Basic Concepts of Chemical

Bonding
A Comparison of Ionic and Covalent
Bonds
Energetics of Ionic Bonding
• We already discussed making ions (ionization
energy and electron affinity).
• It takes energy (endothermic) to create a cation,
Ionization Energy
• Energy is released (exothermic) by making the
anion Electron Affinity
• The formation of the solid releases a huge amount
of energy (exothermic).
• This makes the formation of salts from the
elements exothermic.
Energetics of Ionic Bonding—

• Many factors affect the

energy of ionic bonding.
• Start with the metal and
nonmetal elements:
Na(s) and Cl2(g).
• Make gaseous atoms:
Na(g) and Cl(g).
• Make ions: Na+(g) and Cl–
(g).
• Combine the ions: NaCl(s).
Lattice Energy
– the energy required to completely separate a mole of a solid
ionic compound into its gaseous ions.

• The energy associated with electrostatic interactions is

governed by Coulomb’s law:

Q1Q2
Eel = 
d
Lattice Energy
• Lattice energy increases with:
– increasing charge on the ions
– decreasing size of ions
Factors Affecting Melting Point
• Primary factor is the charge on the ions. A greater charge
leads to a greater bond energy. For example, MgO vs.
NaCl. Which one will have a higher melting point and
why?

• If both compounds are made of ions with equal charges,

then the size of the ions must be considered. Smaller ions
have a greater attraction to each other. For example, LiF
vs. KBr. Which one will have a higher melting point and
why?
The Covalent Bond
Covalent Bond: A bond that results from the
sharing of electrons between atoms.
Covalent Bonding
• In covalent bonds, atoms share
electrons.
• There are several electrostatic
interactions in these bonds:
– attractions between electrons
and nuclei,
– repulsions between electrons,
and
– repulsions between nuclei.
• For a bond to form, the
attractions must be greater
than the repulsions.
Potential Energy and Separation
Distance
What does this graph tell us?
● Illustrates the energy between
two atoms as a function of
distance

● The “lowest” part of the curve

shows the energy (436 kJ/mol)
that would be necessary to
break the bond between atoms
as well as the ideal bond length
(74 pm)

● Atoms repel at short distances

● Atoms are attracted to one

another at longer distances but
eventually are too far apart to
experience attractive forces
Polar Covalent Bonds:
Electronegativity
Electronegativity: The ability of an atom in a molecule
to attract the shared electrons in a covalent bond.
Polar Covalent Bonds:
Electronegativity
Polar Covalent Bonds:
Electronegativity
NaCl Cl2

HCl
Polar Covalent Bonds
• The electrons in a covalent bond are not always
shared equally.
• Fluorine pulls harder on the electrons it shares with
hydrogen than hydrogen does.
• Therefore, the fluorine end of the molecule has
more electron density than the hydrogen end.
Electronegativity and
Polar Covalent Bonds
• When two atoms share electrons unequally, a
polar covalent bond results.
• Electrons tend to spend more time around the
more electronegative atom. The result is a
partial negative charge (not a complete transfer
of charge). It is represented by δ–.
• The other atom is “more positive,” or δ+.
Polar Covalent Bonds
The greater the
difference in
electronegativity,
the more polar is
the bond.
Bonding in Alloys
● What are alloys?
○ A combination of metals or metals combine with one or more
other elements
■ Ex. brass, bronze, sterling silver, steel
● Two main categories of alloys
○ Interstitial: Form between atoms with different radii; decreased
malleability
■ ex: steel in which carbon occupies the interstices in iron
○ Substitutional: Form between atoms with similar radii; same
malleability
■ ex: in certain brass alloys, other elements, usually zinc,
substitute for copper
Practice Problems
● Iron and carbon atoms can be alloyed to form steel. What type of alloy
do they form? How do you know?
○ An interstitial alloy because the radius of carbon is very small relative to the
atomic radius of iron.

● Why might interstitial alloys be less malleable or ductile?

○ When atoms fill the interstitial spaces, the lattice becomes more rigid

● Draw a particle level diagram of this alloy:

