CHAPTER 10 - Lecture Notes

CHEM101 F15: Chapter 10: Chemical Bonding I
Bonding
a chemical bond forms when the potential
energy of the bonded atoms is less than the
potential energy of the separate atoms
consider following interactions:
nucleus-to-nucleus repulsion
electron-to-electron repulsion
nucleus-to-electron attraction
Potential Energy Between Charged Particles

1 q1 q2
E potential
4 0 r
0 is a constant
= 8.85 x 10-12 C2/Jm

for charges with the same sign, Epotential is + and the
magnitude gets less positive as the particles get farther apart
for charges with the opposite signs, Epotential 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
Bonding theories
The goals of a bonding theory are:
to support experimental measurements of molecules:
and predict these properties for other molecules
bond lengths
bond angles
magnetic properties
bond dissociation energies
spectra
easier to design experiments with a predicted structure in hand
Bonding theories can be very complicated due to the

mathematics of quantum mechanics involved
Assumptions help to simplify the mathematics

Keep in mind the goal is always to explain data
Bonding theories
Lewis Theory
Positions of the electrons in the molecule are not considered

Quickest bonding theory to employ
Valence-bond Theory
Atomic orbitals overlap where electrons are shared

Atomic orbitals are averaged to give geometries (VSEPR theory)
Explains geometries, multiple bonding
Easy to employ
Molecular Orbital Theory
New molecular orbitals for the entire molecule are calculated

Explains bond order, stability, magnetism, spectroscopy, resonance
Difficult to employ for polyatomic molecules
Lewis Theory Overview
Valence electrons play a fundamental role in

chemical bonding.
Electron transfer from a metal atom to a nonmetal
atom creates charged particles or ions. An
ionic interaction results. Ionic compounds form.
Sharing of electrons (usually between nonmetal
atoms) leads to covalent bonds. Molecular
compounds form.
The octet rule - Electrons are transferred or shared to
give each atom a noble gas configuration
Lewis Structures of atoms
A chemical symbol represents the nucleus

and the core e-.
Dots around the symbol represent valence e-.
Si
Al
As
Se
Bi
Sb
Ar
Lewis Structures of ions
Add or remove electrons to make the

appropriate ion.
Label the ion with its charge. Brackets may
be used around atom and its Lewis dots.
[ I ]
Al3+
Practice Example:
Draw Lewis Structures for the following atoms and ions:
C
ClNe
O2-
Cl
B3+
Ca
Li
Ca2+
EXAMPLE 10-2
Writing Lewis Structures of Ionic Compounds. Write Lewis
structures for the following compounds: (a) BaO; (b) MgCl2 ;
(c) aluminum oxide.
O
2+
Ba [ O ]
2-
Ba
BaO
Note the use of the fishhook arrow to denote a

single electron movement. A double headed
arrow means that two electrons move.
Ionic Compounds
Mg
Cl
2[ Cl ]
2+
Mg
MgCl2
Cl
Covalent Bonding sharing electrons between nonmetal atoms
Line convention for showing covalent bonds
Practice Examples:
Draw Lewis Structures of the following compounds
HF
CH4
CaO
CLICKER QUESTION
Multiple Covalent Bonds

More than one pair of electrons can be shared between two atoms
to satisfy the octet rule
O
O C O
O C O
O C O
In the molecule carbon dioxide, carbon shares four electrons with

each oxygen this creates two double bonds in the molecule
Multiple Covalent Bonds
N N
N N
N N
In the nitrogen molecule, the nitrogen atoms share six electrons

this creates a triple bond in the molecule
Coordinate Covalent Bonds

When a bond forms between two atoms, each atom has not
necessarily donated one electron to the bond. When a single atom
contributes both of the electrons to the bond, a coordinate
covalent bond forms
+
Cl
H N H
Cl
H N
When ammonia interacts with hydrochloric acid, the nitrogen atom

donates two electrons to the hydrogen. The hydrogen atom leaves its
electron with the chlorine. Two ions are formed, ammonium and
chloride. The ammonium ion contains a coordinate covalent bond.
Writing Lewis Structures

