UNIT 4: CHEMICAL

BONDING
General Chemistry I (CHY2021)
Mr. Robert Johnson
University of Technology, Jamaica
Unit Content
 Introduction to Bonding
 Types of Bonds
 Ionic, covalent, dative, metallic
 Intermolecular Forces of Attraction
 Covalent bond polarity
 VSEPR Theory
 Molecular Geometry
 Valence bond and Molecular Orbital Theories

2
 Introduction to Bonding
3

 Chemical bonds: attractive forces that hold atoms or ions together to

form compounds or substances.
 Valence electrons are involved.
 Lewis symbols: simple ways of showing valence electrons in an atom.
 Valence electrons only shown:

 Duet/Octet Rule:
 atoms will chemically bond to complete their valence shell, i.e., have 2
electrons (1st period) or 8 electrons in their valence shells (2nd period), 18
electrons etc.
 It’s all about “being happy”.
 Ionic Bonding
5

 Ionic bond – an attractive (electrostatic) force between

oppositely charged ions; cations and anions.
 Example: sodium chloride
 Ionic Bonding
6

 Ionic bonds are very strong bonds.

 Formed between a metal and a non-metal.
 Electrons completely transferred from one atom to another –
forming ions, e.g., NaCl.

 Using Lewis symbols: NOTE:

 - 
Na + Cl  Na + [Cl]
+ Octet complete
  for both Na & Cl
 Ionic Bonding
7

 It should be remembered that metal atoms tend to

form ions having a similar charge to their group.
 Group VIA & VIIA elements tend to form anions
with 2- & 1- charge e.g. O2-, S2- & F-, Cl-
 Show how ionic bonding develops between Ca and
Cl.

CaCl2
 Properties of Ionic Compounds
8

 Rigid 3-D lattice.

 Ions held together by strong electrostatic forces.
 Crystalline, brittle solids at room T.
 High BP and MP (1000 – 1500C).
 Many are soluble in water and other polar solvents.
 Solutions conduct electricity.
 For naming, metal is always first, non-metal second
(e.g. sodium chloride).
 Covalent Bonding
9

 Electrons shared between two atoms to form a

molecule.
 Covalent bonds formed between atoms with similar
affinity for electrons, i.e., non-metals.
 Examples:

 Both non-metal atoms share electrons to form a full

valence shell (octet rule).
 Covalent Bonding
10

 Shared electrons are not in a fixed position between

the nuclei.
 Electron density concentrated between the two nuclei:

 Atoms held together by attraction of both nuclei to

electron cloud between them.
 Covalent Bonding
11

 Some atoms have to share more than 2e to achieve

octet/noble gas configuration.
 Single covalent bond: 1 pair or e- shared
 Double covalent bond: 2 pairs or e- shared
 Triple covalent bond: 3 pairs of e- shared
 Covalent Bonding
12

Properties of Molecules:
 Covalent bonds weaker than ionic bonds

 Lower MP & BP’s.

 Usually liquids or gases at room temperature.

 Usually sparingly soluble in water but soluble in

organic solvents.
 Dative covalent bonding
13
 Dative Covalent Bonding
14

 So far, the shared e has come from both atoms involved in the
covalent bond formation.

 Coordinate or dative covalent bonding:

A: + B  A:B
 A covalent bond in which both electrons come from one of the
atoms, e.g., H3O+, NH4+:
 Metallic Bonding
15

 Metallic bonds present between the atoms in metals.

  Different from ionic bonds.
 Metal ions are fixed while their loosely held
electrons move freely throughout the lattice structure:
 Metallic Bonding
16

 Hence, metallic bonding can be considered to be

electrostatic attraction between cations (+ve) surrounded
by a ‘sea’ of delocalised electrons (-ve) (‘electron-sea’
model).
 The e-’s are shared by all the metal cations.

 Metals are able to conduct electricity in solid (and liquid)

state due to these mobile electrons.
 Metallic Bonding
17

Properties of Metals:
 Metallic bonds very strong  high MP, BP, density.

