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4: Bonding

Lecture 7: Bonds between atoms, ions and


Outline of lecture

1. Learning outcomes

2. Why important

3. Review of basic concepts

4. Atomic bonding

5. Bonds in engineering materials

1. Learning Outcomes

At the end of this lecture you should be able to do the following:

• Describe a simplified model of the atom.

• Define the following terms: atomic number, atomic mass unit, Avagadro’s
number, mole, isotope.
• Interpret the periodic table.
• Describe (giving examples) the following types of bond: ionic, covalent, metallic,
van der Waals, hydrogen.
• Explain the form of the force and energy versus interatomic separation graphs.
• Demonstrate an awareness of which properties can be explained by reference to
atomic bonding and which cannot.

You will be able to answer all questions on Tutorial sheet 4.

2. Why important
• So far, we have studied various mechanical properties.

• In this part of the course, we investigate the origins of the various properties.


• The main reason is, if we understand the origins of the various desirable
properties, we may be able to control them.

• Thus, we may be able to develop materials with particularly desirable properties

or combinations of properties.

Imagine.. A material with a Young’s modulus equivalent to a ceramic, the yield

strength of a Ti-alloy, the toughness of mild steel and the density of a polymer?

3. Review of basic concepts
3.1 Definitions

Make sure you know the meaning of, and understand, these terms:

• Atom
• Nucleus
• Electrons
• Atomic number
• Isotope
• Atomic weight
• Atomic mass unit
• Polarity
• Avogadro’s number
• Mole

3.2 Simplified (Bohr) model of the atom

• Atoms
– Nucleus
– Electrons
– Protons
– Neutrons

• Orbital electrons
- These orbit the nucleus in shells.
- Position of electrons described by quantum mechanics
- Each shell has an energy level which binds its electrons to the
- Full shells, containing 2,8 or 18 electrons are stable.
- Behaviour of an atom depends strongly on whether its outer 2
shells are full (2,8 or 18 electrons).
3.3 Mass & Charge: Bohr model of Carbon 12 atom

Inner orbital with two electrons

Nucleus with 6 protons
and 6 neutrons

Outer orbital with 4 electrons

• The nucleus contains almost all the mass of the atom

• Each proton and neutron has a mass of about 1.66x10-24 g
• This is called the atomic mass unit
• The mass of an electron is 0.911x10-27 g, so electrons make negligible
contribution to the atomic mass.
• An electron has a negative charge of -1.6 x10-19 C, a proton a positive charge
of +1.6 x10-19 C, a neutron has no charge, making an atom neutral in charge overall.

3.4 Classification of elements

• The number of protons in the nucleus is known as the atomic number of the

• We thus write the chemical identification of the element, carbon, as:

6 Atomic number
12.011 Atomic weight

• The position in the periodic table is based upon the above description of the

• The number of electrons orbiting the nucleus in the atom will equal to the number
of protons in the nucleus.

3.5 The Periodic Table

From Callister Chapter 2, page 23

4. Atomic Bonding
The type of atomic bonding which occurs depends strongly on the electrons in the
outer two shells, and whether they are full shells or not.

• Metals
– Have outer shells nearly empty, i.e. containing 1, 2 or 3 electrons.

• Non-metals
– Have outer shells nearly full, i.e. lacking 1,2 or 3 electrons.

• Metalloids (intermediate)
– Somewhere between metals and non-metals.

Types of bond
• Strong primary bonds
– Outer shell electrons are transferred or shared.
– Ionic bonding → transfer of electrons
– Covalent bonding → share of electrons
– Metallic bonding → pooling of electrons

• Weaker secondary bonds

– More subtle attractions between positive and negative charges (with no
transfer or share taking place).
– Van der Waals
– Hydrogen bonds

Usually, more than 1 of the above types of bond will be present in a material.

4.1 Ionic bonding (happiness is a full shell)
• Occurs between dissimilar atoms e.g. Na and Cl by electron transfer.

• The resulting compound NaCl contains Na+ and Cl- ions. In this case, one
electron is transferred from Na to Cl.

• To separate these ions, we must supply energy (e.g. heat) to return the electron.
How much energy will govern the melting point of the compound.

• The more electrons transferred, the more energy we must supply e.g. melting
point MgO > NaCl

Na+ Ionic bond Cl-

• Ionic bonds are nondirectional

(2,8,1) (2,8,7)
4.2 Covalent bonding (Atoms that play together, stay together)
• Occurs between atoms and these bonds are directional

• When an element has about 4 electrons in its outer shell, a lot of energy would be
needed to transfer them all to form an ion.

• Another possibility (energetically favourable) is that the electrons will be shared.

• Take Carbon atoms. They have (2,4 electrons), i.e. 4 in the outer shell. If these
electrons take the formation of a regular tetrahedron:

If other C atoms ‘park’ Two C atoms share

at the corner sites 8 electrons (4 from
each atom)

Structure of diamond
C atom at centre

4.3 Metallic Bonding (or swimming is fun)

• Metals with 1,2 or 3 electrons in the outer shell can donate them to form part of
a sea or cloud of electrons, surrounding the resultant ions.

