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Engineering Materials (CUPE 127)

Atomic Structure and Bonding

27 OCTOBER 2022
MS. P. MUTEKWA
[email protected]
+263787088959
 WHY ATOMIC STRUCTURE? 2
 The type of bond allows us to explain a material’s properties.
 Consider carbon allotropes, graphite and diamond.

Graphite Diamond
1. Graphite is relatively soft and has a 1. Diamond is the hardest known material-
“greasy” feel to it hardness of 10
2. Layered structure with a planar 2. Crystalline structure made up of
geometry- layers can be separated easily, tetrahedral units- rigid covalent bond
network which is difficult to break
3.Graphite is a reasonably good conductor 3.Diamond is a poor conductor of electricity,
acts as an insulator

 Disparities in properties are directly attributable to a type of inter atomic bonding

found in graphite that does not exist in diamond
 1. THE STRUCTURE OF THE ATOM 3

 The atomic number of an element is equal to the number of electrons or

protons in each atom.

 The atomic mass of a specific atom may be expressed as the sum of the
masses of protons and neutrons within the nucleus.

 The Avogadro number of an element is the number of atoms or molecules in

a mole.

 The atomic mass unit of an element is the mass of an atom expressed as

1/12 the mass of a carbon atom.
2. Deviations from Expected Electronic Structures 4

The energy levels of the quantum shells

do not fill in strict numerical order.

The Aufbau Principle is a graphical

device that predicts deviations from the
expected ordering of the energy levels.

By following the arrows, the order in

which the energy levels of each
quantum level are filled is predicted: 1s,
2s, 2p, 3s, 3p, etc.
 3. Valence 5
The valence of an atom is the number of electrons in an atom that
participate in bonding or chemical reactions.

Usually, the valence is the number of electrons in the outer s and p

energy levels.

The valence of an atom is related to the ability of the atom to enter

into chemical combination with other elements.
Examples of the valence are
 Mg : 1s2 2s2 2p6 3s2 valence = 2
 Al : 1s2 2s2 2p6 3s23p1 valence = 3
 Si : 1s2 2s2 2p6 3s2 3p2 valence = 4
 4 Atomic Stability and Electronegativity
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 If an atom has a valence of zero, the element is inert (non-reactive).
 An example is argon, which has the electronic structure: 1s2 2s2 2p6 3s23p6

 Other atoms prefer to behave as if their outer s and p levels are either completely
full, with eight electrons, or completely empty.

 Aluminium has three electrons in its outer s and p levels. An aluminum atom readily
gives up its outer three electrons to empty the 3s and 3p levels. The atomic
bonding and the chemical behaviour of aluminum are determined by how these
three electrons interact with surrounding atoms.

 On the other hand, chlorine contains seven electrons in the outer 3s and 3p levels.
The reactivity of chlorine is caused by its desire to fill its outer energy level by
accepting an electron.
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Electronegativity describes the tendency of an atom to gain an electron.

Atoms with almost completely filled outer energy levels—such as chlorine—are

strongly electronegative and readily accept electrons.

Atoms with nearly empty outer levels—such as sodium—readily give up electrons

and have low electronegativity.

High atomic number elements also have low electronegativity because the outer
electrons are at a greater distance from the positive nucleus, so that they are not as
strongly attracted to the atom.

Elements with low electronegativity are sometimes described as electropositive.

