Notes in ChE 324

Prepared: Engr. Brenda T. Domingo Coloma, ChE

ATOMIC STRUCTURE

Four Levels of Material Structure:

 Atomic structure  Microstructure and
 Atomic arrangement  Macrostructure

Atomic structure:
It influences how atoms are bonded together. Understanding how atoms are bonded helps in the categorization of
materials as metals, semiconductors, ceramics, and polymers. It permits one to draw conclusions concerning the
mechanical properties and physical behavior of these four classes of materials
Structure of the Atom:
An atom is composed of a nucleus surrounded by electrons. The nucleus contains neutrons and positively charged
protons & carries a net positive charge. The negatively charged electrons are held to the nucleus by an electrostatic
attraction. The number of electrons and protons in the atom are equal, thus the atom is electrically neutral. The
electrical charge carried by each electron and proton is 1.60x10 -19 coulomb (C).

Atomic number – of an element is equal to the number of electrons or protons in each atom. The mass of each
proton and neutron is 1.67x10-24 g and the mass of each electron is only 9.11x10 -28 g.

Atomic Mass (M) – equal to the average number of protons and neutrons in the atom. It is the mass of the
Avogadro’s Number, NA, of atoms. NA = 6.023x1023 mol-1, number of atoms or molecules in a mole.

Atomic Mass – has a units of g/mol, an alternative unit is the atomic mass unit or amu, which is 1/12 of the mass of
carbon 12.

Electronic Structure of the Atom:

Electrons occupy discrete energy levels within an atom. Each electron possesses a particular energy, with no more
than two electrons in each atom having the same energy. Also implying that there is a discrete energy difference
between any two energy levels.

Quantum numbers – determine the energy level to which each electron belongs.
The number of possible energy levels is determined by the 1 st three quantum numbers:
1. Principal Quantum Number (n = 1, 2, 3, 4, ….) – refer to the quantum shell to which the electron
belongs. Quantum Shells are also assigned a letter: K for n = 1, L for n = 2, M for n = 3, & so on.

2. Azimuthal Quantum Number (l = 0, 1, 2, 3, ......, n-1) – determines the number of energy levels in
each quantum shell. If n = 2, then there are also two azimuthal quantum numbers (l = 0, l = 1).
The azimutahl quantum numbers are designated by lowercase letters:
s for l = 0, p for l = 1, d for l = 2, f for l = 3

3. Magnetic Orbital Quantum Number ( ml) – gives the number of energy levels, or orbitals, for each
azimuthal quantum number.
The total number of magnetic quantum numbers for each l is 2l + 1.
The values of ml are given by whole numbers between – l and +l.
For l = 2, there are 2(2) + 1 = 5 magnetic quantum numbers, with values -2, -1, 0, +1, & +2.

4. Spin Quantum Number (ms) – The Pauli Exclusion Principle specifies that no more than two
electrons with opposing electronic spins may be present in each orbital.
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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

The spin quantum number reflects the different spins of the electrons.
It is assigned values of +½ and –½. See figure for a sodium atom.

Atomic Structure of Sodium

Electronic Configuration – a shorthand notation frequently used to denote the electronic structure of an atom.
It combines the numerical value of the principal quantum number, the lowercase letter notation for the
azimuthal number, and a superscript showing the number of electrons in each orbital.
For an atomic number of 32: The electronic configuration is 1s 22s22p63s23p6 3d104s2p2

Valence – of an atom is related to the ability of the atom to enter into chemical combination w/ other
elements and is often determined by the number of electrons in the outermost combined sp level.
Mg: 1s22s22p63s2 ; valence = 2
2 2 6 2 1
Al: 1s 2s 2p 3s 3p ; valence = 3
Valence – also depends on the nature of the chemical reaction.

Atomic Stability and Electronegativity

Electronegativity – describes the tendency of an atom to gain an electron.
Atoms with almost completely filled outer energy levels (such as Cl) are strongly negative and readily
accept electrons. High atomic number elements have low electronegativity because the outer elements
are at a greater distance from the positive nucleus. Electrons are not as strongly attracted to the atom.

