Dedan Kimathi University of Technology

Programme: BSc Industrial chemistry, Leather

Technology, BSc Polymer& BSc Chemical Engineering

Fundamentals of Inorganic Chemistry SCH 1101

By
Dr. Okerio Onyancha

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INTRODUCTION
Inorganic chemistry involves the study, interpreting, correlating, and predicting the properties and
structures of inorganic and organometallic compounds. Inorganic chemistry deals with the properties
of all the elements of the periodic table. Inorganic compounds ranges from ionic, covalent and
metals. Inorganic chemistry has huge impact on our everyday lives and on other scientific disciplines.
The chemical industry is greatly dependent on it. Inorganic chemistry is essential to the formulation
and improvement of modern materials such as catalysts, semiconductors, optical devices,
superconductors, and advanced ceramic materials. The environmental and biological impact of
inorganic chemistry is also huge.

Inorganic chemistry does not include the investigation of hydrocarbons compounds

composed of carbon and hydrogen that are the parent material of all other organic
compounds. The study of organic compounds is called organic chemistry.

Inorganic chemists have made significant advances in understanding the minute particles that
compose our world. These particles, called atoms, make up the elements, which are the building
blocks of all the compounds and substances in the world around us.

History of Chemistry
The Greeks were the first to try to explain why chemical changes occur. By about 400 B.C. they had
proposed that all matter was composed of four fundamental substances: fire, earth, water, and air.
The Greeks also considered the question of whether matter is continuous, and thus infinitely divisible
into smaller pieces, or composed of small indivisible particles. One supporter of the latter position
was Democritus, who used the term atomos (which later became atoms) to describe these ultimate
particles. However, because the Greeks had no experiments to test their ideas, no definitive
conclusion about the divisibility of matter was reached.

The next 2000 years of chemical history were dominated by a pseudoscience called alchemy.
Alchemists were often mystics and fakes who were obsessed with the idea of turning cheap metals
into gold. However, this period also saw important discoveries: Elements such as mercury, sulfur, and
antimony were discovered, and alchemists learned how to prepare the mineral acids.

The foundations of modern chemistry were laid in the sixteenth century with the development of
systematic metallurgy (extraction of metals from ores) by a German, Georg Bauer, and the medicinal
application of minerals by a Swiss alchemist called Paracelsus.

The first “chemist” to perform truly quantitative experiments was Robert Boyle (1627–1691), an Irish
scientist, who carefully measured the relationship between the pressure and volume of gases. When
Boyle published his book The Sceptical Chemist in 1661, the quantitative sciences of physics and
chemistry were born. In addition to his results on the quantitative behavior of gases, Boyle’s other
major contribution to chemistry consisted of his ideas about the chemical elements. Boyle held no
preconceived notion about the number of elements. In his view a substance was an element unless it
could be broken down into two or more simpler substances. As Boyle’s experimental definition of an
element became generally accepted, the list of known elements began to grow, and the Greek system
of four elements finally died. Although Boyle was an excellent scientist, he was not always right. For
example, he clung to the alchemist’s views that metals were not true elements and that a way would
eventually be found to change one metal to another.

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THE ATOM
Definition: An atom is the smallest particle of an element that can enter into a chemical combination.
The word atom comes from the Greek term atomos which means indivisible. John Dalton (1766-1844)
an English chemist and physicist was the first to present the atomic theory and supported it with
experiments. Dalton’s atomic theory is the basis of modern chemistry.

Elements are substances that cannot be decomposed into two or more simpler substances by ordinary
physical or chemical means. The word ordinary excludes the processes of radioactive decay, whether
natural or artificial, and high-energy nuclear reactions that do transform elements into one another.
When a substance contains two or more chemical elements, we call it a compound.

For example, hydrogen and oxygen are elements because no further chemical separation is possible,
whereas water is a compound because it can be separated into hydrogen and oxygen by passing an
electric current through it Binary compounds are substances, such as water, that contain two elements,
ternary compounds contain three elements, quaternary compounds contain four elements, and so on.

Figure 1 chemical elements

Indirect Evidence for the Existence of Atoms: Laws of Chemical Combination

Law of conservation of mass: Mass is neither created nor destroyed in chemical reactions; it is
conserved.
Law of definite proportions: In a given chemical compound, the proportions by mass of the elements
that compose it are fixed, independent of the origin of the compound or its mode of preparation.

Law of multiple proportions: When two elements form a series of compounds, the masses of one
element that combine with a fixed mass of the other element are in the ratio of small integers to each
other.
Law of combining volumes: The ratio of the volumes of any pair of gases in a gas phase chemical
reaction (at the same temperature and pressure) is the ratio of simple integers.

Dalton’s atomic theory

1. Elements are composed of extremely small particles called atoms, and all atoms f an element are
identical, same size, mass and chemical properties.
2. Atoms of one element are different from atoms of other elements.
3. Compounds are composed of atoms of more than one element. In any compound the ratio of the
number of atoms of any two elements present is either an integer or simple fraction.
4. A chemical reaction involves only the separation, combination or rearrangement of atoms. It does
not result in their creation or destruction.

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Problem with Dalton’s theory
Although some of Dalton’s were wrong, they did not affect the basic one that atoms do exist.
The errors were:-
1. Atoms are indestructible. However, atoms like uranium can be split.
2. All atoms of an element have identical. The fact is some elements have atoms of
more than one kind which differ slightly in mass and are called isotopes. Isotopes of a
given element have same chemical properties.

The atomic structure

The atom consists of the following fundamental particles/subatomic particles.
1. Electrons
2. Protons
3. Neutrons
The protons and the neutrons are found together in the tiny and extremely dense core particle called
the nucleus located in the center of the atom. The electrons occupy the volume near the nucleus.
The main landmarks in the evolution of atomic structure are :
• 1896 J.J. Thomson’s discovery of the electron and the proton
• 1909 Rutherford’s Nuclear Atom
• 1913 Mosley’s determination of Atomic Number
• 1913 Bohr Atom
• 1921 Bohr-Bury Scheme of Electronic Arrangement
• 1932 Chadwick’s discovery of the neutron

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Discovery of fundamental particles
The electron
In 1890, Sir William Crooks discovered that discharging electricity through a gas at low
pressure, a beam of rays was given off at the cathode (negative electrode). Crookes called them
cathode rays. The cathode rays were discovered to be particles.

Figure 2 Production of cathode rays

In 1897, a British physicist J. J. Thomson constructed an apparatus (cathode ray tube) for quantitative
measurement of the properties of cathode ray particles.
Thomson passed a high voltage between the cathode and the anode of the tube and then studied the
deflection of cathode rays in the presence of magnetic and electric field.
Since a hole was made at the anode of the tube, the cathode particles passed through it to strike the
surface at the tube at position 1where it produced a bright phosphor that coated the inner surface.
By applying only a magnetic field near the cathode tube, the cathode rays were bent towards point 2.
By applying only electric field, the cathode particles were deflected to point 3 (towards positive plates).
Thomson concluded that the rays were electrically charged. They were shown to carry a negative charge
since they were attracted to the positively charged plate and repelled by negatively charged one.

By carefully controlling the charge on the plates and the magnet both around the tube, Thomson was
able to make the cathode ray strike the tube at point 1, i.e. he cancelled the effect of magnetic field by
applying an electric field. From his measurements, he calculated the ratio of charge/mass (e/m) was -
1.76×10-11CKg-1. (C = coulomb-SI unit of charge. The negative sign reflects the negative charge of the
particle). Thomson obtained the same value regardless of the nature of the gas used. He deducted that
these negatively charged particles are present in all matter and that they are fundamental particles of
matter. They were named electrons.

