WERABE UNIVERSITY

College of Natural and Computational Sciences

Department of chemistry

Chemistry for pre-University Remedial program

Chapter two: Chemical Bonding and Molecular structure

by muktar H 1
 2. Chemical Bonding and Structure
2.1. Introduction

 The attractive force which holds atoms, ions, and molecules together
is called chemical bond

 Since these forces of attraction are intramolecular forces, they have

an effect on the chemical properties as well as the physical
properties of the chemical

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 The Octet Rule

 All noble gases except helium (1s2 ) have ns2 np6 electron
configurations (where n indicates the highest occupied shell)
 The noble gases are quite unreactive because they have very stable
electron configurations (outer shells with eight electrons)
 Many Atoms undergoing reactions also tend to gain or lose electrons until
they have achieved an outer shell that contains an octet of electrons (eight
electrons

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 2.2. Types of Chemical Bonding

 Atoms can combine to form three types of bond:

1. Ionic bonding (metal with non-metal )
2. Covalent bonding (non-metal with non-metal)
3. Metallic bonding (metal with metal )

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 2.2.1. Ionic Bonding
• An ionic bond is formed by the electrostatic attraction between positive and
negative ions. Also known as electrovalent bond

• The bond is formed by complete transfer of electron from the valence shell of
one atom to the valence shell of the other

• The atom that loses electrons becomes a cation (positive ion), and the atom that
gains electrons becomes an anion (negative ion

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 Lewis dot symbols

• Symbol of an element and one dot for each valence electron

• Electron configurations shows all electrons, Lewis dot symbols shows valence
electrons

Fore example, Cl: [Ne]3s2 3p5

N: 1s22s22p3

• A Lewis structure is a combination of Lewis symbols that represents either the

transfer or the sharing of electrons in a chemical bond.
Example -
Sodium Chloride (NaCl)
 Formation of ionic bond
• Enormous amount of energy is released when the ions come together and form a
solid ionic compound. Fore example,

• The negative of this value, 1050 kJ, is the lattice energy of LiF. The lattice energy
(U) is the enthalpy change that occurs when 1 mol of ionic solid separates into
gaseous ions. It indicates the strength of ionic interactions, which influence melting
point, hardness, solubility, and other properties.
 Factors Affecting the Formation of Ionic Bonds
• The formation of ionic bonding is influenced by various factors. The
following factors favours the formation of ionic compound.

• Low Ionization energy (IE) of metal

• High Electron affinity of non metal (EA)

• Larger Lattice energy which in turn depends on

– Magnitude of charges => directly proportional.

– Distance between the charges => inversely proportional

 Lattice Energies from the Born–Haber Cycle
• Finding the lattice energy of an ionic solid by experiment is difficult.
However, it can be found indirectly using the Born–Haber cycle

• Hess’s law states that an overall reaction’s enthalpy change is the

sum of the enthalpy changes for the individual reactions that make it
up:
• ∆Htotal = ∆H1 + ∆H2 + ∆H3 + ∆H4 + ∆H5

• ∆Hlattice energy = -∆H5

• Example-1
1. based on the following data calculate the lattice energy
& Cl-
of that required to breaking NaCl in to Na+
– Sublimation energy of Na ∆Hsub = +107KJ/mol
– I.E of Na ∆HI.E = +502KJ/mol
– Bond energy of Cl2, ∆Hbond = +242KJ/mol
– Electron affinity of Cl, ∆HE.A = -355KJ/mol
– ∆H0 of NaCl = -411KJ/mol
f
– ∆Hlattice = ?
Solution
∆H0 of NaCl = ∆H + ∆H + 1/2∆H + ∆H + ∆H
f sub I.E bond E.A lattice
∆H = ∆H of NaCl - (∆H + ∆H + 1/2∆H + ∆H )
0
lattice f sub I.E bond E.A
242
-∆Hlattice = -411KJ/mol – (107KJ/mol + 502KJ/mol + KJ/mol -
2
355KJ/mol)
∆Hlattice = +786KJ/mol 11
EXAMPLE-2

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  Name ionic compounds

• To name an ionic compound that is formed from a metal and a non-

metal, follow the given procedure
1. Write the name of the metal .
2. Modify the last characters of the name of the non-metal to end it
with ide. Example
• NaCl = sodium chloride.
• MgO = magnesium oxide
• Na3N = sodium nitride.

