Inorganic Chemistry I | Dr. Nyamato G.S.

Inorganic Chemistry I
Course Content: Early theories of the atom (Thomson’s model, Rutherford’s model, Bohr’s
model and the hydrogen spectra); Particle-wave duality of matter; Qualitative treatment of the
Schrodinger equation in deduction of s, p, d, f orbitals; The Aufbau Principle, Pauli exclusion
principle, Hund’s rule and the building up of the periodic table; Groups and periods of the periodic
table; the periodic table and electron configuration. The Mole concept and balancing of ionic
(redox) equations. Electronegativity, electron affinity, ionization energy; nature of ionic and
covalent compounds-as influenced by these factors. Hybridization of atomic orbitals and shapes
of simple molecules and ions; Common oxidation states of the elements; naturally occurring and
artificially made isotopes and their applications.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

The Early Theories of the Atomic Structure

The first clear atomic hypothesis for the existence of atoms was presented in 1803 by John
Dalton (1766-1844). He suggested that:
1. All matter is composed of extremely small particles called atoms.
2. Atoms cannot be created nor destroyed-in a chemical reaction, atoms of different
elements are separated, joined or rearranged. They are never changed into atoms
of another element.
3. All atoms of the same element are alike and different from those of any other
element.
4. A compound is a specific combination of atoms of more than one element.
Towards the end of the 19th century, it was realized that the atom is not indivisible but
consists of a number of sub-atomic particles. In 1897, J.J. Thomson (1856-1940) discovered the
electron by experimenting with the cathode ray tube (is a tube that has a piece of metal, called an
electrode, at each end. Each electrode is connected to a power source)-the bulky electronic part of
an old television sets. When the power is turned on, the electrodes become charged and produce a
stream of charged particles which travel from the cathode to the anode. Thomson used the cathode
ray tube with a magnet and discovered that the green beam it produced was made up of negatively
charged material. He performed a number of experiments and found that the mass of one of these
particles was almost 2,000 times lighter than a hydrogen atom. Thus, it was determined that atoms
contain electrons and since the atom was neutral, it was suggested that besides electrons, an atom
also contained positive charges.
In 1904, Thomson suggested that an atom consisted of a uniform positive sphere of matter
on which electrons were embedded. This became to be known as the “plum budding” model of the
atom.
In 1910, Ernest Rutherford (1871-1937) did some experiments on Thomson’s plum
budding model. The members of his lab fired a beam of positively charged particles called alpha
particles at a very thin sheet of gold foil. It was observed that almost all the alpha particles passed
directly through the foil without deflection. Although the explanation for these results was not
immediately obvious, the findings were clearly inconsistent with Thomson’s model.
By 1911, Rutherford was able to explain these observations. According to him, the greater
part of the mass of an atom is concentrated in the part he called the nucleus. He postulated further

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 Inorganic Chemistry I | Dr. Nyamato G.S.

that most of the total volume of an atom is empty space in which electrons move around the
nucleus. Thus, most of alpha particles passed through the foil because they did not encounter the
minute nucleus of any gold foil atom. Occasionally, however, an alpha particle came close to a
gold nucleus and the repulsion between the highly charged gold nucleus and the alpha particles
was strong enough to deflect the less massive alpha particle.
To explain his observations, Rutherford developed a new model of the structure of the
atom. According to Rutherford, the electrons move about the nucleus in fixed orbits like planets
revolving around the sun. According to classical physics, however, an electrically charged particle,
such as an electron, moving in a circular path should continuously lose energy by emitting
electromagnetic radiation. Hence, as the electron loses energy, it should spiral into the positively
charged nucleus. This spiraling obviously does not occur since hydrogen atoms are stable. So, how
can we explain this apparent violation of the laws of physics?

Quantization of Energy
When solids are heated, they emit radiation, as seen in the red glow of an electric stove
burner and the bright white light of a tungsten lightbulb. The wavelength distribution of the
radiation depends on temperature; a red-hot object is cooler than a white-hot one.
During the late 1800s, a number of physicists were studying this phenomenon, trying to
understand the relationship between the temperature
and the intensity and wavelengths of the emitted
radiation. The prevailing laws of physics could not
account for the observations. 1n 1900 a German
physicist named Max Planck (1858-1947) solved the
problem by assuming that energy can be either
released or absorbed by atoms only in discrete
"chunks" of some minimum size. Planck gave the
name quantum (meaning "fixed amount") to the
smallest quantity of energy that can be emitted or
absorbed as electromagnetic radiation. He proposed
that the energy, E, of a single quantum equals a
constant times the frequency of the radiation:

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 Inorganic Chemistry I | Dr. Nyamato G.S.

E = hν
Where, h is called Planck's constant and has a value of 6.626 X 10-34 joule-second (J-s).
According to Planck's theory, matter is allowed to emit and absorb energy only in whole-
number multiples of hν, such as hν, 2hν, 3hν, and so forth. Because the energy can be released only
in specific amounts, we say that the allowed energies are quantized-their values are restricted to
certain quantities. Planck's revolutionary proposal that energy is quantized was proved correct, and
he was awarded the 1918 Nobel Prize in Physics for his work on the quantum theory.

The Photoelectric Effect and Photons

A few years after Planck presented his theory, scientists began to see its applicability to a
great many experimental observations. In 1905, Albert Einstein (1879-1955) used Planck's
quantum theory to explain the photoelectric effect-the ejection of electrons from a metal surface
upon exposure to photons of sufficiently high energy. Experiments had shown that light shining on
a clean metal surface causes the surface to emit electrons. It was found that:
1. The frequency of the incident light must be greater than a certain value called the
threshold frequency in order for the electrons to be emitted from the surface.
2. The kinetic energy, K.E, of the emitted electrons is directly proportional to the
frequency of the incident light but independent of its intensity.
3. Electrons are emitted even if the intensity of radiation is very low provided the
threshold frequency has been attained.
To explain the photoelectric effect, Einstein assumed that the radiant energy striking the
metal surface does not behave like a wave but rather as if it were a stream of tiny energy packets,
called photons. Einstein deduced that each photon must have an energy equal to Planck's constant
times the frequency of the light:
Energy of photon = E = hν
Thus, radiant energy itself is quantized.
Under the right conditions, a photon can strike a metal surface and be absorbed. When this
happens, the photon can transfer its energy to an electron in the metal. A certain amount of energy-
called the work function-is required for an electron to overcome the attractive forces that hold it in
the metal. If the photons have less energy than the work function, electrons do not acquire
sufficient energy to escape from the metal surface, even if the light beam is intense. If light of a

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 Inorganic Chemistry I | Dr. Nyamato G.S.

high frequency is, therefore, used the electrons will not only be emitted but will also acquire some
kinetic energy. Thus,
E = hν = K.E + w
Where w is the work done to overcome the attractive forces.
Thus, K.E = hν-w. This shows that the higher the frequency, the greater the K.E of the
ejected electrons.
Einstein won the Nobel Prize in Physics in 1921 for his explanation of the photoelectric
effect. The idea that the energy of light depends on its frequency helps us understand the diverse
effects that different kinds of electromagnetic radiation have on matter. For example, the high
frequency (short wavelength) of X-rays causes X-ray photons to have energy high enough to cause
tissue damage and even cancer. Thus, signs are normally posted around X-ray equipment warning
us of high-energy radiation.
SAMPLE EXERCISE
1. Calculate the energy of one photon of yellow light with a wavelength of 589 nm.
ν = c/λ
ℎ𝑐
E = hν = = 2.03 ×105 J/mol
𝜆

2. (a) A laser emits light with a frequency of 4.69 X 1014 s-1. What is the energy of
one photon of the radiation from this laser? (b) If the laser emits a pulse of energy
containing 5.0 X 1017 photons of this radiation, what is the total energy of that
pulse? (c) If the laser emits 1.3 x 10-2 J of energy during a pulse, how many photons
are emitted during the pulse?
Answers: (a) 3.11 X 10-19 J, (b) 0.16 J, (c) 4.2 X 1016 photons

The Line Spectra (the hydrogen spectra)

A particular source of radiant energy may emit a single wavelength, as in the light from a
laser or produce radiation containing many different wavelengths, as in the light from lightbulbs
and stars. When the radiation containing many different wavelengths is separated into its different
wavelength components, a spectrum is produced. The resulting spectrum consists of a continuous
range of colors-violet merges into blue, blue into green, and so forth, with no blank spots. This
rainbow of colors, containing light of all wavelengths, is called a continuous spectrum. The most

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 Inorganic Chemistry I | Dr. Nyamato G.S.

familiar example of a continuous spectrum is the rainbow produced when raindrops or mist acts
as a prism for sunlight.
Not all radiation sources produce a continuous spectrum. When a high voltage is applied
to tubes that contain different gases under reduced pressure, the gases emit different colors of light.
The light emitted by neon gas is the familiar red-orange glow of many "neon" lights, whereas
sodium vapor emits the yellow light characteristic of some modern streetlights. When light coming
from such tubes is passed through a prism, only a few wavelengths are present in the resultant
spectra, as shown in below. Each wavelength is represented by a colored line in one of these
spectra. A spectrum containing radiation of only specific wavelengths is called a line spectrum.