1.
Find the total number of valence electrons for all the atoms in
the molecule or ion
2.
3.
4.
5.
6.
Number of valence electrons = group # U.S. system

Remember to add electrons for anions, subtract electrons for cations
Choose the central and terminal atoms

Draw two electrons between each pair of connected atoms to
represent one covalent bond
Add lone pairs to the outer atoms (except H) to give complete
octets
Place all remaining electrons in lone pairs on the central atom
If an octet does not form on the central atom, draw multiple
bonds between central and outside atoms
Writing Lewis Structures - Helpful hints:

H forms only one covalent bond and is not the central atom; only
forms single bonds
C forms 4 covalent bonds; is almost always the central atom; often
forms multiple bonds
N forms 3 covalent bonds and 1 lone pair; often forms multiple
bonds (especially triple)
O forms 2 covalent bonds and 2 lone pairs
(sometimes 1 c. bond and 3 lone pairs); often forms double bonds
Halogen, X, forms 1 covalent bond and 3 lone pairs and is usually on
the outside of the central atom; only forms single bonds
Central atoms are usually those with the lowest electronegativity
Lewis structures should be as symmetric and compact as possible
Example 1: Lewis structure for H2O

1. Add up valence electrons: H1; H1; O-6; total = 8
2. Choose central and terminal atoms
H O H
3.
Draw atoms with pairs connecting atoms
HOH
4.
5.
Add lone pairs to outer atoms none in this case for H atoms
Place remaining electrons on central atom
HOH
Add up electrons to check
NOTE: Can also draw lines for bonds; one line represents one pair of
electrons:
O
Example 2: CS2
1. Find the total number of valence electrons:
C 4 ; S 6; S 6; total =16
2. Choose the central and terminal atoms
S C
S
3. Draw atoms with pairs connecting
S:C:S
4. Add lone pairs to the outer atoms (except H) to give complete octet
S C S
5. Place all remaining electrons in lone pairs on the central atom (no
electrons left)
6. If an octet does not form on the central atom, draw multiple bonds
between central and outside atoms
OR
S C S
S C S
S C S
Practice Example:
Draw Lewis structures for the following molecules:
PCl3
CH3Cl
CN-
Formal Charge
A method used to keep track of how electrons are shared in a

Lewis structure
When more than one Lewis structure is feasible, formal charges can
be used to choose the correct structure
How formal charges are applied to atoms in a Lewis structure
A charge is assigned to each atom in the structure

FC = valence e-1s in free atom lone pair e-1s bond pair e-1s
The sum of formal charges must equal the total charge on the molecule or ion
The correct structure will contain the smallest possible formal charges
Example: CS2
FC (C) = 4-0-4 = 0
FC (S) = 6-4-2 = 0
Formal Charge
What if we had drawn CS2 in the following way?
S C S
FC (C) = 4-0-4 = 0
FC (Sl) = 6-6-1 = -1
FC (Sr) = 6-2-3 = +1
The formal charges are not as small as possible

Hint: Make Lewis structures as symmetric as possible
EXAMPLE 10-7
Using the Formal Charge in Writing Lewis Structures. Write
the most plausible Lewis structure of nitrosyl chloride, NOCl,
one of the oxidizing agents present in aqua regia.
2+
2-
2+
Practice Example:
Use the concept of Formal Charge to determine the correct