Electropositivity – describes the tendency of an atom to give up electrons.

Atoms with nearly empty outer levels (Na), readily give up electrons and are strongly electropositive.

Atomic Bonding:
There are four important mechanisms by which atoms are bonded in solids.
1. Ionic Bond – bond between an electropositive & an electronegative atom.
The electropositive atom donates its electrons & the electronegative atom accepts the electrons filling its
outer energy shell. The atom that contributes the electrons is left with a net positive charge and is a cation,
while the atom that accepts the electrons acquires a net negative charge and is an anion. The oppositely
charged ions are now attracted to each other and produce the ionic bond. The ionic bond has no
directionality.

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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

Attraction between sodium and chloride ions producing NaCl

Because the electrons are localized, the electrical conductivity is relatively

poor. When voltage is applied to an ionic material, the entire ions must
move to cause a current to flow. Ion movement is slow and the electrical
conductivity is poor. The bonding energy is relatively high, thus high melting
materials are expected. Ceramics are examples of materials with ionic
bonding. Ceramics are very brittle but are good insulators. These are used
effectively to sustain high temperature environments, & as insulators &
dielectrics.

2. Covalent Bond – results when electrons are equally shared by the atoms in a molecule.
Covalent bonding requires that electrons be shared between atoms in such a way that each atom has its outer sp
orbital filled. The shared electron is considered to belong to both atoms. The number of covalent bonds
possible for a particular atom is determined by the number of valence electrons. Covalent bond is directional,
i.e., it is between specific atoms & may exist only in the direction between one atom & another that participates in
the electron sharing. This bond is common to non-metallic elemental molecules as well as molecules containing
dissimilar atoms. It is also found in elemental solids such as diamond.

Covalent bonds in Silicon Atoms

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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

Covalent bonds can be very strong as in diamond with a very high melting point (>3550 oC) but it can also be as
weal as bismuth with a low melting point (270 oC). Materials with this type of bond have poor ductility, poor
electrical conductivity, and poor thermal conductivity but they can be good insulators. For an electron to move
and carry a current, the covalent bond must be broken, requiring high temperatures or voltages. Silicon exhibit
some conductivity only at high temperature and it is called semiconductor. The electrical conductivity of silicon in
IC comes from impurities or “dopants” purposely added to it. Polymeric materials are also covalently bonded and
they are as brittle as solids. Ceramic materials based on the silicates and advance ceramics are all covalently
bonded. The yare used for their hardness, wear & temperature resistance properties.

3. Metallic bond – the final primary bond type found in metal alloys.
The metallic elements w/c have a low electronegativity give up their valence electrons to form a “sea” of electrons
surrounding the atoms. The valence electrons move freely within the electron sea and become associated with
several atom cores. The positively charged atom cores are held together by mutual attraction to the electron,
thus producing a strong metallic bond.

The valence electrons form a sea of electrons

Because their electrons are not fixed in any position, metals are good electrical conductors. Under the influence
of an applied voltage, the valence electrons move, causing a current to flow if the circuit is complete.

electrons in the electron sea can easily move & carry a current

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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

The “free flowing electrons” are responsible for the extremely good electrical and thermal conductivities of
metals. It also explains the optical opacity & reflectivity of metals. The oscillation of the free electrons absorbs
the energy of the incident light at all wavelengths & thus makes the metal opaque. The oscillating electrons also
emit light waves (photons) & gives metal reflectivity. The unsaturated bonding in metals also explains the close-
packing of atoms, their alloying properties, & the superior mechanical properties of toughness & ductility w/
sufficient strength. Metals are closely packed, the reason why they have higher densities compared to ionically &
covalently bonded materials. The free electrons are not also sensitive to what type of positive core they are
bonded to, so that the positive core can be substituted with other types (substitutional or solid solution or
alloying).
In addition, the electrons are not confined to particular sires & the positive cores can be moved apart for some
distance without breaking the bond. This makes the metal ductile.
Also metals have sufficient strength & toughness that owe to their dominant use in engineering applications.