When scientists first detected the line spectrum of hydrogen in the mid-1800s, they were
fascinated by its simplicity. At that time, only the four lines in the visible portion of the spectrum
were observed. These lines correspond to wavelengths of 410 nm (violet), 434 nm (blue), 486 nm
(blue-green), and 656 nm (red). In 1885, a Swiss schoolteacher named Johann Balmer showed that
the wavelengths of these four visible lines of hydrogen fit an intriguingly simple formula that
related the wavelengths of the visible line spectrum to integers. Soon Balmer's equation was
extended to a more general one, called the Rydberg equation, which allowed the calculation of the
wavelengths of all the spectral lines of hydrogen:

1 1 1
= RH (𝑛21 − )
𝜆 𝑛2 2

In this formula λ is the wavelength of a spectral line, RH is the Rydberg constant (1 .096776
X 107 m-I), and n1 and n2 are positive integers, with n2 being larger than n1.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Later, additional lines were found to occur in the ultraviolet and infrared regions of the
hydrogen spectrum; Lyman series (UV region), Paschen series (IR), Brackett series (IR) and Pfund
series (IR). For Lyman series: n1 = 1, n2 = 2, 3, 4, 5 …
Balmer series, n1 = 2, n2 = 3, 4, 5 …
Paschen series, n1 = 3, n2 = 4, 5, 6 …
Brackett series, n1 = 4, n2 = 5, 6, 7 …
Pfund series, n1 = 5, n2 = 6, 7, 8 …

Bohr’s model of the atom

In 1913, a Danish Physicist Neil Bohr (1885-1962) proposed a model of the atom that could
account for the spectra of hydrogen-like atoms using Rutherford’s planetary model and Planck’s
quantum theory. The theory is based on the following postulates:
1. Electrons in an atom rotate only on specific or definite circular orbits. Each orbit is
associated with a definite amount of energy and the energy of the electron remains
constant so long as it stays in that orbit. If an electron is at an orbit near the nucleus,
the atom possesses minimum energy. Such a state is called the unexcited state.
When an electron moves to the next or further orbits, its energy increases and the
state of the atom is excited.
2. The emission or absorption of energy, in the form of radiation, can only occur when
an electron moves from one stationary state to another. This energy is emitted or
absorbed as a photon, E = hν.
Starting with these postulates and using classical equations for motion and for interacting
electrical charges, Bohr calculated the energies corresponding to each allowed orbit for the
electron in the hydrogen atom. Ultimately, the energies that Bohr calculated fit the formula:
1 1
E = (-hcRH) (𝑛2 ) = (-2.18 × 10-18 J) (𝑛2 )
Where h, c, and RH are Planck's constant, the speed of light, and the Rydberg constant, respectively.
Each orbit corresponds to a different value of n, and the radius of the orbit gets larger as n increases. What
happens to the orbit radius and the energy as n becomes infinitely large? The radius increases as n2, so we
reach a point at which the electron is completely separated from the nucleus. When n = ∞, the energy is
zero:
1
E = (-2.18 × 10-18 J) (∞2) = 0

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 Inorganic Chemistry I | Dr. Nyamato G.S.

When an electron makes a transition from a state of energy Ei to a final state of energy Ef, the
change in energy is:
ΔE = Ef - Ei = Ephoton = hν
Thus,
ℎ𝑐 1 1
ΔE = hν = = (-2.18 × 10-18 J) (𝑛2 𝑓 − )
𝜆 𝑛2 𝑖

If we solve for 1/λ, we find that this equation derived from Bohr's theory corresponds to
the Rydberg equation, which was obtained using experimental data:
1 1 1
= -RH (𝑛2 𝑓 − )
𝜆 𝑛2 𝑖

Thus, the existence of discrete spectral lines can be attributed to the quantized jumps of
electrons between energy levels.

Limitations of the Bohr Model

▪ While the Bohr model explains the line spectrum of the hydrogen atom, it cannot
explain the spectra of other atoms.
▪ Bohr also avoided the problem of why the negatively charged electron would not
just fall into the positively charged nucleus by simply assuming it would not
happen.
▪ Bohr assumed that an electron is located at definite distance from the nucleus and
is revolving around it with definite velocity, i.e. associated with a fixed value of
momentum. This is against the Heisenberg’s uncertainty principle according to
which it is impossible to determine simultaneously with certainty the position and
the momentum of a particle.

The Wave Behaviour of Matter

In the years following the development of Bohr's model for the hydrogen atom, the dual
nature of radiant energy became a familiar concept. Depending on the experimental circumstances,
radiation appears to have either a wavelike or a particle-like (photon) character. Louis de Broglie
(1892-1987), who was working on his Ph.D. thesis in physics at the Sorbonne in Paris, argued that
because electromagnetic radiation could be considered to consist of particles, called photons, yet
at the same time exhibit wave-like properties, then the same might be true of electrons. De Broglie
suggested that as the electron moves about the nucleus, it is associated with a particular

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 Inorganic Chemistry I | Dr. Nyamato G.S.

wavelength. He went on to propose that the characteristic wavelength of the electron, or of any
other particle, depends on its mass, m, and on its velocity, v, (where h is Planck's constant):
ℎ
𝜆=
𝑚𝑣
The quantity mv for any object is called its momentum.
Because de Broglie's hypothesis is applicable to all matter, any object of mass m and
velocity v would give rise to a characteristic matter wave. However, the above equation indicates
that the wavelength associated with an object of ordinary size, such as a golf ball, is so tiny as to
be completely out of the range of any possible observation.
This dual nature is called wave-particle duality. The German physicist Werner Heisenberg
proposed that the dual nature of matter places a fundamental limitation on how precisely we can
know both the location and the momentum of any object. The limitation becomes important only
when we deal with matter at the subatomic level (that is, with masses as small as that of an
electron). Heisenberg's principle is called the uncertainty principle. When applied to the
electrons in an atom, this principle states that it is inherently impossible for us to know
simultaneously both the exact momentum of the electron and its exact location in space.
De Broglie's hypothesis and Heisenberg's uncertainty principle set the stage for a new and
more broadly applicable theory of atomic structure. In this new approach, any attempt to define
precisely the instantaneous location and momentum of the electron is abandoned. The wave nature
of the electron is recognized, and its behavior is described in terms appropriate to waves. The
result is a model that precisely describes the energy of the electron while describing its location
not precisely, but in terms of probabilities.
In 1926 the Austrian physicist Erwin Schrodinger (1887-1961) proposed an equation,
now known as Schrodinger's wave equation that incorporates both the wave-like behavior and the
particle-like behavior of the electron. To do so, he introduced the wavefunction, ψ (psi), a
mathematical function of the position coordinates x, y, and z which describes the behaviour of an
electron. The Schrodinger equation, of which the wavefunction is a solution, for an electron free
to move in one dimension is:

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 Inorganic Chemistry I | Dr. Nyamato G.S.

