Atoms and Bonds

• How are atoms arranged?

• How are they joined together?
• Why are atomic arrangements
and bonding important?
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 What is in an atom?
Electrons – 9.11 x 10-31 kg
• Atom Protons
Neutrons – 1.67 x 10-27 kg

• Atomic number (Z) = # of protons in nucleus of atom

= # of electrons of neutral species

• Atomic mass (A) = mass of protons + mass of neutrons

Electron orbits
Bohr’s model of Electrons are assumed
to revolve around the
atomic structure Nucleus atomic nucleus in
discrete orbit

3
 What is the Atomic Weight?
The Atomic weight of an element
refers to the weighted average of the
atomic masses of the atom’s
naturally occurring isotopes.

Isotopes are atoms of the same element

that have the same atomic number (Z)
but different atomic mass (A)

1
atomic mass unit (amu) = of the atomic mass of 12C
12

Atomic weight = weight of 6.022 x 1023 atoms or molecules

amu per atom = mass per mole
1 amu/atom = 1g/mol
e.g. the atomic weight of iron is 55.847 amu/atom or 55.847 g/mol.
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 Calculate the number of atoms in 100g of
silver (Ag) if the atomic weight of silver is
107.868 g/mol. 107.868 g/mol 100g
NA = 6.023 x 1023 atoms/mol
atoms mol
Number of Ag atoms= × ×g
mol g
(100g )( 6.023 × 10 23
atoms/mol )
=
107.868 g/mol
= 5.58 ×1023
Ans: 5.58 × 1023
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 Valence electrons in atoms
• Valence electrons are the electrons in
the outermost shell
• Why are they important?
• Valence electrons determine all of the
following properties:
1) Chemical properties
2) Electrical properties
3) Thermal properties
4) Optical properties

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 Atomic Models
• There were some “weaknesses” in Bohr’s model
of the atom, so the atomic model that is more
widely used now is the Wave-Mechanical model
• Electrons are considered to have wavelike and
particle-like properties.
– This means that electrons is considered to be at
various locations around the nucleus which is
described by a probability distribution.

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 Bohr’s model –discrete orbitals

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 Wave mechanical model-an electron
“cloud”

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 Bohr vs Wave Mechanical model

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 Electron Configuration & Quantum
Numbers
– Atoms are usually defined by their electron
configuration, i.e how the electrons are arranged
in an atom, and…
– Every electron in an atom is described by
quantum numbers.

Quantum # Designation
n = principal (energy level or shell) K, L, M, N, O (1, 2, 3…)
l = subshells (shape of orbitals) s, p, d, f (0, 1, 2, 3,…)
ml = magnetic (orientation) 1, 3, 5, 7 (# of energy
states)
ms = spin moment +½, −½

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 Quantum Numbers

Table 2.1 The Number of Available Electron States in Some of the Electron
Shells and Subshells
 Physical representation of the quantum
numbers

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 Different shapes of the orbitals

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 How to write the Electron Configurations
• Electrons have discrete energy states
and tend to occupy the lowest available energy state.
Energy
4d
4p N-shell n = 4
Increasing energy levels

3d
4s

3p M-shell n = 3
3s

2p L-shell n = 2
2s
Adapted from Fig. 2.4,
Callister 7e. 1s K-shell n = 1
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There is a maximum number of electrons in the
electron shell and sub shells

Energy
4d
4p N-shell n = 4

3d
4s
3p M-shell n = 3
3s

2p L-shell n=2
2s

1s K-shell n = 1
 How to write Electron Configurations
The lowest energy states are filled first
• Remember to start at the
1s
Increasing energy

beginning of each arrow,

2s 2p and then follow it all the way
to the end, filling in the
3s 3p 3d sublevels that it passes
4s 4p 4d 4f through.
5s 5p 5d 5f • In other words, the order for
6s 6p 6d filling in the sublevels
becomes; 1s, 2s, 2p, 3s, 3p,
7s 7p 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f,
5d, 6p, 7s, 5f, 6d, 7p.

