Atomic Structure and

Interatomic Bonding
Atomic Structure and Interatomic Bonding

charge magnitude of electron

1.60 x 10-19 C
mass of protons and neutrons
approximately
1.67 x 10-27 kg
mass of an electron
9.11 x 10-31 kg.
 Atomic Structure and Interatomic Bonding

Each chemical element is characterized by the

number of protons in the nucleus, or the
atomic number (Z)
For an electrically neutral or complete atom, the
atomic number also equals the number of
electrons.
The atomic mass (A) of a specific atom may be
expressed as the sum of the masses of protons
and neutrons within the nucleus.
Thus atoms of some elements have two or more
different atomic masses, which are called
isotopes.
 Atomic Structure and Interatomic Bonding

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 for
computations of atomic weight.
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.
 Atomic Structure and Interatomic Bonding

In one mole of a substance there are 6.023 x

10-23 (Avogadro’s number) atoms or molecules.
These two atomic weight schemes are related
through the following equation:
1 amu/atom (or molecule) 1 g/mol
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
ATOMIC MODELS
During the latter part of the nineteenth century it
was realized that many phenomena involving
electrons in solids could not be explained in terms
of classical mechanics. What followed was the
establishment of a set of principles and laws that
govern systems of atomic and subatomic entities
that came to be known as quantum
mechanics.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
One early outgrowth of
quantum mechanics
was the simplified Bohr
atomic model, in which
electrons are assumed
to revolve around the
atomic nucleus in
discrete orbitals, and the
position of any particular
electron is more or less
well defined in terms of
its orbital.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
The electrons are arranged
in a particular pattern - for
example, in a diagram like
this one for sodium:"
The circles are NOT orbits. The electrons are NOT moving
around the nucleus along the circles.
The circles represent energy levels. The electrons on the
circle closest to the nucleus have the lowest energy. The
eight electrons on the next circle have a higher energy,
and the one on the outer circle has the highest energy.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
Another important quantum-mechanical principle
stipulates that the energies of electrons are
quantized; that is, electrons are permitted to have
only specific values of energy. 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). Often, it is convenient
to think of these allowed electron energies as
being associated with energy levels or states.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
This Bohr model was eventually found to have some
significant limitations because of its inability to explain
several phenomena involving electrons. A resolution
was reached with a wave-mechanical model, in which
the electron is considered to exhibit both wavelike and
particle-like characteristics. With this model, an electron is
no longer treated as a particle moving in a discrete orbital;
but rather, position is considered to be the probability of an
electron’s being at various locations around the nucleus. In
other words, position is described by a probability
distribution or electron cloud.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
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’sprobability density are specified by three of
these quantum numbers. Furthermore, 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, . . .
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
noted that this quantum number, and it only, is also
associated with the Bohr model. This quantum number is
related to the distance of an electron from the nucleus, or its
position. The second quantum number, l, signifies the
subshell, which is denoted by a lowercase letter—an s, p, d,
or f ; it is related to the shape of the electron subshell. In
addition, the number of these subshells is restricted by the
magnitude of n. Associated with each electron is a spin
moment, which must be oriented either up or down. Related
to this spin moment is the fourth quantum number, ms , for
which two values are possible ( +1/2 and -1/2), one for each
of the spin orientations.
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
The preceding discussion has dealt primarily with
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
 Atomic Structure and Interatomic Bonding

ELECTRONS IN ATOMS
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.
 Atomic Structure and Interatomic Bonding

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 that are
arrayed in a given column or group have similar
valence electron structures, as well as chemical
and physical properties. These properties change
gradually and systematically, moving horizontally
across each period
 Atomic Structure and Interatomic Bonding

THE PERIODIC TABLE

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. The alkali and the alkaline earth metals
(Li, Na, K, Be, Mg, Ca, etc.) are labeled as Groups IA and
IIA, having, respectively, one and two electrons in
excess of stable structures.
 Atomic Structure and Interatomic Bonding

