MODULE-II

CHEMICAL BONDING

General Chemistry
CHEM-1001
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 CONTENTS

Covalent Bond; sigma and pi bond; single, double and triple bonds;
Ionic Bond;
Octet stability,
Lewis dot structure,
VSEPR Theory,
Valence Bond Theory,
LCAO-MO; H2; CO
Periodic trends of chemical properties,
Inter-molecular and Intra-molecular bonding (Hydrogen Bonding, Van
Der Waals forces, London Forces, etc); dipole moment; polarizibility
of molecules;
Band theory of solids; conductors; semiconductors; insulators;
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 CHEMICAL
CHEMICAL BONDING
BONDING
• Molecules of chemical substances are made of two or
more atoms joined together by some force, called as
Chemical Bond

•This force results from the interaction between the

various atoms and helps to form a stable molecule

• Covalent bond results from sharing electrons

between the atoms. Usually found between
nonmetals.
• Ionic or Electrovalent bond results from the
transfer of electrons from a metal to a nonmetal.
• Coordinate covalent bond occurs in metal complex
• Metallic bond: attractive force holding pure metals 3
together.
 IONIC
IONIC BONDING
BONDING

COVALENT
COVALENT BONDING
BONDING

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 Ionic Bond

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Between atoms of metals and nonmetals with very
different electronegativity
Bond formed by transfer of electrons

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Produce charged ions all states. Conductors and have
high melting point.
An electronegativity difference of 2 is essential for a
compound to be ionic.
Ionic compounds are solids at room temperature and are
hard and brittle.
Examples: NaCl, CaCl2, K2O

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IONIC BONDING
 electrons are transferred between valence shells of atoms
 ionic compounds are made of ions
NOT MOLECULES

Ionic compounds are called Salts or Crystals

 Always formed between metals and non-metals

[METALS ]+ [NON-METALS ]-

Lost e- Gained e-
 IONIC BONDING
 occurs when Electronegativity difference (ΔEN )is between 1.7
and 3.3
 Look up e-neg of the atoms in the bond and subtract
NaCl (Na: 0.9 Cl: 3.0, Difference = 2.1)
CaCl2
 Compounds with polyatomic ions
NaNO3
PROPERTIES OF IONIC COMPOUNDS

 hard solid @ 22oC SALTS

Crystals
 high mp temperatures

 nonconductors of electricity in solid

phase
 good conductors of electricity in liquid
phase or dissolved in water (aq)
 Why Ionic Compounds exist as Crystals?

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Positive and negative ions attract each other with
electrostatic force that extends in all directions.

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This means that ions will be bonded to a number
of oppositely charged ions around them. This
leads to formation of an alternating cation-anion
pattern of crystal lattice.

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 Why Ionic Compounds are hard and
brittle?

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Crystals are made of alternate positive and
negative ions such that opposite ions lie over
one another. When external force is applied

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even a slight shift brings like ions close to one
another. This make the ionic compounds hard
and brittle.

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Why Ionic Compounds have high melting
points?

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Since in crystal lattice the positive and
negative ions are tightly held in their

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positions in the lattice, only at high
temperature do the ions acquire sufficient
kinetic energy to overcome their attractive
forces and attain the freedom of movement
as in a liquid.

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Solubility of Ionic compounds in Water
When a crystal of an ionic substance is placed in

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water, the polar water molecules detach the
positive and negative ions from the crystal
lattice by their electrostatic pull. These ions then

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get surrounded by water molecules and can lead
an independent existence and are thus dissolved
in water.

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 Ionic Crystals
Ionic compounds exist as crystal lattice structures with

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particular patterns of alternating positive and negative ions.
The unit cell is the smallest group of ions that is repeated.
Different types of crystal structures can form.

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•the relative sizes and charges of the ions affect the type of
crystal structure that an ionic compound will form.

NaCl forms a cubic crystal lattice

structure.

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Properties of Ionic Compounds
Melting and Boiling Points

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• high due to very strong attractions between ions
Solubility

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• ionic compounds are soluble in water when the
attractive forces between the ions and water
molecules are stronger than the attractive forces
among the ions themselves

• When sodium chloride (NaCl) dissolves in

water, attractive forces between water
molecules and NaCl ions act to break apart the 13

ionic bonds.
Mechanical Properties
• hard and brittle, so will break apart when struck

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Ionic crystal will
break on smooth

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planes, where like
charges become
aligned.

Conductivity
• solids do not conduct because ions cannot move
• compounds conduct when dissolved in water and14
ions can move
 Characteristics of Ionic Bond
 Solids at room temperature

 High melting point

 Hard and brittle

 Soluble in water

Conductors of electricity

 Do not exhibit isomerism

 Ionic reactions are fast.

 COVALENT BOND
bond formed by the sharing of electrons
Occurs when ΔEN is less than 1.7
 Between nonmetallic elements of similar
electronegativity.
 Formed by sharing electron pairs

 Polar when electrons are shared unequally nonpolar

when shared equally
 All polyatomic ions and diatomics are covalent bonds

 Stable non-ionizing particles, they are not conductors at any state

 Examples; O2, CO2, C2H6,

H2O, SiC
POLAR COVALENT BONDS

when electrons are shared

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unequally
H2O

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water is a polar molecule because oxygen
is more electronegative than hydrogen, and
therefore electrons are pulled closer to
oxygen.

NONPOLAR COVALENT BONDS

when electrons are shared equally

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H2 or Cl2
COVALENT BONDING

molecules

 Pairs of e- are shared between non-metal atoms

 electronegativity difference < 2.0

 forms polyatomic ions

PROPERTIES OF MOLECULAR SUBSTANCES

Covalent
bonding
 Low m.p. temp and b.p. temps
 relatively soft solids as compared to ionic compounds

 nonconductors of electricity in any phase

 Characteristics of Covalent Bond

 Gases, liquids or solids at room temperature

 Low melting points and boiling points

Neither hard nor brittle

Soluble in non-polar organic solvents

Non-conductors of electricity

Exhibit isomerism

Molecular reactions
  Metallic bonding
 Occurs between like atoms of a metal in the free state
 Valence e- are mobile (move freely among all metal atoms)
 Positive ions in a sea of electrons

 Metallic characteristics
 Highmp temps, ductile, malleable, shiny
 Hard substances
 Good conductors of heat and electricity as (s) and (l)
Examples; Na, Fe, Al, Au, Co

It’s the mobile electrons

that enable me-tals to
conduct electricity!!!!!!
 Metallic Bonding
Chemists use the electron-sea model to describe metallic
bonding. The model proposes that the valence electrons of

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metal atoms move freely among the ions, forming a “sea” of
delocalized electrons that hold the metal ions rigidly in
place.

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Microscopic analysis
shows that the
structure of metals
consists of
aggregates of
crystals.
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 Metals Form Alloys
Metals do not combine with metals. They form

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Alloys which is a solution of a metal in a metal.
Examples are steel, brass, bronze and pewter.

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 Characteristics of Metallic Bond

 Luster or Reflectivity

Electric conductivity

Heat conductivity

Ductility and Malleability

Electron emission
 Properties of Metals
Melting and Boiling Points

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• the stronger the bonding forces, the higher the melting and
boiling points of pure metals

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Periodic table trends include:
1. For Group 1, melting points decrease as the atomic number
increases. 24
2. For Groups 1 to 6, across a period, melting points increase as
atomic number increases.
 Properties of Metals
Electrical and Thermal Conductivity

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• Metals are good conductors because their electrons
are free to move from one atom to the next.

