Chapter 1

Chemical Bonding and Chemical Structure

 Review of Chemical Bonding
• Valence Electrons: Outermost electrons
• s and p electrons for main group elements
• Responsible for chemical properties of
atoms
• Participate in chemical reactions

Valence Electron
Core Electrons
 Ionic Bonding
• Ions: atoms that have a charge due to gain or loss of
electrons
– Anion: (-) charged atom
– Cation: (+) charged atom
• Ionic Bond: a bond formed through the transfer of
one or more electrons from one atom or group of
atoms to another atom or group of atoms
Formula Unit
• Ionic bonds are omni-directional
• Can dissociate into free ions

7
 Covalent Compounds
• Covalent Compounds: compounds composed of atoms
bonded to each other through the sharing of electrons
• Electrons NOT transferred
• No + or – charges on atoms
• Non-metal + Non-metal
• Also called “molecules”
• Examples:
– H2O
– CO2
– Cl2
– CH4
 Octet Rule
• Octet Rule: the tendency for atoms to seek 8
electrons in their outer shells
– Natural electron configuration of the Noble Gases
– Done by gaining, losing, or sharing electrons
– Increases stability
– H and He seek a “Duet”
 or H-H

Duet

or
 Elements want to achieve the stable electron configuration
of the nearest noble gas
n=2
n=3

Ne

Atoms tend to gain, lose or share electrons until they are

surrounded by 8 electrons Octet Rule
 Nobel Gas Has a Stable Electron Configuration

Ne; 1s2, 2s2, 2p6

Ar; [Ne] 3s2, 3p6

Ar
Example of Ionic Bonding
+
_
Na + F Na + [ F ]
11 9 10

Electronic configuration of Neon achieved in both cases

There are two types of bonding;
Ionic Bonding refers to electrostatic forces between ions, usually a
metal cation and a non-metal anion
Covalent Bonding results from the sharing of two electrons between
two atoms (usually non-metals) resulting in molecules
Octet Rule applies

H + H H H
number of electrons around each atom = He

Cl + Cl Cl Cl
number of electrons around each atom = Ar

Triple bond
N + N N N
number of electrons around each atom = Ne

Each Covalent Bond contains two electrons

 Carbon has 4 valence electrons

H H
H C H H C H Ne
H H Neon
methane
H C

Stable Octet required

Covalent Bonding – Atoms Share Electrons

Hydrogen molecule, H2

Concentration of negative charge between two

nuclei occurs in a covalent bond

7A elements (e.g. F) have one valence electron for covalent bonding,

so to achieve octet
6A elements (e.g. O) use two valence electrons for covalent bonding,
so to achieve octet
5A elements (e.g. N) use three valence electrons for covalent bonding,
so to achieve octet
4A elements (e.g. C) use four valence electrons for covalent bonding,
so to achieve octet
Carbon dioxide, CO2 Total Number of valence electrons = 4 + (2 x 6) = 16

O + C + O O C O = O C O
Double bonds
Rules for Drawing Lewis Structures
• First sum the number of valence electrons from each atom
• The central atom is usually written first in the formula
• Complete the octets of atoms bonded to the central atom (remember that H
can only have two electrons)
• Place any left over electrons on the central atom, even if doing so it results in
more than an octet
• If there are not enough electrons to give the central atom an octet , try
multiple bonds

E.g. 1. PCl3 Total Number of valence electrons = 5 + (3 x 7) = 26

Cl P Cl Cl P Cl Cl P Cl
Cl Cl
Cl
 E.g. 2; CHBr3
Total Number of valence electrons = 4 + 1 + (3 x 7) = 26

Br
Br C H
Br

Exceptions to the Octet Rule in Covalent Bonding

1. Molecules with an odd number of electrons

2. Other Natural Radicals, which do not obey Lewis Structures (e.g.
O2)
2. Molecules in which an atom has less than an octet
3. Molecules in which an atom has more than an octet
 1. Odd Number of Electrons
NO Number of valence electrons = 11

N O Resonace Arrows
N O
Resonance occurs when more than one valid Lewis structure can be written for a
particular molecule (i.e. rearrange electrons)

NO2
Number of valence electrons = 17

O N O O N O O N O
Molecules and atoms which are neutral (contain no formal charge) and with an unpaired
electron are called Radicals