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Figure 3 Thomson’s cathode ray tube, which was used to measure the charge to mass ratio of electrons

Thomson reasoned that since atoms were electrically neutral, and cathode rays were negatively, they
must also contain positive charges. Thomson proposed a model of the atom in which the positive and
the negative particles were embedded in some sort of matrix. The model was called the plum pudding
model.

https://www.youtube.com/watch?v=Rb6MguN0Uj4
https://www.youtube.com/watch?v=fUvBQL3WG50

Figure 4 Plum pudding model proposed by Thomson

The value of the electric charge was found by R.A. Milliken through is oil drop experiment.
The charge of the electron is -1.60×10-19 C. The mass of the electron was then calculated from
Thomson’s charge to mass ratio.
e/m= -1.76×1011CKg-1

Solving for the mass m, and substituting -1.60×10-19 coulombs for electron gives;
-1.60×10-19 C
M= -1.76×1011CKg-1

M= 9.11× 10-31Kg

Discovery of Protons
In the early 1900s, Thomson also proved that positively charged particles are a fundamental part of the
atom. Thomson used a modified cathode-ray tube filled with hydrogen gas. By passing a spark through
the gas, he was able to bump the electrons off of the hydrogen atoms, leaving particles known as ions.
Thomson accelerated the hydrogen ions through an electric field and observed that the ions deflected
toward the negatively charged electrode (electric conductor). As a result, Thomson correctly concluded
that hydrogen ions contain positively charged particles; these particles are now referred to as protons.
Experiments using an instrument known as a mass spectrometer revealed that protons have a mass
roughly 1800 times greater than that of electrons. The mass spectrometer also showed that each element
is differentiated by the number of protons it contains (known as the atomic number). The elements are
arranged in the periodic table by increasing atomic number. For example, hydrogen has one proton,
helium has two, and lithium has three.

Radioactivity
In 1895, the German physicist Wilhelm Röntgen noticed that cathode rays caused glass and metals to
emit very unusual rays. This highly energetic radiation penetrated matter, darkened covered

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photographic plates, and caused a variety of substances to fluoresce. Because these rays could not be
deflected by a magnet, they could not contain charged particles as cathode rays do. Röntgen called them
X rays because their nature was not known.

Not long after Röntgen’s discovery, Antoine Becquerel, a professor of physics in Paris, began to study
the fluorescent properties of substances. Purely by accident, he found that exposing thickly wrapped
photographic plates to a certain uranium compound caused them to darken, even without the stimulation
of cathode rays. Like X rays, the rays from the uranium compound were highly energetic and could not
be deflected by a magnet, but they differed from X rays because they arose spontaneously.
One of Becquerel’s students, Marie Curie, suggested the name radioactivity to describe this
spontaneous emission of particles and/or radiation. Since then, any element that spontaneously emits
radiation is said to be radioactive. Three types of rays are produced by the decay, or breakdown, of
radioactive substances such as uranium. Two of the three are deflected by oppositely charged
metal plates. Alpha (α) rays consist of positively charged particles, called α particles, and therefore ar
e deflected by the positively charged plate. Beta (β) rays, or β particles, are electrons and are deflected
by the negatively charged plate. The third type of radioactive radiation consists of high-energy rays
called gamma (ᵞ) rays . Like X rays, g rays have no charge and are not affected by an external field.

Radioactive Decay
Radioactive nuclei can undergo decomposition in various ways. These decay processes fall into two
categories: those that involve a change in the mass number of the decaying nucleus and those that do
not. We will consider the former type of process first.

An alpha particle, or α particle, is a helium nucleus (4He). Alpha-particle production is a very

common mode of decay for heavy radioactive nuclides. For example, 238U, the predominant isotope of
natural uranium (99.3%), decays by α-particle production:

Another decay process in which the mass number of the decaying nucleus changes is spontaneous
fission, the splitting of a heavy nuclide into two lighter nuclides with similar mass numbers. Although
this process occurs at an extremely slow rate for most nuclides, it is important in some cases. For
instance, spontaneous fission is the predominant mode of decay for 254 Cf.

The most common decay process in which the mass number of the decaying nucleus remains constant
is beta-particle production. For example, the thorium- 234 nuclide produces a β particle and is
converted to protactinium-234:

The β particle is assigned the mass number 0, since its mass is tiny compared with that of a proton or neutron.
Because the value of Z is -1 for the β particle, the atomic number for the new nuclide is greater by 1
than for the original nuclide. Thus the net effect of β-particle production is to change a neutron to a

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proton. We therefore expect nuclides that lie above the zone of stability) to be β- particle producers.
Although the β particle is an electron, the emitting nucleus does not contain electrons.

A gamma ray, or γ ray, refers to a high-energy photon. Frequently, gamma ray production
accompanies nuclear decays and particle reactions, such as in the y-particle decay of 238U:

in which two γ rays of different energies are sometimes produced in addition to the α particle. The
emission of γ rays is one way a nucleus with excess energy (in an excited nuclear state) can relax to its
ground state.

Positron production occurs for nuclides below the zone of stability (those nuclides whose
neutron/proton ratios are too small). The positron is a particle with the same mass as the electron but
opposite charge. An example of a nuclide that decays by positron production is sodium-22:

Note that the net effect of this process is to change a proton to a neutron, causing the product nuclide
to have a higher neutron/proton ratio than the original nuclide. When a positron collides with an
electron, the particulate matter is changed to electromagnetic radiation in the form of high-energy
photons:

This process, which is characteristic of matter–antimatter collisions, is called annihilation and is

another example of the interchange of the forms of matter.

Electron capture is a process in which one of the inner-orbital electrons is captured by the nucleus,
as illustrated by the process

Often a radioactive nucleus cannot reach a stable state through a single decay process. In such a case a decay
series occurs until a stable nuclide is formed. A well-known example is the decay series that starts with 92
238U and ends with 82 206Pb, as shown below similar series exist for 235U:

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9
The discovery of the atomic nucleus
An experiment crucial to the understanding of the structure of the atom was carried out by Ernest
Rutherford in 1911. The Rutherford experiment as it is known consisted of bombarding a thin metal
foil with alpha particles. The experiment is shown diagrammatically in figure 2. Most of the alpha
particles sailed through as if the foil was virtually empty space. However, a significant number of alpha
particles were deflected at very large angles. Some were even deflected backwards towards the source.
Rutherford reason for such observation to occur, there would be a massive positive force concentrated
in a small region of space. Rutherford’s experiment demonstrated that the total positive charge in an
atom is localized in a small region of space which he called the nucleus. Since most of the alpha
particles passed through the foil indicating they did not come near the nucleus, implying most of the
atom is empty space. Rutherford put forward an atomic model similar to the solar system, in which the
electrons are orbiting the nucleus.

Figure 5 Alpha particles scattered in all direction by a tin metal foil in Rutherford’s gold leaf experiment

Rutherford model laid the foundation of the model picture of the atom. However it did not tell anything
as to the position of the electrons and how they were arranged around the nucleus. Rutherford
recognised that electrons were orbiting around the nucleus. But according to the classical laws of
Physics an electron moving in a field of force like that of nucleus, would give off radiations and

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gradually collapse into the nucleus. Thus Rutherford model failed to explain why electrons did not do
so.

Figure 6 Rutherford’s model of the atom

Discovery of the neutron

The works of Thomson and Rutherford and gave a correct view of the atom, there was still a problem
of what made the reminder of the mass of atom. It was postulated that there must be additional particles
in the atomic nucleus. Rutherford only about half the nuclear mass could be accounted by protons. This
led him to suggest that there were other particles in the nucleus that had a mass close or equal to that
of the proton, but with no electrical charge. This suggestion initiated a search that finery ended in 1932
with the discovery of the neutrons by Sir James Chadwick.
In 1932 Sir James Chadwick directed a stream of alpha particles (24He ) at a beryllium target.
He found that a new particle was ejected. It has almost the same mass (1.674 × 10–24 g) as
that of a proton and has no charge.

Figure 7 Experiment for discovery of neutrons

He named it neutron. The assigned relative mass of a neutron is approximately one atomic mass unit
(amu). Thus : A neutron is a subatomic particle which has a mass almost equal to that of a
proton and has no charge.

In summary, the atom was shown to consist of the electrons, protons and neutrons. The properties of
these fundamental particles are shown in table 1.

Table 1 Properties of subatomic particles

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A nuclide is a particular type of atom and possesses a characteristic atomic number, Z, which is equal
to the number of protons in the nucleus; because the atom is electrically neutral, Z also equals the
number of electrons. The mass number, A, of a nuclide is the number of protons and neutrons in the
nucleus.