The mobile electrons make metals:

 Good conductors of electricity and heat.

 Malleable, ductile.

 Alloys:
 Mixtures of elements that have metallic properties e.g.
Cu/Zn in brass.
COVALENT COMPOUNDS
(MOLECULES)
Polarity in covalent bonds
Intermolecular forces
Molecular shapes
 Bond Polarity
19

 Why are some molecules’ bonds polar while others aren’t?

 This is related to the atom’s E.N.

 Trend for Electronegativity
20
Polarity in Covalent Bonds
Non-polar bonds:
 Electrons are shared equally between the two atoms.

 Bonding between atoms of the same element (H , Cl , O ).

2 2 2

Polar bonds:
 Electrons are not equally shared.

 One atom has higher electronegativity than the other.

 Bonding e-’s spend more time around the atom that has the

higher electronegativity.
 Polarity in Covalent Bonds

22
 Predicting polarity of Covalent Bonds
23

 Non-polar/slightly polar if difference = 0 – 0.4

 Polar covalent bond if difference > 0.5 and < 2.0
 Ionic bond if difference > 2.0
Compound F2 HF LiF

Electronegativity
4.0 - 4.0 = 0 4.0 - 2.1 = 1.9 4.0 - 1.0 = 3.0
Difference

Nonpolar Polar Ionic (non-

Type of Bond
covalent covalent covalent)
Polar Covalent Bonds
 When a dipole exists you have a polar molecule.
 Partial +ve and –ve charges on the atoms:

 Dipole moment,  = Qr
 a quantitative measure of the magnitude of the
polarity.
 Polar molecules have a permanent dipole moment,
non-polar molecules have no dipole moment.
Polar Covalent Bonds
 The greater the difference in E.N., the more
polar the bond.
Intra and Inter-Molecular Forces
 Intramolecular attractions (covalent bonds):
 holds the individual atoms within a molecule together.

 Intermolecular attractions:
 attractions between neighbouring molecules, especially
I liquids and solids:
Intermolecular Forces
 These are the forces that determine if a substance is a
solid, liquid, or gas.
 In liquids and solids these can be relatively strong.

At least 5 types:
 Ion-dipole forces (40-600 kJ/mol)

 Dipole-dipole forces (5-20 kJ/mol)

 London dispersion forces (0.05 – 40 kJ/mol)

 Dipole-Induced dipole (2 -10 kJ/mol)

 Hydrogen bonding (4-50 kJ/mol)

Ion-Dipole Forces
 Electrostatic forces between ions
and a molecule that is polar. i.e
permanent dipole.
 Cations attracted to –ve end of
dipole, anions attracted to +ve
end of dipole.
 Apply to ionic compounds in
polar solvents, e.g., NaCl in
water.
 Strength of charge depends on
magnitude of charge on the ions
as well as well as how polar the
polar molecule (dipole) is.
 Ion-Dipole: How salts dissolve
29

The polar solvent attacks the cation/ion of the salt and dislodge them from the
lattice.
 Ion-Dipole
30
 Dipole-Dipole
31

 Attractive forces among polar

molecules.
 When dipoles come close, +ve
end of dipole A attracts –ve
end of dipole B.
 Examples: H–Cl, H–F, sucrose
(C12H22O12)
 Strength depends on how polar
the molecule is and distance
between them.
 Dipole-Dipole Forces
32
Hydrogen Bonding
 Special type of dipole-dipole
interaction.
 It is the attractive force that
exists between a
hydrogen atom that is
covalently bonded to an
electronegative atom of one
molecule then partially
bonded to an electronegative
atom in a neighboring
molecule with a lone pair of
e.
 The EN atoms have to be
O,N, or F in both
 Hydrogen bonding in the body
34
Initiation vs Reception in H-bond
 In the ethanol molecule, the H
atom from the –OH bond can
initiate H bonding with
neighboring H2O molecules.
 Its O atom can also receive a H-
bond from the H atom in a
neighbouring H2O molecule.
 Not so for dimethyl ether with
H2O. Its H cannot initiate H
bonding as they are all bonded to a
C atom.
 It can however receive H bonding

from the H atom of H2O molecules

via its O atom.
 Dipole-Induced Dipole
36

 This type of attraction arises

when an atom or molecule
that is nonpolar (He, Cl2)
becomes polarized by a
neighbouring molecule with
a permanent dipole (HCl).
 In other words, the dipole as
it approaches the nonpolar
molecule induces a
temporary dipole in its
electronic arrangement.
 London (Dispersion) Forces

 Weakest of the intermolecular forces.

