Bonding &

Molecular Structure
 Chemical Bonding
A chemical bond is formed when the valence electrons
between atoms reorganize.
Ionic Bond:
• One or more valence electrons is transferred from one atom to
another, creating a positive and negative ion.
• The bond is the attractive force between the ions.

Covalent Bond:
• Valence electrons are shared between atoms.
• No ions are formed.
 The Life (and Death) of G. N Lewis
• Proposed the concept of the covalent bond
after drawing cubical structures to represent
the position of electrons in specific atoms.

• Nominated for the Nobel Prize 34

times but never won.
• Mysterious circumstances
surround his death in his lab at
UC Berkeley.
• While working with HCN,
he collapsed under a work bench
and died.
• Suicide, accident or heart attack?
 Lewis Dot Structures
When drawing a Lewis dot structure, a bond results when one or
more electron pairs is shared between two atoms.

We count each bond as two electrons.

Each atom is surrounded by eight electrons (or an octet)

 Drawing Lewis Dot Structures
A set of rules can make drawing Lewis dot structures easy.
1. Determine the arrangement of atoms in a molecule.
-The central atom has lowest electron affinity or biggest size.
- Hydrogen and halogens are typically terminal atoms,
preferring to form only one bond each.
2.Determine the total number of valence electrons.
- Count up the valence e- for each atom in the molecule.
- For an anion, add the number of e- equal to the charge.
- For a cation, subtract the number of e- equal to the charge.
3.Make a single bond between each pair of atoms.
4.If any e- remain, add them as lone pairs to terminal atoms.
5.If the central atom does not have an octet, change lone pairs
into bonding pairs to form multiple bonds.
 Drawing Lewis Dot Structures
Draw the Lewis structure for NO2+.
Central Atom: N
Number of valence e-: 5 (N) + 2 x 6 (O) – 1 (charge) = 16
Single bond between each atom:
2 bonds = 4 electrons

Add lone pairs of e- to terminal atoms:

2 bonds = 4 electrons
6 lone pairs = 12 electrons

Make central atom have an octet:

4 bonds = 8 electrons
4 lone pairs = 8 electrons
 Predicting Lewis Structures
What is the Lewis structure of C2F4?
Central Atoms: C
Number of valence e-: 2 x 4 (C) + 4 x 7 (F) = 36
Single bond between each atom:
5 bonds = 10 electrons

Add lone pairs of e- to terminal atoms:

5 bonds = 10 electrons
12 lone pairs = 24 electrons

Make central atoms have an octet:

6 bonds = 12 electrons
12 lone pairs = 24 electrons
 Formal Charges
The charge on an atom in a molecule or polyatomic ion.
The formal charges should add to the overall charge on the ion,
or should add to zero for a neutral compound.

Formal charge = group number – [lone pair e- + ½ (bonding e-)]

The group number gives the number of valence electrons.
The lone pairs “belong” to the atom that they surround.
Bond pairs are divided equally between the bonded atoms.
Where does the charge reside in ClO-?
Number of valence e-: 7 (Cl) + 6 (O) + 1 (charge) = 14

Formal charge (Cl) = 7 – [6 + ½ (2)] = 0 Formal charge (O) = 6 – [6 + ½ (2)] = -1

 Formal Charges
Where does the charge reside in CN-?

Number of valence e-: 4 (C) + 5 (N) + 1 (charge) = 10

Formal charge (C) = 4 – [2 + ½ (6)] = -1 Formal charge (N) = 5 – [2 + ½ (6)] = 0

Where does the charge reside in NF4+?

Number of valence e-: 5 (N) + 4 x 7 (F) - 1 (charge) = 32

Formal charge (N) = 5 – [0 + ½ (8)] = +1 Formal charge (F) = 7 – [6 + ½ (2)] = 0

 Resonance Structures
The possible structures of a molecule where more than one
Lewis structure can be written, differing in the number of
bond pairs between a given set of atoms.

The structure for ozone is the combination of the

two resonance structures drawn above.

Since the central oxygen has one single bond and one double
bond drawn to it, the average bond length is 1.5.
 Resonance Structures
How many resonance structures exist for CO32-?
Draw them.

No single structure accurately describes the carbonate ion.

The actual structure is a combination of the three resonance forms.

There is an equal distribution of electrons

over all the atoms involved.

Where do the formal charges belong?

 VSEPR Model
Lewis structures allow us to predict the three-dimensional
geometry of molecules and ions.

The valence shell electron-pair repulsion theory states that

molecular geometry is determined based on the repulsion
between electron pairs.