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Table1 Summary of formula of ionic-compounds.

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  Ionic Compounds (Salts)
• Composed entirely of ions not contain molecules
• Electrically neutral (Ex: Na+ and Cl- combine to form NaCl)
• Properties:
 Crystal lattice (geometric pattern)
 High melting points (solids at room temp.)
 Brittle and hard
 Liquid (molten) state conducts electricity; solid state does not
 Solutions are good conductors

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 Covalent Bonds and Molecular Geometry
Formation of Covalent Bonding

Consider the formation of a hydrogen molecule (H2 ). When two isolated hydrogen
atoms come close together, various attractive and repulsive forces begin to develop
between them

The magnitudes of the various attractive and repulsive forces between nuclei and
electrons in a covalent bond depend on how close together the atoms are.
There is an optimum distance between nuclei, called the bond length, where net
attractive forces are maximized and the H−H molecule is most stable.

Therefore, a covalent bond is formed when a pair of electrons is shared between

two atoms. Formation of a bond always results in greater electron density between
the nuclei.
• There are different types of covalent bonds like polar and non-polar and coordinate
covalent bonds.

• 1. A polar-covalent bond is a covalent bond in which the bonded atoms have an

unequal attraction for the shared electrons. Example: hydrogen-chlorine bond (H-Cl)

• Polar covalent bonding occurs because one atom has a stronger affinity for electrons
than the other. When electrons are shared but shared unequally.

• Non-polar covalent bond is a covalent bond in which the bonding electrons are shared
equally by the bonded atoms, resulting in a balanced distribution of electrical charge.
Example; hydrogen-hydrogen bond (H: H), Cl2. The electrons are shared equally.
• 3. Coordinate Covalent bond: A coordinate covalent bond (also
called a dative bond) is formed when one atom donates both of the
electrons to form a single covalent bond. These electrons originate
from the donor atom as an unshared pair.
 Representation of Covalent Bonds (Drawing Lewis Structures)
• The representation of covalent bonding through Lewis symbols and shared
electron pairs is called a Lewis structure. The Lewis structure for a
hydrogen chloride formed from hydrogen and chlorine atoms is:

• Example – Hydrogen chloride

Lone pairs

Bond pairs

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  Steps to Drawing Lewis Structures

1. Determine the total number of valence electrons (sum the valence

electrons of each atom). Add 1 electron for each negative charge and
subtract 1 electron for each positive charge

2. Draw skeletal structure with the central atom being the least
electronegative element.

3. Place electron pairs around terminal atoms so that each (except

hydrogen) has an octet

4. Place extra electrons on the central atom. Add multiple bonds if

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atoms lack an octet
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  Types of Covalent Bonds
• Different covalent bond types share a different
number of electrons
Water (H2O) Carbon Dioxide (CO2) Nitrogen (N2)
- - - -
- - -

-
- -
++ + + +
-
- -
+ ++ + ++
+ + + + + ++
+ + - + + + + + + - - + + +
- - +
+ + +
-
+ + - + + + + + +
+ + + +
- -
- -
-
-

- - - -
- -

Single Bonds Double Bonds Triple Bonds

Share 2 Electrons Share 4 Electrons Share 6
Electrons
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  Resonance
 Molecule or polyatomic ion with several different acceptable Lewis
formulas with the same arrangement of atoms is called Resonance. Example: Consider the

ozone (O3 ), carbonate ion, (CO32-) and NO2-

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 Lewis Structures and Formal Charge

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  Formal charge guidelines
• A Lewis structure with no formal charges is generally better than one with formal charges.
• Small formal charges are generally better than large formal charges.
• Negative formal charges should be on the more electronegative atom(s).

Example:- Identify the best structure for the isocyanate ion below

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  Exceptions to the Octet rule in Covalent
Bonding
1. Less than octet (central atom is deficient of electrons):
 Molecules whose central atoms have fewer than eight electrons
(Below octet).

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2. More than octet (expanded octet rule):
• Molecules whose central atoms have more than eight electrons
(Expanded octet).