O2 O O O O
Oxygen is a ground state
"diradical"
 2. Less than an Octet

Includes Lewis acids such as halides of B, Al and compounds of Be

BCl3 Cl
Group 3A atom only has six electrons around it
B
Cl Cl
However, Lewis acids “accept” a pair of electrons readily from Lewis
bases to establish a stable octet

Cl H Cl H
_ +
Cl Al + N H Cl Al N H
Cl H Cl H
Lewis acid Lewis base salt
 AlX3

Aluminium chloride is an ionic solid in which Al3+ is surrounded by

six Cl-. However, it sublimes at 192 °C to vapour Al2Cl6 molecules

Cl Cl Cl
Al Al
Cl Cl Cl
B2H6
A Lewis structure cannot be written for diborane. This is explained
by a three-centre bond – single electron is delocalized over a B-H-B

H H H
B B
H H H
Octet Rule Always Applies to the Second Period =
n2 ; number of orbitals
2s, 2px, 2py, 2pz ---orbitals cannot hold more than two electrons
Ne [He]; 2s2, 2px2, 2py2, 2pz2

n=2
n=3
 Third Period ; n2 = 32 = 9 orbitals

Ar [Ne]; 3s2, 3px2, 3py2, 3pz2 3d0 3d0 3d0 3d0 3d0

n=3
 3. More than an Octet
Elements from the third Period and beyond, have ns, np and unfilled
nd orbitals which can be used in bonding

PCl5 P : (Ne) 3s2 3p3 3d0

Number of valence electrons = 5 + (5 x 7) = 40 Cl
10 electrons around the phosphorus
Cl
Cl P
Cl
SF4 Cl
S : (Ne) 3s2 3p4 3d0
Number of valence electrons = 6 + (4 x 7) = 34
F F
S
The Larger the central atom, the more atoms you F F
can bond to it – usually small atoms such as F, Cl
and O allow central atoms such as P and S to
expand their valency.
 Electronegativity
• The measure of the ability of an atom to
attract electrons to itself
– Increases across period (left to right) and
– Decreases down group (top to bottom)
– fluorine is the most electronegative element
– francium is the least electronegative element
Electronegativity Scale
 Types of Bonding

1) Non-Polar Covalent Bond:

• Difference in electronegativity
values of atoms is 0.0 – 0.4
• Electrons in molecule are
equally shared ENCl = 3.0
• Examples: Cl2, H2, CH4 3.0 - 3.0 = 0
Pure Covalent
2) Polar Covalent Bond:
• Difference in
electronegativity values
of atoms is 0.4 – 1.7/2.0
• Electrons in the molecule
are not equally shared ENCl = 3.0
• The atom with the higher ENH = 2.1
EN value pulls the electron 3.0 – 2.1 = 0.9
cloud towards itself Polar Covalent
• Partial charges
• Examples: HCl, ClF, NO
 Electrostatic Potential Maps
• A graphical depiction of electron distribution

28
3) Ionic Bond:
• Difference in EN
above 1.7-2.0
• Complete transfer
of electron(s) ENCl = 3.0
ENNa = 0.9
• Whole charges
3.0 – 0.9 = 2.1
Ionic
 Dipole Moment (m)
• Depends on charge separation and distance
• m = qr (a vector quantity)
• q = magnitude of charge
• r = vector from site of + charge to site of – charge
• Units = Debyes (D)
Molecular Polarity
 Lewis Dot Structures
1) Count the number of valence electrons present in
the molecule
2) Determine the arrangement of atoms. Generally,
the atom that occurs least often is central. Join the
terminal atoms to the central atom(s) using shared
pairs of electrons (bonds)
3) Place any remaining electrons around the terminal
atoms to satisfy the octet rule
• Exception: Hydrogen
4) Place any remaining electrons on the central
atom(s) to satisfy the octet rule
5) Check to make sure:
• You’ve used the correct number of valence
electrons
• Everyone has an octet (or duet)
• Everyone is doing what they like to do
6) If the number of electrons around the
central atom is less than 3, change the single
bonds to multiple bonds
 What Things Like To Do
1) Halogens
• Like to be terminal
• Like to have one bonding pair
(two shared electrons) and 3
lone pairs (non-bonding
electrons)
2) Carbon
• Likes to have 4 bonding pairs
and no lone pairs
• Likes to bond to other carbons
• Likes to be central
3) Silicon
• Likes to do what carbon does
• Notice, it sits under C on the
periodic table
4) Oxygen
• Like to have 2 bonding pairs
and 2 lone pairs
5) Sulfur
• Likes to do what O does
6) Nitrogen
• Likes to have 3 bonding pairs
and 1 lone pair
7) Phosphorous
• Likes to do what N does
8) Hydrogen
• Likes to be terminal with only 1
bond
• Do not put lone pairs on H
9) Boron
• Likes to have 3 bonds and no lone
pairs
• Likes a sextet instead of an octet
(what everybody else besides
Hydrogen likes)
10) *Note:
• A double bond = 2 bonding pairs
• A triple bond = 3 bonding pairs
 Problems
• Draw the Lewis Dot Structures for the
following molecules
1) CO2
2) P2H4
3) O3
4) NO3-
 Drawing Resonance Structures
-1

