Engg 1021
FUNDAMENTALS OF MATERIAL
SCIENCE AND ENGINEERING
1
MODULE 2
ATOMIC STRUCTURE AND
INTERATOMIC BONDING
2
DID YOU KNOW….
The secret to this remarkable ability is the presence
of an extremely large number of microscopically small
hairs on each of their toe pads. When these hairs
come in contact with a surface, weak forces of
attraction (i.e., van der Waals forces) are established
between hair molecules and molecules on the surface.
WHY STUDY ATOMIC STRUCTURE AND
INTERATOMIC BONDING?
• An important reason to have an understanding of interatomic
bonding in solids is that in some instances, the type of bond allows
us to explain material properties.
• In the processing/structure/properties/performance scheme
– For silicon, its electron configuration determines the type of primary bonding,
which in turn affects its electron band structure.
– For polymer fibers, electron configurations of the constituent éléments affect
the type of primary bonding; bonding type has an influence on the structures
of polymer molecules.
ATOMIC STRUCTURE
• The Solar System model also called the Bohr model, after
Neils Bohr, who discovered electron shells in 1913.
Atoms = nucleus (protons and neutrons) +
electrons
FUNDAMENTAL CONCEPTS
• Each chemical element is characterized by the number of
protons in the atomic nucleus, or the atomic number (Z).
• For an electrically neutral or complete atom, the atomic
number also equals the number of electrons.
• This atomic number ranges in integral units from 1 for
hydrogen to 92 for uranium, the highest of the naturally
occurring elements.
FUNDAMENTAL CONCEPTS
• The atomic mass (A) of a specific atom may be
expressed as the sum of the masses of protons and
neutrons within the nucleus.
• Although the number of protons is the same for all
atoms of a given element, the number of neutrons (N)
may be variable. Thus, atoms of some elements have
two or more different atomic masses, which are called
isotopes.
FUNDAMENTAL CONCEPTS
• 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) may be used to compute atomic
weight. A scale has been established whereby
1 amu = 1/12 of the atomic mass of the most common isotope of
carbon, carbon 12 (12C) (A = 12.00000). Within this scheme, the
masses of protons and neutrons are slightly greater than unity, and
A ≈Z+N
FUNDAMENTAL CONCEPTS
• The atomic weight of an element or the molecular weight of a
compound may be specified on the basis of amu per atom
(molecule) or mass per mole of material.
• In one mole of a substance, there are
6.022 X 1023 (Avogadro’s number) atoms or molecules.
ELECTRONS IN ATOMS
• An understanding of the behavior of electrons in atoms
and crystalline solids necessarily involves the discussion
of quantum-mechanical concepts.
• Quantum mechanics - A branch of physics that deals
with atomic and subatomic systems; it allows only
discrete values of energy that are separated from one
another. By contrast, for classical mechanics, continuous
energy values are permissible.
BOHR ATOMIC MODEL
QUANTUM NUMBERS
• Using wave mechanics, every electron in an atom is characterized by
four parameters called quantum numbers. The size, shape, and
spatial orientation of an electron’s probability density are specified by
three of these quantum numbers.
• Bohr energy levels separate into electron subshells, and quantum
numbers dictate the number of states within each subshell. Shells are
specified by a principal quantum number n, which may take on integral
values beginning with unity; sometimes these shells are designated by
the letters K, L, M, N, O, and so on, which correspond, respectively, to n
= 1, 2, 3, 4, 5, . . . , as indicated in Table 2.1.
Principal
Visualizing Electron Orbitals
ELECTRON CONFIGURATIONS
• electron states - values of energy that are permitted for electrons
• To determine the manner in which these states are filled with
electrons, we use the Pauli exclusion principle, another quantum-
mechanical concept. This principle stipulates that each electron
state can hold no more than two electrons, which must have
opposite spins. Thus, s, p, d, and f subshells may each
accommodate, respectively, a total of 2, 6, 10, and 14 electrons;
ELECTRON CONFIGURATIONS
• When all the electrons occupy the lowest possible energies in
accord with the foregoing restrictions, an atom is said to be in its
ground state.
• The electron configuration or structure of an atom represents
the manner in which these states are occupied. In the
conventional notation the number of electrons in each subshell is
indicated by a superscript after the shell–subshell designation.
• Valence electrons are those that occupy the outermost shell.
These electrons are extremely important; they participate in
the bonding between atoms to form atomic and molecular
aggregates. Furthermore, many of the physical and chemical
properties of solids are based on these valence electrons.
• stable electron configurations - the states within the outermost or
valence electron shell are completely filled. (neon, argon,
krypton)
• Ne, Ar, Kr, and He are the inert, or noble gases, which are
virtually unreactive chemically.