Lewis structure for NH2CN
Resonance
When two or more Lewis structures are equally feasible, but none
represents the true structure
Resonance hybrid
The correct structure is considered an weighted average of the
resonance structures (NOTE: the different resonance structures may
or may not contribute equally to the average)
Resonance structures of O3
- +
+ -
O
O O
O
O O
Resonance hybrid of O3
+ -
O
O O
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 391
Practice Example
Draw resonance structures for the SO2 molecule
CLICKER QUESTION
Exceptions to the Octet Rule
Odd-Electron Species
Radicals
Incomplete Octets
Boron, Hydrogen
Expanded Valence Shells
Period 3 and up
Odd-Electron Species
Species that contain unpaired electrons are called radicals
Highly reactive species (also called free radicals)
Form when molecules are fragmented in flames or in photochemical

reactions
Harmful to molecules in the human body
Written with a single dot to emphasize the unpaired electron
HCH
or
CH3
Be careful radicals usually have a formal charge of 0
Incomplete Octets
Some species do not have an electron deficiency and cannot complete
their octets
Hydrogen can have no more than two electrons
Boron has only three electrons to share and has a very low
electronegativity
In compounds, boron tends to form only three bonds (example; BH3)

BF3 has some alternate Lewis structures with full octets, but the formal
charges indicate that only three bonds are formed
Expanded Octets
Some atoms can have up to 12 electrons surrounding them. They
usually involve larger atoms (period 3 and up)
Experimental evidence supports Lewis structures with expanded

octets
The explanation involves the empty d orbitals available for

filling. (More on this in Chapter 11)
Examples:
Cl
Cl
F
S
Cl
Cl
Cl
Practice Example:
Draw Lewis structures for the following molecules:
AsF5
BCl3
SF5-
CLICKER QUESTION
The Polarity of Bonds

What is a polar bond?
H2
H-H
Cl2
Cl-Cl
HCl
H-Cl
In the molecules H2 and Cl2, the shared electrons are equally attracted to
both atoms, so the bond is considered non-polar.
In the molecule HCl, the shared electrons are more strongly attracted to
the chlorine atom, so the bond is considered polar.
Electron-rich
Electron-poor
slight negative charge
slight positive charge + H
Cl
Polar covalent bond

Electronegativity the ability of an atom to attract electrons in a
covalent bond
Electronegativity has no units and ranges from 0.0 to 4.0 for
elements
Higher values for electronegativity indicate a greater attraction
for electrons
Fluorine has the highest electronegativity
Non-metals have higher electronegativities than metals
The Polarity of Bonds dependent on electronegativity

electronegativity is a periodic function
((e

To determine if a bond is polar, compare the electronegativities of
the two atoms that share the electrons of the bond
If the difference in electronegativity (DEN)
Is very small (<0.5) non-polar covalent bond
Has an intermediate value polar covalent bond
Is large (>2.0) ionic bond
Example: H-Cl
EN (H) = 2.1
EN (Cl) = 3.0
DEN = 3.0-2.1 = 0.9
So the bond is polar covalent; electrons are more attracted to Cl
because it has a higher EN than H

The dipole moment, m, is the product of a partial charge and distance
(bond length).
A polar covalent bond is said to have a dipole moment and is shown
using a cross-base arrow. The arrow points toward the atom with the
higher electronegativity:
Cl
NOTE: For HCl, m = 1.03 Debye, which corresponds to a partial charge

of about 17% of the charge on an electron
The Polarity of Bonds - Electrostatic potential maps

It is sometimes convenient to use maps of electrostatic potentials to
depict the polarities of molecules
The following scale is used along with examples:
Practice Example:
Determine which of the following bonds are polar. Classify each
as non-polar covalent, polar covalent, or ionic in character. Use
the cross-based arrow symbol for the polar covalent bonds.
H-Br
N-H
P-Cl
C-H
Shapes of Molecules
Lewis structures show the atom-to-atom connections in a molecule,
but they do not necessarily show the correct three-dimensional
shape of a molecule
Example: H2O
Lewis structure of H2O
Geometry of H2O (from experiment)

[a = 104.45o; d1=d2=95.8 pm)
HOH
Valence-Shell Electron-Pair Repulsion (VSEPR) Theory

Valence electrons in bonds and lone pairs make up negatively
charged electron clouds which repel one another
How to use VSEPR:
1. Draw the Lewis structures and choose the atom of interest
(usually the central atom)
2. Count the number of electron groups surrounding the atom of
interest
Each lone pair counts as one electron group