where me is the mass of an electron, V is the potential energy of the electron, and E is its
total energy.
Although the wave function itself has no direct physical meaning, the square of the wave
function, ψ2, provides information about an electron's location when the electron is in an allowed
energy state. That is, the probability of finding an electron at a given location is proportional to
the square of the wavefunction at that point. According to this interpretation, there is a high
probability of finding the electron where ψ2 is large, and the electron will not be found where ψ2
is zero.
For the hydrogen atom, the allowed energies are the same as those predicted by the Bohr
model. However, the Bohr model assumes that the
electron is in a circular orbit of some particular radius
about the nucleus. In the quantum mechanical model, the
electron's location cannot be described so simply.
According to the uncertainty principle, if we know the
momentum of the electron with high accuracy, our
simultaneous knowledge of its location is very uncertain. In the quantum mechanical model, we
therefore speak of the probability that the electron will be in a certain region of space at a given
instant. As it turns out, the square of the wave function, ψ2, at a given point in space represents the
probability that the electron will be found at that location. For this reason, ψ2 is called either the
probability density or the electron density.
One way of representing the probability of finding the electron in various regions of an
atom is as shown below. The regions with a high density of dots correspond to relatively large
values for ψ2 and are therefore regions where there is a high probability of finding the electron.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Atomic Orbitals
The wavefunction of an electron in an atom is called an atomic orbital. Each orbital
describes a specific distribution of electron density in space, as given by the orbital's probability
density. Chemists use hydrogenic atomic orbitals to develop models that are central to the
interpretation of inorganic chemistry, and we shall spend some time describing their shapes and
significance.
Each of the wave functions obtained by solving the Schrodinger equation for a hydrogenic
atom is uniquely labelled by a set of three integers called quantum numbers. These quantum
numbers are designated n, l, and ml: n is called the principal quantum number, l is the orbital
angular momentum quantum number (formerly the ‘azimuthal quantum number’), and ml is
called the magnetic quantum number. Each quantum number specifies a physical property of
the electron:
1. The principal quantum number, n, specifies the energy, i.e. the average radius of the
energy level, and can have positive integral values of 1, 2, 3, and so forth. A level is a
region in space where electrons with the same value of n are located. As n increases, the
orbital becomes larger, and the electron spends more time farther from the nucleus. An
increase in n also means that the electron has a higher energy and is therefore less tightly
bound to the nucleus.
2. The angular momentum quantum number, l, defines the shape of the orbital and can
have integral values from 0 to (n - 1) for each value of n. l characterizes the energy sub-
level which is an ingredient of the level n. The value of l for a particular sub-level is
generally designated by the letters s, p, d, and f, corresponding to l values of 0, 1, 2, and
3, respectively. Usually in atoms, l does not go beyond 3. The collection of orbitals with
the same value of n is called an electron shell. All the orbitals that have n = 3, for

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 Inorganic Chemistry I | Dr. Nyamato G.S.

example, are said to be in the third shell. Further, the set of orbitals that have the same
n and l values is called a subshell. Each subshell is designated by a number (the value
of n) and a letter s, p, d or f (corresponding to the value of l). For example, the orbitals
that have n = 3 and l = 2 are called 3d orbitals and are in the 3d subshell.
Value of l 0 1 2 3

Letter used s p d f

3. The magnetic quantum number, m1, describes the orientation of the orbital in space
and for a sub-level with quantum number l, there are 2l+1 individual orbitals. These
orbitals are distinguished by the magnetic quantum number, ml, which can have the
2l +1 integer values from -l down to +l. For example, a d subshell of an atom (l = 2)
consists of five individual atomic orbitals that are distinguished by the values ml -2, -1,
0, +1, +2. Thus there is only one orbital in an s subshell (l = 0), the one with ml = 0: this
orbital is called an s orbital. There are three orbitals in a p subshell (l = 1), with quantum
numbers ml = -1, 0, +1; they are called p orbitals. The five orbitals of a d subshell (l =
2) are called d orbitals, and so on.
The Table below summarizes the possible values of the quantum numbers l and ml for
values of n through n = 4. From the Table, the total number of orbitals in a shell is n2, where n is
the principal quantum number of the shell.
Relationship among Values of n, l, and m1 through n = 4
n Possible Subshell Possible values of Number of Total Number
Values of l Designation ml Orbitals in of Orbitals in
subshell shell
1 0 1s 0 1 1
2 0 2s 0 1
1 2p -1, 0, 1 3 4
3 0 3s 0 1
1 3p -1, 0, 1 3
2 3d -2, -1, 0, 1, 2 5 9
4 0 4s 0 1
1 4p -1, 0, 1 3
2 4d -2, -1, 0, 1, 2 5
3 4f -3, -2, -1, 0, 1, 2, 3 7 16

The restrictions on the possible values of the quantum numbers give rise to the following
very important observations:

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 Inorganic Chemistry I | Dr. Nyamato G.S.

1. The shell with principal quantum number n will consist of exactly n subshells.
2. Each subshell consists of a specific number of orbitals. Each orbital corresponds to
a different allowed value of ml.
3. The total number of orbitals in a shell is n2, where n is the principal quantum
number of the shell. The resulting number of orbitals for the shells-1, 4, 9, 16---is
related to a pattern seen in the periodic table: We see that the number of elements
in the rows of the periodic table-2, 8, 18, and 32-equals twice these numbers.

Representation of Orbitals
The s Orbitals
All of the s orbitals (1s, 2s, 3s, 4s, and so forth) are spherically symmetric. Recall that the l quantum
number for the s orbitals is 0; therefore the ml quantum number must be 0. Therefore, for each
value of n, there is only one s orbital. An s orbital is normally represented by a spherical surface
with the nucleus at its center. The surface is called the boundary surface of the orbital and defines
the region of space within which there is a high probability (typically 90%) of finding the electron.

The p Orbitals
The electron density in p orbitals is not distributed in a spherically symmetric fashion as in an s
orbital. Instead, the electron density is concentrated in two regions on either side of the nucleus,
separated by a node at the nucleus. We say that this dumbbell-shaped orbital has two lobes. For
each value of n, the three p orbitals have the same size and shape but differ from one another in
spatial orientation. We usually represent p orbitals by drawing the shape and orientation of their
wave functions, as shown below. It is convenient to label these as the px, py and pz orbitals.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

The d Orbitals
They are determined by quantum number l = 2. Thus, there are five possible values for the
ml quantum number: -2, -1, 0, 1, and 2. The different d orbitals in a given shell have different
shapes and orientations in space, as shown below.

The dxy, dxz and dyz lie in the xy, xz, and yz planes, respectively, with the lobes oriented
between the axes. The lobes of the dx2-
y2 orbital also lie in the xy plane, but the
lobes lie along the x and y axes. The dz2
orbital looks very different from the
other four: There are in fact six possible
combinations of double dumb-bell
shaped orbitals around three axes: three
with lobes between the axes, as in dxy, dxz and dyz, and three with lobes along the axis. One of these
orbitals is dx2-y2. The dz2 orbital can be thought of as the superposition of two contributions, one
with lobes along the z- and x-axes and the other with lobes along the z- and y-axes. Even though
the dz2 orbital looks different from the other d orbitals, it has the same energy as the other four d
orbitals.
When n is 4 or greater, there are seven equivalent f orbitals (for which l = 3). The shapes
of the f orbitals are even more complicated than those of the d orbitals.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Many Electron Atoms

The Aufbau principle
Although the shapes of the orbitals for many-electron atoms are the same as those for
hydrogen, the presence of more than one electron greatly changes the energies of the orbitals. In
hydrogen the energy of an orbital depends only on its principal quantum number, n. For example,
the 3s, 3p, and 3d subshells all have the same energy. In a many-electron atom, however, the
electron-electron repulsions cause the different subshells to be at different energies.
The building-up principle (Aufbau) is a procedure for arriving at the lowest energy electron
configuration of many electron atoms. Simply put, the principle states that: electrons of a many
electron atom occupy the orbitals in the order of increasing energy. The order of increasing energy
of the atomic orbitals in many-electron atoms is described by Kletchkovsky’s rule: the energy of
the orbitals increase in accordance with the increase in the sum of the principal and orbital
quantum numbers, n+l. when the sum values are equal, then energy is less in the orbital with a
bigger value of l and a small value of n. For example:
a) 3d orbital has a sum of n+l = 3+2 = 5
b) 4p orbital has a sum of n+l = 4+1 = 5
Thus, 3d has less energy since its l value is bigger and n value is smaller.
Using this rule, we can show that the energy of orbitals rise in the following manner:
1s ˂ 2s ˂ 2p ˂ 3s ˂ 3p ˂ 4s ˂ 3d ˂ 4p ˂ 5s ˂ 4d ˂ 5p ˂ 6s ˂ 4f ˂ 5d ˂ 6p ˂ 7s ˂ 5f…….

Orbital quantum number, l

0 1 2 3
Principal quantum number, n

1 1s
2 2s 2p
3 3s 3p 3d
4 4s 4p 4d 4f
5 5s 5p 5d 5f
6 6s 6p 6d
7 7s 7p 7d

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Electron Spin and the Pauli Exclusion Principle

When scientists studied the line spectra of many-electron atoms in great detail, they noticed
a very puzzling feature: Lines that were originally thought to be single were actually closely spaced
pairs. In 1925 the Dutch physicists George Uhlenbeck and Samuel Goudsmit proposed a solution
to this dilemma. They postulated that electrons have an intrinsic property, called electron spin,
which causes each electron to behave as if it were a tiny
sphere spinning on its own axis. This observation led to the
assignment of a new quantum number for the electron, the
spin magnetic quantum number, is denoted ms (the
subscript s stands for spin).
Two possible values are allowed for ms, +½ or -½,
which was first interpreted as indicating the two opposite
directions in which the electron can spin. A spinning charge
produces a magnetic field. The two opposite directions of spin therefore produce oppositely
directed magnetic fields, as shown below. These two opposite magnetic fields lead to the splitting
of spectral lines into closely spaced pairs.
In 1925 the Austrian-born physicist Wolfgang Pauli (1900-1958) discovered the principle
that governs the arrangements of electrons in many-electron atoms. The Pauli Exclusion Principle
states that no two electrons in an atom can have the same set of four quantum numbers n, l, ml,
and ms. For a given orbital, the values of n, l, and m1 are fixed. Thus, if we want to put more than
one electron in an orbital and satisfy the Pauli Exclusion Principle, our only choice is to assign
different ms, values to the electrons. Because there are only two such values, we conclude that an
orbital can hold a maximum of two electrons and they must have opposite spins.