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Malleability and Ductility
• Based on the electron-sea model, metals can be
shaped because, when struck, the metal ions can
slide by one another while the electrons still
surround them.
Hardness
• The variation between metals is due to differences in
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crystal size (smaller ones make harder metals).
 Alloys
Alloys are solid mixtures of two or more metals.
•the addition of the second metal, even in a very small amount, can
significantly affect the properties of a substance
•in some cases, non-metal atoms, such as carbon, are added

If atoms of the second If atoms of the second metal

metal are similar in are much smaller than atoms
size to the first metal, of the first metal, they will fit in
spaces between the larger
they take the place of 26
atoms.
those atoms.
 CHEMICAL
CHEMICAL BONDS
BONDS

Bond Type Single Double Triple

# of e’s 2 4 6
Notation — = 
Bond order 1 2 3
Bond
Increases from Single to Triple
strength
Bond length Decreases from Single to Triple
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AVERAGE
AVERAGEBOND
BONDENTHALPIES
ENTHALPIES(KJ/MOL)
(KJ/MOL)

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 STRENGTH
STRENGTHOF
OFCOVALENT
COVALENTBONDS
BONDS

AVERAGE
AVERAGEBOND
BONDLENGTHS
LENGTHSFOR
FORSOME
SOMESINGLE,
SINGLE,DOUBLE,
DOUBLE,AND
AND
TRIPLE
TRIPLEBONDS
BONDS

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BOND
BOND POLARITY
POLARITY AND
AND ELECTRONEGATIVITY
ELECTRONEGATIVITY
• Electronegativity: The ability of one atoms in a
molecule to attract electrons to itself.
• Pauling set electronegativities on a scale from 0.7
(Cs) to 4.0 (F).
• Electronegativity increases across a period and but
decreases down a group

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 BOND
BOND POLARITY
POLARITY AND AND ELECTRONEGATIVITY
ELECTRONEGATIVITY
• There is no sharp distinction between bonding types.
• The positive end (or pole) in a polar bond is represented
+ and the negative pole -.

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CHEMICAL
CHEMICALBONDS,
BONDS,LEWIS
LEWISSYMBOLS,
SYMBOLS,AND
ANDTHE
THEOCTET
OCTETRULE
RULE

• Valence is the number of bonds formed by an atom in a

molecule

• The electrons in the outer energy level of an atom are

referred to as the valence electrons since they take part in
chemical bonding

The electronic configuration of Na is 2, 8, 1 and that of Cl is 2, 8,

7. Thus sodium has 1 valence electron and chlorine has 7

Bonding and Non-bonding Electrons

• The valence electrons actually involved in bond formation are
called bonding electrons.

• The remaining valence electrons still available for bond formation

are referred to as non-bonding electrons

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Lewis Symbols of Elements or Electron Dot Structures
Origin: The electronic theory of valence

In chemical bond formation, atoms interact by losing, gaining,

or sharing of electrons so as to acquire a stable noble gas
configuration
OR

Atoms interact by electron-transfer or electron-sharing to

achieve the stable outer shell of eight electrons or OCTET
(Rule of Eight)

STEP BY STEP METHOD:

• A Lewis symbol of an element consists of an element’s
symbol and
surrounding dots to represent the number of valence
electrons
• Place a pair of electrons around each bond
• Complete octets of surrounding atoms
• Place leftover electrons in pairs on the central atom
• If there are not enough electrons to give the central atom an
octet,
CHEMICAL
CHEMICALBONDS,
BONDS,LEWIS
LEWISSYMBOLS,
SYMBOLS,AND
ANDTHE
THEOCTET
OCTET
RULE
RULE

Octet Rule
• All noble gases except He has an s2p6 configuration.
• Octet rule: atoms tend to gain, lose, or share electrons until they
are surrounded by 8 valence electrons (4 electron pairs).
• Caution: there are many exceptions to the octet rule.
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 LEWIS
LEWIS STRUCTURES
STRUCTURES

H O H
H2O 8e- H O H AX2E2

2 bond pairs 2 lone pairs

X E

CO2 16e- O C O AX2 O C O

2 bond pairs
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X
DRAWING
DRAWINGLEWIS
LEWISSTRUCTURE
STRUCTUREFOR
FORCHARGED
CHARGEDSPECIES
SPECIES

Formal Charge
• Consider: C N

• For C:
• There are 4 valence electrons (from periodic table).
• In the Lewis structure there are 2 nonbonding electrons and 3 from the
triple bond. There are 5 electrons from the Lewis structure.
• Formal charge: 4 - 5 = -1.
• For N:
• There are 5 valence electrons.
• In the Lewis structure there are 2 nonbonding electrons and 3 from the
triple bond. There are 5 electrons from the Lewis structure. 36
• Formal charge = 5 - 5 = 0.
 EXCEPTION
EXCEPTION TO
TO THE
THE OCTET
OCTET RULE
RULE

Central Atoms Having Less than an Octet

• Relatively rare.
• Molecules with less than an octet are typical for compounds of
Groups 1A, 2A, and 3A.
• Most typical example is BF3.
• B has 3 and F has 7 valance electrons
• Formal charges indicate that the Lewis structure with an
incomplete octet is more important than the ones with double
bonds.

BF3 24e- F B F
F 37
 ANOTHER
ANOTHER EXCEPTION
EXCEPTION TO
TO THE
THE OCTET
OCTET RULE
RULE
Central Atoms Having More than an Octet
• This is the largest class of exceptions.
• Atoms from the 3rd period onwards can accommodate more than
an octet.
• Beyond the third period, the d-orbitals are low lying energy
orbitals to participate in bonding and accept the extra electron
density.
• P has 5 and F has 7 valance electrons

F F
PF5 40e- F P F
38

F
 MOLECULAR
MOLECULAR SHAPES
SHAPES –– 3D
3D NOTATIONS
NOTATIONS
There are three fundamental geometries for molecular shape:

on the plane into plane out of plane

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MOLECULAR
MOLECULARSHAPES
SHAPES

40
 VSEPR
VSEPR
THEORY
THEORY
How do we determine the shapes of molecules and ions?
What does VSEPR stand for?
Valence Shell Electron Pair Repulsion
Why is this important to know?
It explains how molecules and ions behave.
For example:
It explains why water molecules are so good at dissolving
ionic substances even though water does not have an ionic
bond.
Another example:
It explains why part of a soap molecule attracts water while
the other part attracts grease and oils.
 VSEPR
VSEPR THEORY:
THEORY: BASIC
BASIC PROCEDURE
PROCEDURE
1) Determine the central atom (usually the atom with the lowest
subscript and/or the atom capable of forming the most bonds).
2) Draw the electron dot structure and bar diagram
3) Determine the molecular geometry using ALL electron pairs
AND atoms around the central atom.
4) Modify the geometry to determine the molecular shape if non-
bonding electron pairs exist by ignoring them, BUT LEAVE
THE ATOMS OF BONDED PAIRS WHERE THEY ARE.
This is done because even if the electrons have no atom
attached, these unbounded electron pairs still affect the shape
of the structure.

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UNIT 2 Chapter 4: Chemical Bonding and Properties of Section 4.2
Guidelines
Matter for Using VSEPR Theory to
Predict Molecular Shape
 VSEPR
VSEPR THEORY:
THEORY: EXAMPLE:
EXAMPLE: BEH
BEH22
 Central Atom?
Be (only 2 electrons)
 Electron Dot?

 Bar Diagram? H Be H

 Geometry? Hint: WhatHis the furthest

Be H
apart you can spread two
atoms attached to a central atoms?

 Shape? Ignore any unbonded pairs of electrons —not necessary

in this case.  LINEARH Be H

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 VSEPR
VSEPRTHEORY:
THEORY:EXAMPLE:
EXAMPLE:BF
BF33
 Central Atom?
B (3 electron system)
 Electron Dot?
F B F
 Bar Diagram? F Note that B violates the octet rule—
this is an exception!
F—B—F
F
 Geometry? Hint: What is the furthest apart you can
spread three atoms attached to a central atom?
F
B
F F
 Shape? Ignore any unbonded pairs of electrons —
not necessary in this case. 45
 trigonal planar
 VSEPR
VSEPRTHEORY:
THEORY:EXAMPLE:
EXAMPLE:CH
CH44
 Central Atom?
C (4 electron system)
 Electron Dot? H
H C H
H
H
 Bar Diagram?
H C H
H
 Geometry? Hint: What is the furthest apart you can spread four
atoms attached to a central atom? Think in 3D!
 Shape? Ignore any unbounded pairs of electrons —not
necessary in this case.
H
 tetrahedral
C
46
H H
H
 VSEPR
VSEPRTHEORY:
THEORY:EXAMPLE:
EXAMPLE:NH
NH33
 Central Atom?
N (5 electron system)
 Electron Dot? H N H
 Bar Diagram? H
H N H
H
 Geometry? Hint: What is the furthest apart
you can spread three atoms plus one
unbounded pair of electrons attached to a
central atom? Think in 3D!
 Shape? Ignore any unbonded pairs of
electrons —it is necessary in this case.
~107o
 trigonal pyramidal N 47
H
H
H
 VSEPR
VSEPRTHEORY:
THEORY:EXAMPLE:
EXAMPLE:HH22O
O
 Central Atom?
O (6 electron system)
 Electron Dot?
O H
H
 Bar Diagram? O H
H
 Geometry? Hint: What is the furthest apart you
can spread two atoms plus two unbonded pairs of
electrons attached to a central atom? Think in
3D!
 Shape? Ignore any unbonded pairs of electrons —
it is necessary in this case.
~104.5o
 bent O 48
H
H
 VSEPR
VSEPR THEORY
THEORY
In conclusion:
 Since water (also called the universal solvent) is bent it
is able to dissolve ionic substances:
O side tends to be –
(the electron pairs
hybridize into one O
group) H
H
H sides tend to be +

