Study Unit 3:

Basic
Concepts of
Chemical
Bonding

Faculty of Science
Department of Chemistry
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Learning Outcomes...
 Understand the forces involved in chemical bonding.
 Explain clearly the following concepts:
 Chemical bond
 Ionic bond
 Covalent bond
 Metallic bond
 Describe (or explain) the Octet Rule.
 Explain and apply the concept of Lewis Symbols in chemical bonding.
 Describe the relationship between bond length and bond enthalpy.

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 The nature of
chemical bonds
Introduction…
Chemical Bond
Forces that hold atoms together in a compound/molecule
 Interatomic electrostatic interactions.
 Formation of stable compounds if the attractive forces between
positive protons and negative electrons over compensate the
proton-proton and electron-electron repulsion.
 e- distribution between the atoms determine the nature of the
bond.

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Introduction…
INTRAMOLECULAR FORCES – hold atoms together in a molecule
Different types of bonds:

 Ionic bond  metal + non-metal

 Electrostatic attraction between ions
Strong

 Covalent bond  non-metal + non-metal

 Sharing of electrons

 Metallic  metal + metal

 Metal valence electrons bonded to several other atoms

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Introduction…

INTERMOLECULAR FORCES

Forces of attraction or repulsion which act between neighbouring

particles (atoms, molecules or ions).
• They are weak compared to the intramolecular forces, the forces
which keep a molecule together.

• EG. The covalent bond holding H2O together (H bonded to O) is stronger

than the Van Der Waals forces holding a series of H2O molecules together

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 Introduction… Weak
INTERMOLECULAR FORCES
Dipole-dipole forces:
electrostatic interactions between permanent dipoles in molecules.
Ion-dipole forces:
Ion-dipole and ion-induced dipole forces are similar to dipole-dipole and
induced-dipole interactions but involve ions
Van der Waals forces:
is the sum of the attractive or repulsive forces between molecules (or
between parts of the same molecule) other than those due to covalent bonds
or the electrostatic interaction of ions with one another or with neutral
molecules or charged molecules. That includes:
H-Bond; the bond that forms when a H atom is directly bonded to either
O, N, or F- then it is an. If it is polar, then it is a dipole;
Dispersion force; London if it is nonpolar.
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 IONIC COVALENT METALLIC

e-s transferred from

e-s shared between e-s are delocalised
Bond formation a metal to a non-
two non-metals between metals
metal
Type of structure crystal lattice true molecules ‘electron sea’
Physical state solid liquid or gas solid
Melting point high low very high

Solubility in water yes usually not no

Electrical yes yes

no
conductivity (solution or liquid) (any form)
maleable, ductile,
Other properties odouress
lustrous
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 Lewis Structures
and the Octet rule
The Octet rule…
Chemical rule of thumb that states that atoms of main-group elements
tend to combine in such a way that each atom has eight electrons in its
valence shell, giving it the same electronic configuration as a noble gas.

Lewis structures
Representations of atoms/molecules showing all valence electrons, bonding and
nonbonding.

H: 1s1 Cl: [Ne]3s23p5

1e- + 7e- = 8e-

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 Octet rule…
 Atoms gain, lose or share their valence e- and form bonds in order to obtain a full
octet
 Full octet = 8 valence e-
 Full energy level stability ~ Noble Gases

Electron Dot Diagrams

 show valence e- as dots
 distribute dots like arrows in an orbital diagram
 4 sides = 1 s-orbital, 3 p-orbitals
X
Eg: oxygen
2s 2p O
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Electron-Dot Symbols
Electron-dot symbol: number of valence e- around symbol = group
number of element.

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Types of Bonds
Types of bonds
Metallic Bond – .Sea of electrons’

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Metallic bonds…
• Metallic bond - force of attraction between valence electrons and the metal
atoms.
• Sharing of many detached electrons between many positive ions, where
the electrons act as a "glue" giving the substance a definite structure.
• It is unlike covalent or ionic bonding.