ELECTRON CONFIGURATIONS
The way in which the electrons are distributed among the various orbitals of an atom is
called the electron configuration of the atom. The most stable electron configuration of an atom-
the ground state-is that in which the electrons are in the lowest possible energy states. If there were
no restrictions on the possible values for the quantum numbers of the electrons, all the electrons
would crowd into the 1s orbital because it is the lowest in energy. The Pauli Exclusion Principle
tells us, however, that there can be at most two electrons in any single orbital. Thus, the orbitals

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 Inorganic Chemistry I | Dr. Nyamato G.S.

are filled in order of increasing energy, with no more than two electrons per orbital. For example,
consider the lithium atom, which has three electrons. The 1s orbital can accommodate 2 of the
electrons. The third one goes into the next lowest energy orbital, the 2s. This electron configuration
is usually represented by the symbol of the occupied subshell and a superscript, indicating the
number of electrons in that subshell. Thus, the electron configuration for lithium is written as
Is22s1. This configuration can also be represented in what is called an orbital diagram, where
each orbital is denoted by a box and each electron by a half arrow. i.e.

Li
1s 2s
A half arrow pointing up represents an electron with a positive spin magnetic quantum
number (ms = +½) and a half arrow pointing down represents an electron with a negative spin
magnetic quantum number (ms = -½). In fact, chemists and physicists often refer to electrons as
"spin-up" and "spin-down" rather than specifying the value for ms. Electrons having opposite
spins are said to be paired when they are in the same orbital. An unpaired electron is one not
accompanied by a partner of opposite spin. In the lithium atom, the two electrons in the ls orbital
are paired and the electron in the 2s orbital is unpaired.

Hund’s rule
Let’s now consider the electron configurations of the elements change as we move from
element to element across the periodic table. Hydrogen has one electron, which occupies the ls
orbital in its ground state.

H : 1s1 He : 1s2

1s 1s
The next element, helium, has two electrons. Because two electrons with opposite spins
can occupy an orbital, both of helium's electrons are in the ls orbital. The two electrons present in
helium complete the filling of the first shell. This arrangement represents a very stable
configuration, as is evidenced by the chemical inertness of helium. For the third electron of lithium,
the change in principal quantum number represents a large jump in energy and it represents the
start of a new shell occupied with electrons. The element that follows lithium is beryllium; its
electron configuration is ls22s2. Boron, atomic number 5, has the electron configuration ls22s22p1.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

The fifth electron must be placed in a 2p orbital because the 2s orbital is filled. Because all the
three 2p orbitals are of equal energy, it does not matter which 2p orbital is occupied.
With the next element, carbon, we encounter a new situation. We know that the sixth
electron must go into a 2p orbital. However, does this new electron go into the 2p orbital that
already has one electron, or into one of the other two 2p orbitals? This question is answered by
Hund's rule, which states that for degenerate orbitals, the lowest energy is attained when the
number of electrons with the same spin is maximized. This means that electrons enter each orbital
of a given type singly and with identical spins before any pairing of electrons of opposite spins
occurs within those orbitals. Thus, a carbon atom in its ground state has two unpaired electrons.
Similarly, for nitrogen in its ground state, Hund's rule requires that the three 2p electrons singly
occupy each of the three 2p orbitals. For oxygen and fluorine, we place four and five electrons,
respectively, in the 2p orbitals. To achieve this, we pair up electrons in the 2p orbitals.
Hund's rule is based in part on the fact that electrons repel one another. By occupying
different orbitals, the electrons remain as far as possible from one another, thus minimizing
electron-electron repulsions.

Condensed Electron Configurations

The filling of the 2p subshell is complete at neon, which has a stable configuration with
eight electrons (an octet) in the outermost occupied shell. The next element, sodium, atomic
number 11, marks the beginning of a new row of the periodic table. Sodium has a single 3s electron
beyond the stable configuration of neon. We can therefore abbreviate the electron configuration of
sodium as
Na: [Ne]3s1
Writing the electron configuration as [Ne]3s1 helps focus attention on the outermost
electrons of the atom, which are the ones largely responsible for the chemical behavior of an
element. In general, in writing the condensed electron configuration of an element, the electron
configuration of the nearest noble-gas element of lower atomic number is represented by its
chemical symbol in brackets. For example, we can write the electron configuration of lithium as
Li: [He]2s1
We refer to the electrons represented by the symbol for a noble gas as the noble-gas core
of the atom. More usually, these inner-shell electrons are referred to as the core electrons. The

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 Inorganic Chemistry I | Dr. Nyamato G.S.

electrons given after the noble-gas core are called the outer-shell electrons. The outer-shell
electrons include the electrons involved in chemical bonding, which are called the valence
electrons. For lighter elements (those with atomic number of 30 or less), all of the outer-shell
electrons are valence electrons.

ELECTRON CONFIGURATIONS AND THE PERIODIC TABLE

The periodic table is structured so that elements with the same pattern of outer-shell
(valence) electron configuration are arranged in columns. For example, the electron configurations
for the elements in groups 2 (2A) and 13 (3A) are given below. It’s evident that all the 2 elements
have ns2 outer configurations, while the all the 13 elements have ns2np1 configurations.

Group 2 (2A) Group 13 (3A)

Be [He]2s2 B [He]2s2p1
Mg [Ne]3s2 Al [Ne]3s2p1
Ca [Ar]4s2 Ga [Ar]3d104s24p1
Sr [Kr]5s2 In [Kr]4d105s25p1
Ba [Xe]6s2 Tl [Xe]4f145d106s26p 1
Ra [Rn]7s2

Earlier, we saw that the total number of orbitals in each shell is equal to n2: 1, 4, 9, or 16.
Because each orbital can hold two electrons, each shell can accommodate up to 2n2 electrons: 2,
8, 18, or 32. The structure of the periodic table reflects this orbital structure. The first row has two
elements, the second and third rows have eight elements, the fourth and fifth rows have 18
elements, and the sixth row has 32 elements (including the lanthanide metals). Some of the numbers
repeat because we reach the end of a row of the periodic table before a shell completely fills. For
example, the third row has eight elements, which corresponds to filling the 3s and 3p orbitals. The
remaining orbitals of the third shell, the 3d orbitals, do not begin to fill until the fourth row of the
periodic table (and after the 4s orbital is filled). Likewise, the 4d orbitals do not begin to fill until
the fifth row of the table, and the 4f orbitals don't begin filling until the sixth row.
All these observations are evident in the structure of the periodic table. Hence, the periodic
table is the best guide to the order in which orbitals are filled- the electron configuration of an
element can easily be written based on its location in the periodic table (as summarized in the table
below). Notice that the elements can be grouped by the type of orbital into which the electrons are
placed. On the left are two columns of elements (depicted in blue). These elements, known as the

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 Inorganic Chemistry I | Dr. Nyamato G.S.

alkali metals (group 1A) and alkaline earth metals (group 2A), are those in which the valence s
orbitals are being filled. On the right is a pink block of six columns. These are the elements in
which the valence p orbitals are being filled. The s block and the p block of the periodic table
together are the representative elements, which are sometimes called the main-group elements.
In the middle of the periodic table is a gold block of ten columns containing the transition
metals. These are the
elements in which the
valence d orbitals are
being filled. Below the
main portion of the
table are two tan rows
containing 14 columns.
These elements are
often referred to as the
f-block metals, because
they are the ones in which the valence f orbitals are being filled. Recall that the numbers 2, 6, 10,
and 14 are precisely the number of electrons that can fill the s, p, d, and f subshells, respectively.
Recall also that the 1s subshell is the first s subshell, the 2p is the first p subshell, the 3d is the first
d subshell, and the 4f is the first f subshell. The Figure below gives the valence ground-state
electron configurations for all the elements.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Elements in the same column of the table contain the same number of electrons in their
valence orbitals, the occupied orbitals that hold the electrons involved in bonding. For example, O
([He]2s22p4) and S ([Ne]3s23p4) are both members of group 6A. The similarity of the electron
distribution in their valence s and p orbitals leads to similarities in the properties of these two
elements. When we compare O and S, however, it is apparent that they exhibit differences as well,
not the least of which is that oxygen is a colorless gas at room temperature, whereas sulfur is a
yellow solid. One of the major differences between atoms of these two elements is their electron
configurations: the outermost electrons of O are in the second shell, whereas those of S are in the
third shell. Thus, electron configurations can be used to explain differences as well as similarities
in the properties of elements.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

