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Atomic Structure &

Interatomic Bonding
Dr. Mamdouh Salem

References: most of the figures are from:

• “Materials Science and Engineering, An Introduction”, Callister et al.
• “The science and Engineering of Materials”, Askeland et al.
Cairo University – Faculty of Engineering Dr. Mamdouh Salem 1

Introduction
• The type of bond allows us to explain the properties of materials.
• Consider carbon, which may exist as both graphite and diamond.

Graphite Diamond
Hardness Soft and has a The hardest known
“greasy” feel material
Electrical Reasonably good Poor conductor
Conductivity conductor

• The properties differences are directly attributable to the type of interatomic bonding.

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Atomic structure:
• Each atom consists of a very small nucleus composed of protons
and neutrons, which is encircled by moving electrons.
• Both electrons and protons are electrically charged (1.602×10!"#
C), where neutrons are electrically neutral.
• The mass of protons and neutrons is almost 1.67×10!$%kg, while
the electron mass is almost 9.11×10!&"kg.

• The atomic number (Z): the number of protons in the nucleus.

• For an electrically neutral or complete atom, the atomic number
also equals the number of electrons.
• The atomic number ranges in integral units from 1 for hydrogen
to 92 for uranium.

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Atomic structure:
• The atomic mass (A): the sum of masses of protons and neutrons in the nucleus.
• Atoms having the same atomic number (number of protons) but different atomic mass
(different number of neutrons “N”) are called isotopes.
• The atomic weight of an element corresponds to the weighted average of the atomic
masses of the atom’s naturally occurring isotopes.
• The atomic mass unit (amu) is defined as "⁄"$ of the atomic mass of the most common
carbon isotope (carbon 12), for which A = 12.000.
• The masses of protons and neutrons are slightly greater than one amu.

• One mole of a substance contains 6.022×10$& (Avogadro’s number) atoms.

• The atomic weight is usually expressed as

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Electrons in atoms
• The behavior of electrons in atoms is discussed through quantum-
mechanical concepts.
• Bohr atomic model is one of the simplified quantum mechanics
models.
• In Bohr model:
• Electrons are assumed to revolve around the atomic nucleus in
discrete orbitals.
• The energies of electrons are quantized; that is, electrons are Schematic representation
permitted to have only specific values of energy. of the Bohr atom
• An electron may change energy, but in doing so it must make a
quantum jump either to an allowed higher energy (with absorption
of energy) or to a lower energy (with emission of energy).
• These are called energy levels or states.

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Electrons in atoms
• Bohr model was not able to explain several phenomena
involving electrons.
• An alternative model is the wave-mechanical model.
• An electron is no longer treated as a particle moving in
a discrete orbital; rather, position is considered to be the
probability of an electron’s being at various locations
around the nucleus.
• Electron position is described by a probability
distribution or electron cloud.
• The figure shows a comparison of the (a) Bohr and (b)
wave mechanical atom models in terms of electron
distribution.

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Quantum numbers
• Every electron in an atom is characterized by four parameters called quantum numbers.
• Bohr model was further refined by wave mechanics, in which the introduction of three
new quantum numbers gives rise to electron subshells within each shell.
• Shells are specified by the principal quantum number “n”, which may take on integral
values (1, 2, 3, 4, 5, .. ) or by the letters (K, L, M, N, O, ..).
• The second quantum number “l” signifies the subshell (s , p , d , or f). The number of
these subshells is restricted by the magnitude of “n”.
• The number of energy states for each subshell is determined by the third quantum
number “ml”. There are 1, 3, 5 and 7 energy states for subshells s, p , d , and f,
respectively.
• Associated with each electron is a spin moment, which must be oriented either up or
down, which is defined through the fourth quantum number “ms”.

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Quantum numbers

• The smaller the principal quantum number, the lower the energy level.
• Within each shell, the energy of a subshell level increases with the value of the
l quantum number.

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Quantum numbers
• Electrons fill the energy states according to the
order shown below.