• Metals have low ionization energy. Therefore, the valence electrons

can be delocalized throughout the metals. Delocalized electrons are
not associated with a particular nucleus of a metal, instead, they are
free to move throughout the whole crystalline structure forming a
"sea" of electrons

• The electrons and the positive ions in the metal have a strong attractive
force between them. Therefore, metals often have a high melting or boiling
points. The principle
Department is similar to that of ionic bonds.
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Types of bonds
Ionic Bonding - Crystal Lattice

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Ionic Bond….
Chemical bond that involves the electrostatic attraction between oppositely
charged ions.

These ions represent atoms that have lost one or more electrons to form cations
and atoms that have gained one or more electrons to form anions.

In the simplest case, the cation is a metal atom and the anion is a nonmetal atom,
but these ions can be of a more complex nature, e.g. molecular ions like NH4+ or
SO42- .

Requirements for an ionic bond to form

• Two atoms must be different.
• Ionization potential of one atom must be small.
• Electron affinity of second atom must be high.
• Electro negativity of second atom must be high.
• Difference of E.N. between two should be greater than or equal to 1.7
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Ionic Bond….

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 Energetics of Ionic Bonds…

Ionisation Energy
 It takes 495 kJ/mol to remove electrons from
sodium.

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Energetics of Ionic Bonds…

Electron Affinity
 We get 349 kJ/mol back by giving electrons
to chlorine.

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 Energetics of Ionic Bonds…
The electrostatic attraction between the newly-formed sodium cation and
chloride anion accounts for the exothermic nature of the reaction.

Lattice energy:
The energy required to completely separate a mole of a solid ionic
compound into its gaseous ions.

The energy associated with electrostatic interactions is

governed by Coulomb’s law:
Q 1Q 2
Eel =  d

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Lattice energy increases with:
The charge on the ions.
Decreasing distance
between ions.

Lattice energy accounts for the tendency for metals to stop losing electrons once
they attain a noble gas configuration because energy would be expended that
cannot be overcome by lattice energies.
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Ionic bonds…
• Energy  spent when removing electrons from metals
• Energy  gained when non-metals accept electrons

• Lattice energy
• The energy associated with electrostatic interactions between
cations and anions

 Amount of energy required to turn a solid ionic compound into a gas

 Lattice energy increases with the charge on the ions.
 It also increases with decreasing size of ions.
 Greater the lattice energy, higher the melting point.

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Questions

Arrange the following ionic compounds in order of increasing lattice

energy: NaF; CsI; CaO.
CsI  NaF  CaO

Which substance would you expect to have the greatest lattice energy?
AgCl; CuO; CrN
CrN

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Ionic bonds…
 Need a low ionisation energy (IE) for the metal
Total e- transfer from atom with low IE (metal) to atom with high IE
(non-metal)
 Need a high electron affinity (EA) for the non-metal
Energy change accompanying the addition of an electron to a
gaseous atom.
Lewis diagram show transfer of e-

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 Ionic bonds…
•eg. calcium sulphide (CaS)

Ca + S  Ca2+
+ S 2-

•eg. magnesium fluoride (MgF2)

Mg + F  2+
Mg + 2 F –

F
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Types of bonds
Covalent Bonding – True Molecules

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Covalent bonds…
• In Covalent bonds atoms share
electrons.

• There are several electrostatic interactions

in these bonds:
 Attractions between electrons and nuclei
 Repulsions between electrons
 Repulsions between nuclei

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Overlap and Bonding

We think of covalent bonds forming

through the sharing of electrons by
adjacent atoms.

In such an approach this can only occur

when orbitals on the two atoms overlap.

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A covalent bond…
The stable balance of attractive and repulsive forces between atoms
when they share electrons.

The sharing of electrons allows each atom to attain the equivalent of a

full outer shell (octet), corresponding to a stable electronic
configuration.

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Polar Covalent Bonds
Though atoms often form
compounds by sharing electrons,
F2 HF the electrons are not always shared
equally.