This negative side

tends to attract
positive ions
O
H These positive ends 49
H tend to attract
negative ions
 VSEPR
VSEPR MODEL
MODEL
The Effect of Nonbonding Electrons
• By experiment, the H-X-H bond angle decreases on
moving from C to N to O:
H

H C H H N H O
H H H H
109.5O 107O 104.5O
• Since electrons in a bond are attracted by two nuclei, they do not repel as
much as lone pairs.
• Therefore, the bond angle decreases as the number of lone pairs increases
Shapes of Larger Molecules
• In acetic acid, CH3COOH, there are three central atoms
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MOLECULAR
MOLECULARSHAPE
SHAPEAND
ANDMOLECULAR
MOLECULARPOLARITY
POLARITY

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MOLECULAR
MOLECULARSHAPE
SHAPEAND
ANDMOLECULAR
MOLECULARPOLARITY
POLARITY

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ELECTRON-DOMAIN
ELECTRON-DOMAINGEOMETRIES
GEOMETRIESAS
ASAAFUNCTION
FUNCTIONOF
OF
THE
THENUMBER
NUMBEROF
OFELECTRON
ELECTRONDOMAINS
DOMAINS

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54
VSEPR
VSEPRMODEL
MODEL

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UNIT 2 Chapter 4: Chemical Bonding and Properties of Section 4.2
Matter

Electron Groups and Molecular Shapes

If one or more electron groups around a central atom is a lone pair, different
strengths of repulsive forces will alter bond angles to differing degrees.
SUMMARY
SUMMARY OF
OF VSEPR
VSEPR MOLECULAR
MOLECULAR SHAPES
SHAPES

e-pairs Notation Name of VSEPR shape Examples

2 AX2 Linear HgCl2 , ZnI2 , CS2 , CO2
3 AX3 Trigonal planar BF3 , GaI3
AX2E Non-linear (Bent) SO2 , SnCl2
4 AX4 Tetrahedral CCl4 , CH4 , BF4-
AX3E (Trigonal) Pyramidal NH3 , OH3-
AX2E2 Non-Linear (Bent) H2O , SeCl2
5 AX5 Trigonal bipyramidal PCl5 , PF5
AX4E Distorted tetrahedral TeCl4 , SF4
(see-sawed)
AX3E2 T-Shaped ClF3 , BrF3
AX2E3 Linear I3- , ICl2-
6 AX6 Octahedral SF6 , PF6-
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AX5E Square Pyramidal IF5 , BrF5
AX4E2 Square Planar ICl4- , BrF4-
UNIT 2 Chapter 4: Chemical Bonding and Properties of Section 4.2
Matter

Some Exceptions When Drawing

Lewis Structures
Co-ordinate Covalent Bonds:
• one atom contributes both electrons
• bonds behave the same way as other covalent
bonds and therefore are not indicated in Lewis
structures The ammonium ion has a
co-ordinate covalent bond.

Expanded Octet (Expanded Valence):

•central atom has more than an octet of electrons
•a feature of some Period 3 and higher elements

For SF6(g), 12 electrons are

around the central atom.
UNIT 2 Chapter 4: Chemical Bonding and Properties of Section 4.2
Matter
Some Exceptions When Drawing
Lewis Structures
An Incomplete Octet:
• central atom has fewer than an octet of electrons

In BF3(g), boron has an

Resonance Structures: incomplete octet.
• measured bond lengths may not support Lewis
structures
• one of two or more Lewis structures that show
same relative position of atoms but different
positions of electron pairs
Actual bond lengths in ozone
are between those of single
and double bonds.

TO PREVIOUS
SLIDE
COVALENT
COVALENT BONDING
BONDING AND AND ORBITAL
ORBITALOVERLAP
OVERLAP
• Lewis structures and VSEPR do not explain why a bond
forms.
• How do we account for shape in terms of quantum
mechanics?
• What are the orbitals involved in bonding?
• We use Valence Bond Theory:
• Bonds form when orbitals on atoms overlap.
• There are two electrons of opposite spin in the orbital overlap.

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 Quantum Mechanics and Bonding
Quantum mechanics is used to explain and describe chemical
bonding. It is also used to account for shapes of molecules.

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Valence Bond (VB) Theory explains bond formation
and molecular shapes based on orbital overlap.

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•The region of overlap has a maximum capacity of two
electrons, which have opposite spins.
•There should be maximum overlap of orbitals, since
the greater the overlap, the stronger and more stable
the bond.
•After the bond formation the combining atoms in a
molecule retain their identity
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•Atomic orbital hybridization is used to help explain
the shapes of some molecules.
Valence bond theory VBT
The VBT was developed in 1927 by Heitler and London. According to this
theory when two atoms come closer to each other, due to the mutual
rearrangement or overlapping of their electron clouds, energy changes

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are produced. Due to this overlapping, the maximum electron density
occurs somewhere between the two atoms. After the bond formation the
combining atoms in a molecule retain their identity
The formation of stable bonds requires:

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(i)The electron should have opposite spin
(ii) the greater overlapping of the electron of the clouds
Linus Pauling and J.C. Slater extended this theory further as follows:
(a)Extent of overlapping of the electron wave functions determines the
strength of a bond. The strongest bond will be formed between the
orbitals of two atoms that overlap to the maximum extent.
(b)When the two orbitals have identical stability of energy, the one which
is more directional concentrated would form a stronger bond.
(c)s-orbital because of their spherically symmetrical shape does not show
preference to any direction.
(d)The direction of the bond formed will be in that direction in which the
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orbitals are concentrated. For ex. When two px orbitals overlap, the bond
is formed along x-direction as the two px orbitals have maximum electron
density in the x-direction.
Limitations of VBT

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(i)The formation of coordinate bond where only one atom
donates a lone pair of electrons to the other atom,
molecule or ion.

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(ii)The formation of odd electron molecules such as H2+,
NO, O3 etc. where no electron pairing takes place.
(iii)The paramagnetic nature of O2 molecule
(iv)The formation and structure of several molecules
which involves resonance and hybridization.
(v)VBT fails to explain the formation of O2+ and O2- ions

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 VALENCE
VALENCE BOND
BOND
THEORY
THEORY

Linus Pauling stated valence bond theory

Overlap of Atomic Orbitals

The sharing of electrons between atoms is viewed as an overlap
of atomic orbitals of the bonding atoms.

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 When H – H distance = 74 pm,
Repulsion = Attraction
 strongest bond
 optimal overlap
 lowest energy

74 pm

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 At H – H distance > 74 pm,
Repulsion < Attraction

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 weaker bond
 too little overlap
 atoms come closer

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74 pm

> 74 pm

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 At H – H distance < 74 pm,
Repulsion > Attraction

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 weaker bond
 too much overlap
 atoms get further apart

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74 pm

< 74 pm

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Because of orbital overlap, the bonding electrons localize
in the region between the bonding nuclei such that

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There is a high probability of finding the electrons in the
region between the bonding nuclei.

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Overlap of two half-filled orbitals leads to the formation
of a covalent bond.

1s 1s

 

1s-1s overlap gives a H – H single bond 70

HF:
1s 2s 2p
H  F    

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1s-2p overlap gives a H – F single bond

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1s 2s 2p
H  F    

Non-bonding electrons
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 F2: The 2p-2p overlap gives a F – F single bond
2s 2p 2s 2p

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F     F    
2s 2p 2s 2p

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F     F    

Non-bonding electrons
Each F atom has three pairs of non-bonding electrons
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F F
Identify the non-bonding electrons in O2 molecules
Two 2p-2p overlaps give a O=O double bond

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2s 2p 2s 2p
O     O    

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2s 2p 2s 2p
O     O    

Non-bonding electrons
Each O atom has two pairs of non-bonding electrons 73
O O
 Overlap of an empty orbital with a fully-filled orbital
leads to the formation of a co-ordinate covalent bond
or dative bond

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H H

+
H N + H H N H

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H H

Represented by an arrow  pointing from the electron

pair donor to the electron pair acceptor.

