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Chapter 7

Covalent Bonds and Molecular


Structure

The Covalent Bond


Covalent bond formed by the sharing of
electrons between two nonmetal atoms
Forces involved in the bond
Electrostatic attraction between proton and
electron
Electrostatic repulsion between electron and
electron

When will a bond form?

Strengths of Bonds
Bond dissociation energy the amount of
energy required to break a bond
Energy increases as the length of the bond gets
shorter

Bond length and covalent radius.


Internuclear distance
(bond length)

Internuclear distance
(bond length)

Covalent
radius

Covalent
radius

Internuclear distance
(bond length)

Internuclear distance
(bond length)

Covalent
radius

Covalent
radius

Strengths of Bonds
Single bonds > double bonds > triple bonds

Problem
Arrange the following bonds in order of
increasing bond strength.
A.
B.
C.
D.
E.

C-I < C-Br < C-Cl < C-F


C-F < C-Cl < C-Br < C-I
C-Br < C-I < C-Cl < C-F
C-I < C-Br < C-F< C-Cl
none of these orders is correct

Problem
Select the strongest bond in the following
group.
A.
B.
C.
D.
E.

C-S
C-O
C=C
CN
C-F

Electron Dot Structures

Electron dot symbols


Aid in understanding the formation of bonds between atomic nuclei
Elemental symbol represents the type of element and all core electrons;
the valence electrons are represented by dots around the symbol

Electron Dot Structures


A metal in an ionic loses its electrons to achieve
an octet or pseudo-octet (transition elements) in
its outermost shell
A nonmetal in an ionic compound gains
electrons to achieve an octet in its outermost
shell
Period 1 and 2 elements of a covalent
compound share enough electrons to achieve
an octet

Electron-Dot Structures
Ionic:

Covalent:

Electron Dot Structures


Using electron dot symbols build
H2, H2O, CH4, O2, N2, HCN, CO2
Least electronegative atom is often central (except
H)

Naming Binary Molecular


Compounds
Electronegativity indicates how well an
elements nuclei attract the electrons in a
covalent bond

The Periodic Table and


Electronegativity

Electron Dot Structures


Using electron dot symbols build
H2, H2O, CH4, O2, N2, HCN, CO2
Least electronegative atom is often central (except
H)

Electron Dot Structures


Single bond: A covalent bond formed by
sharing one electron pair.
Double bond: A covalent bond formed by
sharing two electron pairs.
Triple bond: A covalent bond formed by sharing
three electron pairs.
Single bonds are longer (weaker) than double bonds
Double bonds are longer (weaker) than triple bonds

Electron-dot Structures
Step 1: Count the total valence electrons.
Step 2: Identify the central atom
- Often least electronegative
Step 3: Place all other atoms around the central
atom
Step 4: Draw a single bond between each
external atom and the central atom
subtracting 2 electrons for each bond
drawn from the total valence electrons.

Electron-dot Structures
Step 5: Distribute remaining valence
electrons around the external
atoms giving the external atoms
an octet
Step 6: If valence electrons still remain,
place them on the central atom in pairs
Step 7: Verify that each atom has an octet
Hydrogen needs only 2 electrons
Boron needs only 6 electrons

Electron-Dot Structures
Step 8: If the central atom does not have an
octet, form a multiple bond by bringing a
pair of electrons in from the external
atom
Step 9: Calculate formal charge and minimize
the formal charge if acceptable
Period 3 elements and greater can have expanded octets if
one is necessary to minimize formal charge
Formal charge = # valence electrons for the atom 1 for
every dot on the atom 1 for every line around the atom

Problems
BF3
PF3
C2H6
I3+
NH4+
SO42 KClO3

Electron-dot Structures and


Resonance
How is the double bond formed in O3?
Move lone pair from
this oxygen?

or

O
Or from this
oxygen?

The correct answer is that both are correct,


but neither is correct by itself.

Electron-Dot Structures and


Resonance
When multiple structures can be drawn, the actual
structure is an average of all possibilities.
The average is called a resonance hybrid. A
straight double-headed arrow indicates resonance.

Problem
S3
PO43 CO32 NO2

Molecular Shapes: The VSEPR


Theory
The approximate shape of molecules
is given by
Valence-Shell Electron-Pair Repulsio
n (VSEPR)
.

