Atomic Structure and Interatomic Bonding

• How are atoms arranged?

• How are they joined together?
• Why are atomic arrangements
and bonding important?

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 Carbon: Graphite vs. Diamond

• Soft, “greasy” • Hardest material known

• Good electric conductor • Poor electric conductor
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 Atomic Structure
Bohr model of atomic structure Orbital Electron
Electrons are assumed to
Nucleus revolve around the atomic
Protons & Neutrons nucleus in discrete orbitals

• Electrons – 9.11 x 10-31 kg

• Atom • Protons
– 1.67 x 10-27 kg
• Neutrons

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

= # of electrons of neutral species

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

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 Atomic Structure
• Isotopes have same atomic number (Z) but
different atomic mass (A)

• Atomic weight of an element corresponds to the

weighted average of the atomic masses of the
atom’s naturally occurring isotopes.

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
Avogadro’s number
1 amu/atom = 1 g/mol
• e.g. the atomic weight of iron is 55.85 amu/atom or 55.85 g/mol.
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 Atomic Models
• There were some limitations in Bohr’s
Figure 2.3,
Callister 8ed. model of the atom, so the atomic model
widely used now is the Wave-Mechanical
model
• Electron is considered to have wavelike
and particle-like characteristics
– Electron is at various locations around
the nucleus which is described by a
probability distribution or electron cloud

Bohr Wave-Mechanical
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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
– Every electron in an atom is described by quantum numbers.

Quantum # Designation
n = principal (energy level or shell) 1, 2, 3… (K, L, M, N, O..)
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

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Shape and Orientation of an Electron Subshell

f
https://www.coursehero.com/sg/general-chemistry/quantum-theory/ 8
 Energy Levels of Electrons
Electrons... • have discrete energy states
• tend to occupy lowest available energy state
Energy
4d
4p N-shell n = 4

3d
Increasing energy levels

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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 Maximum Number of Electrons
Table 2.1 The Number of Available Electron States in Some of the Electron Shells and Subshells

Energy
4d
4p N-shell n = 4

3d

4s

3p M-shell n = 3

Pauli exclusion principle 3s

• Each electron state – holds no 2p

L-shell n=2
more than 2 electrons 2s

1s K-shell n = 1
Adapted from Fig. 2.4, Callister 7e.

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 How to write Electron Configurations
• The way in which electrons are
1s arranged in orbitals in an atom.
Increasing energy

2s 2p • The lowest energy states are filled first

3s 3p 3d • Remember to start at the beginning
4s 4p 4d 4f of each arrow, and then follow it all
5s 5p 5d 5f the way to the end, filling in the
6s 6p 6d sublevels that it passes through.
7s 7p • In other words, the order for filling in
the sublevels becomes: 1s, 2s, 2p,
3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f,
5d, 6p, 7s, 5f, 6d, 7p.
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 How to write Electron Configurations
Energy
e.g. Fe ⇒ atomic # (Z) = 26 4d
4p N-shell n = 4
= 26 protons

Increasing energy levels

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

1s2 2s2 2p6 3s2 3p6 4s2 3d 6 Adapted from Fig. 2.4, Callister 7e.

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

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 Valence Electrons
• Valence electrons are the electrons in the outermost shell
e.g Fe: 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 Valence electrons

• Valence electrons determine all of the following properties:

1) Chemical
2) Electrical
3) Thermal
4) Optical

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 Electron Configurations
e− per subshell
• Vanadium (V)
2 6 10 14
– Atomic number = 23

• Fe3+
– Atomic number for Fe = 26

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Table 2.2. The listing of
the expected electron Subshell d has 5
configurations for some energy states.
of the common elements 3d

1s
2s 2p Therefore, it is more
3s 3p 3d stable to have 5 of
4s 4p 4d 4f them filled with
5s 5p 5d 5f electrons as compared
6s 6p 6d to 4s2.
7s 7p

Table 2.2, Callister 7e.

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 The Periodic Table
• Rows: Increasing Atomic Number
• Columns: Similar Valence Structure, chemical & physical properties

Inert gases – filled

electron shells and
stable electron
configurations.