Isotopes
Mass spectrometry developed after Thomson had shown how relative atomic and molecular masses
could be measured directly by observing the deflections of ions in electric and magnetic fields.
Refinements of Thomson’s technique made it possible to measure relative masses extremely accurately
and led to the discovery of the isotopes of many elements. Atoms with the same atomic number but
different mass numbers are called isotopes. Most elements consist of atoms having several different
mass numbers. For example, there are two kinds of boron atoms, one with a mass of about 10 u (10B)
and a second with a mass of about 11 u (11B). All atoms of an element have the same number of
protons—five in the case of boron. To have different masses, isotopes must have different numbers of
neutrons. The nucleus of a 10B atom (Z = 5) contains five protons and five neutrons, whereas the
nucleus of a 11B atom contains five protons and six neutrons. Scientists often refer to a particular
isotope by giving its mass number (for example, uranium-238, 238U).

Nuclides of the same element possess the same number of protons and electrons but may have different
mass numbers; the number of protons and electrons defines the element but the number of neutrons may
vary. Nuclides of a particular element that differ in the number of neutrons and, therefore, their mass
number, are called isotopes. Isotopes of some elements occur naturally while others may be produced
artificially.

Elements that occur naturally with only one nuclide are monotopic and include phosphorus, 31
15P, and fluorine, 19 9F.

Example

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13
QUANTUM MECHANICS AND ATOMIC THEORY

ELECTROMAGNETIC RADIATION AND ATOMIC SPECTRA

How electrons are distributed about the nucleus is called the atom’s electronic structure. The basic
clue to the electronic structure of the various elements comes from the light emitted when atoms of
the element are excited /energized. If a high voltage is applied to atoms of an element in the gas phase
at low pressure, the atoms absorb energy and are said to be “excited.” The excited atoms can then
emit light, and a familiar example is the coloured light from neon advertising signs. The light falling
on Earth from the Sun, or the light emitted by a very hot object, consists of a continuous spectrum of
wavelengths. In contrast, the light from excited atoms consists of only a few different wavelengths of
light. The spectrum obtained in this manner, such as that for excited H atoms is called a line emission
spectrum.

The line emission spectra of hydrogen, mercury, and neon are below, and you can see that every
element has a unique spectrum. Indeed, the characteristic lines in the emission spectrum of an element
can be used in chemical analysis, both to identify the element and to determine how much of it is
present.

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Line emission spectra of hydrogen, mercury, and neon. Excited gaseous elements produce
characteristic spectra that can be used to identify the elements as well as to determine how much of each element
is present in a sample.

What is the significance of the line spectrum of hydrogen? It indicates that only certain energies are
allowed for the electron in the hydrogen atom. In other words, the energy of the electron in the
hydrogen atom is quantized. Changes in energy between discrete energy levels in hydrogen produce
only certain wavelengths of emitted light.

Electromagnetic Energy
Energy can be transmitted through space by electromagnetic radiations. Some forms of radiant energy
are radio waves, visible light, infrared light, ultraviolet light, X-rays and γ-radiations. They resemble
water waves, but unlike water waves, what oscillates is no matter. The oscillations are
systematic fluctuations in the intensities of very tiny electrical and magnetic forces. A wave
conveys energy from the vibrating object to a distant place. The wave travels at right angle to
the vibratory motion of the object.

Figure 8. Wave motion caused by vibrating source

Characteristics of waves

1. Wavelength (λ): the distance between two successive crests or troughs of a wave. It
is denoted by Greek letter lamda (λ). It is expressed in meters, angstroms or
centimetres.
2. Frequency (ν): number of waves which pass a given point in a second. The
frequency is denoted by letter nu and its SI units is hertz (Hz) 1Hz= 1cycle /second

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 3. Speed or velocity of a wave (c): distance through which a wave travels in one
second. It is expressed c/second. If the speed of a wave is c m/second, it means the
distance travelled by a wave in I second is c metres.
4. Wave number: this is reciprocal of wavelength and is given by the symbol nu bar

Speed is related to frequency and wavelength by the following expression

ϲ =λν

or speed= wavelength × frequency

The velocity of electromagnetic radiation in vacuum is 3.0 × 108 m/s. Alternatively;

λν = ϲ = 3.0 × 108 m/s

Examples:

1. A yellow light has a wavelength of 600 nanometers. What is the frequency in Herts
2. A certain FM radio station broadcasts at a frequency of 93.5 MHz what is the wavelength
expressed in meters?

ELECTROMAGNETIC SPECTRUM
Radiation provides an important means of energy transfer. For example, the energy from the sun
reaches the earth mainly in the forms of visible and ultraviolet radiation, and the glowing coals of a
fireplace transmit heat energy by infrared radiation. In a microwave oven the water molecules in food
absorb microwave radiation, which increases their motions. This energy is then transferred to other
types of molecules via collisions, causing an increase in the food’s temperature.

Electromagnetic radiation comes in a large range of frequencies called the electromagnetic spectrum.
Each portion of the spectrum has a name.

Figure 9 Electromagnetic spectrum showing boundaries

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Continuous spectrum

The light emitted by the sun is white in colour. It is composed of light waves in the range 4000-
800 angstroms. Each wave has a characteristic colour. When a beam of white (visible light) is
passed through a prism different wavelengths are refracted through different angles. It ranges
from red through orange, yellow, green, blue indigo, and violet. This series of bands forms a
continuous spectrum.

Atomic spectrum
Light given off by a gas such as hydrogen when an electric discharge is passed (excited)
through is of a characteristic colour. The colour of light produced indicates the wavelength of
the radiation emitted. The frequencies of light given off by an excited atom of an element are
unique to that element; each element has its own characteristic atomic spectrum. A spectrum
in which each line represents a specific wavelength of radiation emitted by atoms is referred to
as line spectrum or atomic emission spectrum of the element. Absorption spectrum is obtained
when visible light is passed through vapour of an element and certain wavelengths are
absorbed. The absorbed wavelength are found missing from the transmitted light. Absorption
spectrum is the opposite of emission spectrum.

Figure 10 Wavelength of colour bands in continuous spectrum

Hydrogen spectrum
When an electric discharge is passed though hydrogen gas at low pressure and the light emitted
examined by a spectroscope, a spectrum consisting of a number of lines is obtained. The lines
constitute the spectrum of hydrogen.

In 1884 J.J. Balmer observed that there were four prominent coloured lines in the visible
hydrogen spectrum:

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 • a red line with a wavelength of 6563 Å.
• a blue-green line with a wavelength 4861 Å.
• a blue line with a wavelength 4340 Å.
• a violet line with a wavelength 4102 Å.
The above series of four lines in the visible spectrum of hydrogen was named as the Balmer
Series. By carefully studying the wavelengths of the observed lines, Balmer was able
empirically to give an equation which related the wavelengths (λ) of the observed lines. The
Balmer Equation is

where R is a constant called the Rydberg Constant which has the value 109, 677 cm– 1 and n
= 3, 4, 5, 6 etc. That is, if we substitute the values of 3, 4, 5 and 6 for n, we get, respectively,
the wavelength of the four lines of the hydrogen spectrum.
In addition to Balmer Series, four other spectral series were discovered in the infrared and
ultraviolet regions of the hydrogen spectrum. These bear the names of the discoverers. Thus in
all we have Five Spectral Series in the atomic spectrum of hydrogen:

Name Region where located

(1) Lyman Series Ultraviolet
(2) Balmer Series Visible
(3) Paschen Infrared
(4) Brackett Infrared
(5) Pfund Series Infrared

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Quantum theory of radiation
In 1900, Max Plank a German physicist proposed that electromagnetic radiation is carried by
tiny packets of energy called photons. He called the unit of wave or packet of energy quantum
(plural quanta).
Quantum theory of electromagnetic radiations
1. When atoms or molecules absorb or emit radiant energy, they do so in separate
‘units of waves’ called quanta or photons. Thus light radiations obtained from
energised or ‘excited atoms’ consist of a stream of photons and not continuous waves.
2. The energy, E, of a quantum or photon is given by the relation
E = hν ……(1)
where ν is the frequency of the emitted radiation, and h the Planck’s Constant. The
value of h = 6.62 × 10– 27 erg sec. or 6.62 × 10– 34 J sec.
We know that c, the velocity of radiation, is given by the equation
c = λν ...(2)
Substituting the value of ν from (2) in (1), we can write
E =hc/λ

Thus the magnitude of a quantum or photon of energy is directly proportional to

the frequency of the radiant energy, or is inversely proportional to its wavelength,
λ.
3. An atom or molecule can emit (or absorb) either one quantum of energy (hν) or
any whole number multiple of this unit.
Thus radiant energy can be emitted as hν, 2hν, 3hν, and so on, but never as 1.5 hν, 3.27 hν,
5.9 hν, or any other fractional value of hν i.e. nhν

Example: calculate the magnitude of energy of a photon associated with light of wavelength
6057.8 Å
Solution

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THE BOHR MODEL OF THE ATOM
The discovery of that the energy of electrons were quantized led to attempts to develop
theoretical models of the way electrons behave in atoms. The goals were to explain how
electrons move, where they are located, and how they change energy to give off photons of
light.
In 1913 Niels Bohr, a Danish physicist proposed a theoretical model of the hydrogen atom. He
chose the hydrogen atom because it was the simplest, having only one electron about the
nucleus and it also produced the simplest spectrum with few lines.
Postulates of Bohr’ theory
1. Electrons travel around the nucleus in specific permitted circular orbits and in
no others. Electrons in each orbit have a definite energy and are at a fixed distance
from the nucleus. The orbits are given the letter designation n and each is numbered 1,
2, 3, etc. (or K, L, M, etc.) as the distance from the nucleus increases.