Restrictions
•Pauli Exclusion Principle: In 1926, Wolfgang Pauli discovered that a set of quantum
numbers is specific to a certain electron. That is, no two electrons can have the same values
for n, l, ml, and ms. Although the first three quantum numbers identify a specific orbital and
may have the same values, the fourth is significant and must have opposite spins.
•Hund's Rule: Orbitals may have identical energy levels when they are of the same principal
shell. These orbitals are called degenerate, or "equal energy." According to Hund's Rule,
electrons fill orbitals one at a time. This means that when drawing electron configurations
using the model with the arrows, you must fill each shell with one electron each before
starting to pair them up. Remember that the charge of an electron is negative and electrons
repel each other. Electrons will try to create distance between it and other electrons by staying
unpaired. This further explains why the spins of electrons in an orbital are opposite.
•Heisenberg Uncertainty Principle: It is impossible to precisely measure the momentum
and position of an electron at the same time. As the momentum of the electron is more and
more certain, the position of the electron becomes less certain, and vice versa. This
helps explain integral quantum numbers and why n=2.5 cannot exist as a principal quantum
number. There must be an integral number of wavelengths (n) in order for an electron to
maintain a standing wave. If there were to be partial waves, the whole and partial waves
would cancel each other out and the particle would not move. If the particle was at rest, then
its position and momentum would be certain. Because this is not so, n must have an integral
value. It is not that the principal quantum number can only be measured in integral numbers,
it is because the crest of one wave will overlap with the trough of another, and the wave will
cancel out.
EXAMPLE
• Write the electron configuration of aluminum (Z = 13) in
ground state.
Al = 1 s 2 2 s 2 2 p6 3 s 2 3 p1
THE PERIODIC TABLE
• All the elements have been classified according to electron
configuration in the periodic table. Here, 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.
ELECTRONEGATIVITY
• Electronegativity - how willing atoms are to accept electrons
• Metals are electropositive – can give up their few valence
electrons to become positively charged ions
• Subshells with one electron - low electronegativity
• Subshells with one missing electron -high electronegativity
• Electronegativity increases from left to right
BONDING FORCES AND ENERGIES
• An understanding of many of the physical properties of materials
is enhanced by a knowledge of the interatomic forces that bind
the atoms together.
• Perhaps the principles of atomic bonding are best illustrated by
considering how two isolated atoms interact as they are brought
close together from an infinite separation. At large distances,
interactions are negligible, because the atoms are too far apart
to have an influence on each other; however, at small separation
distances, each atom exerts forces on the other. These forces are
of two types, attractive (FA) and repulsive (FR), and the magnitude
of each depends on the separation or interatomic distance (r);
PRIMARY BONDING
• Three different types of primary or chemical bond are
found in solids - ionic, covalent, and metallic.
• 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
Primary Bonding: e- are transferred or shared
SECONDARY BONDING
• Secondary or physical forces and energies are also
found in many solid materials
• they are weaker than the primary ones, but nonetheless
influence the physical properties of some materials
Secondary Bonding: no e- transferred or shared
PRIMARY INTERATOMIC BONDS
IONIC BONDING
• Ionic bonding is always found in compounds that are
composed of both metallic and nonmetallic elements, elements
that are situated at the horizontal extremities of the periodic
table.
• 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 an electrical charge, they become ions.
Sodium chloride (NaCl) is the classic ionic material.
Coulombic -- positive
and negative ions, by
virtue of their net
electrical charge, attract
one another.
Strong Coulombic interaction between a
positive atom (lost an electron, Na+) and a
negative atom (an extra electron, Cl-)
IONIC BONDING
• Ionic bonding is termed nondirectional---the magnitude of
the bond is equal in all directions around an ion.
• It follows that for ionic materials to be stable, all
positive ions must have as nearest neighbors negatively
charged ions in a three-dimensional scheme, and vice
versa. The predominant bonding in ceramic materials is
ionic.
PROPERTIES OF IONIC COMPOUNDS
• Ionic materials are characteristically hard and brittle
and, electrically and thermally insulative.
• Mutual ionization by electron transfer
Anion = negatively charged atom
• Cation = positively charged atom
COVALENT BONDING
• In covalent bonding, stable electron configurations are
assumed by the sharing of electrons between adjacent
atoms.
• HIGHLY directional in the direction of the greatest
orbital overlap
• The carbon atom has four valence
electrons, whereas each of the four
hydrogen atoms has a single valence
electron. Each hydrogen atom can acquire
a helium electron configuration (two 1s
valence electrons) when the carbon atom
shares with it one electron.
• The carbon now has four additional
shared electrons, one from each
hydrogen, for a total of eight valence
electrons, and the electron structure of
neon. The covalent bond is directional;
that is, it is between specific atoms and
may exist only in the direction between
one atom and another that participates in
the electron sharing.