Molecular Shapes: The VSEPR


Theory
Molecular
formula

Step 1
Lewis
structure

Step 2

Electron-group
arrangement

Count all e- groups around central


atom (A) Single, Double and Triple
bonds are all counted as 1 e- group
Step 3
Bond
angles

Note lone pairs and


double bonds
Count bonding
Step 4 and nonbonding egroups separately.
Molecular
shape
(AXmEn)

Problem
Determine the shape of the molecules for
which Lewis Structures have been
developed.

Valence Bond Theory


If, in order for a bond to form, a pair of
electrons must be shared, then how does
C form molecules with 4 bonds?
Valence Bond Theory hybrid orbitals

Valence Bond Theory


Basic Principle
A covalent bond forms when the orbtials of two atoms overlap
and are occupied by a pair of electrons that have the highest
probability of being located between the nuclei.
Themes
A set of overlapping orbitals has a maximum of two electrons
that must have opposite spins.
The greater the orbital overlap, the stronger (more stable) the
bond.
The valence atomic orbitals in a molecule are different from
those in isolated atoms.

Valence Bond Theory


Key Points
The number of hybrid orbitals obtained equals the number of
atomic orbitals mixed.
The type of hybrid orbitals obtained varies with the types of
atomic orbitals mixed.
Types of Hybrid Orbitals
sp

sp2

sp3

sp3d

sp3d2

Valence Bond Theory


The conceptual steps from molecular formula to the hybrid orbitals
used in bonding.

Step 1
Molecular
formula

Step 2
Lewis
structure

Step 3
Molecular shape
and e- group
arrangement

Hybrid
orbitals

Problems
Carbon uses ______ hybrid orbitals in
ClCN.
A.
B.
C.
D.
E.

sp
sp2
sp3
sp3d
sp3d2

The bonds in ethane.


both C are sp3 hybridized

s-sp3 overlaps to bonds

sp3-sp3 overlap to form a bond


relatively even
distribution of electron
density over all bonds

The and bonds in ethylene (C2H4)


overlap in one position -

p overlap -

electron density

The and bonds in acetylene (C2H2)


overlap in one position -

p overlap -

Polar Covalent Bonds:


Electronegativity
Electronegativity represents the ability of an
atom to attract a shared pair of electrons
Higher the EN the more the electrons in a
bond will be pulled toward the atom
Most electronegative atom is F

EN down a group
EN across a period from left to right w/ few
exceptions

Polar Covalent Bonds:


Electronegativity

Problem
Which of the following elements is the
most electronegative?
A.
B.
C.
D.
E.

S
Ru
Si
Te
Cs

Problem
Arrange calcium, rubidium, sulfur, and
arsenic in order of decreasing
electronegativity.
A.
B.
C.
D.
E.

S > As > Rb > Ca


S > As > Ca > Rb
As > S > Rb > Ca
As > S > Ca > Rb
None of these orders is correct.

Polar Covalent Bonds:


Electronegativity
% Ionic Character: As a general rule for two
atoms in a bond, we can calculate an
electronegativity difference (EN ): EN =
EN(Y) EN(X) for XY bond.

If EN < 0.5 the bond is covalent.

If EN 0.5 - < 2.0 the bond is polar covalent.

If EN > 2.0 the bond is ionic.

Problem
Select the most polar bond amongst the
following.
A.
B.
C.
D.
E.

C-O
Si-F
Cl-F
C-F
C-I

Molecular Orbital Theory


The molecular orbital (MO) model provides a
better explanation of chemical and physical
properties than the valence bond (VB) model.
Atomic Orbital: Probability of finding the electron
within a given region of space in an atom.
Molecular Orbital: Probability of finding the electron
within a given region of space in a molecule.

Molecular Orbital Theory


Additive combination of orbitals () is
lower in energy than two isolated 1s orbitals
and is called a bonding molecular orbital.

Molecular Orbital Theory


Subtractive combination of orbitals () is
higher in energy than two isolated 1s
orbitals and is called an antibonding
molecular orbital.

Molecular Orbital Theory


Molecular Orbital Diagram for H2:

Molecular Orbital Theory


Molecular Orbital Diagrams for H2 and
He2:

Molecular Orbital Theory


Additive and subtractive combination of p
orbitals leads to the formation of both sigma
and pi orbitals.

Molecular Orbital Theory


Second-Row MO Energy Level Diagrams:

Molecular Orbital Theory


Bond Order is the number of electron pairs
shared between atoms.

Bond Order is obtained by subtracting the


number of antibonding electrons from the
number of bonding electrons and dividing by 2.