Adapted from Fig. 2.6,

Callister 7e.
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 Electronegativity
• Electronegativity is the ability of an

give up 1e
atom to attract electrons to itself.

give up 2e

accept 2e
accept 1e
give up 3e

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, 17
3rd edition. Copyright 1960 by Cornell University.
 Primary Bonding
• Primary bonding:
a) Ionic bonding
b) Covalent bonding
c) Metallic bonding e.g. NaCl
• Involves valence electrons – electrons
in the outermost levels interact first
• When the outer shells are unfilled,
atoms gain, lose, or borrow electrons
which is the basis of bonding.
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 Ionic Bonding
Ionic bond = metal + nonmetal
Donates Accepts
electrons electrons

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

Na (cation) + − Cl (anion)
stable Coulombic stable
attraction
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 Ionic Bonding
• Occurs between +ve and -ve ions
• Requires electron transfer
• Large difference in electronegativity required
e.g: MgO
Mg: Z = 12 O: Z = 8
Dissimilar electronegativities
Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

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

[Ne] [Ne]
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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.
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 Covalent Bonding
• Similar electronegativities ∴ share electrons
• Bonds determined by valence – s & p orbitals
• Example: CH4 Methane gas minus
Valence e−
C 1s2 2s2 2p2 H At most 8 − N’ covalent bonds
C: has 4 valence e−, ∴ For C, 8 – 4 = 4
needs 4 more covalent bonds
H C H
H 1s1
H: has 1 valence e−,
needs 1 more H shared electrons from carbon atom
shared electrons from hydrogen atoms
Adapted from Fig. 2.10, Callister 7e.

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 Covalent Bonding
• Covalent bonds are formed by a sharing of the valence electrons
• Formed by elements whose electronegativities are close
• Covalent bond model: an atom can have at most 8 − N’ covalent bonds,
where N’ = number of valence electrons
• Nonmetallic Elemental Molecules; e.g. F2, Cl2
• Hydrogen Compounds; e.g., HF, HNO3
• Elemental Solids; e.g., C (diamond), Si, Ge
• Near Group-IVA Solid Compounds; e.g. GaAs, InSb, SiC
• Covalent bonds can be very strong, e.g. diamond (Tm > 3550 °C); can also
be very weak, e.g. Bismuth (Tm ~ 270 °C)
• Polymeric materials exhibit covalent type bonding.
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 Mixed Ionic + Covalent Bonding
• Many compounds exhibit Ionic-Covalent Mixed Bonding
• Semiconducting compounds such as GaAs, ZnSe
• Depends on relative positions in periodic table or difference in
electronegativities
 
2
( X −XB )
− A
1 − e
% Ionic Character = 4  ×100%
 
 
– where XA & XB are the
• Example – MgO: XMg = 1.2, XO = 3.5 electronegativities

 
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 how the ionic bonds between the following atoms would be
 
2
−
( XA−XB )
1 − e
% IC = 4  ×100%
 
Electronegativity charges  
from periodic table XA & XB % Ionic
Sodium and Chlorine

Carbon and Nitrogen

Potassium and Sulphur

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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
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 Metallic Bonding
• Found in metals and their alloys, e.g. Ti, Zn, Ni, etc.
• Electrons shared by all atoms
– Electrons are not bound to any particular atom – free to drift
– “sea of electrons” around “ion cores”

• Ion cores
– Atom gives up e− to the “sea”, leaving remaining atom with a positive ionic
charge
– The ion contains the large & heavy nucleus and thus is FIXED in space
• Electrons act as ‘glue’ to hold the ion cores together

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 849 kJ/mol (8.8
eV/atom) for W.
• Melting temperatures: −39 °C for Hg and
3410 °C for W.
• Properties: http://207.10.97.102/chemzone/lessons/03bonding/mleebonding/metallicblue.gif

• Good electrical conductivity

• High melting points
• High hardness
• Can be reshaped
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 Secondary Bonding
• Secondary (van der Waals), or physical bonds are weak in
comparison to the primary (or) chemical bonds.
• 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.
• It is evidenced for 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
Adapted from Fig. 2.15, Callister 7e.

• Melting and boiling temperatures for HF and H2O are abnormally

high due to hydrogen bonding.
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So why are interatomic bonds important?

• Because Bonding Influences Properties

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Bonding Type → Properties
Graphite:
• Strong covalent bonds within layers
• BUT van der Waals between layers
→ layers can slide
→ therefore, they are soft & greasy
(lubricant)

Diamond:
• Strong covalent (directional) bonds
→ hardest known material

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 High Bonding Energy → High Tm
• Bond length, r • Large r → negligible interactions
F
F
• Small r → atom exerts force on the other
r

Equilibrium spacing or

Bonding Energy

Bonding Energy – minimum High bonding energy, Eo →

energy required to break the bond high melting temperature, Tm
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 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
Ao Lo
Steep slope → high modulus

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Bonding Energies and Melting Temperatures
for Various Substances

Adapted from Table 2.3, Callister 7e.

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 Summary
• Two atomic models: Bohr and Wave-mechanical
• The four electron quantum numbers are n, l, m1 and ms
• Electron Configuration – the manner in which possible
electron states are filled with electrons.

• Primary Bonds:
– Ionic, Covalent, Metallic
• Secondary Bonding or van der Waals Bonding
– Weak bonds between electric dipoles
– Hydrogen Bonding
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