 Present in atoms and non-polar molecules.
 Occurs due to temporary displacement between nuclei and
electrons.
 Because of the constant motion of the electrons, an atom or
molecule can develop a temporary (instantaneous) dipole
when its electrons are distributed unsymmetrically about
the nucleus.
London (Dispersion) Forces
 Electrons temporarily shift to
one side of atom or molecule,
forming a temporary dipole:
 Temporary dipole interacts
with neighbouring molecule,
causing an induced dipole.
 For a moment, a force of
attraction exists between
molecules.
 London forces exist in all
molecules.
 London Dispersion Force
39

Temporary dipole develops

Non polar molecules

Dipole induced in its neighbor Temporary dipoles disappear

and attraction occurs
Factors affecting the strength of L.D.F.

 Molecular Size CH4

Boiling point/°C
-161
C3H6 - 42
C6H18 126

 Larger and heavier atoms and molecules exhibit stronger

dispersion forces than smaller and lighter ones.
 The strength of the LDF depends on how large the electron cloud
is, that can be distorted due to the movement of electrons within
the molecule.
 The larger the molecule the greater the number of electrons per
molecule, the greater the extent of displacement between nuclei
and electron, the greater the strength of the LDF.
Factors affecting the strength of L.D.F.

 Molecular Shape

 Longer molecules have more surface area exposed

between the molecules.
 Therefore more temporary displacement between
nuclei and electrons per molecule.
 Hence stronger LDF between longer molecules.
 Long flat molecules can lie closer together - these
attractions are at their most effective if the molecules
are really close.
 LDF
42
 Summary
43
So far…
 Types of Chemical Bonds
 Ionic, covalent, dative, metallic
 Lewis Structures
 Resonance structures
 Polar and non-polar molecules (covalent)
 Intermolecular Forces
 London forces
 Ion-dipole
 Dipole-dipole
 Hydrogen bonds
Molecular Shapes:
The VSEPR Model
Lewis Structures
 Lewis structures are diagrams that
show the bonding between atoms
within a molecule, and the lone pairs
of electrons that may exist in the
molecule. 
 The structures show each atom and
its position in the structure of the
molecule, lines are drawn between
atoms that are bonded to one another
 (pairs of dots can be used instead
of lines).
 Excess electrons that form lone pairs
are represented as pairs of dots, and
are placed next to the atoms.
 Drawing Lewis structure (steps)
47
 Lewis Structure
48

 Derive the Lewis structure of the following:

 HCN

 SF
4

 CO32-,
 IF4+

Point to note when drawing Lewis structures:

 The least EN atom is usually placed in the centre but

never H.
 O and Halides are usually made terminal atoms.
 Lewis structures
49

Step 1) H = 1v.e; C = 4 v.e; N = 5 v.e. Total = 10 v.e.

Step 2) Draw Skeleton. H –C—N ; 10 – 4 = 6 e left

Step 3) C—H bond wont accept further e so place 2 e

pairs between C—N . . 6 - 4 = 2 e

Step 4) Place 2 remaining e on N.