Schematic representation of the relative

energies of the electrons for the various
https://openoregon.pressbooks.pub/gschemistry/chapter/6-4-electronic-
structure-of-atoms-electron-configurations/
shells and subshells.
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Electron configurations Schematic

representation of
• In regards to the manner in which the states the filled and
are filled with electrons, Pauli exclusion lowest unfilled
principle stipulates that: no two electrons may energy states for a
have the same four quantum numbers. sodium atom.
• This implies that each electron state can hold
no more than two electrons, which must have
opposite spins.
• The electrons fill up the lowest possible
energy states in the electron shells and
subshells, two electrons (having opposite
spins) per state.
• The number of electrons in each subshell is
indicated by a superscript after the shell–
subshell designation.

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Electron configurations
• Valence electrons are those that occupy the outermost shell. They are extremely
important since they participate in the bonding between atoms.
• When the states within the outermost or valence electron shell are completely filled,
the atom then have a stable electron configurations.
• Elements having stable electron configuration are the inert, or noble gases, which
are virtually unreactive chemically.
• Some atoms of the elements that have unfilled valence shells assume stable electron
configurations by gaining or losing electrons to form charged ions, or by sharing
electrons with other atoms.
• This is the basis for some chemical reactions, and also for atomic bonding in solids.

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The periodic table

• In the periodic table, the
elements are situated
with increasing atomic
number, in seven
horizontal rows called
periods.
• All elements arrayed in
a given column have
similar valence electron
structures.
• The properties change
gradually when moving
horizontally or
vertically.
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The periodic table

• Elements on the left are
termed electropositive
elements, they give up their
few valence electrons to
become positively charged
ions.

• Elements situated on the • The figure shows the electronegativity values for
right-hand side of the table
various elements arranged in the periodic table.
are electronegative, they
readily accept electrons to • The electronegativity increases in moving from left to
form negatively charged right and from bottom to top.
ions. • Atoms are more likely to accept electrons if their outer
shells are almost full and if they are less “shielded”
from the nucleus.
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Atomic bonding in solids:

• Consider two isolated atoms that are brought together from a very large distance.

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Binding forces and energies:

• When the two atoms are separated by a very large distance, no forces exist between them.
• As the two atoms get closer, attractive force (𝐹' ) arises between he two atoms.
• When the two atoms become very close, a repulsive force (𝐹( ) arises due to the electron
cloud around the nucleus.
• The net force (𝐹) = 𝐹' + 𝐹( ) is zero at a distance (𝑟*), where the two atoms are in
equilibrium.
• For many atoms, 𝑟*~0.3 nm.
• At (𝑟*), the net potential energy is minimum, which is the bonding energy (E0) (the
energy required to separate these two atoms to an infinite separation).
• The bonding energy is higher in solids than fluids and is much smaller for gases.
• The equilibrium distance (𝑟*) may vary based on the surrounding atoms.

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Binding forces and energies r

• High binding energy implies that higher energy is needed in order to increase the
distance between the two atoms.
• Materials having high bonding energy (with –ve sign) will have:
• High the melting temperature: The distance between atoms increases as the material
transforms from solid to liquid. Accordingly, a material having high binding energy will
require more heat energy in order to increase the distance between atoms.
• High stiffness (high elastic modulus): Elastic deformation is carried out through
stretching the atomic bonds (increasing distance between atoms). More work is needed
to increase the distance between atoms for a material having high binding energy.
• Low coefficient of thermal expansion: Heating a material causes the distance between
atoms to increase, and therefore the material expands. Heating a material having high
binding energy will not cause the distance between atoms to increase significantly,
resulting in small thermal expansion (i.e. low coefficient of thermal expansion).
∆𝐿
= 𝛼 ∆𝑇
𝐿*
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Atomic bonding
• Primary bonding:
1. Ionic bonding.
2. Covalent bonding.
3. Metallic bonding.

o For each type, the bonding necessarily involves the valence electrons.
o Each of these three types of bonding arises from the tendency of the atoms to
assume stable electron structures, like those of the inert gases, by completely
filling the outermost electron shell.

• Secondary bonding: much weaker than primary bonding.