4. Van der Waals Bonds – bonds that join molecules or groups of atoms by weak electrostatic attraction.
Many plastics, ceramics, water and other molecules are permanently polarized. Some portions of the molecule
are positively charged while the other portions are negatively charged. The electrostatic attraction between the
positively charged regions of one molecule and the negatively charged regions of a second molecule weakly
bonds the two molecules together. Van der Waals bonding is a secondary bond, however the atoms within the
molecule (or group of atoms) are joined by strong covalent or ionic bonds. Heating water until it boils breaks the
Van der Waals bonds and converts the water to steam. However, much higher temperatures are required to
break the covalent bonds joining oxygen and hydrogen atoms in water. Van der Waals bonds can dramatically
change the properties of materials.

Example:
Polymers normally have covalent bonds, so it is expected that PVC plastics are very brittle, but this material
contains many long, chain-like molecules.

Within each chain, bonding is covalent, but the individual chains are bonded to one another by Van der
Waals bonds. PVC can be deformed by breaking the Van der Waals bonds, permitting the chains to slide
pas one another.

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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

Chains slide past one another when the Van der Waals bonds are broken.

5. Mixed Bonding: In most materials, bonding between atoms is a mixture of two or more types.
Example: Fe is bonded by a combination of metallic and covalent bonding which prevents atoms from packing
as efficiently as expected.
Compounds formed from two or more metals may be bonded by a mixture f metallic ionic bonds, particularly
when there is a large difference in electronegativity between the elements. Many ceramics and semiconducting
compounds (combinations of metallic & non-metallic cmpds), have a mixture of covalent & ionic bonding. As the
electronegativity difference between the atoms increases, the atomic bonding becomes more ionic. The fraction
of covalent bonding can also be estimated.

BONDING ENERGY AND INTERATOMICSPACING

Interatomic spacing – is the equilibrium distance between atoms caused by a balance between repulsive and
attractive forces.
In the metallic bond, the attraction between the electrons and the atom core is balanced by the repulsion
between the atom cores. Equilibrium separation occurs when the total energy of the pair of atoms is at a
minimum or when no net force is acting to either attract or repulse the atoms. The minimum energy is the
bonding energy

Bonding energy - is the energy required to create or break the bond.

Materials having a high bonding energy also have a high strength and a high melting temperature. Ionically
bonded materials have a high bonding energy because of the large difference in electronegativities between the
ions. Metals have lower bonding energies, because the electronegativities of the atoms are similar. The higher
the bonding energy, the more negative E is, the higher are the melting point & the modulus of elasticity while the
thermal expansion decreases.

Two Types of Forces:

Attractive force, FA is a long range positive electrostatic (Coulombic) attractive force, that exist when
there is chemical affinity, bringing the atoms very close together.
Repulsive force, FB is a negative repulsive force, due to the mutual repulsion of the electrons.
Net bonding force, FN is the sum of the attractive & repulsive forces that is, F N = FA + FR. At equilibrium,
FA + FR = 0.
Mathematically, Energy and Force are related by:
E = F dr where r is the distance
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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

For atomic systems,

E =  FN dr =  FA dr +  FR dr ; E = EA + ER

Where EN, EA, ER are respectively the net, attractive, and repulsive energies for 2 isolated & adjacent
rooms. The attractive energy is negative and long-range. The repulsive energy is short-range & arises
when the electron clouds of the two atoms begin to overlap.
The total energy is the sum of the attractive and the repulsive energies; E N = EA + ER

atoms are separated by an equilibrium spacing that corresponds to the bonding energy of the atoms or ions.

The force distance curve for two materials

This shows the relationship between atomic bonding and the modulus of elasticity. A steep dF/da slope gives a high
modulus.

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Notes in ChE 324
Prepared: Engr. Brenda T. Domingo Coloma, ChE

The energy separation curve for two atoms

Materials that display a steep curve w/ a deep trough have low linear coefficients of thermal expansion. Coefficient of
thermal expansion describes how much a material expands or contracts when its temperature is changed. It is also
related to the strength of the atomic bonds.