Practice Problems
● Many metals are alloyed in order to increase their strength. Gold can be
alloyed with many metals. For example, gold (radius 144 pm) and silver
(radius 144 pm) can be alloyed to form white gold. Which of the
following metals would be best to make a substitutional alloy with gold?
○ Silver (radius 128 pm)
○ Platinum (radius 175 pm)
○ Palladium (radius 163 pm)
○ Zinc (radius 139 pm) <--- (Closest to the size of a gold atom, so substitutes well)
Electron-Dot Structures
Electron-Dot Structures (Lewis Structures): A
representation of an atom’s valence electrons by using
dots and indicates by the placement of dots how the
valence electrons are distributed in the molecule.
Electron-Dot Structures
Electron-Dot Structures of
Polyatomic Molecules
Step 1: Valence Electrons
• Count the total number of valence electrons for
all atoms in the molecule.
• Add one additional electron for each negative
charge in an anion or subtract one for each
positive charge in a cation.
Electron-Dot Structures of
Polyatomic Molecules
Step 2: Connect Atoms
• Draw lines to represent bonds between atoms.
• For hydrogen and second row atoms, use the
number of bonds listed below.
• For third row and greater atoms, they may have
more bonds than predicted by the octet rule.
• The least electronegative atom is usually the
central atom.
Electron-Dot Structures of
Polyatomic Molecules
Step 3: Assign Electrons to the Terminal Atoms
• Subtract the number of electrons used for
bonding in the previous step from the total
number determined in step 1.
• Complete each terminal atom’s octet (except
for hydrogen).

Step 4: Assign Electrons to the Central Atom

• If unassigned electrons remain after step 3,
place them on the central atom.
Electron-Dot Structures of
Polyatomic Molecules
Step 5: Multiple Bonds
• If no unassigned electrons remain after step 3
but the central atom does not yet have an octet,
use one or more lone pairs of electrons from a
neighboring atom to form a multiple bond
(either a double or a triple).
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for H2O.
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for CCl4.
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for H3O1+.
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for CH2O.
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for SF6.
Electron-Dot Structures of
Polyatomic Molecules
Draw an electron-dot structure for ICl3.
Electron-Dot Structures and
Resonance
Draw an electron-dot structure for O3.
Electron-Dot Structures and
Resonance
Move a lone pair from this oxygen?

Step 4: O O O

Or, move a lone pair from this oxygen?

O O O O O O

Resonance
Resonance
• The organic compound
benzene, C6H6, has two
resonance structures.
• It is commonly depicted as
a hexagon with a circle
inside to signify the
delocalized electrons in the
ring.
Formal Charges
# of # of # of
Formal 1
= valence e- - bonding - nonbonding
Charge in free atom 2 e- e-

Calculate the formal charge on each atom in O3.

O O O

1 1 1
6 - (4) - 4 = 0 6 - (6) - 2 = +1 6 - (2) - 6 = -1
2 2 2
Exceptions to the Octet Rule
• There are two types of ions or molecules that do not follow the octet
rule:
• Ions or molecules with less than an octet
• Ions or molecules with more than eight valence electrons (an expanded octet)
Fewer Than Eight Electrons

• Consider BF3:
• Giving boron a filled octet places a negative charge on
the boron and a positive charge on fluorine.
• This would not be an accurate picture of the
distribution of electrons in BF3.
Fewer Than Eight Electrons
Therefore, structures that put a double bond
between boron and fluorine are much less
important than the one that leaves boron with
only 6 valence electrons.
Fewer Than Eight Electrons
The lesson is: if filling the octet of the central
atom results in a negative charge on the central
atom and a positive charge on the more
electronegative outer atom, don’t fill the octet of
the central atom.
More Than Eight Electrons
• The only way PCl5 can exist
is if phosphorus has 10
electrons around it.
• It is allowed to expand the
octet of atoms on the 3rd
row or below.
• Presumably d orbitals in
these atoms participate in
bonding.
More Than Eight Electrons
Even though we can draw a Lewis structure for the
phosphate ion that has only 8 electrons around the
central phosphorus, the better structure puts a double
bond between the phosphorus and one of the oxygens.
More Than Eight Electrons
• This eliminates the charge on the phosphorus and the
charge on one of the oxygens.
• The lesson is: when the central atom in on the 3rd
row or below and expanding its octet eliminates some
formal charges, do so.
 Molecular Geometry and Bonding
Theories
Molecular Shapes
• Lewis Structures show bonding and lone pairs, but
do not denote shape.
• However, we use Lewis Structures to help us
determine shapes.
• Here we see some common shapes for molecules
with two or three atoms connected to a central atom.
What Determines the
Shape of a Molecule?
• Simply put, electron
pairs, whether they be
bonding or nonbonding,
repel each other.
• By assuming the
electron pairs are placed
as far as possible from
each other, we can
predict the shape of the
molecule.

• This is the Valence-Shell Electron-Pair

Repulsion (VSEPR) model.
Molecular Shapes: the VSEPR Model
VSEPR: Valence-Shell Electron-Pair Repulsion model

Electrons in bonds and in lone pairs can be thought of

as “charge clouds” that repel one another and stay as
far apart as possible, this causing molecules to
assume specific shapes.