EFFECTIVE NUCLEAR CHARGE

Because electrons are negatively charged, they are attracted to nuclei, which are positively
charged. Many of the properties of atoms depend on their electron configurations and on how
strongly their outer electrons are attracted to the nucleus. The force of attraction between an
electron and the nucleus depends on the magnitude of the net nuclear charge acting on the electron
and on the average distance between the nucleus and the electron. The force of attraction increases
as the nuclear charge increases, and it decreases as the electron moves farther from the nucleus.
In a many-electron atom, each electron is simultaneously attracted to the nucleus and
repelled by the other electrons. Estimation of the net attraction of each electron to the nucleus by
considering how it interacts with the average environment created by the nucleus and the other
electrons in the atom gives rise to what is called effective nuclear charge, Zeff· The effective
nuclear charge acting on an electron in an atom is smaller than the actual nuclear charge because
the effective nuclear charge also accounts for the repulsion of the electron by the other electrons
in the atom-in other words, Zeff < Z.
A valence electron in an atom is attracted to the nucleus of the atom and is repelled by the
other electrons in the atom. In particular, the electron density that is due to the inner (core)
electrons is particularly effective at partially canceling the attraction of the valence electron to the
nucleus. We say that the inner electrons partially shield or screen the outer electrons from the
attraction of the nucleus. We can therefore write a simple relationship between the effective nuclear
charge, Zeff, and the number of protons in the nucleus, Z:
Zeff = Z - S
The factor S is a positive number called the screening constant. It represents the portion of
the nuclear charge that is screened from the valence electron by the other electrons in the atom.

Periodic Trends in Atomic Radii

▪ Within each column (group), atomic radius tends to increase from top to bottom.
This trend results primarily from the increase in the principal quantum number (n)
of the outer electrons. As we go down a column, the outer electrons have a greater
probability of being farther from the nucleus, causing the atom to increase in size.
▪ Within each row (period), atomic radius tends to decrease from left to right. The
major factor influencing this trend is the increase in the effective nuclear charge

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(Zeff) as we move across a row. The increasing effective nuclear charge steadily
draws the valence electrons closer to the nucleus, causing the atomic radius to
decrease.
Periodic Trends in Ionic Radii
Like the size of an atom, the size of an ion depends on its nuclear charge, the number of
electrons it possesses, and the orbitals in which the valence electrons reside. The formation of a
cation vacates the most spatially extended occupied orbitals in an atom and decreases the number
of electron-electron repulsions. Therefore, cations are smaller than their parent atoms.
The opposite is true of anions. When electrons are added to an atom to form an anion, the
increased electron-electron repulsions cause the electrons to spread out more in space. Thus, anions
are larger than their parent atoms. For ions carrying the same charge, size increases as we move
down a column in the periodic table. As the principal quantum number of the outermost occupied
orbital of an ion increases, the radius of the ion increases.
A group of ions, all containing the same number of electrons, is called an isoelectronic
series. For example, each ion in the isoelectronic series O2-, F-, Na+, Mg2+, Al3+ has 10 electrons.
In any isoelectronic series we can list the members in order of increasing atomic number; therefore,
nuclear charge increases as we move through the series. Because the number of electrons remains
constant, the radius of the ion decreases with increasing nuclear charge, as the electrons are more
strongly attracted to the nucleus.

IONIZATION ENERGY
The ionization energy of an atom or ion is the minimum energy required to remove an
electron from the ground state of the isolated gaseous atom or ion. The first ionization energy, I1,
is the energy needed to remove the first electron from a neutral atom. The second ionization energy,
I2, is the energy needed to remove the second electron, and so forth, for successive removals of
additional electrons. The greater the ionization energy, the more difficult it is to remove an
electron. The values of ionization energy for a given element increase as successive electrons are
removed: I1 < I2 < I3, and so forth. This trend exists because with each successive removal, an
electron is being pulled away from an increasingly more positive ion, requiring increasingly more
energy.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Every element exhibits a large increase in ionization energy when electrons are removed
from its noble-gas core. This observation supports the idea that only the outermost electrons, those
beyond the noble-gas core, are involved in the sharing and transfer of electrons that give rise to
chemical bonding and reactions. The inner electrons are too tightly bound to the nucleus to be lost
from the atom or even shared with another atom.

ELECTRON AFFINITIES
The energy change that occurs when an electron is added to a gaseous atom is called the
electron affinity because it measures the attraction, or affinity, of the atom for the added electron.
For most atoms, energy is released when an electron is added.
It is important to understand the difference between ionization energy and electron affinity:
Ionization energy measures the ease with which an atom loses an electron, whereas electron
affinity measures the ease with which an atom gains an electron.

CHEMICAL BONDS, LEWIS SYMBOLS, AND THE OCTET RULE

Whenever two atoms or ions are strongly attached to each other, we say there is a
chemical bond between them. There are three general types of chemical bonds: ionic, covalent,
and metallic.
The term ionic bond refers to electrostatic forces that exist between ions of opposite
charge. Ionic substances generally result from the interaction of metals on the left side of the
periodic table with nonmetals on the right side (excluding the noble gases, group 8A). A covalent
bond results from the sharing of electrons between two atoms. The most familiar examples of
covalent bonding are seen in the interactions of nonmetallic elements with one another. Metallic
bonds are found in metals, such as copper, iron, and aluminum. Each atom in a metal is bonded to
several neighboring atoms. The bonding electrons are relatively free to move throughout the three-
dimensional structure of the metal.

Lewis Symbols
The electrons involved in chemical bonding are the valence electrons, which, for most
atoms, are those residing in the outermost occupied shell of an atom. The American chemist G. N.

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Lewis (1875-1946) suggested a simple way of showing the valence electrons in an atom and
tracking them in the course of bond formation, using what are now known as Lewis electron-dot
symbols, or merely Lewis symbols. The Lewis symbol for an element consists of the chemical
symbol for the element plus a dot for each valence electron. Sulfur, for example, has the electron
configuration [Ne]3s23p4; its Lewis symbol therefore shows six valence electrons:
..
. S.
..
The dots are placed on the four sides of the atomic symbol: the top, the bottom, and the left
and right sides.
The Octet Rule
Atoms often gain, lose, or share electrons to achieve the same number of electrons as the
noble gas closest to them in the periodic table. The noble gases have very stable electron
arrangements, as evidenced by their high ionization energies, low affinity for additional electrons,
and general lack of chemical reactivity. Because all noble gases (except He) have eight valence
electrons, many atoms undergoing reactions also end up with eight valence electrons. This
observation has led to a guideline known as the octet rule: Atoms tend to gain, lose, or share
electrons until they are surrounded by eight valence electrons.
An octet of electrons consists of full s and p subshells in an atom. In terms of Lewis
symbols, an octet can be thought of as four pairs of valence electrons arranged around the atom.
There are many exceptions to the octet rule, but it provides a useful framework for introducing
many important concepts of bonding.

IONIC BONDING
When sodium metal, Na(s), is brought into contact with chlorine gas, Cl2(g), a violent
reaction ensues. The product of this very exothermic reaction is sodium chloride, NaCl(s). The
formation of Na+ from Na and Cl- from Cl2 indicates that an electron has been lost by a sodium
atom and gained by a chlorine atom-we can envision an electron transfer from the Na atom to the
Cl atom. Two of the atomic properties we discussed earlier give us an indication of how readily
electron transfer occurs: the ionization energy, which indicates how easily an electron can be
removed from an atom, and the electron affinity, which measures how much an atom wants to gain
an electron. Electron transfer to form oppositely charged ions occurs when one of the atoms readily

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gives up an electron (low ionization energy) and the other atom readily gains an electron (high
electron affinity). Thus, NaCI is a typical ionic compound because it consists of a metal of low
ionization energy and a nonmetal of high electron affinity.
Ionic substances possess several characteristic properties. They are usually brittle
substances with high melting points. They are usually crystalline. Furthermore, ionic crystals often
can be cleaved; that is, they break apart along smooth, flat surfaces. These characteristics result
from electrostatic forces that maintain the ions in a rigid, well-defined, three-dimensional
arrangement
COVALENT BONDING
The vast majority of chemical substances do not have the characteristics of ionic
materials. Most of the substances with which we come into daily contact-such as water-tend to be
gases, liquids, or solids with low melting points. Many, such as gasoline, vaporize readily. Many
are pliable in their solid forms-for example, plastic bags and paraffin.
For the very large class of substances that do not behave like ionic substances, what is the
nature of bonding between their atoms? G. N. Lewis reasoned that atoms might acquire a noble-
gas electron configuration by sharing electrons with other atoms. A chemical bond formed by
sharing a pair of electrons is called a covalent bond.
The hydrogen molecule, H2, provides the simplest example of a covalent bond. When two
hydrogen atoms are close to each other, electrostatic interactions occur between them. The two
positively charged nuclei repel each other, the two negatively
charged electrons repel each other, and the nuclei and electrons
attract each other. Because the H2 molecule exists as a stable
entity, the attractive forces must exceed the repulsive ones. Thus,
the atoms in H2 are held together principally because the two
nuclei are electrostatically attracted to the concentration of
negative charge between them. In essence, the shared pair of
electrons in any covalent bond acts as a kind of "glue" to bind atoms together.