THE PERIODIC TABLE

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 nonmetals by virtue of their valence
electron structures.
Periodic Trends for Electronegativity

Electronegativity is a chemical property that describes an

atom's ability of attracting and binding to electrons. Since
electronegativity describes a largely qualitative property,
there is no standardized method of calculating
electronegativity. However, the scale that most chemists use
in quantifying electronegativity is the Pauling Scale, named
after the chemist Linus Pauling. The numbers assigned by the
Pauling scale are dimensionless due to electronegativity being
largely qualitative.
As you move to the right across a period of elements, electronegativity
increases. When the valence shell of an atom is less than half full, it requires
less energy to lose an electron than gain one and thus, it is easier to lose an
electron. Conversely, when the valence shell is more than half full, it is easier to
pull an electron into the valence shell than to donate one.

As you move down a group, electronegativity decreases. This is because the
atomic number increases down a group and thus there is an increased distance
between the valence electrons and nucleus, or a greater atomic radius.

Important exceptions of the above rules include the noble gases, lanthanides,
and actinides. The noble gases possess a complete valence shell and do not
usually attract electrons. The lanthanides and actinides possess a more
complicated chemistry that does not generally follow any trends. Therefore,
noble gases, lanthanides, and actinides do not have electronegativity values.

As for the transition metals, while they have values, there is little variance
among them as you move across the period and up and down a group. This is
because of their metaliic properties that affect their ability to attract electrons
as easily as the other elements.
Periodic Trends for Ionization Energy

Ionization Energy is the amount of energy required to remove an

electron from a neutral atom in its gaseous phase. Conceptually,
ionization energy is considered the opposite of electronegativity. The
lower this energy is, the more readily the atom becomes a cation.
Therefore, the higher this energy is, the more unlikely the atom
becomes a cation. Generally, elements on the right side of the periodic
table have a higher ionization energy because their valence shell is
nearly filled. Elements on the left side of the periodic table have low
ionization energies because of their willingness to lose electrons and
become cations.
The ionization energy of the elements within a period
generally increases from left to right. This is due to valence
shell stability.
The ionization energy of the elements within a group
generally decreases from top to bottom. This is due to
electron shielding.
The noble gases possess very high ionization energies
because of their full valence shell as indicated in the graph.
Note that Helium has the highest ionization energy of all the
elements.
Periodic Trends for Electron Affinity
Like the name suggests, electron affinity describes the ability of an atom to accept
an electron. Unlike electronegativity, electron affinity is a quantitative measure that
measures the energy change that occurs when an electron is added to a neutral gas
atom. When measuring electron affinity, the more negative the value, the more of an
affinity to electrons that atom has.

Electron affinity generally decreases down a group of elements because each

atom is larger than the atom above it (this is the atomic radius trend, which will be
discussed later in this text). This means that an added electron is further away from
the atom's nucleus compared to its position in the smaller atom. With a larger distance
between the negatively-charged electron and the positively-charged nucleus, the force
of attraction is relatively weaker. Therefore, electron affinity decreases. Moving from
left to right across a period, atoms become smaller as the forces of attraction become
stronger. This causes the electron to move closer to the nucleus, thus increasing the
electron affinity from left to right across a period.
Electron affinity increases from left to right within a period. This is
caused by the decrease in atomic radius.
Electron affinity decreases from top to bottom within a group. This is
caused by the increase in atomic radius.
 ATOMIC RADIUS

Measures of atomic radius

Unlike a ball, an atom doesn't have a fixed radius. The
radius of an atom can only be found by measuring the
distance between the nuclei of two touching atoms, and
then halving that distance.
Atomic radius decreases from left to right within a period. This is caused by
the increase in the number of protons and electrons across a period. One
proton has a greater effect than one electron; thus, a lot of electrons will get
pulled towards the nucleus, resulting in a smaller radius.
Atomic radius increases from top to bottom within a group. This is caused by
electron shielding.        
Periodic Trends for Melting Point