Working from an electron-dot structure, count the

number of “charge clouds,” and then determine the
molecular shape.
Electron Domains
• We can refer to the
directions to which
electrons point as
electron domains. This
is true whether there is
one or more electron pairs
pointing in that direction.
• The central atom in this
molecule, A, has four
electron domains.
Electron-Domain Geometries
• The Table shows the
electron-domain
geometries for two
through six electron
domains around a
central atom.
• To determine the
electron-domain
geometry, count the
total number of lone
pairs, single, double,
and triple bonds on
the central atom.
Molecular Shapes: the VSEPR Model
Two Charge Clouds
Molecular Shapes: the VSEPR Model
Three Charge Clouds
Trigonal Planar Electron Domain

• There are two molecular geometries:

– trigonal planar, if all electron domains are
bonding, and
– bent, if one of the domains is a
nonbonding pair.
Molecular Shapes: the VSEPR Model
Four Charge Clouds
Molecular Shapes: the VSEPR Model
Four Charge Clouds
Tetrahedral Electron Domain

• There are three molecular geometries:

– tetrahedral, if all are bonding pairs,
– trigonal pyramidal, if one is a nonbonding pair, and
– bent, if there are two nonbonding pairs.
Nonbonding Pairs and Bond Angle
• Nonbonding pairs are physically
larger than bonding pairs.
• Therefore, their repulsions are
greater; this tends to compress
bond angles.
Multiple Bonds and Bond Angles

• Double and triple

bonds have larger
electron domains than
single bonds.
• They exert a greater
repulsive force than
single bonds, making
their bond angles
greater.
Expanding beyond the Octet Rule
• Remember that some elements can break the
octet rule and make more than four bonds (or
have more than four electron domains).
• The result is two more possible electron
domains: five = trigonal bipyramidal;
six = octahedral
Trigonal Bipyramidal Electron Domain

• There are two distinct

positions in this
geometry:
– Axial
– Equatorial
• Lone pairs occupy
equatorial positions.
Molecular Shapes: the VSEPR Model
Five Charge Clouds
Trigonal Bipyramidal
Electron Domain

• There are four

distinct molecular
geometries in this
domain:
– Trigonal
bipyramidal
– Seesaw
– T-shaped
– Linear
Molecular Shapes: the VSEPR Model
Five Charge Clouds
Molecular Shapes: the VSEPR Model
Six Charge Clouds
Octahedral Electron Domain
• All positions are
equivalent in the
octahedral domain.
• There are three
molecular
geometries:
– Octahedral
– Square pyramidal
– Square planar
Molecular Shapes: the VSEPR Model
Six Charge Clouds
Larger Molecules
In larger molecules, it
makes more sense to
talk about the
geometry about a
particular atom rather
than the geometry of
the molecule as a
whole.
 Molecular Shape and
Molecular Polarity
• When there is a difference in electronegativity between
two atoms, then the bond between them is polar.
• It is possible for a molecule to contain polar bonds, but
not be polar.
• For example, the bond dipoles in CO2 cancel each other
because CO2 is linear.
Dipoles
• When two equal, but
opposite, charges are
separated by a distance, a
dipole forms.
• A dipole moment, ,
produced by two equal but
opposite charges separated
by a distance, r, is calculated:
 = Qr
• It is measured in debyes (D).
 Comparison of the
Polarity of Two Molecules
A NONPOLAR molecule A POLAR molecule
 Molecular Shape and
Molecular Polarity
• In water, the molecule is not linear and the bond dipoles
do not cancel each other.
• Therefore, water is a polar molecule.
 Molecular Shape and
Molecular Polarity
• The overall polarity of a molecule depends on its
molecular geometry.
Hybrid Orbitals
• Hybrid orbitals form by “mixing” of atomic orbitals to create
new orbitals of equal energy, called degenerate orbitals.
• When two orbitals “mix” they create two orbitals; when three
orbitals mix, they create three orbitals; etc.
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 valence electrons
2 unpaired electrons
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 valence electrons
4 unpaired electrons
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 nonequivalent orbitals
Hybridization and sp3 Hybrid
Orbitals
How can the bonding in CH4 be explained?

4 equivalent orbitals
Other Kinds of Hybrid Orbitals
Types of Bonds
• Two types of bonds:
• Sigma (σ) bond
• Pi (π) bond
• -Bonds: electron density lies on the axis between
the nuclei.
• All single bonds are -bonds.
• -Bonds: electron density lies above and below the
plane of the nuclei.
• A double bond consists of one -bond and one -
bond.
• A triple bond has one -bond and two -bonds.
Sigma () and Pi () Bonds

• Sigma bonds are characterized by

– head-to-head overlap.
– cylindrical symmetry of electron density about the internuclear
axis.
• Pi bonds are characterized by
– side-to-side overlap.
– electron density above and below the
internuclear axis.