BOND POLARITY AND ELECTRONEGAT IVITY

The concept of bond polarity helps describe the sharing of electrons between atoms. A
nonpolar covalent bond is one in which the electrons are shared equally between two atoms, as in

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the Cl2 and N2. In a polar covalent bond, one of the atoms exerts a greater attraction for the bonding
electrons than the other.
Electronegativity is defined as the ability of an atom in a molecule to attract electrons to
itself. The greater an atom's electronegativity, the greater is its ability to attract electrons to itself.
The electronegativity of an atom in a molecule is related to its ionization energy and electron
affinity, which are properties of isolated atoms. The ionization energy measures how strongly a
gaseous atom holds on to its electrons, while the electron affinity is a measure of how strongly an
atom attracts additional electrons. An atom with a very negative electron affinity and high
ionization energy will both attract electrons from other atoms and resist having its electrons
attracted away; it will be highly electronegative.
Within each period there is generally a steady increase in electronegativity from left to
right; that is, from the most metallic to the most nonmetallic elements. With some exceptions
(especially within the transition metals), electronegativity decreases with increasing atomic
number in any one group.

DRAWIN G LEWIS STRUCTURES

Lewis structures can help us understand the bonding in many compounds and are
frequently used when discussing the properties of molecules. For this reason, drawing Lewis
structures is an important skill that you should practice. Procedure:
1. Sum the valence electrons from all atoms. For an anion, add one electron to the
total for each negative charge. For a cation, subtract one electron from the total for
each positive charge.
2. Write the symbols for the atoms to show which atoms are attached to which, and
connect them with a single bond. Chemical formulas are often written in the order
in which the atoms are connected in the molecule or ion. The formula HCN, for
example, tells you that the carbon atom is bonded to the H and to the N. In many
polyatomic molecules and ions, the central atom is usually written first, as in CO32-
and SF4.
3. Complete the octets around all the atoms bonded to the central atom. Remember,
however, that you use only a single pair of electrons around hydrogen.

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 Inorganic Chemistry I | Dr. Nyamato G.S.

4. Place any leftover electrons on the central atom, even if doing so results in more
than an octet of electrons around the atom.
5. If there are not enough electrons to give the central atom an octet, try multiple
bonds. Use one or more of the unshared pairs of electrons on the atoms bonded to
the central atom to form double or triple bonds.
EXAMPLES
1. Draw the Lewis structure for phosphorus trichloride, PC13, BrO3- ion, ClO2- ion, PO43- ion
and HCN.

MOLECULAR SHAPES
Lewis structures, unfortunately, do not indicate the shapes of molecules; they simply show
the number and types of bonds between atoms. The overall shape of a molecule is determined by
its bond angles, the angles made by the lines joining the nuclei of the atoms in the molecule. The
bond angles of a molecule, together with the bond lengths, accurately define the shape and size of
the molecule.
Most molecules conform to the general formula ABn in which the central atom A is bonded
to n B atoms. For example, both CO2 and H2O are AB2 molecules, whereas SO3 and NH3 are AB3
molecules, and so on. The possible shapes of ABn molecules depend on the value of n. An AB2
molecule must be either linear (bond angle = 180°) or bent (bond angle ≠ 180°). For example, CO2
is linear, and SO2 is bent. For AB3 molecules, the two
most common shapes place the B atoms at the comers of
an equilateral triangle. If the A atom lies in the same
plane as the B atoms, the shape is called trigonal planar.
If the A atom lies above the plane of the B atoms, the shape is called trigonal pyramidal.
In general, the shape of any particular ABn molecule can usually be derived from one of
the five basic geometric structures shown below. Why do so many ABn molecules have shapes
related to these basic structures, and can we predict these shapes? When A is a representative
element (one of the elements from the s block or p block of the periodic table), we can answer
these questions by using the valence-shell electron-pair repulsion (VSEPR) model.

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THE VSEPR MODEL

Imagine tying two identical balloons together at their ends as shown in (a) below; the
balloons naturally orient themselves to point away from each other-they try to “get out of each
other’s way” as much as possible. If a third balloon is added, the balloons orient themselves toward
the vertices of an equilateral triangle, as shown in (b). If a fourth balloon is added, they adopt a
tetrahedral shape, (c).

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Somehow, electrons in molecules behave like the balloons shown above. Recall that a
single covalent bond is formed between two atoms when a pair of electrons occupies the space
between the atoms. A bonding pair of electrons thus defines a region in which the electrons will
most likely be found. We will refer to such a region as an electron domain. Likewise, a
nonbonding pair (or lone pair) of electrons defines an electron domain that is located principally
on one atom. For example, the Lewis structure of NH3 has four electron domains around the central
nitrogen atom (three bonding pairs and one nonbonding pair):
nonbonding pair
..
H N H

H
bonding electrons

Each multiple bond in a molecule also constitutes a single electron domain. Thus, O3 has
three electron domains around the central oxygen atom (a single bond, a double bond, and a
nonbonding pair of electrons):

.. .. ..
:O.. O O
..
In general, each nonbonding pair, single bond, or multiple bond produces an electron. In
general, each nonbonding pair, single bond, or multiple bond produces an electron domain around
the central atom.
The VSEPR model is based on the idea that electron domains are negatively charged and
therefore repel one another. Like the balloons above, electron domains try to stay out of one
another’s way. The best arrangement of a given number of electron domains is the one that
minimizes the repulsions among them. In fact, the analogy between electron domains and balloons
is so close that the same preferred geometries are found in both cases. Hence, the shapes of
different ABn molecules or ions depend on the number of electrons domains surrounding the
central A atom.
The arrangement of electron domains about the central atom of an ABn molecule or ion is
called its electron-domain geometry. In contrast, the molecular geometry is the arrangement of

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 Inorganic Chemistry I | Dr. Nyamato G.S.

only the atoms in a molecule or ion-any nonbonding pairs are not part of the description of the
molecular geometry. In the VSEPR model, we predict the electron domain geometry. From
knowing how many electron domains are due to nonbonding pairs, we can then predict the
molecular geometry of a molecule or ion from its electron-domain geometry.
EXERCISE
1. Use the VSEPR model to predict the molecular geometry of (a) O3, (b) SnC13- (c) IF5
Answers: (a) bent; (b) trigonal pyramid (c) Square pyramid
2. Predict the electron-domain geometry and the molecular geometry for (a) SeCl2, (b) CO32-
Answers: (a) tetrahedral, bent; (b) trigonal planar, trigonal planar

COVALEN T BONDING AND ORBITAL OVERLAP

The marriage of Lewis's notion of electron-pair bonds and the idea of atomic orbitals leads
to a model of chemical bonding called valence-bond theory. In the Lewis theory, covalent
bonding occurs when atoms share electrons, which concentrates electron density between the
nuclei. In the valence-bond theory, we visualize the buildup of electron density between two nuclei
as occurring when a valence atomic orbital of one atom shares space, or overlaps, with that of
another atom.
The overlap of orbitals allows two electrons of opposite spins to share the common space
between the nuclei, forming a covalent bond. For example, in H2, each atom of hydrogen has a
single electron in a 1s orbital and as the orbitals overlap, electron density is concentrated between
the nuclei. Because the electrons are simultaneously attracted to both nuclei, they hold the atoms
together, forming a covalent bond. Similarly, the same idea applies to HCl where the 3p orbital of
Cl overlaps with the 1s orbital of H.