2. While in these specific orbits, an electron does not radiate (or lose) energy.
Therefore in each of these orbits the energy of an electron remains the same i.e. it
neither loses nor gains energy. Hence the specific orbits available to the electron in an
atom are referred to as stationary energy levels or simply energy levels.
3. An electron can move from one energy level to another by quantum or photon
jumps only. When an electron resides in the orbit which is lowest in energy (which is
also closest to the nucleus), the electron is said to be in the ground state. When an
electron is supplied energy, it absorbs one quantum or photon of energy and jumps to
a higher energy level. The electron then has potential energy and is said to be in an
excited state.
The quantum or photon of energy absorbed or emitted is the difference between the
lower and higher energy levels of the atom
ΔE = Ehigh – Elow = hν

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 4. The angular momentum (mvr) of an electron orbiting around the nucleus is an integral
multiple of Planck’s constant divided by 2π.
Bohr’s explanation of hydrogen spectrum
The single electron in hydrogen atom at ordinary temperature resides in the first orbit (n = 1)
and is in the lowest energy state (ground state). When energy is supplied to hydrogen gas in
the discharge tube, the electron moves to higher energy levels viz., 2, 3, 4, 5, 6, 7, etc.,
depending on the quantity of energy absorbed. From these high energy levels, the electron
returns by jumps to one or other lower energy level. In doing so the electron emits the excess
energy as a photon. This gives an excellent explanation of the various spectral series of hydrog
en. Lyman series is obtained when the electron returns to the ground state i.e., n = 1 from higher
energy levels (n2 = 2, 3, 4, 5, etc.). Similarly, Balmer, Paschen, Brackett and Pfund series are
produced when the electron returns to the second, third, fourth and fifth energy levels
respectively.

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Figure 11 Hydrogen atom spectral series

Example: Find the wavelength in Å of the line in Balmer series that is associated with the
drop of the electron from the fourth orbit. The value of Rydberg constant is 109676 cm-1.
Solution
The wavelengths in the Balmer Series are given by

𝟏 𝟏 𝟏
= 𝑹 ( 𝟐 − 𝟐)
𝝀 𝟐 𝒏

Where λ= wavelength, R= (Rydberg’s constant) 109676 cm-1; n =4

Therefore
𝟏 𝟏 𝟏
= 𝟏𝟎𝟗𝟔𝟕𝟔 ( 𝟐 − 𝟐 )
𝝀 𝟐 𝟒
𝟑
= 𝟏𝟎𝟗𝟔𝟕𝟔 ( )
𝟏𝟔
𝟏𝟔
𝝀= = 𝟒. 𝟖𝟑 × 𝟏𝟎−𝟓 cm
𝟏𝟎𝟗𝟔𝟕𝟔 × 3

λ in Å =4.83 ×10-5 ×108 =4830

Therefore wavelength of the spectral line is 4830 Å

22
SHORTCOMINGS OF THE BOHR ATOM
(1) The great success of the Bohr’s theory was in its ability to predict lines in the hydrogen
atom spectrum. But it was spectacularly unsuccessful for every other atom containing
more than one electron.
(2) We no longer believe in well-defined electron orbits as was assumed by Bohr. In
fact, in view of modern advances, like dual nature of matter, uncertainty principle, any
mechanical model of the atom stands rejected.
(3) Bohr’s model of electronic structure could not account for the ability of atoms to
form molecules through chemical bonds. Today we only accept Bohr’s views regarding
quantization as nobody has explained atomic spectra without numerical quantization and no
longer attempted description of atoms on classical mechanics.
(4) Bohr’s theory could not explain the effect of magnetic field (Zeeman effect) and electric
field (Stark effect) on the spectra of atoms.

Energy of electrons in hydrogen atom

Bohr attributed the emission of radiation by an energized hydrogen atom to the electron dropping from
a higher-energy allowed orbit to a lower one and emitting a quantum of energy (a photon) in the form
of light. Bohr’s theory enables us to explain the line spectrum of the hydrogen atom. Radiant energy
absorbed by the atom causes the electron to move from a lower-energy state (characterized by a smaller
n value) to a higher-energy state (characterized by a larger n value). Conversely, radiant energy (in the
form of a photon) is emitted when the electron moves from a higher-energy state to a lower-energy
state.
During emission, the electron drops to a lower energy state characterized by the principal quantum
number nf (the subscripts i and f denote the initial and final states, respectively). This lower energy state
may be either a less excited state or the ground state. The difference between the energies of the initial
and final states is
△E = Ef - Ei

The equation can be written as

𝟏 𝟏
△ 𝑬 = 𝒉𝒗 = 𝑹𝑯 ( − )
𝒏𝟐𝒊 𝒏𝟐𝒇

Where RH is Rydberg’s constant = 2.18 ×10-18 J

The number n is an integer called principal quantum number, it has values n = 1, 2, 3……..
When a photon is emitted, ni > nf and change in energy is negative.
When a photon is absorbed, ni < nf and the change in energy is positive

23
Example

What is the wavelength of a photon (in nanometers) emitted during a transition from the
n i = 5 state to the nf = 2 state in the hydrogen atom?
Solution
𝟏 𝟏
△ 𝑬 = 𝒉𝒗 = 𝑹𝑯 ( − )
𝒏𝟐𝒊 𝒏𝟐𝒇

𝟏 𝟏
△ 𝑬 = 𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝐉 ( 𝟐 − 𝟐 )
𝟓 𝟐

△ 𝑬 = −𝟒. 𝟓𝟖 × 𝟏𝟎−𝟏𝟗 𝐉

The negative sign indicates that this energy is associated with emission and can be omitted
from the calculation of the wavelength.
Since △ 𝑬 = 𝒉𝒗 we can calculate the wavelength as follows;
𝑐
𝜆=
𝑣
𝑐ℎ
𝜆=
△𝐸
3.0 × 108 m/s × 6.63 × 10−34 Js
𝜆=
4.58 × 10−19 J

λ= 4.34 × 10-7 m
given (1m =1×109 nm), then
λ=434 nm

Calculation of Bohr radius

Consider an electron of charge e revolving around a nucleus of charge Ze, where Z is the atomic
number and e the charge on a proton. Let m be the mass of the
electron, r the radius of the orbit and the tangential velocity
of the revolving electron.
The electrostatic force of attraction between the nucleus and the
electron (Coulomb’s law),
𝒛𝒆 × 𝒆
=
𝒓𝟐

The centrifugal force acting on the electron

𝑚𝑣 2
=
𝑟
Bohr assumed that these two opposing forces must be
balancing each other exactly to keep the electron in orbit. Thus,

24
 𝒛𝒆 × 𝒆 𝑚𝑣 2
=
𝒓𝟐 𝑟
For hydrogen Z = 1, therefore,

𝒆𝟐 𝑚𝑣 2
=
𝒓𝟐 𝑟
Multiplying both sides by r

𝑒
= 𝑚𝑣 2
𝑟

According to one of the postulates of Bohr’s theory, angular momentum of the revolving electron
is given by the expression

Substituting the value into the equation

Solving for r

Since the value of h, m and e had been determined experimentally, substituting these values in, we
have

25
Energy of electron in each orbit
For hydrogen atom, the energy of the revolving electron, E is the sum of its kinetic energy and potential energy.