 Formal Charge
50

 This can inform us on which part of a molecule/ion is

charged or which resonance structure is more stable.
 F.C. = valency of free atom -(# of bonding e-/2)- (# of non-
bonding e- )
 Formal charge Rules
51

 The sum of the formal charges in a Lewis structure

must equal zero for a neutral molecule and must equal
the magnitude of the charge for a poly-atomic ion.
 Where formal charges are required, they should be as
small as possible.
 Negative formal charges usually appear on the most
electronegative atoms; positive formal charges, on the
least electronegative atoms.
 Structures having formal charges of the same sign on
adjacent atoms are unlikely.
D. Gordon-Smith, UTECH
 Formal Charge calculation (example)
52
 Formal Charge example
53

 Let’s also try the two plausible structures for NO 2+

D. Gordon-Smith, UTECH
 VSEPR Model
54

 VSEPR model is used to determine molecular

shapes.
 Total number of valence electrons around atoms used
– central atom most important.
 Number of electron pairs (domains) around central
atom is used to predict shape of molecule.
The VSEPR Model
 Bonding and nonbonding electrons are treated as
charge clouds.
 Charge clouds repel each other, so they are placed as
far way from each other as possible.
 Step 1: count number of electron-charged clouds
surrounding central atom (use Lewis structure).
 Step 2: Arrange charge clouds in space as far away
from each other as possible.
The VSEPR Model
Example: NH3
 Count number of charge clouds (electron
domains) in Lewis structure:
Molecular Geometry
 VSEPR prediction is not always same as the actual or the
molecular geometry of the molecule.
 Molecular geometry is defined by the positions of the atoms
in the molecules only, not the nonbonding pairs of e-:
Molecular Geometry See Table in handout
for more shapes.

 Each VSEPR prediction may have

more than one molecular
geometry.
 Example: 4 electron domains
VSEPR – tetrahedral

Molecular geometry –
3 bonding + 1 nonbonding pairs:
trigonal pyramidal
2 bonding + 2 nonbonding pairs:
bent
59 D. Gordon-Smith, UTECH
60
Bonding Theories
 VSEPR provided simple way to predict molecular shapes.
 However, it does not explain why or how bonding occurs
between atoms.
 Also, magnitude of electron-repulsion affects shape.
 Lone pair – Lone pair > Lone Pair – Bonded Pair > Bonded Pair -
Bonded Pair

 Two other theories:

 Valence Bond Theory
 Molecular Orbital Theory

61
Bonding Theories-Valence Bond Theory

 In Lewis structures, covalent bonding occurs when atoms share

electrons, the electron density concentrated between the two nuclei.

 Valence bond theory considers that the electrons pairs shared in

covalent bonding are concentrated in the region where the valence
atomic orbital of one atom overlaps with that of another atom.

 In VBT, a bond will be formed if there is overlap of orbitals on two

atoms and these orbitals are populated by a max of two 2 e.

 e- pair attracted by both nuclei  holding atoms together  covalent

bond.
Valence Bond Theory
Examples:
 H2: overlap of two 1s orbitals:
 HCl: one 1s orbital of H and one lobe of 3p orbital of
Cl.
 Cl2: Two lobes of two 3p orbitals from two Cl
atoms. H 2 HCl Cl 2

63
 Valence Bond Theory
64

 Not all molecules however can be explained by the

overlap of only pure atomic orbitals like we just
saw for Cl2 and HCl.
 In such cases, they can only be explained by the
formation of hybrid orbitals, namely sp, sp2, sp3
etc.
 Hybrid orbitals
65
Hybridisation
 Consider the molecule methane, CH4: H

VSEPR predicts tetrahedral geometry C

H
and valence bond theory supports that prediction. H
H

Electronic configuration for C: 1s2 2s2 2px1 2py1 2pz0

 4 Valence electrons:
 two paired 2s e-
 Two unpaired 2p e-

66
Hybridisation- sp3
 During hybridisation, atomic orbitals are mixed to
form new hybrid orbitals.
 Total number of orbitals remain the same, e.g.:
 one s orbital + three p orbitals = four sp3 orbitals

67
 Hybridisation

 The four degenerate

sp3 orbitals
 same energy level.
 All together lie in
tetrahedral
arrangement.
CH4
molecule:
 bond

68
68
Hybridisation- sp2
 In some case hybridisation only involves three of
the orbitals rather than all four. They use the 2s
electron and two of the 2p electrons, but leave the
other 2p electron unchanged.
 Three sp2 orbitals are now created, located 120°
from each other and perpendicular the unhybridised
p orbital:
 Video on Hybridization
70

 Please watch this very interesting video on

hybridization. The molecules are in 3D so is more
appealing.
 https://www.youtube.com/watch?v=wPw_LCmyjnI
Hybridisation –sp1
 In other cases, the 2s electron
and one of the 2p electrons
becomes hybridised, and the
other two 2p orbital remain
unchanged.