Equal (non-polar) Unequal (polar)

• Fluorine pulls harder on the electrons it shares with hydrogen than
hydrogen does.
• Therefore, the fluorine end of the molecule has more electron density
than the hydrogen end.

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Bond Polarity
Electronegativity - Ability of atoms in a molecule to attract electrons to
themselves.

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Bond Polarity
Difference in electronegativity between bonding atoms – determines bond
polarity.

When two atoms share electrons unequally, a bond dipole results.

• +/ -  dipole moment

• higher e-neg atom  -
• lower e-neg atom  +

Eg: HCl 2.1 3.0

H = 2.1 (electronegativity)
Cl = 3.0 (electronegativity)
EN = 3.0 – 2.1 = 0.9 Polar covalent bond
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 Polar Covalent Bonds
The greater the difference in electronegativity, the more polar the bond is.

Most polar Least polar

HF = 1.9 HCl = 0.9 HBr = 0.7 HI = 0.4

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 Bond Polarity
Example:
Use electronegativity to determine which bond is ionic, polar covalent
and non-polar covalent.
EN values given in periodic table

Cl2 3.0-3.0=0.0 Nonpolar covalent

HCl 3.0-2.1=0.9 Polar covalent

NaCl 3.0-0.9=2.1 Ionic

Department of Chemistry (If En > 2.0 then its an ionic bond)

Bond Polarity
1. Which bond is most polar in the following molecules?
S-Cl, S-Br, Se-Cl, Se-Br
(use electronegativity values or predict from positions on PT)
Se-Cl

2. Arrange the following in order of increasing polarity?

C-O, O-N, O-H, B-F.
O-N, C-O, O-H, B-F

3. Select the atom in each bond in Q2 with the partial –charge (δ-)

δ-O-N, C-Oδ-, δ-O-H, B-F δ-

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Bond Polarity
Nonpolar • e- are shared equally
covalent • symmetrical e- density
• usually identical atoms

• e- are shared unequally

Polar
• asymmetrical e- density
covalent
• results in partial charges
(dipole)
Ionic
• Complete transfer of e- from
metal (low EN) to non-
metal (high EN)

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Covalent bonding
Covalent – Lewis diagram show sharing of e-
• Nonpolar Covalent - no charges

• Polar Covalent - partial charges

+ -

+
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Covalent bonding…
•eg. ammonia (NH3) molecule

H H
N + H H HH N H H N H

• Each pair of shared electrons between two atoms form a bond

• Single bonds form between N–H in NH3

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Covalent bonding…
•eg. carbon dioxide (CO2) molecule
O
C +  O C O O C O
O
Two shared e- pairs between
two atoms = double bond

•eg. nitrogen (N2) molecule

 N
N N N
N + N
Three shared e- pairs between
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Writing Lewis Structures…
1. Find the sum of valence electrons of all
atoms in the polyatomic ion or molecule.
PCl3
• If it is an anion, add one electron for each
negative charge.
• If it is a cation, subtract one electron for
each positive charge.
5 + 3(7) = 26

2. The central atom is the least

electronegative element that isn’t
hydrogen. Connect the outer
atoms to it by single bonds.
Keep track of the electrons:
26  3(- 2 electrons for each bond) = 20
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Writing Lewis Structures…
3. Fill the octets of the outer
atoms. Keep track of the electrons:
26  6 = 20  18 = 2

4. Fill the octet of the central atom.

Keep track of the electrons:
26  6 = 20  18 = 2  2 = 0

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Writing Lewis Structures…
5. If you run out of electrons before the
central atom has an octet…

1 + 4 + 5 = 10 – 2(2) = 6 …form multiple bonds until it does.

6 – 2(2) = 2

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Lewis structures of molecules and polyatomic ions
•Eg. Cyanic acid HCN
Number of valence electrons available
(numerically equivalent to group number):
H: 1
C: 4
N: 5
Charge: 0
Total: 10
- 8 (bonding e’)
2 electrons left to complete the
octet for nitrogen.