𝑒2
𝐾. 𝐸 = 1/2𝑚𝑣 2 and potential energy 𝑃. 𝐸 = − 𝑟

Substituting the value of 𝑚𝑣 2

Substituting the value of r into the equation

Substituting the values of m, e, and h, we get

26
By using proper integer for n (quantum or orbit number), we can get the energy for each orbit.

Significance of Negative Value of Energy

The energy of an electron at infinity is arbitrarily assumed to be zero. This state is called zero-energy
state. When an electron moves and comes under the influence of nucleus, it does some work and
spends its energy in this process. Thus the energy of the electron decreases and it becomes less than
zero i.e. it acquires a negative value.

Energy of electrons in hydrogen atom

Bohr attributed the emission of radiation by an energized hydrogen atom to the electron dropping from
a higher-energy allowed orbit to a lower one and emitting a quantum of energy (a photon) in the form
of light. Bohr’s theory enables us to explain the line spectrum of the hydrogen atom. Radiant energy
absorbed by the atom causes the electron to move from a lower-energy state (characterized by a smaller
n value) to a higher-energy state (characterized by a larger n value). Conversely, radiant energy (in the

27
form of a photon) is emitted when the electron moves from a higher-energy state to a lower-energy
state.
During emission, the electron drops to a lower energy state characterized by the principal quantum
number nf (the subscripts i and f denote the initial and final states, respectively). This lower energy state
may be either a less excited state or the ground state. The difference between the energies of the initial
and final states is
△E = Ef - Ei

The equation can be written as

𝟏 𝟏
△ 𝑬 = 𝒉𝒗 = 𝑹𝑯 ( − )
𝒏𝟐𝒊 𝒏𝟐𝒇

Where RH is Rydberg’s constant = 2.18 ×10-18 J

The number n is an integer called principal quantum number, it has values n = 1, 2, 3……..
When a photon is emitted, ni > nf and change in energy is negative.
When a photon is absorbed, ni < nf and the change in energy is positive
Example

What is the wavelength of a photon (in nanometers) emitted during a transition from the
n i = 5 state to the nf = 2 state in the hydrogen atom?
Solution
𝟏 𝟏
△ 𝑬 = 𝒉𝒗 = 𝑹𝑯 ( − )
𝒏𝟐𝒊 𝒏𝟐𝒇

𝟏 𝟏
△ 𝑬 = 𝟐. 𝟏𝟖 × 𝟏𝟎−𝟏𝟖 𝐉 ( 𝟐 − 𝟐 )
𝟓 𝟐

△ 𝑬 = −𝟒. 𝟓𝟖 × 𝟏𝟎−𝟏𝟗 𝐉

The negative sign indicates that this energy is associated with emission and can be omitted
from the calculation of the wavelength.
Since △ 𝑬 = 𝒉𝒗 we can calculate the wavelength as follows;
𝑐
𝜆=
𝑣
𝑐ℎ
𝜆=
△𝐸
3.0 × 108 m/s × 6.63 × 10−34 Js
𝜆=
4.58 × 10−19 J

28
 λ= 4.34 × 10-7 m
given (1m =1×109 nm), then
λ=434 nm
POTENTIAL ENERGY AT NTH LEVEL

DUAL NATURE OF ELECTRON

Einstein (1905) suggested that light has a dual character and behaves both as a particle and as a wave.
L. de Broglie (1924) suggested that all material particles in motion such as electrons, protons,
neutrons, atoms, molecules etc. have dual character. According to L. de Broglie, any moving electron
in the atom is a material particle associated with wave properties wid he compared electrons with
photons having negligible masses.
According to L. de Broglie, the wavelength A of a particle of mass m and velocity u is given by the
relation :
ℎ
𝜆 = 𝑚𝑢 where m is the mass and u is the velocity, h planks constant and mu s momentum
Derivation of de Broglie's equation : The relation between the particle nature and wave nature of
electron is known as de Broglie equation. According to Planck, the energy of a quantum of radiation
is given by :
𝐸 = ℎ𝑣………………………………………………………………………………………………..1
According to Einstein, mass and energy are related as :
𝐸 = 𝑚𝑐 2 …………………………………………………………………………………………......2
where c is the velocity of light.
Combining these two, we have :
ℎ𝑣 = 𝑚𝑐 2
ℎ𝑣
or = 𝑚𝑐
𝑐

ℎ
or = 𝑚𝑐
𝑐/𝑣

ℎ
or 𝜆
= 𝑚𝑐
or
ℎ
𝜆=
𝑚𝑐
This equation is applicable for photon. According to L. de Broglie, the above equation can also be applied
to material particles by substituting the mass of the particle m and its velocity u in place of velocity of light
e. Thus, wavelength λ of material particle is given by:
ℎ
𝜆=
𝑚𝑢

This is the de Broglie equation.

29
The momentum of a particle in motion is inversely proportional to wavelength, Planck’s
constant ‘h’ being the constant of proportionality.

The quantum restriction of Bohr’s theory for an electron in motion in the circular orbit is that the angular
momentum (mvr) is an integral multiple (n) of h/2π. That is,

30
The uncertainty principle
Werner Heisenberg in 1927, gave the most celebrated results of quantum mechanics: It is impossible
to specify simultaneously, with arbitrary precision, both the momentum and the position of a particle.
Or 'It is impossible to determine simultaneously both the position and the velocity or momentum of a
small moving particle like an electron'.

According to the uncertainty principle, it is impossible to know simultaneously both the conjugate
properties accurately. For example, the position and momentum of a moving particle are
interdependent and thus conjugate properties also. Both the position and the momentum of the particle
at any instant cannot be determined with absolute exactness or certainty. If the momentum (or

31
velocity) be measured very accurately, a measurement of the position of the particle correspondingly
becomes less precise. On the other hand if position is determined with accuracy or precision, the
momentum becomes less accurately known or uncertain. Thus certainty of
determination of one property introduces uncertainty of determination of the other.

The uncertainty in measurement of position, Δx, and the uncertainty of determination of momentum,
Δp (or Δmv), are related by Heisenberg’s relationship as:

Where h is planks’s constant

It may be pointed out here that there exists a clear difference between the behaviour of large objects like a stone
and small particles such as electrons. The uncertainty product is negligible in case of large objects.

The physical concept of the uncertainty principle may be

clear by assuming that all observations have to be made by
impact of light radiations or photons. If the object is of a
reasonably big size, its position or velocity will not be
changed by the impact of light photons. So, it will be possible
to know both the position and velocity of the object.
However, this is not possible when the object is very small,
such as an electron. It will suffer a change in its path and
velocity due to the impact of even a single photon of light.
The path and velocity of an electron, after the impact of light
photons, may be quite different from the original path and
velocity.

On this basis, Bohr's model in which the electron electrons are considered as particles revolving in
definite orbits, i.e., well defined path, does not hold good. However, it will be more correct to say
that an electron is associated with a certain energy, i.e., it belongs to a definite energy level and not
that it belongs to a definite orbit.

As it is impossible to know the position and the velocity of any one electron on account of its small size, the
best we can do is to speak of the probability or relative chance of finding an electron with a probable velocity.
The old classical concept of Bohr has now been discarded in favour of the probability approach.

32
SSCHRÖDINGER’S WAVE EQUATION
In order to provide sense and meaning to the probability approach, Schrödinger derived an
equation known after his name as Schrödinger’s Wave Equation. Calculation of the probability of
finding the electron at various points in an atom was the main problem before Schrödinger. His
equation is the keynote of wave mechanics and is based upon the idea of the electron as ‘standing
wave’ around the nucleus.

The equation for the standing wave*, comparable with that of a stretched
string is CHRNGER WAVE EQUATION

33
34
Starting from de Broglie's concept, Schrodinger developed the theory of wave mechanics and
obtained a mathematical equation describing the state of an electron in terms of mass (m), total energy
(E), potential energy (V) relative to atomic nucleus, Planck's constant (h) and a quantity 'I' called the
wave function of the electron (or the amplitude of the wave). The equation is called Schrodinger's
wave equation. It can be developed from the general differential equation of wave motion in one
dimension, i.e., along X-axis.