Each bond counts as one electron group (single or multiple bond counts as
one group)
3. Predict the molecular shape by assuming the clouds orient so

that they are as far from one another as possible
Electronic geometry
The geometric shape that electron clouds form around the central
atom such that they are as far apart as possible. Lone pairs and
bonds count as electron clouds
Two charge clouds give linear electronic geometry
central atom is in the center, outer clouds are arranged so that

they point in opposite directions
180o
Practice: Build model of linear geometry. Use brown or silver center atom.
Electronic geometry
Three charge clouds give trigonal-planar electronic

geometry
central atom is in the center of an equilateral triangle; outer

clouds are arranged so that they point to the three corners of the
triangle
120o
Practice: Build model of trigonal-planar geometry. Use brown center atom.
Electronic geometry
Four charge clouds give tetrahedral electronic geometry
central atom is in the center of a tetrahedron, outer clouds are

arranged so that they point to the four corners of a tetrahedron
109.5o
Practice: Build model of tetrahedral geometry. Use black center atom.

Electronic geometry
Five charge clouds give trigonal-bipyramidal electronic geometry
central atom is in the center of an equilateral triangle, outer clouds are

arranged so that they point to the three corners of the triangle and directly
above and below the plane of the triangle
180o
120o
Practice: Build model of trigonal-bipyramidal geometry. Use brown center atom.
Electronic geometry
Six charge clouds give octahedral electronic geometry
central atom is in the center of a square, outer clouds are

arranged so that they point to the four corners of the square and
directly above and below the plane of the square
90
180
Practice: Build model of octahedral geometry. Use silver center atom.
Molecular geometry
The geometric shape that outer atoms form around the central atom
(lone pairs are NOT included)
Choose the center atom of interest (denoted A)

Choose the correct electronic geometry
Each lone pair counts as one electron group (denoted E)
Each bond counts as one electron group (each single or multiple
count as one)
Each atom bound covalently is designated X
Choose the correct molecular geometry based on the number
of outer atoms (denoted X)
Molecular geometry (linear electronic geometry)
Two outer atoms + no lone pairs, AX2
linear molecular geometry
central atom is in the center, outer atoms are
arranged so that they point in opposite directions
bond angles = 180o
Molecular geometries (trigonal-planar electronic geometry)
Three outer atoms + no lone pairs, AX3
trigonal-planar molecular geometry

outer atoms point to the three corners of an
equilateral triangle in one plane
Bond angles = 120o
Two outer atoms + one lone pair, AX2E
bent molecular geometry

outer atoms point to two corners of an equilateral
triangle in one plane
bond angles = 120o
Practice: Use model and remove atoms
Molecular geometries (tetrahedral electronic geometry)
Four outer atoms + no lone pairs, AX4
tetrahedral molecular geometry

outer atoms point to the four corners of a tetrahedron
Bond angles = 109.5o
Three outer atoms + one lone pair, AX3E
trigonal-pyramidal molecular geometry

outer atoms point to three corners of a tetrahedron
bond angles = 109.5o
Two outer atoms + two lone pairs, AX2E2
bent molecular geometry

outer atoms point to two corners of a tetrahedron
Bond angles = 109.5o
The effect of lone pairs

Lone pair electrons exert slightly greater repulsions than
bonding electrons:
Chemistry: A Molecular Approach, Tro 1st edition, 2008, Pearson Prentice Hall, p. 411
Molecular geometries (trigonal-bipyramidal electronic geometry)
Five outer atoms + no lone pairs, AX5
trigonal-bipyramidal molecular geometry

outer atoms point to the three corners of triangle
and above and below plane of triangle
Bond angles = 90, 120o
Four outer atoms + one lone pair, AX4E
see-saw molecular geometry

outer atoms point to two corners of triangle and
above and below plane of triangle
bond angles = 90, 120o
Molecular geometries (trigonal-bipyramidal electronic geometry)
Three outer atoms + two lone pairs, AX3E2