3. Molecules containing an odd number of electrons:

• Even if stable molecules of this kind are rare, they do exist. Some examples are
ClO2, NO and NO2 having 19, 11 and 17 valence electrons respectively

7 electrons around Cl 7 electrons around N 7 electrons around O 24

 2.3. Valence Shell Electron Pair Repulsion Theory and Molecular
Geometry (VSEPR Theory)
• Predicts molecular geometry by examining bonding and non-bonding
electron pairs of electrons on a molecule
– Bonding pair of electrons – electron pair used in a bond
– Non-bonding pair of electrons – lone pair of electrons not used in
bonding
• The assumption is electron pairs will be spaced
out as far apart as possible (negatives charges repel) giving rise to
particular molecular geometries

Repulsion strengths

lone pair -lone pair  lone pair e-bond pair  bond pair-bond pair 28
 How to determine molecule shape:
1. Draw electron dot or structural formula
2. Count the number of bonding and non - bonding pairs of
electrons around the central atom (number of places
electrons are found)
3. Multiple (double, triple) bonds count as one “location” or
“region”
4. Apply the correct geometry predicted by VSEPR Theory based
on the number of bonding and non-bonding electron pairs

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 Predicting the Shapes of Molecules
 There are five broad geometric arrangements (families) of
Electron set Geometry.
– Linear
– Trigonal planar
– Tetrahedral
– Trigonal bipyramidal
– Octahedral
• To classify molecular shapes, we assign AXmEn designation, where m and n are integers,
A is the central atom, X is a surrounding atom, and E is a non bonding valence electron
group (usually a lone pair).
1. Linear geometry (AX2) (sp hybridized)
 In this geometry, there is only one molecular geometry: linear.
 examples of the molecules of this type are CO2, BeCl2, CS2, HCN, etc.
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 Cont.….
2. Trigonal Planar geometry (sp2 hybridized)
There are two molecular geometries:
 Trigonal planar (AX3), if there are no lone pairs: Example: BF3, NO3-,
HCHO, H2CO etc.
 Bent (AX2E), if there is a lone pair. [ex. SO2, (NO2 )-]

3. Tetrahedral geometry (sp3 hybridized)

 There are three molecular geometries:
 Tetrahedral
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(AX4 ), if no lone pairs. [ex. CH4, CCl 4, SiCl4, SO2− .] NH4+,

 Trigonal pyramidal (AX3E), if one is a lone pair. [ex. NH3]

 Bent (AX3E2), if there are two lone pairs. [ex. H2O]
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 Cont.…..
4. Trigonal Bipyramidal geometry (sp3d hybridized)
 There are four distinct molecular geometries in this domain:
 Trigonal bipyramidal (AX5), , if no lone pairs.[ex. SOF4 ,PCl5 ]
 Seesaw (AX4E), if one is a lone pair.[ex. SF4]
 T-shaped (AX3E2), if two is a lone pairs.[ex. BrF3 ,ClF3]
 Linear (AX2E3), if three is a lone pairs.[ex. XeF2]
5. Octahedral geometry (sp3d2 hybridized)
 There are three molecular geometries:
 Octahedral (AX6), if no a lone pairs.[ex. SF6]
 Square pyramidal (AX5E), if one is a lone pair.[ex. BrF5]
 Square planar (AX4E2), if two is a lone pair.[ex. XeF4]

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5

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6

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 Molecular Shape and Molecular Polarity
 Molecular shape affects many properties of the molecule like molecular polarity,
which in turn influence melting and boiling points, solubility, and even reactivity.
 dipole moment: is a vector sum of the bond moments in a molecule.
 Bond moment is a measure of polarity of a diatomic covalent bond
 For a diatomic molecule, the bond moment is the dipole moment.
 The dipole moment of a polyatomic molecules (with more than two atoms), both
shape and bond polarity determines the molecular polarity

To summarize, to be polar a molecule must:

Contain at least one polar covalent bond.
Have a molecular structure such that the sum of the vectors of each bond dipole moment does
not cancel
 General properties of covalent compounds
1. Covalent compounds are generally liquids or gases at ordinary
temperature. For example : water and ethyl alcohol are liquids.
Hydrogen chloride, methane and cabon dioxide are gases. Some
covalent compounds are solids (e.g. sugar)
2. As compared to ionic compounds, covalent compounds have
relatively lower melting points and boiling points.
3. They do not conduct electric current when molten or in
aqueous solution, because they consist of molecules rather
than of ions.
4. Covalent compounds are insoluble in polar solvents such as water.
They are soluble in non- polar solvents such as benzene and
carbon tetrachloride.