Wave equation and hydrogen atom: In the case of hydrogen atom in which a single electron with
charge -e revolves around a pr:oton with charge +e, the potential energy, V = - (e2/r), where r is the
distance between the electron and the nucleus. Substituting the value of V in equation (4), we get

35
This value of E is identical with Bohr's value obtained on the basis of classical mechanics introducing
arbitrarily the fact that the angular momentum is quantised.

Significance of wave function, 'Ψ. The wave function, 'Ψ' in Schrodinger equation has no
physical significance except that it shows the amplitude of the electron wave. The value of Ψ2
gives the probability of finding an electron of a given energy, E, from place to place in a
given region around the nucleus. It is possible to identify region of space around the nucleus
where there is a high probability of finding an electron associated with a certain energy. The
space is known as an atomic orbital.

It may be noted that in Bohr's theory, the electron associated with a certain energy is
supposed to be situated at a certain distance from the nucleus. In wave Mechanics, the
equation for calculating the exact energy of the electron has been derived, but there is great
uncertainty in finding its exact position. This is in conformity with Heisenberg's uncertainty
principle.

When the electron gets excited and it is raised from n to higher energy levels (say n = 2 or n = 3),
the solution of wave equation gives sets of value of 2 which give different shapes to the space
distribution of the electron.

36
CHARGE CLOUD CONCEPT AND ORBITALS
The Charge Cloud Concept finds its birth from wave mechanical theory of the atom. The wave equation for a
given electron, on solving gives a three-dimensional arrangement of points where it can possibly lie. There are
regions where the chances of finding the electron are relatively greater. Such regions are expressed in terms of
‘cloud of negative charge’. We need not know the specific location of the electrons in space but are concerned
with the negative charge density regions. Electrons in atoms are assumed to be vibrating in space, moving
haphazardly but at the same time are constrained to lie in regions of highest probability for most of the time.
The charge cloud concept simply describes the high probability region. The three-dimensional region
within which there is higher probability that an electron having a certain energy will be found, is called
an orbital.
An orbital is the most probable space in which the electron spends most of its time while in constant motion. In
other words, it is the spatial description of the motion of an electron corresponding to a particular energy level.
The energy of electron in an atomic orbital is always the same.

Each energy level corresponds to a three-dimensional electron wave which envelopes the nucleus. This wave
possesses a definite ‘size’, ‘shape’ and ‘orientation’ and thus can be represented pictorially.

QUANTUM NUMBERS AND ATOMIC ORBITALS

Quantum numbers
Electrons under the influence of positive charges of atomic nuclei are confined to the neighbourhood
of the atomic nuclei. The motion of these electrons have been treated as waves. In other words,
equations that describe the wave motions have been applied to represent the electrons. Solutions of
these equations lead to wave functions (A wave function for an electron in an atom is called an
atomic orbital; this atomic orbital describes a region of space in which there is a high probability of
finding the electron). Due to the confinement of the electron in the neighbourhood of the atomic
nuclei, these solutions are associated with some integers called quantum numbers. Therefore,

37
Quantum numbers are sets of numerical values which give acceptable solutions of
Schrodinger wave equation

Each electron in an atom is described by four different quantum numbers. The first three (n, l, ml)
specify the particular orbital of interest, and the fourth (ms) specifies how many electrons can occupy
that orbital.

1. Principal Quantum Number (n): n = 1, 2, 3, …, ∞

Specifies the energy of an electron and the size of the orbital (the distance from the nucleus
of the peak in a radial probability distribution plot). All orbitals that have the same value of n
are said to be in the same shell (level). For a hydrogen atom with n=1, the electron is in its
ground state; if the electron is in the n=2 orbital, it is in an excited state. The total number of
orbitals for a given n value is n2.

2. Angular Momentum (Secondary, Azimunthal) Quantum Number (l): l = 0, ..., n-1.

Specifies the shape of an orbital with a particular principal quantum number. The secondary
quantum number divides the shells into smaller groups of orbitals called subshells
(sublevels). Usually, a letter code is used to identify l to avoid confusion with n:
The values of l depend on the value of the principal quantum number, n. For a given value of
n , l has possible integral values from 0 to ( n -1). If n = 1, there is only one possible value of
l; that is, l = n - 1 = 1- 1 = 0.
The value of l is generally designated by the letters s, p, d, . . . as follows:

The subshell with n=2 and l=1 is the 2p subshell; if n=3 and l=0, it is the 3s subshell, and so
on. The value of l also has a slight effect on the energy of the subshell; the energy of the
subshell increases with l (s < p < d < f).

3. Magnetic Quantum Number (ml): ml = -l, ..., 0, ..., +l.

Specifies the orientation in space of an orbital of a given energy (n) and shape (l). This
number divides the subshell into individual orbitals which hold the electrons; there are 2l+1
orbitals in each subshell. Thus the s subshell has only one orbital, the p subshell has three
orbitals, and so on. For a certain value of l, there are (2l+1 1) integral values of ml as follows:

38
 -l, (-l + 1), . . . 0, . . . (+l - 1), + l
If l = 0, then ml = 0. If l= 1, then there are three values of m l , namely, -1, 0, and 1.

4. Spin Quantum Number (ms): ms = +½ or -½.

Specifies the orientation of the spin axis of an electron. An electron can spin in only one of two
directions (sometimes called up and down).
The Pauli’s exclusion Principle (Wolfgang Pauli, Nobel Prize 1945) states that no two
electrons in the same atom can have identical values for all four of their quantum numbers.
What this means is that no more than two electrons can occupy the same orbital, and that two
electrons in the same orbital must have opposite spins. Using symbols the valid quantum states
can be listed as follows;
1s
2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f 5g
6s 6p 6d 6f 6g 6h
7s 7p 7d 7f 7g

The energy of the subshells gradually becomes larger as the value of the angular
quantum number becomes larger.

Relative energies: s < p < d < f

As a result, two factors control the energy of an orbital for most atoms: the size of the
orbital and its shape.
Summary of the Quantum Numbers, Their Interrelationships, and the Orbital
Information Convey

39
The orbital energy level for many electrons is given below.

Figure 12 Energy level diagram for poly-electron atoms

Atomic orbitals
The wavefunction of an electron in an atom is called an atomic orbital. Chemists use
hydrogenic atomic orbitals to develop models that are central to the interpretation of
inorganic chemistry. Regions where wave functions pass through zero are called nodes. One
of the most important question to ask when studying atomic orbitals is what are their shapes?
Orbitals have specific shapes which are obtained by calculating the angular quantum number.
s Orbitals are represented as spheres, the size of the sphere increases as the principal quantum
number increases.

40
Figure 13 Pictorial representation of s orbitals

p orbitals start with the principal quantum number n = 2, the angular momentum number (l)
values are 0 and 1 the magnetic quantum number ml values are -1,0 and 1. Therefore there are
three 2p orbitals,2 px, 2py and 2pz. the letter subscript indicate the axes along which the orbital
are oriented. These three orbitals are identical in shape, size and energy; they only differ only
in orientation.

Figure 14 Pictorial representation of 2p orbitals

d Orbitals; when l = 2, there are five values of ml which correspond to five d orbitals. The d
orbitals are 3dxy, 3dxz, 3dyz, 3dz2 and 3dx2-y2. All the 3d orbitals are identical except for their
orientation in space.

41
Figure 15 Pictorial representation of 3d orbitals

Atomic number and mass number

Atomic Weight and the Atomic Mass Unit
The atomic weight scale has changed since 1800, but like the 19th-century chemists, we still use
relative masses. Our standard today, however, is carbon-12. A carbon atom having six protons and six
neutrons in the nucleus is assigned a mass value of exactly 12. From chemical experiments and
physical measurements, we know an oxygen atom having eight protons and eight neutrons has 1.3329
times the mass of carbon, so it has a relative mass of 15.9949. Masses of atoms of other elements have
been assigned in a similar manner
Masses of fundamental atomic particles are often expressed in atomic mass units (u). One atomic mass unit, 1
u, is one twelfth of the mass of an atom of carbon with six protons and six neutrons. Thus, such a carbon atom
has a mass of 12.000 u. The atomic mass unit can be related to other units of mass using the conversion factor
1 u= 1.66054 ×10-24 g
Mass Number
Protons and neutrons have masses very close to 1 u. The mass of an electron, in contrast, is only about 1/2000 of
this value. Because proton and neutron masses are so close to 1 u, the approximate mass of an atom can be
estimated if the number of neutrons and protons is known. The sum of the number of protons and
neutrons for an atom is called its mass number and is given the symbol A.
The atomic Number (Z) is the number of protons in the nucleus of each atom of the element.
In a neutral atom the number of equals the number of electrons, so atomic number also indicates
the number of electrons present in the atom.