T-shaped molecular geometry
outer atoms point to two corners of triangle and
above plane of triangle
Bond angles = 90o
Two outer atoms + three lone pairs, AX2E3

linear molecular geometry
outer atoms are arranged so that they point opposite
one another
Bond angles = 180o
Molecular geometries (octahedral electronic geometry)
Six outer atoms + no lone pairs, AX6

Octahedral molecular geometry
outer atoms point to four corners of sqare and above
and below plane of square
Bond angles = 90o
Five outer atoms + one lone pair, AX5E

square-pyramidal molecular geometry
outer atoms point to the four corners of a square
and above plane of square
Bond angles = 90o
Four outer atoms + two lone pairs, AX4E2

square-planar molecular geometry
outer atoms point to the four corners of a square
Bond angles = 90o
Shapes of Molecules
Example: H2O
O H
Four charge clouds = tetrahedral electronic geometry

Two atoms + two lone pairs = bent molecular geometry
Bond angles <109.5o
O
H
H
Practice Examples:
Determine the electronic and molecular geometries of the
following molecules:
PCl3
AsF5
SF5-
CLICKER QUESTION
The Polarity of Molecules

Two factors determine the polarity of molecules:
1. The polarity of the bonds in the molecule

2. The molecular geometry
The Polarity of Molecules will determine the PHYSICAL
PROPERTIES of the molecule (boiling point, density, melting
point, etc.)
Dipole Moments of MOLECULES:
A molecule will have a net dipole moment only if the individual dipole
moments of the bonds do not cancel each other out.
CHEM102 W15: Chapter 10: Chemical Bonding I
Determining whether a molecule is polar (has a net dipole moment):

1. Determine the correct molecular geometry
2. Determine the polarity of bonds using differences in electronegativity
3. Use cross-based arrows to show polarities
4. Determine if a net dipole moment exists for the molecule (the use of
vectors is sometimes helpful for this)

Example 1: H-Cl
1. Correct geometry is linear

H-Cl
2. Difference in electronegativity is:
1.4 = (3.5-2.1)
3. Mark the bonds with cross-based arrows
Cl
4. The molecule HCl is polar. The net polarity is toward the

chlorine.
H Cl
Vector addition
.
Chemistry: A Molecular Approach, Tro 1st edition, 2008, Pearson Prentice Hall, p. 420

Example 2: H2O
1. Correct geometry is bent
O
H
H
2.
Difference in electronegativity;
1.4 = (3.5-2.1)
Mark the bonds with cross-based arrows
O
H
The molecule H2O is polar. The net polarity is toward the oxygen.
Chemistry: A Molecular
Approach, Tro 1st edition,
2008, Pearson Prentice
Hall, p. 419

Example 3: CCl4 and CHCl3
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Madura, Bissonnette 10th ed., 2011, Pearson Prentice Hall, p. 432
Practice Examples:
Determine which of the following molecules are polar:
PCl3
AsF5
CLICKER QUESTION
Bond Order
indicates the number of shared electron pairs in a bond
Single bond: bond order = 1

Double bond: bond order = 2
Triple bond: bond order = 3
Bond Length
the distance between the centers of the two atoms joined by a
covalent bond
bond length decreases with increasing bond order
you can approximate the bond length by averaging the covalent
radii of the two atoms joined by the covalent bond (use single
bonds only)
Estimating Bond Lengths

Recall the covalent radius is based on atoms of the same
element bonded covalently
To determine the bond length for two different atoms, use the
average of the covalent radii
General Chemistry: Principles and Modern Applications, Petrucci, Harwood, Herring, Madura, 9th edition, 2007, Pearson Prentice Hall, p. 347,
407

Recall the covalent radius is based on atoms of the same
element bonded covalently

Example: Estimate the bond length of an O-Cl single bond
Cl covalent radius = 199 pm
O covalent radius = 145 pm
O-Cl single bond = (199+145) = 172 pm
Bond dissociation energy

