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4: Bonding

Lecture 7: Bonds between atoms, ions and


molecules

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Outline of lecture

1. Learning outcomes

2. Why important

3. Review of basic concepts

4. Atomic bonding

5. Bonds in engineering materials

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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.

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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.

Why?

• 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?

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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

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3.2 Simplified (Bohr) model of the atom

• Atoms
– Nucleus
– Electrons
Nucleus
– 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
nucleus.
- 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).
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3.3 Mass & Charge: Bohr model of Carbon 12 atom

Inner orbital with two electrons


Nucleus with 6 protons
and 6 neutrons

NOT TO SCALE!
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.

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3.4 Classification of elements

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

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

6 Atomic number
C
12.011 Atomic weight

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

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

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3.5 The Periodic Table

From Callister Chapter 2, page 23


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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.

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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.

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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)
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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

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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
bonding
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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
atom.
• 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).

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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
bond

Without H bonding
water would boil at
-80˚C

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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.

Covalent

Metallic Secondary

Ionic

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5.1 Forces between atoms and bond energy

F F F

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



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• 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:

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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)

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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

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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
(diamond)
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


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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
dr
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!
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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?

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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)

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

As

U  Fdr

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

F
dU

mA

nB
0 at r  ro
dr r m 1 n 1
r
• 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…)


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