42
The mass number (A) is the total number of neutrons and protons present in the nucleus of
an atom of an element.
mass number = number of protons + number of neutrons
=atomic number + number of neutrons
The number of neutrons in an atom is equal to the mass number minus the atomic number
(A-Z). for example the mass number of oxygen is 16 (16O) and he atomic number 8(number
of protons) then the number of neutrons is 8.
The accepted way to denote the atomic number and mass number of an atom of an element
(X) is as follows:

Examples

The chemical properties of an element are determined primarily by the protons and electrons
in its atoms; neutrons do not take part in chemical changes under normal conditions. Therefore,
isotopes of the same element have similar chemistries, forming the same types of compounds
and displaying similar reactivities.

Isotopes
Contrary to Dalton’s Atomic theory, all atoms of a given element are not necessarily identical. In fact, most
elements have been shown to be composed of two or more types of atoms mixed in a fixed proportion.
(1) The different atoms of such an element contain equal number of protons and, therefore, have the same
atomic number.
(2) The atoms which vary from one another have different number of neutrons in the nucleus. Thus they have
different atomic masses.
The atoms of an element which have the same number of protons and different number of neutrons are
called Isotopes.
Alternatively, isotopes may be defined as:
The atoms of an element which have the same atomic number but different atomic masses or mass
numbers.
SYMBOLIC REPRESENTATION OF ISOTOPES
In denoting particular isotopes of an element, the following notation has been internationally
adopted. The symbol of the element is written with atomic mass at the head and atomic number at
the bottom. Alternatively, the name of the element is followed by the atomic mass with a hyphen (-)
in between. Thus the isotopes of carbon (atomic number 6) having atomic masses 12 and 14 may be
written as

43
Isotope Abundance
A sample of water from a stream or lake will consist almost entirely of H2O where the H atoms are
the 1H isotope. A few molecules, however, will have deuterium (2H) substituted for 1H. We can
predict this outcome because we know that 99.985% of all hydrogen atoms on earth are 1H atoms.
That is, the percent abundance of 1H atoms is 99.985%.

The atomic weight of an element is the average mass of a representative sample of atoms. For boron, for
example, the atomic weight is 10.811. If isotope masses and abundances are known, the atomic mass of an
element can be calculated using equation below

WHAT ARE ISOBARS?

The atoms which have the same mass number but different atomic numbers are called isobars.
Isobars
The word isobar meaning ‘equally heavy’ is taken from the Greek isos = equal, and barys =
heavy.

WHAT ARE ISOTONES?

Atoms which have different atomic number and different atomic masses but the same number
of neutrons are called Isotones.

Isotones are different elements having entirely different atomic structure. They have different
physical and chemical properties.
Some other examples of isotones are :

44
 The atomic mass of an element is usually closer to the mass of the most abundant isotope or isotopes.

Electron configuration
The distribution of electrons among the orbitals of an atom is called the electron configuration.
The four quantum numbers n l ml, and ms enable us to label completely an electron in any
orbital in any atom. The general symbolic notation employed for the purpose is nla where the
numerical value of n = 1, 2, 3 etc., represents the principal quantum number, the letter designate
of l (s for l = 0, p for l = 1 and so on) stands for the orbital and the superscript a gives the
number of electrons in the orbital. Thus 3s2 indicates that two electrons are present in the first
subshell s (l = 0) of the third shell (n = 3).

denotes the number of electrons in the

3S2 orbital or subshell

denotes the principal

quantum number n
denotes the angular momentum
quantum number l

The electron configuration can also be represented by an orbital diagram that shows the spin
of the electron.

1s1 1s2

Electron configuration of some elements;

Hydrogen (Z=1) 1s1

Helium (Z=2) 1s2
Lithium (Z=3) 1s22s1
Beryllium (Z=4) 1s22s2
Boron (Z=5) 1s22s22p1
Carbon (z=6) 1s22s22p2
Nitrogen (Z=7) 1s22s22p3
Oxygen (Z=8) 1s22s22p4

45
Fluorine (Z=9) 1s22s22p5
Neon (Z=10) 1s22s22p6

The above cases are for simple atoms. For complicated atoms which may contain many
electrons and have many energy levels or orbitals, the ‘building up’ process for the electrons
is governed by the following rules:
Rule 1. Each electron shell can hold a maximum of 2n2 electrons where n is the shell number.
Rule 2. These electrons are accommodated in s, p, d and f orbitals, the maximum number of
electrons in each type of orbitals being determined by its electron-holding capacity (for
s = 2, p = 6, d = 10 and f = 14).
Rule 3. In the ground state of an atom, the electrons tend to occupy the available orbitals in
the increasing order of energies, the orbitals of lower energy being filled first. This is called
‘building up principle’ or Aufbau Principle.

Figure 16 Aufbau order of orbital for feeding electrons

Rule 4. Any orbital may have one or two electrons at the most. Two electrons can occupy the
same orbital only if they have opposite spins (Pauli’s exclusion principle).
Rule 5. When several orbitals of equal energy (degenerate orbitals) are available, electrons
prefer to occupy separate orbitals rather than getting paired in the same orbital. Such
electrons tend to have same spins (Hund’s rule). Or the most stable arrangement of electrons
in subshells is the one with the greatest number of parallel spins.
The electron configuration of carbon ( Z= 6) is 1s 2 2s2 2p 2 . The following are different
ways of distributing two electrons among three p orbitals:

46
None of the three arrangements violates the Pauli Exclusion Principle, however only
arrangement (c) satisfies this rule since the electrons spins in (a) and (b) cancel each other.
The electron configurations of all elements except hydrogen and helium are represented by a
noble gas core, which shows in brackets the noble gas element that most nearly precedes the
element being considered, followed by the symbol for the highest filled subshells in the
outermost shells. Thus, the electron configuration of potassium
(Z = 19) is 1s2 2s 2 2p 6 3s 2 3p 6 4s1. Because 1s2 2s 2 2p 6 3s 2 3p 6 is the electron configuration
of argon, we can simplify the electron configuration of potassium by writing [Ar]4s 1 , where
[Ar] denotes the “argon core.”
A few elements exhibit from the standard pattern of the Aufbau procedure. Chromium and
copper prefer having completely filled d orbitals because of greater stability. Fully filled
orbitals are more stable than partially filled orbitals.

47
THE PERIODIC TABLE
History of the periodic table
In 1864 John Newlands noticed that the elements can be arranged in order of atomic mass.
Every eight elements had similar properties.
1n 1869, Demtrim Mendeleev and Lother Meyer independently proposed a tabulation of
elements based on regular recurrence of properties. Mendeleev grouped elements together
more accurately and it made possible the prediction of several elements that had not been
discovered. Mendeleev placed the elements in a table in order of increasing atomic weight. In
doing so Li, Be, B, C, N, O, and F became the first row of the table. The next element then
known, sodium (Na), had properties quite similar to those of lithium (Li), so Na began
the next row of the table. As additional elements were added in order of increasing atomic
weight, elements with similar properties fell in columns or groups.

Figure 17. Mendeleev’s periodic table

The early version of the periodic table had some inconsistences. For example, the atomic
mass of argon (39.95 amu) is greater than that of potassium (39.10 amu). If elements were
arranged solely according to increasing atomic mass, argon would appear in the position
occupied by potassium in our modern periodic table.