Melting points are the amount of energy required to break

a bond(s) to change the solid phase of a substance to a liquid.
Generally, the stronger the bonds between the atoms of
an element, the higher the energy requirement in breaking
that bond. Since temperature is directly proportional to
energy, a high bond dissociation energy correlates to a high
temperature. Melting points are varied and don't generally
form a distinguishable trend across the periodic table.
Metals generally possess a high melting point.
Most non-metals possess low melting points.
The non-metal carbon possesses the highest boiling point of all the
elements. The semi-metal boron also possesses a high melting point.
Periodic Trends for Metallic Character

How easily an atom can lose an electron is a measure of an element's

metallic character.

As you move from right to left across a period, metallic character

increases because the attraction between valence electron and the
nucleus is weaker, thus enabling an easier loss of electrons.

Metallic character increases as you move down a group because the

atomic size is increasing . When the atomic size increases, the outer
shells are farther away. The principle quantum number increases and
average electron density moves farther from nucleus. The electrons of
the valence shell have less of an attraction to the nucleus and, as a
result, can lose electrons more readily, causing an increase in metallic
character.
Metallic characteristics decrease from left to right across a period. This is
caused by the decrease in radius (above it is stated that Zeff causes this)of the
atom which allows the outer electrons to ionize more readily.
Metallic characteristics increase down a group. Electron shielding causes the
atomic radius to increase thus the outer electrons ionizes more readily than
electrons in smaller atoms.
Metallic character relates to the ability to lose electrons, and nonmetallic
character relates to the ability to gain electrons.
 Atomic Structure and Interatomic Bonding

PRIMARY INTERATOMIC BONDS

IONIC BONDING
Perhaps ionic bonding is the easiest to describe and
visualize. It 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, in addition, an electrical charge; that is,
they become ions.
 Atomic Structure and Interatomic Bonding

PRIMARY INTERATOMIC BONDS

COVALENT BONDING
In covalent bonding stable electron 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.
 Atomic Structure and Interatomic Bonding

PRIMARY INTERATOMIC BONDS

METALLIC BONDING
Metallic bonding, the final primary bonding type, is found in
metals and their alloys. A relatively simple model has been
proposed that very nearly approximates the bonding
scheme. 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.
 Atomic Structure and Interatomic Bonding

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 stableelectron structures, and, in addition,
between molecules in molecular structures that are
covalently bonded.
 Atomic Structure and Interatomic Bonding

SECONDARY BONDING
OR VAN DER WAALS BONDING

Secondary bonding forces arise from atomic or

molecular dipoles. In essence, 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,
 Atomic Structure and Interatomic Bonding

SECONDARY BONDING
OR VAN DER WAALS BONDING
FLUCTUATING INDUCED DIPOLE BONDS
A dipole may be created or induced in an atom or molecule
that is normally electrically symmetric; that is, the overall
spatial distribution of the electrons is symmetric with respect
to the positively charged nucleus.
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.
 Atomic Structure and Interatomic Bonding

MOLECULES
At the conclusion of this chapter, let us take a moment to
discuss the concept of a molecule in terms of solid
materials. A molecule may be defined as a group of atoms
that are bonded together by strong primary bonds. Within this
context, the entirety of ionic and metallically bonded solid
specimens may be considered as a single molecule.
However, this is not the case for many substances in which
covalent bonding predominates; these include elemental
diatomic molecules (F2, O2, H2 , etc.) as well as a host of
compounds (H2O, CO2 , HNO3, C6H6, CH4 , etc.).
 Atomic Structure and Interatomic Bonding

MOLECULES
In the condensed liquid and solid states, bonds between
molecules are weak secondary ones. Consequently,
molecular materials have relatively low melting and boiling
temperatures. Most of those that have small molecules
composed of a few atoms are gases at ordinary, or ambient,
temperatures and pressures. 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.