Consider the electron configuration of Be (1s22s2) in its ground state. On the basis of its
electron configuration, Be cannot form a covalent bond because it does not have unpaired

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electrons. However, the element forms divalent compounds such as BeH2, BeCl2 etc. Similarly, B
has only one unpaired electron (1s22s22p1) and yet it is trivalent. How can we explain the valences
of these elements on the basis of the number of unpaired electrons and overlap of atomic orbitals?
This is only possible with the theory of hybridization, according to which different orbitals, before
overlapping and bond formation, mix and pool their energy and form new orbitals known as hybrid
orbitals.
EXAMPLES
i. BeF2
The valence shell electronic configuration of Be is 2s2. Since there are no unpaired
electrons, Be cannot form covalent bonds in its ground state. Thus, in BeF2, the Be atom is not in
its ground state but in the excited state. To get it in the excited state, one of the 2s electrons is
"promoted" to a 2p orbital:

1s 2s 2p 1s 2s 2p
The Be atom now has two unpaired electrons and can therefore form two covalent bonds
with the F atoms. The 2s and 2p orbitals are then “combined” or “mixed” generating new orbitals.

Like p orbitals, each of the new orbitals has two lobes. Unlike p orbitals, however, one lobe
is much larger than the other. The two new orbitals are identical in shape, but their large lobes
point in opposite directions. These two new orbitals are hybrid orbitals. Because we have
hybridized one s and one p orbital, we call each hybrid an sp hybrid orbital. According to the
valence-bond model, a linear arrangement of electron domains implies sp hybridization.
Thus, for BeF2, the orbital diagram for the formation of the two sp hybrid orbitals is
written as:

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 Inorganic Chemistry I | Dr. Nyamato G.S.

1s sp 2p
The electrons in the sp hybrid orbitals can form two electron bonds with the two fluorine
atoms.

ii. BF3

B in ground state
1s 2s 2p

B in excited state
1s 2s 2p
In BF3, mixing the 2s and two of the 2p orbitals yields three equivalent sp2 hybrid orbitals.
These three hybrid orbitals are directed towards the three corners of an equilateral triangle in a
plane having an angle of 120°. The three sp2 hybrid orbitals make three equivalent bonds with
three fluorine atoms, leading to the trigonal planar geometry of BF3.

iii. CH4
An s orbital can also mix with all three p orbitals in the same subshell. For example, the
carbon atom in CH4 forms four equivalent bonds with the four equivalent bonds with four
hydrogen atoms. The process results from the mixing of the 2s and all the three 2p atomic orbitals
of carbon to create four equivalent sp3 hybrid orbitals.
The repulsion between the four orbitals is smallest if they point to the corners of a regular
tetrahedron and make a bond angle of 109°28ʹ. Each of the four sp3 hybrid orbitals is singly

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occupied and overlaps with the 1s orbital of four hydrogen atoms and forms four equivalent bonds
in CH4 molecule.
The idea of hybridization is used in a similar way to describe the bonding in molecules
containing nonbonding pairs of electrons. In H2O, for example, the
electron domain geometry around the O atom is approximately
tetrahedral. Thus, the four electron pairs can be envisioned as occupying
sp3 hybrid orbitals. Two of the hybrid orbitals contain nonbonding pairs
of electrons, while the other two are used to form bonds with hydrogen
atoms.

Hybridization Involving d Orbitals

The concept of hybridization can be applied to molecules where the central atom has more
than an octet of electrons around it, such as PF5 and SF6. This is achieved by utilizing unfilled d
orbitals with the same value of the principal quantum number, n. Mixing one s orbital, three p
orbitals, and one d orbital leads to five sp3d hybrid orbitals. These hybrid orbitals are directed
toward the vertices of a trigonal bipyramid, e.g. in PCl5. Similarly, mixing one s orbital, three p
orbitals, and two d orbitals gives six sp3d2 hybrid orbitals that are directed toward the vertices of
an octahedron.
Overall, hybrid orbitals provide a convenient model for using valence bond theory to
describe covalent bonds in molecules with geometries that conform to the electron-domain
geometries predicted by the VSEPR model. The picture of hybrid orbitals has limited predictive
value. However, when we know the electron-domain geometry, we can employ hybridization to
describe the atomic orbitals used by the central atom in bonding.
The following steps allow us to predict the hybrid orbitals used by an atom in bonding:
1. Draw the Lewis structure for the molecule or ion.
2. Determine the electron-domain geometry using the VSEPR model.
3. Specify the hybrid orbitals needed to accommodate the electron pairs based on their
geometric arrangement.
These steps are illustrated by the figure below which shows how hybridization employed
by N in NH3 is determined.

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

EXERCISE
1. Indicate the hybridization of orbitals employed by the central atom in (a) NH2-, (b) SF4
Answers: (a) sp3 (b) sp3d
2. Predict the electron-domain geometry and the hybridization of the central atom in (a)
SO32- (b) SF6.
Answers: (a) tetrahedral, sp3; (b) octahedral, sp3d2

MULTIPLE BONDS
In the covalent bonds we have considered thus far, the electron density is concentrated
along the line connecting the nuclei {the internuclear axis). In other words, the line joining the two
nuclei passes through the middle of the overlap region. These bonds are called sigma (σ) bonds.
To describe multiple bonding, we must consider a second kind of bond that results from the overlap
between two p orbitals oriented perpendicularly to the internuclear axis.
This sideways overlap of p orbitals produces a pi (Π) bond. A Π bond is a covalent bond
in which the overlap regions lie above and below the internuclear axis. In almost
all cases, single bonds are σ bonds. A double bond consists of one σ bond and
one Π bond, and a triple bond consists of one σ bond and two Π bonds. For
example in ethylene, the σ bonding framework is formed from sp2 hybrid orbitals
on the carbon atoms. The unhybridized 2p orbitals on the C atoms are used to make a Π bond.

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

The Mole Concept-assignment

In everyday life we use counting units such as a dozen (12 objects) and a gross (144 objects)
to deal with modestly large quantities. In chemistry the unit for dealing with the number of atoms,
ions, or molecules in a common-sized sample is the mole, abbreviated mol. A mole is the amount
of matter that contains as many objects (atoms, molecules, or whatever objects we are considering)
as the number of atoms in exactly 12 g of isotopically pure 12C. From experiments, scientists have
determined this number to be 6.0221421 X 1023. Scientists call this number Avogadro's number,
in honor of the Italian scientist Amedeo Avogadro (1776-1856).

EXERCISE: Converting Moles to Number of Atoms

1. Calculate the number of H atoms in 0.350 mol of C6H12O6.
Answers: Moles C6H12O6----> molecules C6H12O6----> atoms H
= 2.53 X 1024 H atoms.
2. How many oxygen atoms are in (a) 0.25 mol Ca(NO3)2 and (b) 1.50 mol of sodium
carbonate?
Answers: (a) 9.0 x 1023, (b) 2.71 X 1024

Oxidation-Reduction Reactions
Oxidation refers to the loss of electrons, and reduction refers to the gain of electrons. Thus,
oxidation-reduction reactions occur when electrons are transferred from an atom that is oxidized
to an atom that is reduced. The concept of oxidation state/oxidation number was devised as a way
of tracking track of the electrons in oxidation-reduction reactions. Oxidation occurs when the
oxidation number increases, whereas reduction occurs when the oxidation number decreases. For
example, consider the reaction that occurs when zinc metal is added to a strong acid:

0 +1 +2 0

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

The oxidation number of Zn changes from 0 to +2, and that of H changes from + 1 to 0.
Thus, this is an oxidation-reduction reaction. Electrons are transferred from zinc atoms to hydrogen
ions, and therefore Zn is oxidized and H+ is reduced. Hence, oxidation is the process of donating
electrons, which is accompanied by a rise in the oxidation state. The substance that makes it

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 Inorganic Chemistry I | Dr. Nyamato G.S.

possible for another substance to be oxidized is called either the oxidizing agent or the oxidant.
The oxidizing agent removes electrons from another substance by acquiring them itself; thus, the
oxidizing agent is itself reduced. Similarly, a reducing agent, or reductant, is a substance that
gives up electrons, thereby causing another substance to be reduced. The reducing agent is
therefore oxidized in the process.
Consider the following redox reaction that occurs in the nickel-cadmium (nicad) battery, a
rechargeable "dry cell" used in battery-operated devices, to generate electricity:

0 +4 -2 +1 -2 +2 -2 +1 +2 -2 +1

Cd(s) + NiO2(s) + 2H2O(l) Cd(OH)2(s) + Ni(OH)2(s)

Cd increases in oxidation state from 0 to +2, and Ni decreases from +4 to +2. Because the
Cd atom increases in oxidation state, it is oxidized (loses electrons) and therefore serves as the
reducing agent. The Ni atom decreases in oxidation state as NiO2 is converted into Ni(OH)2. Thus,
NiO2 is reduced (gains electrons) and therefore serves as the oxidizing agent.
EXERCISE
Identify the oxidizing and reducing agents in the oxidation-reduction reaction
2 H2O(1) + Al(s) + MnO4-(aq) ---> Al(OH)4-(aq) + MnO2(s)
Answer: Al(s) is the reducing agent; MnO4-(aq) is the oxidizing agent.