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 Electron Configurations
Energy
4d
e.g. Fe 4p N-shell n = 4
⇒ atomic # (Z) = 26

Increasing energy levels

3d
= 26 protons = 26 electrons
for a neutral 4s
Fe
1s 3p M-shell n = 3
2s 2p 3s
3s 3p 3d
4s 4p 4d 4f
2p
5s 5p 5d 5f L-shell n = 2
2s
6s 6p 6d
7s 7p
20 electrons 1s K-shell n = 1

1s2 2s2 2p6 3s2 3p6 4s2 3d 6

rearranged ∴ 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 Valence electrons

Adapted from Fig. 2.4, 20

Callister 7e.
 Electron Configurations
e− per subshell
• Vanadium (V)
2 6 10 14
– Atomic number = 23
V: 1s2 2s2 2p6 3s2 3p6 4s2 3d 3
∴ V : 1s2 2s2 2p6 3s2 3p6 3d3 4s2

• Fe3+
– Atomic number for Fe = 26
– Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2
• Do not start from 23 electrons
∴Fe3+ : 1s2 2s2 2p6 3s2 3p6 3d5 • List the configuration of Fe
• Throw away the valence
electrons
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 Subshell d has 5
energy states.
3d
Therefore, it is more
stable to have 5 of
them filled with
1s
electrons as
2s 2p compared to 4s2.
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p

Adapted from Table 2.2,

Callister 7e.
The Periodic Table &
Electronegativity
 The Periodic Table

Adapted from Fig. 2.6, Callister 7e.

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 The Periodic Table
• Rows: Increasing Atomic Number Filled electron
shells and
• Columns: Similar Valence Structure stable electron

inert gases
give up 1e configurations.
give up 2e

accept 2e
accept 1e
give up 3e

H He
Li Be O F Ne
Na Mg S Cl Ar Adapted from
Fig. 2.6,
K Ca Sc Se Br Kr Callister 7e.

Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Elements of Group IA have one valence electron.

Elements in Group IVA have four valence electrons, etc
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 Electronegativity
• Another characteristic of an element is its electronegativity
• Electronegativity is the ability of an atom to attract electrons to
itself.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.
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 In your own time, find out:

• What is:
• an orbital
• Hund’s rule
• Pauli Exclusion Principle
• A quantum number

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 Announcement

• If anyone would like to volunteer to man

the Engineering Booth this coming
Open Day (23 to 24th March 2019),
please let me know. You will get:
• A T-shirt
• A Certificate of Appreciation
• Meal vouchers

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 Atomic Bonding

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 Interactions Between Atoms

• Electrons in the outermost levels will interact

first.
• When the outer shells are unfilled, atoms
gain, lose, or borrow electrons which is the
basis of bonding.

e.g. NaCl
 Types of Bonding- Primary bonds

• Primary bonds involve the interactions

between valence electrons
• There are 3 types of Primary Bonding:
a) Ionic bonding
b) Covalent bonding
c) Metallic bonding

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 Ionic Bonding
• Occurs between +ve and -ve ions
• Involves electron transfer
• Large difference in electronegativity required
e.g: MgO
Mg: Z = 12 O: Z = 8
Dissimilar electronegativity
Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4
[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]
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 Ionic Bonding
Ionic bond – metal + nonmetal
Donates Accepts
electrons electrons

e.g. NaCl
Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + − Cl (anion)
stable Coulombic stable
attraction
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 Examples of Ionic Bonding
• Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Dissimilar electronegativities

Give up electrons Acquire electrons

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University.

40
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 Covalent Bonding
• Occurs between atoms of similar electronegativity
and involves sharing of electrons
• bonds determined by valence – s & p orbitals
dominate bonding
• Example: CH4 Methane gas shared electrons
H
from carbon atom
C 1s 2s 2p
2 2 2
C: has 4 valence e−,
needs 4 more H C H

H 1s1 shared electrons

H: has 1 valence e−, H from hydrogen atoms
needs 1 more

Formed by elements whose

electronegativities are close
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 Covalent Bonding
• Nonmetallic Elemental • Elemental Solids; e.g.,
Molecules; e.g. F2, Cl2 C (diamond), Si, Ge
• Hydrogen Compounds; • Near Group-IVA Solid
e.g., HF, HNO3 Compounds; e.g. GaAs

• Covalent bonds are formed by sharing of the valence minus

electrons
• Covalent bond model: an atom can have at most 8 − N’
covalent bonds, where N’ = number of valence electrons
• Covalent bonds can be very strong, e.g. diamond, SiC,
Si, etc.; and also can be very weak, e.g. Bismuth
• Polymeric materials exhibit covalent type bonding.

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 Metallic Bonding
• Electrons shared by all atoms
– “sea of electrons” around “ion cores”
• Ion Cores
– Atoms give up e− to the “sea”, leaving remaining
atoms with a positive ionic charge
• The ion contains the large & heavy nucleus and
thus is FIXED in space
• Generally found in metals and their alloys such as Ti,
Ni, Zn, etc.