F3B + NH3
O
O
O O N
O O
F3B NH3 74
 INTERPRETATION
INTERPRETATION OF
OF THE
THE FORMATION
FORMATION OF
OF
COVALENT
COVALENT BONDS
BONDS IN
IN TERMS
TERMS OF
OFVALENCE
VALENCE
BOND
BOND THEORY
THEORY

27 April 2020
(a) NH4+ H
H N H

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H
By Lewis model, the structure is
4 single bonds are formed, one of them is a dative bond
By VB
Theory
2s 2p 1s 1s
N     3H  H+
75
 H
Three 2p-1s(half-filled) overlaps lead to the
formation of three N – H single bonds. H N

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H
By VB Theory

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2s 2p 1s 1s
N     3H  H+
One 2s(fully-filled)-1s(vacant) overlap leads to the
formation of one N  H dative bond.
H H

+
H N + H H N H 76

H H
(b) HCN
By Lewis model, the structure is H-CN
 one H-C single bond and

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one CN triple bond.

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By VB Theory
2s 2p
C   
 Only 2 single bonds can be formed
 Promotion of a 2s electron to a 2p orbital
2s 2p
77

C*    
 C* N H
2s 2p 2s 2p 1s
        

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 The overlap of one orbital (?) of C* with an 1s orbital of H gives the
C-H single bond.
 Overlaps of three orbitals (???) of C* with three 2p orbitals of N

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give the CN triple bond.
C* N H
2s 2p 2s 2p 1s
        

 The 2s electrons on N are non-bonding

electrons
H C N
 The energy released by forming a stronger triple bond outweighs the
78
energy required for promoting an electron from a 2s orbital to a 2p
orbital.
(c) SO2
By Lewis model, the three possible structures are
OS=O, O=SO, O=S=O

27 April 2020
Most stable
no separation of opposite formal charges

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By VB Theory
3s 3p
S    
 Only two single bonds can be formed
 One 3p electron has to be promoted to a 3d orbital
Expansion of Octet
79
By VB Theory
3s 3p
S    

27 April 2020
octet expansion

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3s 3p 3d
S*     

The energy released by forming of two stronger double

bonds outweighs the energy required for promoting an
electron from a 3p orbital to a 3d orbital.
80
 3s 3p 3d

S*     

27 April 2020
2s 2p S
2O     O O

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 Overlaps of two half-filled orbitals (??) of S* with two half-filled 2p
orbitals of an oxygen atom give a S=O double bond.
 A total of two S=O bonds are formed with two O atoms
3s 3p 3d
S*     

2s 2p S
2O     O O 81

Non-bonding electrons: S* 3s2 ; O 2s2 and 2p2

 THE CONCEPT OF
RESONANCE
According to VB theory, the two less stable structures of SO2,
OS=O and O=SO do ‘exist’.

27 April 2020
Each of these structures contributes in certain extent to the real
structure of SO2.
If  SO2 represents the wave function of the real structure

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of SO2 molecules, then
 SO2  a O  S O  b OS O  c O  S O
where  O  S O  O S O  O  S O
are the wave functions of the three possible structures and

a>b=c>0
82
In other words, the real structure of SO2 is the
resonance hydrid of the three possible structures.
 

27 April 2020
O=S=O OS=O O=SO

More contribution Less contribution

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3s 3p
S     O=SO

2s 2p 2s 2p

O     O*   

83
A S=O double bond is formed by 3p(half-filled)-2p(half-filled)
overlaps between S and O.
 3s 3p
S     O=SO

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2s 2p 2s 2p
O     O*   

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A OS dative bond is formed by 3p(fully-filled)-2p(empty)
overlap between S and O*
3s 3p
S     O=SO

2s 2p 2s 2p
O     O*   
84
Formation of dative bond is not favourable because the two
unpaired 2p electrons in O are forced to pair up to give O*
(d) SF2, SF4, SF6
By VB
3s
Theory 3p 2s 2p

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S     F    

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Only two S-F single bonds can be formed by 3p-2p overlaps
between one S atom and two F atoms
 SF2 is formed. F-S-F
To form four S-F single bonds in SF4, a 3p electron in S has to be
promoted to a 3d orbital.

3s 3p 3d
S*      85
 F
F F
F F
S S

27 April 2020
F F F
F
By VB F

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Theory
To form six S-F single bonds in SF6, a 3s electron in S* has to be
promoted to a 3d orbital.
3s 3p
S    
3s 3p 3d
S**      
The energy released by forming more single bonds outweighs 86the
energy required for promoting 3s and 3p electrons to 3d orbitals.
(e) XeF2, XeF4, XeF6

By VB Theory

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5s 5p 2s 2p
Xe     F    

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To form two Xe-F bonds in XeF2, a 5p electron in Xe has to be
promoted to a 5d orbital.
F-Xe-F
5s 5p 5d
Xe*     
87
By VB Theory
5s 5p 5d

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Xe*     
To form four Xe-F bonds in XeF4, a 5p electron in Xe* has to be

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promoted to a 5d orbital.
5s 5p 5d
Xe**      

F F
Xe
88
F F
By VB Theory
5s 5p 5d

27 April 2020
Xe**      
To form six Xe-F bonds in XeF6, a 5p electron in Xe** has to be

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promoted to a 5d orbital.
5s 5p 5d
Xe***       
F
F
F
Xe
F
F 89

F
By VB Theory
5s 5p 5d

27 April 2020
Xe**      

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5s 5p 5d
Xe***       

The energy released by forming more single bonds outweighs

the energy required for promoting 5p electrons to 5d orbitals.

90
Molecular Orbital (MO) Theory (developed by Mulliken in
1932) explains bond formation and molecular shapes based on
the formation of new molecular orbitals.

27 April 2020
According to MO theory:
•Covalent bond formation involves atomic orbital overlap that
results in formation of new orbitals called molecular orbitals.

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•After the bond formation the combining atoms in a molecule
lose their identity, bonding is explained with the help of MO’s
•Molecular orbitals have shapes and energy levels that are
different from those of atomic orbitals.
•The electrons in molecular orbitals are delocalized throughout
the orbital.
•The electrons may be considered either as particles or wave
and therefore electron is described as a wave function (ψ)
91
•The wave function (ψ) describing a MO may be obtained by
linear combination of atomic orbitals (LCAO).
Linear combination of atomic orbitals (LCAO)

Consider tow atoms A aand B which have atomic orbitals described by the the wave
wave functions ψ(A) and ψ(B).

27 April 2020
If the electron clouds of these two atoms overlap when the atoms approach, then the
wave function for the molecule MO ψ(AB) can be otained by a linear combination of the
atomic orbitals ψ(A) and ψ(B):

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ψ(AB) = N(C1 ψ(A) + C2 ψ(B) )
Where N= is a normalizing constant chosen to ensure that the probability of finding a
electron in the whole of the space is unity
And C1 and C2 are constant chosen to give a maximum energy for ψ(AB).

finding an electron in a volume of space dV is ψ2 dV so the probability

The probability of
density for the combination of two atoms as above is related to the wave function
squared:
ψ2(AB) = (C12 ψ(A)2 + 2C1 C2 ψ(A) ψ(B) + C22 ψ(B)2 )
Where C12 ψ(A)2 is related to the probability of finding an electron on atom A if A is an
isolated atom
C22 ψ(B)2 is related to the probability of finding an electron on atom B if B is an isolated92
atom.
The term 2C1 C2 ψ(A) ψ(B) becomes important as the overlap between the two atomic
Rules for LCAO
In deciding which AO may be combined to form MO, three rules must be
considered:
(i)The AO must be roughly of the same energy. This is important when

27 April 2020
considering overlap between tow different types of atoms
(ii)The orbital must overlap one another as much as possible. This implies that
the atoms must be close enough for effective overlap
(iii)In order to produce bonding bonding and antibonding MO, either the

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symmetry of the two AO must remain unchanged when rotated about the
internuclear line, or both AOs change symmetry in an identical manner.

