic compound, the ions form so that the
valence electron configuration of the nonmetal achieves the
electron configuration of the next noble gas atom. The valence
orbitals of the metal are emptied.
8.4 Ions: Electron Configurations and Sizes

Isoelectronic Series

• A series of ions/atoms containing the same number of electrons.

O2-, F-, Ne, Na+, Mg2+, and Al3+

8.4 Ions: Electron Configurations and Sizes

Periodic Table Allows Us to Predict Many Properties

• Trends for:
 Atomic size, ion radius, ionization energy, electronegativity

• Electron configurations

• Formula prediction for ionic compounds

• Covalent bond polarity ranking

8.8 Covalent Bond Energies and Chemical Reactions
The enthalpy change required to break a particular bond in one mole
of gaseous molecules is the bond energy.

Bond Energy
H2 (g) H (g) + H (g) DH0 = 436.4 kJ
Cl2 (g) Cl (g) + Cl (g) DH0 = 242.7 kJ
HCl (g) H (g) + Cl (g) DH0 = 431.9 kJ
O2 (g) O (g) + O (g) DH0 = 498.7 kJ O O
N2 (g) N (g) + N (g) DH0 = 941.4 kJ N N

Bond Energies
Single bond < Double bond < Triple bond
Average bond energy in polyatomic molecules

H2O (g) H (g) + OH (g) DH0 = 502 kJ

OH (g) H (g) + O (g) DH0 = 427 kJ

502 + 427
Average OH bond energy = = 464 kJ
2
Bond Energies (BE) and Enthalpy changes in reactions
Imagine reaction proceeding by breaking all bonds in the reactants
and then using the gaseous atoms to form all the bonds in the
products.
DH0 = total energy input – total energy released
= SBE(reactants) – SBE(products)
H2 (g) + Cl2 (g) 2HCl (g) 2H2 (g) + O2 (g) 2H2O (g)
 Use bond energies to calculate the enthalpy change for:
H2 (g) + F2 (g) 2HF (g)

DH0 = SBE(reactants) – SBE(products)

Type of bonds Number of Bond energy Energy change

broken bonds broken (kJ/mol) (kJ)
H H 1 436.4 436.4
F F 1 156.9 156.9
Type of bonds Number of Bond energy Energy change
formed bonds formed (kJ/mol) (kJ)
H F 2 568.2 1136.4

DH0 = 436.4 + 156.9 – 2 x 568.2 = -543.1 kJ

8.10 Lewis Structures

Lewis Structure

• Shows how valence electrons are arranged among

atoms in a molecule.

• Reflects central idea that stability of a compound

relates to noble gas electron configuration.
8.10 Lewis Structures

Duet Rule
• Hydrogen forms stable molecules where it shares two
electrons.
8.10 Lewis Structures

Octet Rule

• Elements form stable molecules when surrounded by

eight electrons.
8.10 Lewis Structures
Single Covalent Bond H–H
• A covalent bond in which two atoms share one pair of
electrons.

Double Covalent Bond O=C=O

• A covalent bond in which two atoms share two pairs of

electrons.

Triple Covalent Bond NN

• A covalent bond in which two atoms share three pairs of
electrons.
8.10 Lewis Structures
Steps for Writing Lewis Structures

1. Draw skeletal structure of compound showing what

atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e-. Add 1 for each
negative charge. Subtract 1 for each positive charge.
3. Complete an octet for all atoms except hydrogen
4. If structure contains too many electrons, form double
and triple bonds on central atom as needed.
Write the Lewis structure of nitrogen trifluoride (NF3).
Step 1 – N is less electronegative than F, put N in center
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?

3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

F N F

F
Write the Lewis structure of the carbonate ion (CO32-).
Step 1 – C is less electronegative than O, put C in center
Step 2 – Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge – 2e-
4 + (3 x 6) + 2 = 24 valence electrons
Step 3 – Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e-

2 single bonds (2x2) = 4

1 double bond = 4
O C O
8 lone pairs (8x2) = 16
Total = 24
O
8.11 Exceptions to the Octet Rule

The Incomplete Octet

Be – 2e-
BeH2 2H – 2x1e- H Be H
4e-

B – 3e- 3 single bonds (3x2) = 6

3F – 3x7e- F B F
BF3 9 lone pairs (9x2) = 18
24e- Total = 24
F
8.11 Exceptions to the Octet Rule
Odd-Electron Molecules
N – 5e-
NO O – 6e- N O
11e-

The Expanded Octet (central atom with principal quantum number n > 2)

F
F F
S – 6e- 6 single bonds (6x2) = 12
SF6 6F – 42e- S 18 lone pairs (18x2) = 36
48e- Total = 48
F F
F
8.11 Exceptions to the Octet Rule
Let’s Review
• C, N, O, and F should always be assumed to obey the octet rule.
• B and Be often have fewer than 8 electrons around them in their
compounds.
• Second-row elements never exceed the octet rule.
• Third-row and heavier elements often satisfy the octet rule but
can exceed the octet rule by using their empty valence d orbitals.