Metal ions

Cloud of free electrons

• These electrons do not belong to any particular atom or pair of atoms.

• The electrons are quite free to move, thus metals:

– Conduct heat or electricity quite easily.
– Can form a wide range of mixtures with other metals (see alloys later).
– Have bonds that are nondirectional, thus a metal can have its shape changed more
easily (and at nearly constant volume) than say a covalently-bonded ceramic.
– Pack quite closely together, implying generally higher densities than covalent or ionic
4.4 van der Waals Bonding (secondary bonds)

Van der Waals

• Atoms have positively charged particles (protons) and negatively charged

particles (electrons).
• If the distribution of the positive and negative charges becomes asymmetric, then
a net electric charge exists (dipole).
• These dipoles can be temporary or permanent.
• Once in existence, a dipole in one atom can induce a dipole in a neighbouring
• The resultant attraction between two dipoles are known as van der Waals forces
• We see above how this can happen between Argon atoms (a temporary dipole).

4.5 Hydrogen bonds (secondary bonds)
• The hydrogen nucleus, being the smallest, is certain to retain less than its ‘fair
share’ of electrons.
• Thus, molecules containing H atoms will be polar and thus these molecules will
attract each other.
• These molecules will have permanent dipoles, and thus will have greater bond
energies than bonds formed between temporary dipoles
• The water molecule is a good example:

The hydrogen

Without H bonding
water would boil at

5. Bonds in Engineering Materials
• All of the above descriptions of bond types are simplifications.
• The structure of some molecules is still not fully understood.
• Some bonds are combinations of the individual types previously described .
• The bonding in the main classes of engineering material (and also
semiconductors) are shown schematically in the figure below.


Metallic Secondary


5.1 Forces between atoms and bond energy


F  FA  FR FA = attractive force FR = repulsive force

(short range)

At equilibrium:

Forces balance: F  FA  FR  0

and energy is a minimum: U  Fdr

• A power-law model is often used to describe bond energy, e.g.:

m n dU mA nB
U   Ar  Br F  
dr r m 1 r n 1
where A, B, m and n are constants whose values depend on the system

• Typically
– Ionic bonds: m=1
– Covalent bonds: m=2 and n=9
– Metallic bonds: m=1 to 4

• Illustration for an ionic bond: The constant A is given by:

A Z q Z q 
4 0
1 2

o: the permittivity of a vacuum (units C2N-1m-2 or Fm-1 where F is the farad)
Z1, Z2: the valances of the two ion types
q: the electronic charge (1.602 x 10-19 C)

Force and energy versus interatomic separation curves

FN  FA  FR

Equilibrium spacing, ro
when FN=0

EN  U   Fdr

Net energy a minimum

when FN=0

Example bond energies and melting temperatures

Type of Substance Bonding Melting

Bond energy Temp
(kJ/mol) (ºC)
Ionic NaCl 640 801
MgO 1000 2800
Covalent Si 450 1410
C 713 >3550
Metallic Hg 68 -39
Al 324 660
W 849 3410
van der Ar 7.7 -189
Waals Cl2 31 -101
Hydrogen H2O 51 0

Source- Callister Chapter 2, page 28

5.2 Can we predict Young’s modulus? YES, for metals

Assume two layers of atoms, initially separated by ro, pulled apart by a distance dr.

ro dF
F F E is proportional
F to slope F-r curve
ro at r=ro

ro 0 ro r

d 1  d 2U 
It can be shown that Young’s modulus is given by: E    2 
d ro  dr ro

2 q2
For the relevant bond: E 9 2
4 ~ 220 x 10 N/m Very close for many metals!
  o ro

BUT: this analysis does not work for polymers, as the origins of E are different, as we
shall see later in the course!
Can we predict tensile strength? NO, for metals
• UTS from the maximum force value of the F-r curve?

• Depending on the assumptions used, we get predictions in the range of

TS=E/10 to E/15

• These predictions are very much higher than measured strengths for metals:

Steels: TS=E/100

Other metals: TS=E/1000

Some ceramics: Y=E/70

Diamond: Y=E/20

• Question: Why are the UTS predictions so poor for metals?

Can other physical properties be explained? YES
• e.g. Thermal expansion may be explained by reference to the U-r diagram.
• The U-r diagram shows the potential energy between two atoms, at a distance r.
• However, at T>0 K, atoms will also have kinetic energy (they will vibrate).
• This K.E. must be added to the P.E. to give total energy.
• The equilibrium position of vibration moves to the right, as U-r not symmetric.

(at absolute zero)

Assuming a power-law model, derive an expression for the equilibrium atomic
spacing ro in terms of the constants A, B, m and n.


U  Fdr

• and at equilibrium, the net force on the atoms is zero:



0 at r  ro
dr r m 1 n 1
• thus
1/( n  m )
mA nB  nB 
m 1
 n1 i.e. ro   
ro ro  mA 

• ro ~ 0.3 x 10-9 m for many typical crystalline solids

(see tutorial sheet 4, question 1…)