•Wave function which have the same symmetry (or sign) may be regarded as
waves that are in phase which when combined add up to give resultant wave
and is called additive combination
ψ(g) = N{ψ(A) + ψ(B)}
•Similarly wave functions of different signs correspond to waves that are completely
out of phase and which cancel each other by destructive combination and is called
subtractive combination
ψ(u) = N{(ψ(A) +(-ψ(B)}
Note: the sign + and – refer to sign of the wave functions, which 93
determine their symmetry, and have nothing to do with electrical charge;
g stands for gerade (even) and u for ungerade (odd)
 Difference between Bonding MO and Antibonding MO
Bonding MO Antibonding MO
1. It is formed by the additive It is formed by the

27 April 2020
overlap of AOs substractive overlap of AOs

2. Its formation takes place Its formation takes place

when lobes of AOs have when lobes of AOs have

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same sign different sign

3. The energy of bonding MO is The energy of antibonding

lower than that of AOs from MO is higher than that of
which it is formed AOs from which it is formed

4. The electron density is high The electron density is low

in the region between the in the region between the
nuclei of bonded atoms nuclei of bonded atoms
5. Every electron in bonding Every electron in bonding 94
MO contributes toward MO contributes toward
stability of the molecule unstability of the molecule
The relative energies of Mos in increasing order have been
found to be as follows:

27 April 2020
(i)For H2 to N2 : for = or > less than 14

σ1s <σ*1s <σ2s <σ*2s < [π2px= π2py ] <σ2pz <[π*2px= π*2py ] <σ*2pz

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(ii) For O2 to Ne2 < greater than 14

σ1s <σ*1s <σ2s <σ*2s <σ2pz [π2px= π2py ] <[π*2px= π*2py ] <σ*2pz

In elements of lower effective nuclear charge, say from H2 to

N2 the energy difference between the s and p orbitals is least
and there are interactions between pair of orbitals of the
same type. These interactions are essentially repulsive like
between (σ2s and σ2p orbital) and similarly between (σ*2s and
σ*2p orbital). This leads to stabilization of σ2s and σ*2s orbital 95
and destabilization of σ2p and σ*2p orbitals that’s why from H2 to
N2 the order of MO energy level is
MO diagram for Heteronuclear diatomic molecules

The wave function describing a MO( ψ(AB) ) for a

27 April 2020
heteronuclear diatomic molecule can be obtained from LCAO ψ(A)
and ψ(B)

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ψ(AB) = N(C1 ψ(A) + C2 ψ(B) )

Here CA ≠ CB because the electron distribution in the

internuclear region is not symmetrical. Let us assume that
Electronegativity of atom A is greater than the Electronegativity
of atom B. in this case energy of ψ(B) > ψ(A) and atom A with wave
function ψ(A) makes greater contribution to the bonding MO ψ(AB)
because it is having a lower energy and it lies close to the ψ(AB) .
96
Similarly atom B with wave function ψ(B) makes greater
contribution to antibonding MO ψ*(AB) because ψ(B) has higher
 MOLECULAR
ORBITALS
 Molecular orbitals result from the combination
of atomic orbitals.
 Since orbitals are wave functions, they can
combine either constructively (forming a bonding
molecular orbital), or destructively (forming an
antibonding molecular orbital).
 Molecular orbitals form when atomic orbitals with
similar energies and proper symmetry can overlap.
 Atomic orbitals with differing energies or the
wrong spatial orientation (orthogonal) do not
combine, and are called non-bonding orbitals.
NEED FOR MO
THEORY
Valence bond theory fails to explain the bonding in many
simple molecules.
The oxygen molecule has a bond length and strength
consistent with a double bond, and it contains two unpaired
electrons.
Valence bond theory predicts the double bond, but not
the paramagnetism of oxygen.
O=O
: :
: :
Resonance is another example of the limitations of valence
bond theory. Bond lengths and strengths are intermediate
between single, double or triple bonds.
Molecular orbital theory is often a better approach to use
with molecules that have extended π systems.
MOLECULAR ORBITAL
THEORY
In order to simplify things, we’ll consider the
interaction of the orbitals containing valence
electrons to create molecular orbitals.
The wave functions of hydrogen atom A and
hydrogen atom B can interact either
constructively or destructively.
Constructively:
Ψ(σ) or Ψ+ = (1/√2 ) [φ(1sa) + φ(1sb) ]

Destructively:
Ψ(σ*) or Ψ- = (1/√2 ) [φ(1sa) - φ(1sb) ]
MOLECULAR ORBITAL
THEORY

The bonding orbital results in

increased electron density
between the two nuclei, and is
of lower energy than the two
separate atomic orbitals.

The antibonding orbital results

in a node between the two
nuclei, and is of greater energy
than the two separate atomic
orbitals.
MOLECULAR ORBITAL
THEORY

The result is an energy level diagram with the bonding

orbital occupied by a pair of electrons. The filling of
the lower molecular orbital indicates that the molecule
is stable compared to the two individual atoms.
 MOLECULAR ORBITAL THEORY

The bonding orbital

+ -
is sometimes given
the notation σg,
where the g stands
+ for gerade, or
symmetric with
respect to a center
of inversion.

The signs on the molecular orbitals indicate the

sign of the wave function, not ionic charge.
 MOLECULAR ORBITAL THEORY

The anti-bonding
+ -
orbital is
sometimes given
the notation σu,
+ where the u stands
for ungerade, or
asymmetric with
respect to a center
of inversion.
The signs on the molecular orbitals indicate the
sign of the wave function, not ionic charge.
RULES FOR COMBINING
ATOMIC ORBITALS
1. The number of molecular orbitals = the
number of atomic orbitals combined.
2. The strength of the bond depends upon the
degree of orbital overlap.
PERIOD 2 DIATOMIC MOLECULES
For the second period, assume that, due
to a better energy match, s orbitals combine
with s orbitals, and p orbitals combine with p
orbitals.
The symmetry of p orbitals permits end-
on-end overlap along the bond axis, or side-
by-side overlap around, but not along, the
internuclear axis.
MOS USING P ORBITALS
+ - + -

- + -

With the x axis as the bond axis, the px

orbitals may combine constructively or
destructively. The result is a σ bonding orbital and
a σ anti-bonding orbital.
MOS USING P ORBITALS
+ - + -

- + -
The designation σ indicates symmetric
electron density around the internuclear (x) axis.
The + and – signs indicate the sign of the wave
function, and not electrical charges.
MOS USING P ORBITALS
+ - + -

- + -
Some texts will use the symmetry
designations of g (gerade) or u (ungerade) instead
of indicating bonding or anti-bonding.
MOS USING P ORBITALS
+ - + -

- + - σg
For these orbitals, the bonding orbital is
gerade, or symmetric around the bond axis.
MOS USING P ORBITALS
+ - + - σu

- + - σg
For these orbitals, the anti-bonding orbital is
asymmetric about the bond axis, and is
designated as σu. Note that the designations of u
or g do not correlate with bonding or anti-bonding.
Π MOLECULAR ORBITALS
+ -
- +

+
side-by-side -
overlap
The orbital overlap side-by-side is less than
that of overlap along the bond axis (end-on-end).
As a result, the bonding orbital will be higher in
energy than the previous example.
Π MOLECULAR ORBITALS
+ -
- +

+
side-by-side -
overlap
π orbitals are asymmetric with respect to the
bond axis. There is electron density surrounding
the bond axis, with a node along the internuclear
axis.
Π MOLECULAR ORBITALS
+ -
- +

+
πu
side-by-side -
overlap
Some texts use the subscripts g and u instead
of bonding and anti-bonding. In this example, the
bonding orbital is ungerade, or asymmetric about
a center of symmetry.
Π MOLECULAR ORBITALS
+ - πg
- +

+
πu
side-by-side -
overlap

The anti-bonding orbital is gerade, or

symmetric about a center of symmetry.
MOLECULAR ORBITAL DIAGRAM
This is a molecular
orbital energy level σu
diagram for the p
orbitals. Note that the πg
σ bonding orbital is 2p 2p
lowest in energy due to πu
the greater overlap
σg
end-on-end.
MOLECULAR ORBITAL DIAGRAM

The alternate σu
notation is provided on πg
the right side of the
2p 2p
energy level diagram. πu
σg
MOLECULAR ORBITAL DIAGRAMS
1. Electrons preferentially occupy molecular
orbitals that are lower in energy.
2. Molecular orbitals may be empty, or
contain one or two electrons.
3. If two electrons occupy the same molecular
orbital, they must be spin paired.
4. When occupying degenerate molecular
orbitals, electrons occupy separate orbitals
with parallel spins before pairing.
MOLECULAR ORBITAL DIAGRAMS
Although molecular orbitals form from
inner (core) electrons as well as valence
electrons, many molecular orbital diagrams
include only the valence level.
MOLECULAR ORBITAL DIAGRAMS
For O2, there
will be a total of 12
valence electrons
that must be
placed in the
diagram.
MOLECULAR ORBITAL DIAGRAMS
For O2, there
will be a total of 12
valence electrons
that must be
placed in the
diagram.
MOLECULAR ORBITAL DIAGRAMS

For O2, there

will be a total of 12
2p 2p valence electrons
that must be
placed in the
diagram.