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 2.2.3. Metallic Bonding
• A force of attraction between a positively charged metal ion and the electrons in a metal
• Many metal ions pass along many electrons

• Many properties of metals, such as conductivity, ductility, and malleability, result from the freely
moving electrons in the metal
• Usually occurs between atoms of metals

delocalized electron

metal ion

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  Properties of Metallic Bonding

• The freedom of movement of bonding valence electrons is responsible

for the high electrical and thermal conductivity that characterizes the
metals.
• Other properties of metallic bonding contribute to unique properties of
metals. For example.

– Malleability allows a substance such as a metal to be reshaped. By

hammering and bending some metals, you can create thin sheets.

– Ductility allows a substance to be drawn or pulled out into long thin

pieces, such as wires.

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 2.4. Bonding Theories
The two modern chemical bonding theories which use quantum
mechanics are Valence Bond Theory (VBT) and Molecular
Orbital Theory (MOT).

Valence Bond Theory (VBT)

• According to valence bond theory, a covalent bond forms when two

atoms approach each other closely and a singly occupied orbital on
one atom overlaps a singly occupied orbital on the other atom.
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  Sigma () Bonds
• Sigma bonds are characterized by
– Head-to-head overlap.

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  Pi () Bonds
• Pi bonds are characterized by
– Side-to-side overlap.
– Electron density above and below the inter-nuclear axis.

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Examples

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  Hybridization of Orbitals
• Is The mixing up of atomic orbitals of similar energies and formation of equivalent number of entirely
new orbitals of identical shape and energy is known as "hybridization" and the new orbitals so
formed is called as "hybrid orbitals".
1. sp hybrid orbitals

– When two electron sets surround the central atom, you observe a linear molecular shape. the
Combination (mixing) of one s and one p orbital is called sp hybridization and the resultant
orbitals are called sp hybrid orbitals.
For example, we have seen that the VSEPR theory predicts
a linear molecular geometry for BeCl2.
It is hard to see how this can be accommodated using s, and p orbitals. 44
1. sp hybrid orbitals

The 2p orbitals has one

un paired electron

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Hybridization of the 2s with one of the empty 2p orbitals in Be provides the solution
to this problem.

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1. sp hybrid orbitals

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 2. sp2 Hybridization:
 Three electron sets surround the central atom, you observe a trigonal planar
molecular shape.
Is the Combination (mixing) of one s and two p orbitals

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 3. sp3 Hybridization:
 Four electron sets surround the central atom, you observe a tetrahedral
molecular shape.
 Is the Combination (mixing) of one s and three p orbitals

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 4. sp3d Hybridization
 Five electron sets surround the central atom, you observe a trigonal
bipyramidal molecular shape.
 Is the Combination (mixing) of one s, three p and one d orbitals

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 5. sp3d2 Hybridization:
 Five electron sets surround the central atom, you observe a trigonal
bipyramidal molecular shape.
 Is the Combination (mixing) of one s, three p and two d orbitals

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  Molecular Orbital Concept
• Molecular orbital (MO) theory describes covalent bond formation as arising from a
mathematical combination of atomic orbitals on different atoms to form molecular orbitals

Bond Order: ½ (# of electrons in bonding MO’s - antibonding # of electrons in

MO’s) 48
 Cont’d
• Relative MO energy levels for Period 2 homonuclear diatomic
molecules.

MO energy levels for O2, F2, and Ne2 MO energy levels for B2, C2, and N
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Second-Row MO Diagrams

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Example

Questions
Draw the molecular
Orbital diagram and
calculate the bond order
of

A. C2 +
B. O2+

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2008,2014plan A&B EAES, ESSLCE questions from chemical
bonding

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•The end
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