Diamond is simply the three-dimensional
interconnecting structure wherein each carbon atom
covalently bonds with four other carbon atoms
METALLIC BONDING
• Metallic bonding, (nondirectional in character ) the final primary bonding
type, is found in metals and their alloys.
• Metallic materials have one, two, or at most, three valence electrons. With
this model, 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.
They may be thought of as belonging to the metal as a whole, or forming a
“sea of electrons” or an “electron cloud.”
• The remaining nonvalence electrons and atomic nuclei form what are called
ion cores, which possess a net positive charge equal in magnitude to the total
valence electron charge per atom.
The free electrons shield the positively charged ion cores
from mutually repulsive electrostatic forces, which they
would otherwise exert upon one another. These free
electrons act as a “glue” to hold the ion cores together.
SECONDARY BONDING OR VAN
DER WAALS BONDING
• Secondary, van der Waals, or physical bonds are weak in
comparison to the primary or chemical ones; bonding energies
are typically on the order of only 10 kJ/mol (0.1 eV/atom).
• Secondary bonding exists between virtually all atoms or
molecules, but its presence may be obscured if any of the three
primary bonding types is present.
• Secondary bonding is evidenced for the inert gases, which have
stable electron structures, and between molecules in molecular
structures that are covalently bonded.
• Secondary bonding forces arise from atomic or molecular dipoles.
• An electric dipole exists 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, as indicated in
Figure 2.12. Dipole interactions occur between induced dipoles,
between induced dipoles and polar molecules (which have permanent
dipoles), and between polar molecules.
• Hydrogen bonding, a special type of secondary bonding, is found
to exist between some molecules that have hydrogen as one of the
constituents.
FLUCTUATING INDUCED DIPOLE BONDS
• A dipole may be created or induced in an atom or
molecule that is normally electrically symmetric---the
overall spatial distribution of the electrons is symmetric
with respect to the positively charged nucleus.
An electrically symmetric
atom (no dipole)
Van der Waals bonding – because of short-lived
distortions, small electric dipoles are created. 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 weakly
attracted or bonded to the first.
an induced
atomic dipole
POLAR MOLECULE-INDUCED DIPOLE BONDS
• Permanent dipole moments exist in some molecules by virtue of an
asymmetrical arrangement of positively and negatively charged regions.
Such molecules are termed polar molecules.
• A permanent dipole moment arises from net positive and negative charges
that are respectively associated with the hydrogen and chlorine ends of the
HCl 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. Furthermore, the magnitude of this bond will be greater than
for fluctuating induced dipoles.
polar molecule
PERMANENT DIPOLE BONDS
• The strongest secondary bonding type, the hydrogen bond, is a special case of
polar molecule bonding.
• It occurs between molecules in which hydrogen is covalently 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. Thus, the
hydrogen end of the bond is essentially a positively charged bare proton that is
unscreened by any electrons
• Melting and boiling temperatures for hydrogen fluoride and water are
abnormally high in light of their low molecular weights, as a consequence of
hydrogen bonding.
WATER UNIQUENESS
• Upon freezing, most substances experience
an increase in density (or, correspondingly, a
decrease in volume). One exception is water,
which exhibits the anomalous and familiar
expansion upon freezing—approximately 9
volume percent expansion. This behavior may
be explained on the basis of hydrogen
bonding.
• Each H2O molecule has two hydrogen atoms
that can bond to oxygen atoms; in addition,
its single O atom can bond to two hydrogen
atoms of other H2O molecules. Thus, for solid
ice, each water molecule participates in four
hydrogen bonds.
Upon melting, this structure
is partially destroyed, such
that the water molecules
become more closely
packed together. At room
temperature the average
number of nearest-neighbor
water molecules has
increased to approximately
4.5, this leads to an increase
in density.
• Consequences of this anomalous freezing phenomenon are
familiar. This phenomenon explains why icebergs float; why,
in cold climates, it is necessary to add antifreeze to an
automobile’s cooling system (to keep the engine block from
cracking); and why freeze–thaw cycles break up the
pavement in streets and cause pot holes to form.
MOLECULES
• Many of the common molecules are composed of groups of
atoms that are bound together by strong covalent bonds
• These include elemental diatomic molecules (F2, O2, H2, etc.) as
well as a host of compounds (H2O, CO2, HNO3, C6H6, CH4, etc.).
In the condensed liquid and solid states, bonds between
molecules are weak secondary ones. Consequently, molecular
materials have relatively low melting and boiling temperatures.
• On the other hand, many of the modern polymers, being
molecular materials composed of extremely large molecules,
exist as solids; some of their properties are strongly dependent
on the presence of van der Waals and hydrogen secondary
bonds.
HOMEWORK
Identify one general type of traditional or advanced
material, then determine the type of bonds present in that
material. Provide evidences of the bond presence. Write
your output in a one-page short-sized bondpaper and
submit next meeting.
END OF MODULE 2