2s 2s
MO DIAGRAM FOR O2

σ*u
The molecular
π*g
orbital diagram
2p 2p for oxygen
πu
σg
shows two
σ*u
unpaired
2s 2s electrons,
σg consistent with
experimental
data.
BOND ORDER
Bond order is an indicator of the bond
strength and length. A bond order of 1 is
equivalent to a single bond. Fractional bond
orders are possible.

The bond order of the molecule =

(No. of e- in bonding orbtls) - (No. of e-
in anti-bonding orbtls)
2
MO DIAGRAM FOR O2

The bond order

σ*u
of O2 is:
π*g

2p 2p 8-4 = 2
πu 2
σg
σ*u This is
2s 2s consistent with a
σg double bond.
MO DIAGRAM FOR O2

This energy level

σ*u
diagram works
π*g
well for atoms in
2p 2p which the 2s and
πu
2p levels are fairly
σg far apart. These
σ*u are the elements
2s 2s at the right of the
σg table: O, F and Ne.
MO DIAGRAM FOR LI THROUGH N
The elements on the left side of period 2
have a fairly small energy gap between the
2s and 2p orbitals. As a result, interaction
between s and p orbitals is possible. This
can be viewed in different ways.
MO DIAGRAM FOR LI THROUGH N
In some approaches, the s orbital on
one atom interacts with the p orbital on
another. The interaction can be
constructive or destructive.
MO DIAGRAM FOR LI THROUGH N
In another approach, the s and p orbitals
on the same atom interact in what is called
orbital mixing.
Either approach yields the same result.
The σ bonding and anti-bonding orbitals are
raised in energy due to the interaction with a
p orbital.
MO DIAGRAM FOR LI THROUGH N
σ*u
π*g

σg
πu

σ*u

σg
MO DIAGRAM FOR N2

σ*u N2 has 10
π*g valence
electrons.
σg
πu

σ*u

σg
HETERONUCLEAR DIATOMIC
MOLECULES

The more electronegative atom will have

orbitals of lower energy, and therefore
contribute more to the bonding orbitals.
The less electronegative atom has
orbitals of higher energy, and contributes
more to the anti-bonding orbitals.
RULES FOR COMBINING
ATOMIC ORBITALS
For heteronuclear molecules:
1. The bonding orbital(s) will reside
predominantly on the atom of lower orbital
energy (the more electronegative atom).
2. The anti-bonding orbital(s) will reside
predominantly on the atom with greater
orbital energy (the less electronegative
atom).
HF
The 2s and 2px
orbitals on fluorine
interact with the 1s
orbital on hydrogen.
The py and pz orbitals
on fluorine lack proper
symmetry to interact
with hydrogen, and
remain as non-
bonding orbitals.
HF
The anti-bonding
orbital resides
primarily on the less
electronegative atom
(H).
Note that the
subscripts g and u are
not used, as the
molecule no longer has
a center of symmetry.
 DIFFERENCE BETWEEN VBT AND MOT
VBT MOT
1.Ineratomic orbital is produced by 1. Molecular orbitals are formed by
multiplying, exchanging and of all atomic orbitals from the
combinations of space wave valency shell of two atoms.
functions of two electrons. 2. Orbitals of bonded atoms lose
2.Orbitals of bonded atoms cannot their individual identity.
lose their identity. 3. Molecular orbitals are polycentric
3.Atomic orbitals monocentric. 4. Molecular orbital theory explain
4.It explains that inert gases have the non-existence of molecules of
orbital already spin paired, so they inert gases, since number of
have no tendency to form any bonding and antibonding electrons
linkage. are equal
5.Pauli’s exclusion principle decides 5. It explains how electrons are
the spin function combination with originally present in atomic orbitals
wave function as and are distributed in new molecular
  orbitals.
6.VBT introduces a special form to 6. MOT is not capable or predicting
explain the presence of ionic ionic character in a bond.
character in bond. 7. In MOT both bonding and
7.VBT explains the difference antibonding orbitals can have
between bonding and antibonding
27 April 2020 Sample footer electron pairs with opposed135 spins.
orbitals as following:
DETERMINING TYPE OF
INTERMOLECULAR FORCE

27 April 2020
Polar Molecules ?

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H Directly Bonded
to O, N, or F ?

NO YES

Dispersion/ Hydrogen Bonding

London Forces Dipole/Dipole Force
NO
YES

Increasing Strength of Intermolecular Force 136

van der Waals Forces
• van der Waals forces are also known as London forces.
• They are weak interactions caused by momentary changes in
electron density in a molecule.
• They are the only attractive forces present in nonpolar compounds.

Even though CH4 has no net

dipole, at any one instant its
electron density may not be
completely symmetrical,
resulting in a temporary
dipole. This can induce a
temporary dipole in another
molecule. The weak
interaction of these temporary
dipoles constitutes van 137
der Waals forces.
• All compounds exhibit van der Waals forces.
• The surface area of a molecule determines the strength of the van
der Waals interactions between molecules. The larger the surface
area, the larger the attractive force between two molecules, and the
stronger the intermolecular forces.

Figure 3.1
Surface area and
van der Waals forces

138
• van der Waals forces are also affected by polarizability.
• Polarizability is a measure of how the electron cloud around an atom
responds to changes in its electronic environment.

Larger atoms, like iodine,

which have more loosely
held valence electrons, are
more polarizable than
smaller atoms like fluorine,
which have more tightly
held electrons. Thus, two F2
molecules have little
attractive force between
them since the electrons
are tightly held and
temporary dipoles are
139
difficult to induce.
Dipole-Dipole Interactions

• Dipole—dipole interactions are the attractive forces between the

permanent dipoles of two polar molecules.
• Consider acetone (below). The dipoles in adjacent molecules align
so that the partial positive and partial negative charges are in close
proximity. These attractive forces caused by permanent dipoles are
much stronger than weak van der Waals forces.

140
 INTERMOLECULAR
FORCES
Intermolecular forces are attractive forces between molecules.

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Intramolecular forces hold atoms together in a molecule.

Intermolecular vs Intramolecular

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• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)

“Measure” of intermolecular force

Generally, boiling point
intermolecular forces
melting point
are much weaker than
intramolecular forces. Hvap
Hfus
Hsub 141
 INTERMOLECULAR
FORCES
Dipole-Dipole Forces
Attractive forces between polar molecules
• are forces of attraction between polar molecules, which have a

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region of partial positive charge and a region of partial negative
charge

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• are a main reason for melting and boiling point differences
between polar and non-polar molecules
• include hydrogen bonding, as an example of one type
Orientation of Polar Molecules in a Solid

142
 INTERMOLECULAR
Ion-Dipole ForcesFORCES
Attractive forces between an ion and a polar molecule

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•depend on the size and charge of the ion and the magnitude
of the partial charge and size of the molecule
•are involved in the process of hydration

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Ion-Dipole Interaction

143
UNIT 2 Chapter 4: Chemical Bonding and Properties of Section 4.2
Matter
Induced Dipoles
Dipole-induced dipole forces:
• are forces of attraction between a polar molecule and a non-polar molecule
that has an induced (temporary) dipole due to the nearby polar molecule

Ion-induced dipole forces:

• are forces of attraction between an ion and a non-polar molecule that has an
induced dipole due to the nearby ion

A dipole can be induced

in a non-polar molecule.