-1

1. Draw first Lewis structure that maximizes

octets
2. Assign formal charges
3. Move electron pairs from atoms with (-)
formal charge toward atoms with (+) formal
charge

42
 Formal Charge
• Assigned charge for each atom in a molecule/ion
– Electronic bookkeeping – may or may not correspond
to a real charge
– Sum of formal charges on each atom must equal the
total charge on the molecule/ion
• FC = Valence e-’s – Lone Pair e-’s – ½ bonding e-’s
 Carbon Dioxide, CO2

At OXYGEN 6 - (1/ 2)(4) - 4 = 0

• • • •
• •
• O C O •

At CARBON 0
4 - (1/ 2)(8) - 0 =

18, 20 Oct 97 Bonding and Structure 44

Carbon Dioxide, CO2 (2)
An alternate Lewis structure is:

6 - (1 / 2)(2) - 6 =
-1

•
+ • •
•
• O C O •
• • C atom
charge is 0.
6 - (1/ 2)(6) - 2 =
+1
•
• • +•
AND the corresponding
resonance form
• O
• •
C O •

18, 20 Oct 97 Bonding and Structure 45

 Carbon Dioxide, CO2 (3)
Which is the predominant resonance structure?
•
+ • •
•

•
• • • •
•
• O C O •

• O C O • OR • •

•
• •
•
+
Answer ?
Form without formal charges is
• O
• •
C O •

BETTER - no +ve charge on O

• REALITY: Partial charges calculated

by CAChe molecular modeling
-0.73 -0.73
system +1.46
18, 20 Oct 97 Bonding and Structure 46
 Boron Trifluoride, BF3
••
• •
• F •

••
•
• F
••
B
• •
• F
••
•

What if we form a B—F double bond

to satisfy the B atom octet?

18, 20 Oct 97 Bonding and Structure 47

 Boron Trifluoride, BF3 (2)

•
•• +
• F fc = 7 - 2 - 4 = +1 Fluorine
••
•
• F
••
B fc = 3 - 4 - 0 = -1 Boron
•
• F
•
• • To have +1 charge on F, with its very
••
high electron affinity is not good. -
ve charges best placed on atoms
with high EA.
• Similarly -1 charge on B is bad
• NOT important Lewis structure
18, 20 Oct 97 Bonding and Structure 48
 Thiocyanate ion, (SCN)
-
Which of three possible resonance structures
is most important?
A. S=C=N

B. S=C - N

C. S-C N

Calculated partial charges

ANSWER:
C>A>B
-0.16 -0.32
-0.52
18, 20 Oct 97 Bonding and Structure 49
 Molecular Structures of Covalent
Compounds
• Atomic connectivity: How atoms in a molecule are
connected

OR

• Molecular geometry: How far apart atoms are and

how they are arranged in space
– Bond lengths
– Bond angles
– Dihedral angles
 Bond Length
• Distance between nuclei

51
• Increases with atoms in higher rows
• Decreases toward higher atomic number along a row
• Decreases with increasing bond order

52
 Bond Angles
• Angle between each pair of bonds
• Contribute to molecular shape
• Determined by Valence-shell electron-pair
repulsion (VSEPR)
• Use molecular models!
• Line-and-wedge structures

53
Drawing Lewis Dot Structure
With Correct Geometry
 Valence Shell Electron Pair Repulsion
Theory
• VSEPR theory:
– Electrons repel each other
– Electrons arrange in a
molecule themselves so
as to be as far apart as
possible
• Minimize repulsion
• Determines molecular
geometry
 Defining Molecular Shape
• Electron pair geometry: the geometrical
arrangement of electron groups around a
central atom
– Look at all bonding and non-bonding e-’s
• Molecular Geometry: the geometrical
arrangement of atoms around a central
atom
– Ignore lone pair electrons
 VSEPR Theory