BALANCING OXIDATION-REDUCTION EQUATIONS

Whenever we balance a chemical equation, we must obey the law of conservation of mass:
The amount of each element must be the same on both sides of the equation. (Atoms are neither
created nor destroyed in any chemical reaction.) In addition, gains and losses of electrons must be
balanced. In other words, if a substance loses a certain number of electrons during a reaction, then
another substance must gain that same number of electrons. (Electrons are neither created nor
destroyed in any chemical reaction.)
In many simple chemical reactions, balancing the electrons is handled "automatically"; we
can balance the equation without explicitly considering the transfer of electrons. Many redox
reactions are, however, more complex and cannot be balanced easily without taking into account
the number of electrons lost and gained in the course of the reaction. In this section we examine
the method of half reactions, which is a systematic procedure for balancing redox equations.

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

Half-Reactions
Although oxidation and reduction must take place simultaneously, it is often convenient to
consider them as separate processes. For example, the oxidation of Sn2+ by Fe3+:
Sn2+(aq) + 2Fe3+(aq) Sn4+(aq) + 2Fe2+(aq)

Oxidation: Sn2+(aq) Sn4+(aq) + 2e-

half-reactions
Reduction: 2Fe3+(aq) + 2e- 2+
2Fe (aq)

Notice that electrons are shown as products in the oxidation process, whereas electrons are
shown as reactants in the reduction process. The use of half-reactions provides a general method
for balancing oxidation-reduction equations. Generally, H+ (for acidic solutions), OH- (for basic
solutions), and H2O are often involved as reactants or products in redox reactions. Unless H+, OH-
, or H2O are being oxidized or reduced, they do not appear in the skeleton ionic equation. Their
presence, however, can be deduced during the course of balancing the equation.
For balancing a redox reaction that occurs in acidic aqueous solution, the procedure is as
follows:
1. Divide the equation into two half-reactions, one for oxidation and the other for
reduction.
2. Balance each half-reaction.
a) First, balance the elements other than H and O.
b) Next, balance the O atoms by adding H2O as needed.
c) Then, balance the H atoms by adding H+ as needed.
d) Finally, balance the charge by adding e- as needed.
3. Multiply the half-reactions by integers, if necessary, so that the number of electrons
lost in one half-reaction equals the number of electrons gained in the other.
4. Add the two half-reactions and, if possible, simplify by canceling species appearing
on both sides of the combined equation.
5. Check to make sure that atoms and charges are balanced.
As an example, consider the reaction between permanganate ion (MnO4-) and oxalate ion
(C2O42-) in acidic aqueous solution. When MnO4- is added to an acidified solution of C2O42-, the

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

deep purple color of the MnO4- ion fades, as illustrated below. Bubbles of CO2 form, and the
solution takes on the pale pink color of Mn2+.

Titration of an acid solution of Na2C2O4 with KMnO4(aq): (a) As it moves from the burette to
the reaction flask, the deep purple MnO4- is rapidly reduced to extremely pale pink Mn2+ by C2O42-
. (b) Once all the C2O42-in the flask has been consumed, any MnO4- added to the flask retains its
purple color, and the end point corresponds to the faintest discernible purple color in the solution.
(c) Beyond the end point the solution in the flask becomes deep purple because of excess MnO4-.
The ionic equation for the reaction can be written as:
MnO4-(aq) + C2O42-(aq) Mn2+(aq) + CO2(g)
▪ To complete and balance this equation, we first write the two half-reactions (step
1).
MnO4-(aq) Mn2+(aq)

C2O42-(aq) CO2(g)

▪ Next, complete and balance each half-reaction. First, we balance all the atoms
except for H and O (step 2a).
MnO4-(aq) Mn2+(aq)

C2O42-(aq) 2CO2(g)

▪ Next we balance O (step 2b).

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

MnO4-(aq) Mn2+(aq) + 4H2O(l)

▪ The eight hydrogen atoms now in the products must be balanced by adding 8 H+ to
the reactants (step 2c):
8H+(aq) + MnO4-(aq) Mn2+(aq) + 4H2O(l)
▪ There are now equal numbers of each type of atom on the two sides of the equation,
but the charge still needs to be balanced. The total charge of the reactants is 8(1+)
+ (1-) = 7+, and that of the products is (2+) + 4(0) = 2+. To balance the charge, we
must add five electrons to the reactant side (step 3d):
5e- + 8H+(aq) + MnO4-(aq) Mn2+(aq) + 4H2O(l)
▪ Balance the charge in the other half-reaction:

C2O42-(aq) 2CO2(g) + 2e-

▪ Now we need to multiply each half-reaction by an appropriate integer so that the
number of electrons gained in one half-reaction equals the number of electrons lost
in the other (step 3). Thus,
10e- + 16H+(aq) + 2MnO4-(aq) 2Mn2+(aq) + 8H2O(l)

5C2O42-(aq) 10CO2(g) + 10e-

16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq) 2Mn2+(aq) + 8H2O(l) + 10CO2(g)

If a redox reaction occurs in basic solution, the equation must be completed by using OH-
and H2O rather than H+ and H2O. One way to balance these reactions is to balance the half-
reactions initially as if they occurred in acidic solution. Then, count the H+ in each half-reaction,
and add the same number of OH to each side of the half-reaction. In essence, what you are doing
is "neutralizing" the protons to form water on the side containing H+, and the other side ends up
with the OH-. This procedure is illustrated in the following example.
CN-(aq) + MnO4-(aq) CNO-(aq) + MnO2(s) (basic solution)
Step 1: Half-reactions:
CN-(aq) CNO-(aq)

MnO4-(aq) MnO2(s)

Step 2: Balance each half-reaction as if it took place in acidic solution.

© 2016
 Inorganic Chemistry I | Dr. Nyamato G.S.

H2O(aq) + CN-(aq) CNO-(aq) + 2H+(aq) + 2e-

3e- + 4H+(aq) + MnO4-(aq) MnO2(s) + 2H2O(l)

Step 3: We now add OH- to both sides of both half reactions to neutralize H+.
2OH-(aq) + H2O(l) + CN-(aq) CNO-(aq) + 2H+(aq) + 2e- + 2OH-(aq)
3e- + 4H+(aq) + MnO4-(aq) + 4OH-(aq) MnO2(s) + 2H2O(l)+ 4OH-(aq)
Step 4: We now "neutralize" H+ and OH- by forming H2O when they are on the same side of either
half-reaction, and then cancel the water molecules that appear as both reactants and products:
2OH-(aq) + H2O(l) + CN-(aq) CNO-(aq) + 2H2O(l) + 2e-

3e- + MnO4-(aq) + 4H2O(l) MnO2(s) + 2H2O(l)+ 4OH-(aq)

2OH-(aq) + CN-(aq) CNO-(aq) + H2O(l) + 2e-

3e- + MnO4-(aq) + 2H2O(l) MnO2(s) + 4OH-(aq)

Step 5: Equalize the number of e-.
6OH-(aq) + 3CN-(aq) 3CNO-(aq) + 3H2O(l) + 6e-
6e- + 2MnO4-(aq) + 4H2O(l) 2MnO2(s) + 8OH-(aq)

3CN-(aq) + 2MnO4-(aq) + H2O(l) 3CNO-(aq) + 2MnO2(s) + 2OH-(aq)

EXERCISE
1. Complete and balance the following equations by the method of half-reactions:

a) Cr2O72-(aq) + Cl-(aq) Cr3+(aq) + Cl2(g) (acidic solution)

Answer:
14H+(aq) + Cr2O72-(aq) + 6Cl-(aq) 2Cr3+(aq) + 3Cl2(g) + 7H2O(l)

Cu(s) + NO3-(aq) Cu2+(aq) + NO2(g) (acidic solution)

b)
Answer:
4H+(aq) + Cu(s) + 2NO3-(aq) Cu2+(aq) + 2NO2(g) + 2H2O(l)

NO2-(aq) + Al(s) NH3(aq) + Al(OH)4-(aq) (basic solution)

c)
Answer:
NO2-(aq) + 2Al(s) + 5H2O(l) +OH-(a) NH3(aq) + 2Al(OH)4-(aq)

d) Cr(OH)3(s) + ClO-(aq) CrO42-(aq) + Cl2(g) (basic solution)

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 Inorganic Chemistry I | Dr. Nyamato G.S.

Answer:
2Cr(OH)3(s) + 6ClO-(aq) 2CrO42-(aq) + 3Cl2(g) + 2OH-(aq) + 3H2O(l)

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