• When writing the Lewis structure for a molecule, satisfy the

octet rule for the atoms first. If electrons remain after the octet
rule has been satisfied, then place them on the elements having
available d orbitals (elements in Period 3 or beyond).
8.12 Resonance
• More than one valid Lewis structure can be written
for a particular molecule.
+ - - +
O O O O O O

What are the resonance structures of the

carbonate (CO32-) ion?

- - - -
O C O O C O O C O

O O O
- -
 NO3– = 24e–

O O O O O O
N  N  N
O O O
• Actual structure is an average of the resonance
structures.
• Electrons are really delocalized – they can move
around the entire molecule.
 Two possible skeletal structures of formaldehyde (CH2O)

H
H C O H C O
H

An atom’s formal charge is the difference between the number of

valence electrons in an isolated atom and the number of electrons
assigned to that atom in a Lewis structure.

formal charge total number of

total number of 1 total number of
on an atom in a
Lewis structure
=
valence
electrons in the-
free atom
nonbonding
electrons
- 2 ( bonding
electrons )
The sum of the formal charges of the atoms in a molecule or
ion must equal the charge on the molecule or ion.
 -1 +1 C – 4 e- 2 single bonds (2x2) = 4
H C O H O – 6 e- 1 double bond = 4
2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

formal charge total number of

total number of 1 total number of
on an atom in a
Lewis structure
=
valence
-
electrons in the
free atom
nonbonding
electrons
- 2 ( bonding
electrons )
formal charge on C = 4 - 2 - ½ x 6 = -1

formal charge on O = 6 - 2 - ½ x 6 = +1
 0 0
H C – 4 e- 2 single bonds (2x2) = 4
C O O – 6 e- 1 double bond = 4
H 2H – 2x1 e- 2 lone pairs (2x2) = 4
12 e- Total = 12

formal charge total number of

total number of 1 total number of
on an atom in a
Lewis structure
=
valence
electrons in the-
free atom
nonbonding
electrons
- 2 ( bonding
electrons )
formal charge = 4 - 0 -½ x 8 = 0
on C

formal charge = 6 - 4 -½ x 4 = 0
on O
 Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there are no
formal charges is preferable to one in which formal charges are
present.
2. Lewis structures with large formal charges are less likely than
those with small formal charges.
3. Among Lewis structures having similar distributions of formal
charges, the most plausible structure is the one in which
negative formal charges are placed on the more electronegative
atoms.
Which is the most likely Lewis structure for CH2O?

-1 +1 H 0 0
H C O H C O
H
8.13 Molecular Structure: The VSEPR Model

VSEPR Model

• VSEPR: Valence Shell Electron-Pair Repulsion.

• The structure around a given atom is determined

principally by minimizing electron pair repulsions.
 (VSEPR) Model:

Predict the geometry of the molecule from the electrostatic repulsions

between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B
0 lone pairs on central atom

Cl Be Cl

2 atoms bonded to central atom

 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral
lone-pair vs. lone pair > lone-pair vs. bonding > bonding-pair vs. bonding
repulsion pair repulsion pair repulsion
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
trigonal
AB2E 2 1 bent
planar
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

F
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
F
F F
Br
F F
 VSEPR
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar
F F
Xe
F F
Predicting Molecular Geometry
1. Draw Lewis structure for molecule.
2. Count number of lone pairs on the central atom and
number of atoms bonded to the central atom.
3. Use VSEPR to predict the geometry of the molecule.

What are the molecular geometries of SO2 and SF4?

O S O F
AB4E
AB2E F S F
distorted
bent tetrahedron
F
 Dipole Moments and Polar Molecules

electron rich
electron poor
region
region

H F

d+ d

m=Qxr
Q is the charge
r is the distance between charges
1 D = 3.36 x 10-30 C m
 Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CH4

O S

dipole moment dipole moment

polar molecule polar molecule

H C H
O C O

no dipole moment H
nonpolar molecule no dipole moment
nonpolar molecule
 END
OF
CHAPTER 8