TO PREVIOUS
SLIDE
 INTERMOLECULAR
Dispersion Forces FORCES
Attractive forces that arise as a result of temporary dipoles induced in

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atoms or molecules.
•are forces of attraction between all molecules, including non-polar molecules
•are due to spontaneous temporary dipoles that form due to the constant motion

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of electrons in covalent bonds
•depend on the size and shape of the molecules
• the larger and more linear the molecule, the greater the force of
attraction

Random movement of electrons

ion-induced dipole interaction

dipole-induced dipole interaction 145

 INTERMOLECULAR
Dispersion ForcesFORCES
Continued

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Polarizability is the ease with which the electron distribution in the atom or
molecule can be distorted and temporary dipole induced.

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Polarizability increases with:
• greater number of electrons
• more diffuse electron cloud

Dispersion forces
usually increase
with molar mass.

146
 What type(s) of intermolecular forces exist between each of
the following molecules?

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HBr

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HBr is a polar molecule: dipole-dipole forces. There are also dispersion
forces between HBr molecules.

CH4
CH4 is nonpolar: dispersion forces.
S
O
O
SO2
SO2 is a polar molecule: dipole-dipole forces. There are also dispersion
147
forces between SO2 molecules.
 INTERMOLECULAR
Hydrogen Bond FORCES

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The hydrogen bond is a special dipole-dipole interaction between the
hydrogen atom in a polar N-H, O-H, or F-H bond and an electronegative
O, N, or F atom.

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A H…B or A H…A

A & B are N, O, or F

148
IMPORTANCE OF H-BONDS IN H2O
1. Very high boiling point for water (H2O(l)) for
its Molar Mass.

2. The solid form of the material is less dense

than liquid form
• Ice Floats on liquid water.
• Water expands as it freezes
SOLID BENZENE SINKS TO THE
BOTTOM OF LIQUID BENZENE
(RIGHT)
Importance of H-Bonds in H2O
1. Very high boiling point for water
(H2O(l)) for its Molar Mass.
2. Ice floats on liquid water.
• The solid form of the material is less
dense than liquid form
• Water expands as it freezes
3. High specific heat of Water
 INSULATORS, SEMICONDUCTORS,
METALS
 The last completely filled (at least at T = 0 K) band is called the
Valence Band

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 The next band with higher energy is the Conduction Band
 The Conduction Band can be empty or partially filed
The energy difference between the bottom of the CB and the top

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
of the VB is called the Band Gap (or Forbidden Gap)
 Consider a solid with the empty Conduction Band
 If apply electric field to this solid, the electrons in the valence
band (VB) cannot participate in transport (no current)

153
 INSULATORS, SEMICONDUCTORS,
METALS
 The electrons in the VB do not participate in the current, since
 Classically, electrons in the electric field accelerate, so they acquire
[kinetic] energy
 In QM this means they must acquire slightly higher energy and
jump to another quantum state
 Such states must be available, i.e. empty allowed states
 But no such state are available in the VB!

This solid would

behave as an insulator

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 INSULATORS, SEMICONDUCTORS,
METALS
 Consider a solid with the half filled Conduction Band (T = 0K)
 If an electric field is applied to this solid, electrons in the

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CB do participate in transport, since there are plenty of
empty allowed states with energies just above the Fermi
energy

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 This solid would behave as a conductor (metal)

155
 BAND
OVERLAP
 Many materials are conductors (metals) due to the “band
overlap” phenomenon
 Often the higher energy bands become so wide that they
overlap with the lower bands
 additional electron energy levels are then available

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 BAND
OVERLAP
 Example: Magnesium (Mg; Z =12): 1s22s22p63s2
 Might expect to be insulator; however, it is a metal
 3s-band overlaps the 3p-band, so now the conduction band contains 8N
energy levels, while only have 2N electrons
 Other examples: Zn, Be, Ca, Bi

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 BAND
HYBRIDIZATION
 In some cases the opposite occurs
 Due to the overlap, electrons from different shells form hybrid bands,
which can be separated in energy
 Depending on the magnitude of the gap, solids can be insulators
(Diamond); semiconductors (Si, Ge, Sn; metals (Pb)

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 INSULATORS, SEMICONDUCTORS,
METALS
 There is a qualitative difference between metals and insulators

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(semiconductors)
 thehighest energy band “containing” electrons is only partially filled for
Metals (sometimes due to the overlap)
Thus they are good conductors even at very low temperatures

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

 The resisitvity arises from the electron scattering from lattice vibrations and lattice

defects
 Vibrations increases with temperature  higher resistivity

 The concentration of carriers does not change appreciably with temperature

 The difference between Insulators and Semiconductors is

“quantitative”
 The difference in the magnitude of the band gap
 Semiconductors are “Insulators” with a relatively small band gap
 Athigh enough temperatures a fraction of electrons can be found in the
159
conduction band and therefore participate in transport
 INSULATORS VS
SEMICONDUCTORS

 There is no difference between Insulators and Semiconductors at

very low temperatures
 In neither material are there any electrons in the conduction band –
and so conductivity vanishes in the low temperature limit
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 INSULATORS VS
SEMICONDUCTORS

 Differences arises at high temperatures

A small fraction of the electrons is thermally excited into the
conduction band. These electrons carry current just as in metals
 The smaller the gap the more electrons in the conduction band at a
given temperature
 Resistivity decreases with temperature due to higher concentration of
electrons in the conduction band
1 q 2 n
 
27 April 2020 Sample footer  m* 161
 HOLE
S
 Consider an insulator (or semiconductor) with a few electrons excited
from the valence band into the conduction band
 Apply an electric field
 Now electrons in the valence band have some energy sates into which
they can move
 The movement is complicated since it involves ~ 10 23 electrons
CONCEPT OF
HOLES
 Consider a semiconductor with a small number of electrons excited from
the valence band into the conduction band

 If an electric field is applied,

 the conduction band electrons will participate in the electrical current
 the valence band electrons can “move into” the empty states, and thus can also
contribute27toApril
the2020
current Sample footer 162
 HOLES FROM THE BAND STRUCTURE POINT
OF VIEW
 If we describe such changes via “movement” of the “empty”
states – the picture can be significantly simplified
 This “empty space” is a Hole
 “Deficiency” of negative charge – holes are positively charged
 Holes often have a larger effective mass (heavier) than electrons since
they represent collective behavior of many electrons
HOLE
S
 We can “replace” electrons at the top of eth band which have
“negative” mass (and travel in opposite to the “normal”
direction) by positively charged particles with a positive mass,
and consider all phenomena using such particles
 Such particles are called Holes
 Holes are positively charged and move in the same direction
as electrons “they replace”
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 HOLE
CONDUCTION
 To imagine the movement of the hole think of a row of chairs occupied by
people with one chair empty
 To move all people rise all together and move in one direction, so the
empty spot moves in the same direction
CONCEPT OF
HOLES
 If we describe such changes via “movement” of the “empty” states – the
picture will be significantly simplified
 This “empty space” is called a Hole
 “Deficiency” of negative charge can be treated as a positive charge
 Holes act as charge carriers in the sense that electrons from nearby sites can
“move” into the hole
 Holes are usually heavier than electrons since they depict collective
behavior of many electrons

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 CONDUCTI
ON

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165

Electrical current for holes and electrons in the same direction

n-type semiconductor
Extrinsic semiconductors with a larger electron concentration than hole
concentration are known as n-type semiconductors. The phrase 'n-type' comes

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from the negative charge of the electron. In n-type semiconductors, electrons
are the majority carriers and holes are the minority carriers. N-type
semiconductors are created by doping an intrinsic semiconductor with donor
impurities (or doping a p-type semiconductor as done in the making of CMOS

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chips). In an n-type semiconductor, the Fermi energy level is greater than that
of the intrinsic semiconductor and lies closer to the conduction band than the
valence band.

p-type semiconductor
As opposed to n-type semiconductors, p-type semiconductors have a larger hole
concentration than electron concentration. The phrase 'p-type' refers to the
positive charge of the hole. In p-type semiconductors, holes are the majority
carriers and electrons are the minority carriers. P-type semiconductors are
created by doping an intrinsic semiconductor with acceptor impurities (or
doping a n-type semiconductor). P-type semiconductors have Fermi energy
levels below the intrinsic Fermi energy level. The Fermi energy level lies closer
166
to the valence band than the conduction band in a p-type semiconductor.
 Energy Band Diagram
n-type semiconductor p-type semiconductor

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167
 TRENDS
 Objectives:
 Describe trends among the elements for atomic size.
 Explain how ions form.
 Describe periodic trends for first ionization energy,
ionic size, and electronegativity.