The electronegativities of selected elements relative to the position of the elements in
the periodic table. 8
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 5. PERIODIC TABLE
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All the elements are classified according to electron configuration in the periodic
table.
The elements are situated, with increasing atomic number, in seven horizontal rows
called periods.
The arrangement is such that all elements arrayed in a given column or group have
similar valence electron structures, as well as chemical and physical properties.
These properties change gradually, moving horizontally across each period and
vertically down each column.
The elements positioned in Group 0, the rightmost group, are the inert gases,
which have filled electron shells and stable electron configurations.
Group VIIA and VIA elements are one and two electrons deficient, respectively,
from having stable structures.
The Group VIIA elements (F, Cl, Br, I, and At) are sometimes termed the halogens.
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The alkali and the alkaline earth metals (Li, Na, K, Be, Mg,Ca, etc.) are labelled as
Groups IA and IIA, having, respectively, one and two electrons in excess of stable
structures.
The elements in the three long periods, Groups IIIB through IIB, are termed the
transition metals, which have partially filled d electron states and in some cases
one or two electrons in the next higher energy shell.
Groups IIIA, IVA, and VA (B, Si, Ge, As, etc.) display characteristics that are
intermediate between the metals and non metals by virtue of their valence
electron structures.
As may be noted from the periodic table, most of the elements really come under
the metal classification. These are sometimes termed electropositive elements.
Furthermore, the elements situated on the right-hand side of the table are
electronegative.
As a general rule, electronegativity increases in moving from left to right and from
bottom to top.
 6. ATOMIC BONDING
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 There are four important mechanisms by which atoms are bonded in engineered
materials. These are:
o metallic bonds;
o covalent bonds;
o ionic bonds; and
o van der Waals bonds.

 The first three types of bonds are relatively strong and are known as primary bonds
(relatively strong bonds between adjacent atoms resulting from the transfer or
sharing of outer orbital electrons).

 The van der Waals bonds are secondary bonds and originate from a different
mechanism and are relatively weaker.
 6.1 The Metallic Bond
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The metallic elements have electropositive atoms that donate their valence
electrons to form a “sea” of electrons surrounding the atoms.

Aluminium, for example, gives up its three valence electrons, leaving behind a core
consisting of the nucleus and inner electrons.

Since three negatively charged electrons are missing from this core, it has a positive
charge of three.

The valence electrons move freely within the electron sea and become associated
with several atom cores. The positively charged ion cores are held together by
mutual attraction to the electrons, thus producing a strong metallic bond.

Because their valence electrons are not fixed in any one position, most pure metals
are good electrical conductors of electricity at relatively low temperatures (T 300 K).
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 6.2 The Covalent Bond
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Materials with covalent bonding are characterized by bonds that are formed by
sharing of valence electrons among two or more atoms.
For example, a silicon atom, which has a valence of four, obtains eight electrons in
its outer energy shell by sharing its valence electrons with four surrounding silicon
atoms.
Each instance of sharing represents one covalent bond; thus, each silicon atom is
bonded to four neighbouring atoms by four covalent bonds.
Covalent bonds are very strong. As a result, covalently bonded materials are very
strong and hard. For example, diamond (C), silicon carbide (SiC), silicon nitride
(Si3N4), and boron nitride (BN) all have covalent bonds.
These materials also exhibit very high melting points, which means they could be
useful for high-temperature applications.
We cannot simply predict 16
whether or not a material will
be high or low strength,
ductile or brittle, simply
based on the nature of
bonding!

We need additional
information on the atomic,
microstructure, and
macrostructure of the
material; however, the nature
of bonding does point to a
trend for materials with
certain types of bonding and
chemical compositions.
 6.3 The Ionic Bond
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When more than one type of atom is present in a material, one atom may donate
its valence electrons to a different atom, filling the outer energy shell of the second
atom.

Both atoms now have filled (or emptied) outer energy levels, but both have
acquired an electrical charge and behave as ions.

The atom that contributes the electrons is left with a net positive charge and is
called a cation, while the atom that accepts the electrons acquires a net negative
charge and is called an anion.

The oppositely charged ions are then attracted to one another and produce the
ionic bond.