Molecules adopt the shape that minimizes the electron pair

repulsions (ie keeps electron pairs farthest apart!)

The positions of the valence electrons define

the angles between bonds.

VSEPR theory does not work well for

compounds containing transition metals.
 Central Atoms with Single Bond Pairs
The simplest structures involve central atoms with only
single covalent bonds (no lone pairs!)

Central atom does not Expanded octet:

have an octet only 3rd period or higher
 Central Atoms w/ Single Bond Prs & Lone Prs
Electron Pair Geometry:
• The geometry of a moleculeor ion when all electrons (lone and
bonding) are considered.
Molecular Geometry:
• The geometry of a molecule or ion when only bonding electrons
are considered.
• Lone pairs of electrons still occupy space but are not included
in the shape description of the molecule or ion.
Let’s consider ammonia.
Number of valence e-: N (5) + 3 x 1 (H) = 8
 Effect of Lone Pairs on Bond Angles
The arrangement of electrons in ammonia is tetrahedral so
we would expect the bond angles to be 109.5°.
However, the experimentally determined angles are 107.5°.
This is because lone pairs of electrons take up more space
than bonding pairs of electrons and force the bonding pairs
closer together.
lone pair-lone pair > lone pair-bond pair > bond pair-bond pair
Four electron pairs:
Central Atoms with “Expanded Octets”
Central Atoms with “Expanded Octets”

If a molecule has a second lone pair of electrons,

the pairs want to be as far apart as possible,
so they are placed 180° apart.
 Orbital Views of
Bonding: Hybridization
& Molecular Orbitals
 Orbital Overlap
When two hydrogen atoms are brought together, the electrons
from one atom are attracted to the nucleus of the other atom.

There is an optimum
distance at which
energy is lowest.
At a greater distance,
the overlap is less and
the bond is weaker.
At a smaller distance,
repulsion is too high.
 Orbital Overlap
The covalent bond that forms from the overlap of two s orbitals
is called a sigma (s) bond.
Two electrons of opposite spin can be accommodated in an orbital.
One electron comes from each atom.
The greater the orbital overlap, the stronger the bond.

The 2s and 2p electrons not involved in the bond are lone pairs
(or non-bonding electrons).
 Orbital Hybridization
Let’s consider the molecule methane.
C: 1s2 2s2 2p2
2 unpaired electrons in p orbitals (angle of 90°)

All the C-H bonds are the same – how do we explain this?
 Orbital Hybridization
In methane, four orbitals are needed to match the
electron pair geometry of the central carbon atom.
By mixing the 2s and three 2p orbitals on carbon, a new set of
four sp3 hybrid orbitals can be formed.

All sp3 orbitals have

the same energy
and shape.

Each C-H bond is

formed by overlap
of a 1s orbital from
H and an sp3 orbital
from C.
 Types of Hybrid Orbitals
Consider BeCl2

One 2s and one 2p orbital overlap to form two sp orbitals.

Two 2p orbitals are unused.
 Types of Hybrid Orbitals
Consider BF3

One 2s and two 2p orbitals overlap to form three sp2 orbitals.

One 2p orbital is unused. 2pz is perpendicular
to the plane containing
the three sp2 orbitals
 Types of Hybrid Orbitals
Consider NH3 and H2O

Although each compound has a different number of bonding

and lone pairs, the total number of electron pairs is four.
 Hybridization
glycine (H2NCH2COOH)
sp3
sp3

sp2
sp3

Bonds to Central Shape Hybrid Orbs Unused Orbs

Atom
2 Linear sp 2 p orbs
3 Trigonal planar sp2 1 p orbs
4 Tetrahedral sp3 None
5 Trigonal bipyramidal sp3d 4 d orbs
6 Octahedral sp3d2 3 d orbs
 Types of Covalent Bonds
VB theory states that bond formation occurs when orbitals
on adjacent atoms overlap.

s-bond: end-to-end overlap

• Higher e- density along the bond axis between atoms
• One bonding region
• No nodal plane
• Free rotation around the bonds
• Primary bond
 Types of Covalent Bonds
-bond: side-to-side overlap
• Overlap between p orbitals (not hybridized orbitals)
• p orbitals oriented in the same direction (aligned)
• Two bonding regions (above and below s-plane)
• Different regions of electron density to avoid e-/e- repulsion
• Restricted rotation around the double bond sp2
• Secondary bond
• Double bond: one s-bond + one -bond

one unhybridized p orbital

on each carbon
      
  2s
 2p    
3 sp 2 p
2s 2p 3 sp 2 hybrid
p orb.
orb. for š
hybrid orbitals
for š bond