Atomic Size
}

Radius
 Measure27
the
AprilAtomic
2020 Radius - this is half the distance between
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two nuclei of a diatomic molecule.
 TRENDS

Influenced by three factors:

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1. Energy Level
 Higher energy levels are further away from the nucleus.

2. Charge on nucleus (# protons)

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 More charge pulls electrons in closer. (+ and – attract
each other)
3. Shielding effect (blocking effect?)
What do they influence?
 Energy levels and Shielding have an effect on the GROUP
 Nuclear charge has an effect on a PERIOD

169
ATOMIC SIZE - GROUP
TRENDS
 As we increase the atomic number (or go down a group). . .
 each atom has another energy level,

 so the atoms get bigger.

ATOMIC SIZE - PERIOD
H TRENDS
Li
 Going from left to right across a period, the size gets smaller.
Na  Electrons are in the same energy level.
 But, there is more nuclear charge.
K  Outermost electrons are pulled closer.

Rb

Mg Al Si P S Cl Ar
Na

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 Rb

K
Period 2

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Atomic Radius (pm)

Na

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Xe
Li
Kr

Ar

Ne
H

171
3 10
Atomic Number
 S
 Some compounds are composed of particles called “ions”
 An ion is an atom (or group of atoms) that has a positive or negative

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charge
 Atoms are neutral because the number of protons equals electrons
 Positive and negative ions are formed when electrons are transferred

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(lost or gained) between atom
Metals tend to LOSE electrons, from their outer energy level
Sodium loses one: there are now more protons (11) than electrons (10),
and thus a positively charged particle is formed = “cation”
The charge is written as a number followed by a plus sign: Na1+. Now
named a “sodium ion”
Nonmetals tend to GAIN one or more electrons. Chlorine will gain one
Electron. Protons (17) no longer equals the electrons (18), so a charge
of -1.Cl1- is re-named a “chloride ion”. Negative ions are called
172
“anions”
 ENERGY
 Ionization energy is the amount of energy required to
completely remove an electron (from a gaseous atom).

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 Removing one electron makes a 1+ ion.
 The energy required to remove only the first electron is
called the first ionization energy.

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 The second ionization energy is the energy required to
remove the second electron.
 Always greater than first IE.
 The third IE is the energy required to remove a third
electron.
 Greater than 1st or 2nd IE.

173
Symbol First Second Third

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H 1312 Why did these values
increase so much?
He 2731 5247
Li 520 7297 11810

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Be 900 1757 14840
B 800 2430 3569
C 1086 2352 4619
N 1402 2857 4577
O 1314 3391 5301
F 1681 3375 6045
Ne 2080 3963 6276 174
WHAT FACTORS DETERMINE IONIZATION
ENERGY
 The greater the nuclear charge, the greater IE.
 Greater distance from nucleus decreases IE

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 Filled and half-filled orbitals have lower energy,
so achieving them is easier, lower IE.

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 Shielding effect

 The electron on the outermost energy level has

to look through all the other energy levels to see
the nucleus.
 Second electron has same shielding, if it is in
the same period

175
 IONIZATION ENERGY – GROUP
TRENDS
 As you go down a group, the first IE decreases because...
 The electron is further away from the attraction of the

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nucleus, and
 There is more shielding.
IONIZATION ENERGY – PERIOD
IONIZATION ENERGY – PERIOD

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TRENDS
 All the atoms in the same period have the same energy
level.
 Same shielding.
 But, increasing nuclear charge
 So IE generally increases from left to right.
 Exceptions at full and 1/2 full orbitals.

176
 He
He has a greater IE
First Ionization energy
than H.
Both elements have
the same shielding
H since electrons are
only in the first level
But He has a greater
nuclear charge

Atomic number
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First Ionization energy He
 Li has lower IE

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than H
 more shielding

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H
 further away
 These outweigh

Li
the greater
nuclear charge
178
Atomic number
First Ionization energy He
 Be has higher IE

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than Li
 same shielding

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H Be  greater nuclear
charge
Li

179
Atomic number
 He
B has lower IE
First Ionization energy

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than Be
 same shielding

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H  greater nuclear
Be
charge
 By removing an
B
Li electron we make
s orbital filled
180
Atomic number
 27 April 2020 Sample footer
181
Atomic number
C

B
Be

Li
He

H
First Ionization energy
First Ionization energy He

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N

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H C
Be

B
Li

182
Atomic number
 He
Oxygen breaks
First Ionization energy

N
the pattern,
because
H Be
C O removing an
electron leaves
B
it with a half
Li filled p orbital

Atomic number
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First Ionization energy He

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N F

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H C O
Be

B
Li

184
Atomic number
 He Ne
Ne has a
First Ionization energy

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N F lower IE than
He

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C O Both are full,
H Be
Ne has more
shielding
B
Li Greater
distance
185
Atomic number
 He Ne
 Na has a lower
First Ionization energy

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N F IE than Li
 Both are s1

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H C O  Na has more
Be
shielding
B  Greater
Li
distance
Na
186
Atomic number
27 April 2020 Sample footer
187
Atomic number
First Ionization energy
 DRIVING
FORCES
 Full Energy Levels require lots of energy to remove their
electrons.

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 Noble Gases have full orbitals.
 Atoms behave in ways to try and achieve a noble gas
configuration.

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 2nd I.E.
 For elements that reach a filled or half-filled orbital by removing 2
electrons, 2nd IE is lower than expected.
 True for s2
 Alkaline earth metals form 2+ ions.
 3rd I.E.
 Using the same logic s2p1 atoms have low 3rd IE.
 Atoms in the aluminum family form 3+ ions.
 2nd IE and 3rd IE are always higher than 1st IE!!!
188
 TRENDS IN IONIC SIZE:
CATIONS
 Cations form by losing electrons.
 Cations are smaller than the atom they came from – not

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only do they lose electrons, they lose an entire energy
level.
 Metals form cations.

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 Cations of representative elements have the noble gas
configuration before them.
TRENDS IN IONIC SIZE:
ANIONS
Anions form by gaining electrons.
Anions are bigger than the atom they came from – have
the same energy level, but a greater area the nuclear charge
needs to cover. Nonmetals form anions.
Anions of representative elements have the noble gas 189

configuration after them.

 CONFIGURATION OF
IONS
 Ions always have noble gas configurations ( = a full outer level)
 Na atom is: 1s22s22p63s1

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 Forms a 1+ sodium ion: 1s22s22p6

 Same configuration as neon.

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 Metals form ions with the configuration of the noble gas before
them - they lose electrons.
 Non-metals form ions by gaining electrons to
achieve noble gas configuration.
 They end up with the configuration of the noble
gas after them.

190
 ION GROUP
TRENDS
 Each step down a group is adding an energy level
 Ions therefore get bigger as you go down, because of the

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additional energy level.
Li1+
ION PERIOD
TRENDS

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Na1+

K1+  Across the period from left to right, the

nuclear charge increases - so they get
Rb 1+
smaller.
 Notice the energy level changes between

Cs1+ anions and cations.

N3-
O2-
F1-
191

Li1+ Be2+ B3+ C4+

 SIZE OF ISOELECTRONIC
IONS
 Iso- means “the same”
 Isoelectronic ions have the same # of electrons

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 Al3+ Mg2+ Na1+ Ne F1- O2- and N3-
 all have 10 electrons

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 all have the same configuration: 1s22s22p6 (which is the noble
gas: neon)
 Positive ions that have more protons would be smaller (more
protons would pull the same # of electrons in closer)
O2- N3-
F1-
Na 1+
Al13
3+
12 11 10 9 8 7
Mg2+
Ne
192
 TRENDS IN
ELECTRONEGATIVITY
 Electronegativity is the tendency for an atom to attract electrons to itself
when it is chemically combined with another element.
 They share the electron, but how equally do they share it?

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 An element with a big electronegativity means it pulls the electron towards
itself strongly!
ELECTRONEGATIVITY GROUP
TREND

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The further down a group, the farther the electron is away from the
nucleus, plus the more electrons an atom has.
Thus, more willing to share.

ELECTRONEGATIVITY
Low electronegativity. PERIOD
TREND
 Metals are at the left of the table
 They let their electrons go easily
 Thus, low electronegativity
At the right end are the nonmetals
They want more electrons
193
Try to take them away from others
High electronegativity