The energy required to break one mole of covalent bonds for
gaseous species. (units: kJ/mol)
Energy is released when atoms form covalent bonds and absorbed
when bonds are broken to form atoms
Bond broken
435.93 kJ/mol
H2 (g)
H (g) + H (g)
Bond formed
DH = 435.93 kJ
H (g) + H (g)
435.93 kJ/mol
H2 (g)
DH = -435.93 kJ
Chemistry: A Molecular Approach, Tro, 1st edition, 2008, Pearson Prentice Hall, p. 393

Chemical reactions are really a combination of all the bonds
breaking and forming.
Changes of Enthalpy of reactions are a combination of the energy
required to break bonds and the energy released to form bonds
Example:
2H2 (g) + O2 (g) 2 H2O (g)
In effect, we need to break two H-H bonds and one O-O bond and form
four O-H bonds.
This gives: 2x(+436 kJ) + 498 kJ +4x(-464 kJ) = -486 kJ
Bond Energies
Practice Example:
What is the bond order of the nitrogen-to-hydrogen bonds in
NH3?
Estimate the bond lengths in the molecule NH3
Calculate the enthalpy of formation of NH3
average bond lengths: N-N = 145 pm

N=N = 123 pm
H-H = 74 pm
average bond energies: N-N = 163 kJ/mol

N=N = 418 kJ/mol
NN = 946 kJ/mol
H-H = 436 kJ/mol
N-H = 389 kJ/mol

CHAPTER 10 - Lecture Notes

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CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

Potential Energy Between Charged Particles

= 8.85 x 10-12 C2/Jm

CHEM101 F15: Chapter 10: Chemical Bonding I

The goals of a bonding theory are:

to support experimental measurements of molecules:

and predict these properties for other molecules

Bonding theories can be very complicated due to the

Assumptions help to simplify the mathematics

CHEM101 F15: Chapter 10: Chemical Bonding I

Positions of the electrons in the molecule are not considered

Atomic orbitals overlap where electrons are shared

Molecular Orbital Theory

New molecular orbitals for the entire molecule are calculated

CHEM101 F15: Chapter 10: Chemical Bonding I

Lewis Theory Overview

Valence electrons play a fundamental role in

CHEM101 F15: Chapter 10: Chemical Bonding I

Lewis Structures of atoms

A chemical symbol represents the nucleus

CHEM101 F15: Chapter 10: Chemical Bonding I

Lewis Structures of ions

Add or remove electrons to make the

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

Note the use of the fishhook arrow to denote a

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

Covalent Bonding sharing electrons between nonmetal atoms

Line convention for showing covalent bonds

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

Multiple Covalent Bonds

In the molecule carbon dioxide, carbon shares four electrons with

CHEM101 F15: Chapter 10: Chemical Bonding I

Multiple Covalent Bonds

In the nitrogen molecule, the nitrogen atoms share six electrons

CHEM101 F15: Chapter 10: Chemical Bonding I

Coordinate Covalent Bonds

When ammonia interacts with hydrochloric acid, the nitrogen atom

CHEM101 F15: Chapter 10: Chemical Bonding I

Writing Lewis Structures

Number of valence electrons = group # U.S. system

Choose the central and terminal atoms

CHEM101 F15: Chapter 10: Chemical Bonding I

Writing Lewis Structures - Helpful hints:

CHEM101 F15: Chapter 10: Chemical Bonding I

Example 1: Lewis structure for H2O

Draw atoms with pairs connecting atoms

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I

A method used to keep track of how electrons are shared in a

How formal charges are applied to atoms in a Lewis structure

A charge is assigned to each atom in the structure

CHEM101 F15: Chapter 10: Chemical Bonding I

What if we had drawn CS2 in the following way?

The formal charges are not as small as possible

CHEM101 F15: Chapter 10: Chemical Bonding I

Use the concept of Formal Charge to determine the correct

CHEM101 F15: Chapter 10: Chemical Bonding I

CHEM101 F15: Chapter 10: Chemical Bonding I