• Valence shell electron are present as

– Regions of high electron density are created.
– These regions arrange themselves to be as far away as
possible form on another. As a result specific geometries are
created around atoms in the molecule
• Single, double, and triple bonds are counted as one region of
electron density
• Unshared pairs of valence electrons are also counted as one region
of electron density
Drawing the Lewis structure accurately will reveal the number
of electron density regions around the center atoms
 VSEPR Theory
• There are five basic shapes based on the
number of electron density regions around a
center atom(s)
– Illustration of models with next few slides
 VSEPR Theory

Two regions of high electron density

 VSEPR Theory

Three regions of high electron density

 VSEPR Theory

Four regions of high electron density

 VSEPR Theory

Five regions of high electron density

 VSEPR Theory

Six regions of high electron density

 VSEPR Theory
• Encountered geometries
– Electronic geometry – determined by the location
of bond. the regions of electron density around
the center atom(s)
– Molecular geometry – determined by the
arrangement of atom only around the center
atom(s)
• The does not include lone electron pairs. The
molecular shape differs from the electron shape if lone
pairs are present
An example is H2O
 VSEPR Theory
• Lone pairs of electrons occupy more
space than bonding pairs. As a
consequence, there is an order of the
magnitude of repulsions
– lp/lp > lp/bp > bp/bp
As a result, the bond angles around a center atoms
can be distorted (reduced) from the predicted
values
CH4 and H2O What are the H-C-H and H-O-H bond
angles. If a change is observed, why?
 Dihedral Angle
• Also known as the torsional angle
• Rotation can occur along single bonds

71
Valence Bond Theory
 Valence Bond(VB) Theory
• VB theory describes how bonding occurs
• Describes how the atomic orbitals overlap to
produce the bonding geometry predicted by
VSEPR
– Go back and review atomic orbitals if necessary
• Electrons are arranged in atomic orbitals
according to energy. The set of atomic
orbitals, however, may not be of lowest
possible energy upon bonding covalently to
neighboring atoms.
 Valence Bond(VB) Theory
• The valence shell orbitals (atomic orbitals)
commonly combine to change their character
in order to obtain a lower energy ‘mixed’
orbital set for bonding in a particular
geometry
– Which atomic orbitals would participate in
bonding in H, O, and C? These atomic orbitals can
form a new set of hybrid orbitals upon bonding.
• Hybrization – process by which atomic orbital
combine to form a set of ‘mixed’ orbitals of
lower energy when bonding covalently
– The ‘mixed’ orbitals are called hybrid orbitals
 Valence Bond(VB) Theory
• Hybrid orbitals on a center atom align
themselves with the bonding orbitals on
the neighboring atoms
– A ‘good overlap’ is necessary for sharing
electrons in a bond.
Valence Bond(VB) Theory
 Molecular Shapes and Bonding
• Simples structures will be analyzed based on
geometry type.
• Experimentally determined findings will be
discussed in light of these models.
• Terminology
– A – central atom
– B – atoms bonded to A
– U – lone pairs of electrons around A
AB3U represents three atoms bonded to a central
atom with one lone pair. An example would be
NH3
 Types of Bonds
• A sigma (s) bond results when the bonding orbitals
point along the axis connecting the two bonding
nuclei
– either standard atomic orbitals or hybrids
• s-to-s, p-to-p, hybrid-to-hybrid, s-to-hybrid, etc.
• A pi (p) bond results when the bonding orbitals are
parallel to each other and perpendicular to the axis
connecting the two bonding nuclei
– between unhybridized parallel p orbitals
• the interaction between parallel orbitals is not as
strong as between orbitals that point at each other;
therefore s bonds are stronger than p bonds
 Problems
• Write a hybridization and bonding scheme for
acetaldehyde
Molecular Orbital Theory
Bond Order: ½ (# of electrons in bonding MO’s - # of electrons in antibonding MO’s)
 Problems
1) Draw an MO diagram to predict the bond
order of N2
2) Draw an MO diagram to predict the bond
order of CN-
3) Use MO theory to determine the bond order
of Ne2