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Lewis structures of molecules and polyatomic ions…
•Eg. Sulphur trioxide
Number of valence electrons
available:
S: 6
O: 6 x 3
Charge: 0
Total: 24
- 8 (bonding e’)
16 electrons left to
complete the octet for each atom.

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Lewis structures of molecules and polyatomic ions
•Eg. Carbonate (CO32-)
Number of valence electrons
available:
C: 4
O: 6 x 3
Charge: 2
Total: 24
- 8 (bonding e’)
16 electrons left to
complete the octet for each atom.

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Lewis structures of molecules and polyatomic ions
•Eg. Cyanide (CN-)
Number of valence electrons
available:
C: 4
N: 5
Charge: 1
Total: 10
- 6 (bonding e’)
4 electrons left to
complete the octet for each atom.

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Formal Charges…
Lewis Structures
Assigning formal charges.
• For each atom, count the electrons in lone pairs and half the
electrons it shares with other atoms.
• Subtract that from the number of valence electrons for that atom.
• The difference is its formal charge.
• The best Lewis structure is the one with the fewest charges or puts a
negative charge on the most electronegative atom.
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Two possible structures for CO2, both satisfying the octet rule.
Which one will be the dominant structure?

Dominant structure – atoms carry

formal charges closest to zero

Remember: the sum of the formal charges = overall charge

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1. Draw the three possible structures for NCO-

2. Identify the dominant structure for NCO-

Dominant structure: (-) charge on most

electronegative atom.
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Exceptions to the Octet Rule
Three types of ions or molecules that do not follow the octet rule:
• Ions or molecules with an odd number of electrons
• Ions or molecules with less than an octet
• Ions or molecules with more than eight valence electrons (an
expanded octet)

Odd Number of Electrons

Though relatively rare and usually quite unstable and reactive, there
are ions and molecules with an odd number of electrons.

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Fewer Than Eight Electrons
Structures that put a double bond between boron and fluorine are much
less important than the one that leaves boron with only 6 valence
electrons.

If the central atom results in a negative charge on the central atom (B)
and a positive charge on the more electronegative outer atom (F), don’t fill
the octet of the central atom.
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More Than Eight Electrons
1. It is allowed to expand the octet of atoms on the 3rd period or below.
• Presumably d orbitals in these atoms participate in bonding.

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More Than Eight Electrons
1. It is allowed to expand the octet of atoms on the 3rd period or below.
• Presumably d orbitals in these atoms participate in bonding.

2. Even though we can draw a Lewis structure for the phosphate ion that has
only 8 electrons around the central phosphorus, the better structure puts a
double bond between the phosphorus and one of the oxygens.

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Resonance Structures
Molecules that do not have a dominant Lewis structure.

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Resonance Structures

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Covalent Bond Strength
Bond enthalpy:
Strength of a bond  how
much energy is required to
break the bond.

• Average bond enthalpies 

positive, because bond
breaking is an endothermic
process.

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Bond Enthalpy & Bond Length

We can also measure an average bond length for different bond types.
 As the number of bonds between two atoms increases, the bond length
decreases.
 The shorter a bond, the greater its bond enthalpy.
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Can you…
• Write Lewis symbols for atoms and ions?
• Explain how metallic, ionic and covalent bonds form?
• Understand Lattice energy and be able to arrange compounds in order of
increasing Lattice Energy based on the charges and sizes of ions involved?
• Use electronegativity differences to identify non-polar covalent, polar
covalent and ionic bonds?
• Use atomic electron configurations and the octet rule to write Lewis
structures for molecules and polyatomic ions to determine their electron
distribution?

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Can you…
• Calculate formal charges from Lewis structures and use those formal
charges to identify the dominant Lewis structure for a molecule or ion?
• Recognise molecules where resonance structures are needed to
describe the bonding?
• Recognise exceptions to the octet rule and draw accurate Lewis
structures even when the octet rule is not obeyed?
• Understand the relationship between bond type, bond strength
(enthalpy) and bond length?

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