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Ionic bonding
• Always found in compounds that are composed of both
metallic and nonmetallic elements.
• Atoms of a metallic element easily give up their valence
electrons to the nonmetallic atoms.
• In the process all the atoms acquire stable or inert gas
configurations and, in addition, an electrical charge (they
become ions).
• The attractive bonding forces are coulombic; that is,
positive and negative ions, by virtue of their net electrical
charge, attract one another.
• Ionic bond is the predominant bonding in ceramic
materials.
• Ionic materials are hard and brittle, electrically and
thermally insulative.
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Covalent bonding
• Stable electron configurations are assumed by the sharing
of electrons between adjacent atoms.
• Two atoms that are covalently bonded will each contribute
at least one electron to the bond, and the shared electrons
may be considered to belong to both atoms.
• Many nonmetallic molecules are covalently bonded (H2,
CH4, H2O, …).
• This type of bonding is found in elemental solids such as
diamond (carbon), and other solid compounds of elements
located on the right-hand side of the periodic table.
• Covalent bonds may be very strong, as in diamond, or
very weak. Covalent bonds are directional.
• Polymeric materials have covalent bonding.
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Partial ionic & covalent bonding

• It is possible to have interatomic bonds that are partially ionic and partially covalent.
• The degree of either bond type depends on the relative positions of the constituent
atoms in the periodic table (the difference in their electronegativities).
• The wider the separation from the lower left to the upper right-hand corner (more
difference in electronegativity), the more ionic the bond is.
• The percent ionic character (%IC) of a bond between elements A and B (A being the
most electronegative) may be approximated by the expression.

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Metallic bonding
• Metallic materials have one, two, or at most, three valence
electrons.
• These valence electrons are not bound to any particular atom
in the solid and are more or less free to drift throughout the
entire metal (“sea of electrons” or an “electron cloud”).
• The remaining non-valence electrons and atomic nuclei form
what are called ion cores, which possess a net positive charge.
• The free electrons shield the positively charged ion cores
from mutually repulsive electrostatic forces.
• The free electrons act as a “glue” to hold the ion cores
together.
• The metallic bond is nondirectional.

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Secondary (van der Waals) bonding

• Secondary, van der Waals, bonds are weak in comparison to the primary bonds.

• Secondary bonding exists between molecules in molecular structures that are

covalently bonded.

• Secondary bonding forces arise from atomic or molecular dipoles that exist whenever
there is some separation of positive and negative portions of an atom or molecule.

• The bonding results from the coulombic attraction between the positive end of one
dipole and the negative region of an adjacent one.

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Fluctuating induced dipole bonds

• Atoms experience constant vibrational motion that can cause
instantaneous distortions of the electrical symmetry for some atoms
or molecules, creating small electric dipoles.

• One of these dipoles can in turn produce a displacement of the

electron distribution of an adjacent molecule or atom, which
induces the second one also to become a dipole that is then weakly
attracted or bonded to the first.

• The liquefaction and, in some cases, the solidification of the inert

gases and other electrically neutral and symmetric molecules such
as H2 and Cl2 are realized because of this type of bonding.
• This bond is the weakest among other types of bonds.
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Polar molecule-induced dipole bonds

• Permanent dipole moments exist in some molecules by virtue of
an asymmetrical arrangement of positively and negatively
charged regions (polar molecules).

• For a hydrogen chloride molecule, a permanent dipole moment

arises from net positive and negative charges that are
respectively associated with the hydrogen and chlorine ends of Schematic representation of a
polar hydrogen chloride (HCl)
the HCl molecule.
molecule.

• Polar molecules can also induce dipoles in adjacent nonpolar

molecules, and a bond will form as a result of attractive forces
between the two molecules.

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Permanent dipole bonds

• Van der Waals forces will also exist between adjacent polar
molecules, which have bonding energies significantly greater
than for bonds involving induced dipoles.
• The strongest secondary bonding type, the hydrogen bond, is a Schematic representation of
special case of polar molecule bonding. hydrogen bonding in
• It occurs between molecules in which hydrogen is covalently hydrogen fluoride (HF).
bonded to fluorine (as in HF), oxygen (as in H2O), and
nitrogen (as in NH3 ).
• For each H—F, H—O, or H—N bond, the single hydrogen
electron is shared with the other atom, and the hydrogen end
of the bond is essentially a positively charged bare proton that
is unscreened by any electrons.
• This highly positively charged end of the molecule is capable
of a strong attractive force with the negative end of an adjacent
molecule
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