For example, the attraction between sodium and chloride ions produces sodium
chloride (NaCl), or table salt.
Ionic Bond of Sodium Chloride 18
 6.4 Van der Waals Bonding
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If two electrical charges +q and –q are separated by a distance d, the dipole moment
is defined as q×d.
Atoms are electrically neutral, the centres of the positive charge (nucleus) and
negative charge (electron cloud) coincide. Therefore, a neutral atom has no dipole
moment.
When a neutral atom is exposed to an internal or external electric field, the atom may
become polarized (i.e., the centers of positive and negative charges separate). This
creates or induces a dipole moment.
In some molecules, the dipole moment does not have to be induced—it exists by
virtue of the direction of bonds and the nature of atoms. These molecules are known
as polarized molecules.
An example of such a molecule that has a permanently built-in dipole moment is
water (Figure 2-16).
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Molecules or atoms in which there is either an induced or permanent dipole moment attract
each other. The resulting force is known as the van der Waals force.

There are three types of van der Waals interactions, namely London forces, Keesom
forces, and Debye forces.

If the interactions are between two dipoles that are induced in atoms or molecules, we refer
to them as London forces (e.g., carbon tetrachloride)

When an induced dipole (that is, a dipole that is induced in what is otherwise a non-polar
atom or molecule) interacts with a molecule that has a permanent dipole moment, we refer
to this interaction as a Debye interaction. An example of Debye interaction would be
forces between water molecules and those of carbon tetrachloride.

If the interactions are between molecules that are permanently polarized (e.g., water
molecules attracting other water molecules or other polar molecules), we refer to these as
Keesom interactions.
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 6.5 Mixed Bonding
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In most materials, bonding between atoms is a mixture of two or more types.

Iron, for example, is bonded by a combination of metallic and covalent bonding that
prevents atoms from packing as efficiently as we might expect.

Compounds formed from two or more metals (intermetallic compounds) may be

bonded by a mixture of metallic and ionic bonds, particularly when there is a large
difference in electronegativity between the elements.

Because lithium has an electronegativity of 1.0 and aluminium has an

electronegativity of 1.5, we would expect AlLi to have a combination of metallic and
ionic bonding.

On the other hand, because both aluminium and vanadium have electronegativities
of 1.5, we would expect Al3V to be bonded primarily by metallic bonds.
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Many ceramic and semiconducting compounds, which are combinations of metallic
and non-metallic elements, have a mixture of covalent and ionic bonding.

As the electronegativity difference between the atoms increases, the bonding

becomes more ionic.

The fraction of bonding that is covalent can be estimated from the following
equation:

Fraction covalent = exp(–0.25ΔE2)

where ΔE is the difference in electronegativities.

7. BINDING ENERGY AND INTERATOMIC SPACING 24
The equilibrium distance between atoms is caused by a balance between repulsive and
attractive forces.
In the metallic bond, for example, the attraction between the electrons and the ion cores is
balanced by the repulsion between ion cores.
Equilibrium separation occurs when the total interatomic energy (IAE) of the pair of atoms
is at a minimum, or when no net force is acting to either attract or repel the atoms (Figure 2-
18).
The interatomic spacing in a solid metal is approximately equal to the atomic diameter, or
twice the atomic radius r.
The minimum energy in Figure 2-18 is the binding energy, or the energy required to create
or break the bond.
Consequently, materials having a high binding energy also have a high strength and a high
melting temperature.
Ionically bonded materials have a particularly large binding energy (Table 2-2) because of
the large difference in electronegativities between the ions.
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Metals have lower binding energies because the electronegativities of the atoms
are similar.

Other properties can be related to the force-distance and energy-distance

expressions in Figure 2-19.

For example, the modulus of elasticity of a material (the slope (E) of the stress-
strain curve in the elastic region, also known as Young’s modulus) is related to
the slope of the force-distance curve (Figure 2-19).

A steep slope, which correlates with a higher binding energy and a higher melting
point, means that a greater force is required to stretch the bond; thus, the
material has a high modulus of elasticity.
 Additional Reading 28

Coefficient of thermal expansion

Forms of Carbon
 Diamond
 Graphite
 Carbon Nanotubes
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Thank you