 The new hybrid orbitals formed

are called sp1 hybrids
(sometimes just sp hybrids),
because they are made by an s
orbital and a single p orbital
reorganising themselves.
Hybridisation
 Multiple bonds formed when p orbitals overlap:
single bonds =  bonds
multiple bonds =  +  bonds
Hybridization in H2O, NH3
 VSEPR Geometry & Hybridization
74
Molecular Orbital (MO) Theory
 Remember that Atomic orbitals are wave functions whose square gives
the probability of finding an electron within a given region in the atom.

 Molecular orbital considers the molecule has a whole instead of

individual atoms.

 Molecular orbitals-a wave function whose square gives the probability

of finding an electron within a given region in a molecule.

 Molecular orbital theory considers the combination of atomic orbitals to

form molecular orbitals which can be extended over the entire molecule.

75
 Rules for Drawing M.O.
76

 The MO Theory has five basic rules:

1) The number of molecular orbitals = the number of
atomic orbitals combined
2) Of the two MO's, one is a bonding orbital (lower
energy) and one is an anti-bonding orbital (higher
energy)
3) Electrons enter the lowest orbital available
4) The maximum # of electrons in an orbital is 2 (Pauli
Exclusion Principle)
5) Electrons spread out before pairing up (Hund's Rule)
Molecular Orbital (MO) Theory
 When atomic orbital approach each other they may do so
either constructively or destructively…like waves interacting.
 two s AO  two  MO

Antibonding MO:
e- density on opposite
sides of molecule

Bonding MO:
 combine in region
between nuclei
Molecular Orbital (MO) Theory
 MO energy diagram The constructive
for H2: combination is called
(sigma) is lower in
NRG.
The subtractive
combination is called
is higher in NRG.

Bond order = ½ (# bonding e- - # antibonding e-) = ½ (2 – 0) = 1

If bond order > 1, molecule is stable

78
Molecular Orbital (MO) Theory
 MO energy diagram for He2:

Bond order = ½ (2 – 2) = 0
molecule is unstable,  He2
does not exist

79
Molecular Orbital (MO) Theory

 Molecules with p
orbital overlap (6
MO’s):

80 80
Energy levels of MO’s

For configuration with total e  14 VS For configuration with total e > 14

 MO diagram of C2
82

C = 1s2 2s2 2p2

6 6 C = 1s2 2s2 2p2
 Molecular Orbital (MO) Theory
O =1s2 2s2 2p4
8 8O =1s2
2s2 2p4
O2 molecule

*2p

*2p

Energy 2p 2p

2p

2p
O atom O atom

*2s

2s 2s
2s
83
84

N =1s2 2s2 2p3

7 8O =1s2 2s2 2p4
NO

D. Gordon-Smith, UTECH
85

N =1s2 2s2 2p3

7 O- =1s2 2s2 2p5
9
NO-

-
D. Gordon-Smith, UTECH-
Magnetism
 Different molecules behave differently in the
presence of a magnetic field.
 Paramagnetic molecules:
 Attracted to magnetic field
 1 or more unpaired electrons
 Diamagnetic molecules:
 Weakly repelled by magnetic field
 No unpaired electrons
Bond order = ½ (# B.E. - # AB.E)
If bond order > 1, molecule is stable
 Magnetism
87

Unpaired e- Paired e-
 Draw MO’s for the following compounds.
Calculate their bond orders and comment on the
stability of the compound. State whether they are
paramagnetic o-r diamagnetic.
 NO+
 Ne2
 F2 -