A metallic bond is non-directional

(bonds form in any direction)
→ atoms pack closely → high density
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 Metallic Bonding
Metallic bonds may be weak or strong
Bonding energies: range from 68 kJ/mol (0.7 eV/atom) for
Hg to 850 kJ/mol (8.8 eV/atom) for W.
Melting temperatures: −39° C for Hg and 3410°C for W.

Metals can be reshaped High hardness

High melting points Good electrical conductivity
http://207.10.97.102/chemzone/lessons/03bonding/mleebonding/metallicblue.gif
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 Mixed Ionic + Covalent Bonding
• Many compounds exhibit Ionic-Covalent Mixed
Bonding, e.g semiconducting compounds such as
GaAs, ZnSe
• The % ionic bonding can be calculated as:
 
2
−
( XA−XB )
1 − e
% Ionic Character = 4  ×100%
 
 
– where XA & XB are the electronegativity
• Example – MgO: XMg = 1.2, XO = 3.5

 
2
(3.5 −1.2)
−
% ionic character =−
1 e 4
 × 100% =
73.4% ionic
 
26.6% covalent
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 Mixed Ionic + Covalent Bonding
Determine the ionic character between the following
atoms:  ( XA−XB ) 
2
−
1 − e
% Ionic = 4  ×100%
 
Electronegativity charges  
from periodic table XA & XB % Ionic
Sodium and Na E0 0.9 Δ=2.1
Chlorine Cl E0 3.0 68% ionic
Carbon and C E0 2.5 Δ=0.5
Nitrogen N E0 3.0 6% ionic
94% covalent
Potassium and K E0 0.8 Δ=1.7
Sulphur S E0 2.5 51% ionic

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 Covalent vs Ionic Bonding
• Real bonds lie somewhere
between ionic and covalent
• The difference in
electronegativity
corresponds directly to the
percent ionic character of
the bond

Very few materials have pure ionic or covalent bonding;

electronegativity in part defines how much time electrons
spend between ion cores
 Secondary Bonds
• Secondary (van der Waals), or physical bonds
are weak in comparison to the primary (or)
chemical ones.
• Bonding energies are typically on the order of
only 10 kJ/mol (0.1 eV/atom).
• Secondary bonding exists between virtually all
atoms or molecules.
• This is shown in the inert gases, which have
stable electron structures, as well as, between
molecules in molecular structures that are
covalently bonded.
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 Secondary Bonding – Dipole Forces

Adapted from Fig. 2.12, Callister 7e.

Schematic illustration of van der

Waals bonding between two dipoles

• Molecules or atoms attract each other.

• Dipole-dipole forces are attractive forces
between the positive end of one dipole and the
negative end of an adjacent one.
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 Hydrogen Bonding
• Hydrogen bonding is a special type of secondary
bonding
• It is the strongest secondary bonding.
• It occurs between molecules in which hydrogen
is covalently bonded to F, O and N.
• e.g., HF, H2O, NH3

Covalent bond

• Melting and boiling temperatures for HF and H2O

are abnormally high due to hydrogen bonding.
Adapted from Fig. 2.15, Callister 7e.
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So why are interatomic bonds important?

Because Bonding Influences Properties

 Bonding Type → Properties
Graphite have:
• Strong covalent bonds
within layers
• BUT van der Waals
between
→ layers layers
can slide
→ Therefore they are soft
& greasy

Diamond:
• Strong covalent bonds
→ hardest known material

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 Example: High Bonding Energy →
high melting temperature
• Bond length, r
F
F

Equilibrium spacing or

Bonding High bonding energy, Eo →

Energy
high melting temperature, Tm
Bonding Energy – minimum
energy required to break the bond
 Example: High Bonding Energy →
High stiffness
• Elastic modulus, E • E ~ curvature at ro
Energy

unstretched length
ro
r
smaller Elastic Modulus

Elastic modulus larger Elastic Modulus

F ∆L
=E Steep slope → high modulus
Ao Lo
Bonding Energies and Melting Temperatures
for Various Substances

Adapted from Table 2.3, Callister 7e.

 Summary
 Two atomic models: Bohr and Wave-mechanical
 The four electron quantum numbers are n, l, m1
and ms
 Electron Configurations – the manner in which
possible electron states are filled with electrons.
 Primary Interatomic Bonds:
– Ionic, Covalent, Metallic
 Secondary Bonding or van der Waals Bonding
– Weak bonds between electric dipoles
– Hydrogen Bonding is the strongest secondary
bonds