48
In 1913, Henry Moseley, discovered a correlation between what he called atomic number and
the frequency of X rays generated by bombarding an element with high-energy electrons.
With a few exceptions, Moseley found that atomic number increases in the same order as
atomic mass. For example, calcium is the twentieth element in order of increasing atomic mass,
and it has an atomic number of 20. The discrepancies that had puzzled earlier scientists now
made sense. The atomic number of argon is 18 and that of potassium is 19, so potassium should
follow argon in the periodic table.
The table developed by Mendeleev in many ways was similar to the one we use today. One of
the main differences is that Mendeleev’s table lacked the elements in group 0 or 18, helium to
radon.
Modern periodic table
In the modern periodic table the atoms are arranged in the order of their increasing atomic
number. Electron configurations of elements help to explain the recurrence of physical and
chemical properties. The importance and usefulness of the periodic table lie in the fact that we
can use our understanding of the general properties and trends within a group or a period to
predict with considerable accuracy the properties of any element, even though that element
may be unfamiliar to us. The chemical reactivity of the elements is largely determined by their
valence electrons, which are the outermost electrons. For the representative elements, the
valence electrons are those in the highest occupied n shell. All non- valence electrons
in an atom are referred to as core electrons .

The periodic law: The chemical and physical properties of elements vary in a periodic way
with their atomic numbers. The atomic number- the number of protons in the nucleus of an
atom determines the order of elements.

Features of the periodic table

The periodic table contain elements arranged horizontally in periods, but arranged in the order
of increasing atomic number. The vertical columns in the periodic table are called groups.
They are also referred as families of elements because of the similarities that exist among the
members of each group. The periodic table can also be divided into s block, d block and p
block. Some of the groups have acquired common names, for example elements of group 1 are
called alkali metals. Group 2 are called alkaline earth metal and group 18 are called noble
gases or inert gases. The old numbering of groups started from 1A, IIA, IIIA, IVA, VA, VIIA
and noble gases. This system has been replaced by the IUPAC nomenclature where the groups

49
are numbered from 1-18. The International Union of Pure and Applied Chemistry (IUPAC) has
recommended numbering the columns sequentially with Arabic numerals 1 through 18.

Figure 18 The periodic table showing the old and new numbering of groups

50
Figure 19 periodic table showing different blocks

Periodic trends
Periodic trends are specific patterns that are present in the periodic table, which illustrate
different aspects of a certain element, including its size and its properties with electrons. The
main periodic trends include: electronegativity, ionization energy, electron affinity, atomic
radius, metallic character and effective nuclear charge

Effective nuclear charge

The presence of other electrons in an atom reduces the electrostatic attraction between a given
electron and the positively charged protons in the nucleus. The effective nuclear charge (Zeff )
is the nuclear charge felt by an electron when both the actual nuclear charge (Z) and the
repulsive effects (shielding) of the other electrons are taken into account. In general, Zeff is
given by
Zeff = Z - σ
where σ (sigma) is called the shielding constant (also called the screening constant ). The
shielding constant is greater than zero but smaller than Z.
Because the core electrons are, on average, closer to the nucleus than valence electrons, core
electrons shield valence electrons much more than valence electrons shield one another.
Consider the second-period elements from Li to Ne. Moving from left to right, we find the
number of core electrons (1s2 ) remains constant while the nuclear charge increases. However,
because the added electron is a valence electron and valence electrons do not shield each other

51
well, the net effect of moving across the period is a greater effective nuclear charge felt by the
valence electrons as shown in the table below.

The effective nuclear charge also increases as we go down a particular periodic group.
However, this is because the valence electrons are added to increasingly large shells as n
increases, the electrostatic attraction between the nucleus and the valence electrons actually
decreases.
Atomic radius
Atomic radius is one-half the distance between the two nuclei in two adjacent metal atoms
or in a diatomic molecule. For elements that exist as simple diatomic molecules, the atomic
radius is one-half the distance between the nuclei of the two atoms in a particular
molecule.

Figure 20 determining atomic radius

As you move across the periodic table the atomic radius decreases. This is because as you go
across a period, electrons are added to the same energy level. At the same time, protons are
being added to the nucleus. The concentration of more protons in the nucleus creates a "higher
effective nuclear charge." This leads to a stronger force of attraction pulling the electrons
closer to the nucleus resulting in a smaller atomic radius.

As you go down the group, the atomic radius increases. This is because the number of energy
levels increases as you move down a group as the number of electrons increases. Each

52
subsequent energy level is further from the nucleus than the last. Therefore, the atomic radius
increases as the group and energy levels increase.

Ionic radius
Ionic radius the radius of a cation or anion of an atom. When a neutral atom is converted to an
ions, there is change in its radius. If the atom forms an anion, its size (or radius) increases,
because the nuclear charge remains the same but the repulsion resulting from the additional
electron(s) enlarges the domain of the electron cloud. On the other hand, removing one or more
electrons from an atom reduces electron-electron repulsion but the nuclear charge remains the
same, so the electron cloud shrinks, and the cation is smaller than the atom. The ionic radius
increases down the group.

Figure 21 comparison of the atomic radii with ionic radii (a) alkali metal, (b) halogens

Ionization energy
Ionization Energy is the amount of energy (kJ/mol) required to remove an electron from a
neutral atom in its gaseous phase in its ground state. Gaseous atoms are specified in this

53
definition because an atom in the gas phase is virtually uninfluenced by its neighbours and so
there are no intermolecular forces (that is, forces between molecules) to take into account when
measuring ionization energy. For a many-electron atom, the amount of energy required to
remove the first electron from the atom in its ground state, is called the first ionization energy.
The pattern of removal of energy continues to second, third and so on, i.e. second ionization
energy, third ionization energy etc.

Energy + X(g) X+(g) + e- 1st ionization energy

Energy + X+(g) X2+(g) + e- 2nd ionization energy

Energy + X2+(g) X3+(g) + e- 3rd ionization energy

When an electron is removed from an atom, the repulsion among the remaining electrons
decreases. Because the nuclear charge remains constant, more energy is needed to remove
another electron from the positively charged ion. Thus, ionization energies always increase in
the following order:
I1<I2<I3<…………
Ionization energy increases across the periodic table from left to right. As you move across a
period, the atomic radius decreases, that is, the atom is smaller. The outer electrons are closer
to the nucleus and more strongly attracted to the center. Therefore, it becomes more difficult
to remove the outermost electron.
It also increases from as you go up the group. Electrons that are further from the nucleus easier
to remove, the outermost one. "SHIELDING” inner electrons at lower energy levels
essentially block the protons' force of attraction toward the nucleus. It therefore becomes easier
to remove the outer electron.
The plot of first ionization energy with atomic number is shown below. Note that, apart from
small irregularities, the first ionization energies of elements in a period increase with increasing
atomic number. This trend is due to the increase in effective nuclear charge from left to right.
A larger effective nuclear charge means a more tightly held valence electron, and hence a
higher first ionization energy. Noble gases have higher ionization energy stemming from their
large nuclear effective charge. Alkali metals have the lowest first ionization energy. Each has
one valency electron, which is effectively shielded by the completely filled inner shells, hence
it is energetically easy to remove. Alkaline earth metals have higher first ionization energy
than alkali metals. Alkaline earth metals have two valency electrons which do not shield each

54
other well, the effective nuclear charge of alkaline earth metal is higher than those of alkali
metals. Metals have low first ionization energy compared to non-metals. Ionization energy of
metalloids falls in between that of metals and non-metal.

Figure 22 Variation of first ionization energy with atomic number

Z Element First Second Third Fourth Fifth Sixth

1 H 1,312

2 He 2,373 5,251
3 Li 520 7,300 11,815
4 Be 899 1,757 14,850 21,005
5 B 801 2,430 3,660 25,000 32,820
47,26
6 C 1,086 2,350 4,620 6,220 38,000
1
53,00
7 N 1,400 2,860 4,580 7,500 9,400
0
13,00
8 O 1,314 3,390 5,300 7,470 11,000
0
15,20
9 F 1,680 3,370 6,050 8,400 11,000
0
1 15,00
Ne 2,080 3,950 6,120 9,370 12,200
0 0
1 16,60 A table showing
Na 495.9 4,560 6,900 9,540 13,400
1 0
1 18,00 ionization energies
Mg 738.1 1,450 7,730 10,500 13,600
2 0
1 18,40 of the first 20
Al 577.9 1,820 2,750 11,600 14,800
3 0
1 20,00 elements is shown
Si 786.3 1,580 3,230 4,360 16,000
4 0
1 21,00 below.
P 1,012 1,904 2,910 4,960 6,240
5 0
1
S 999.5 2,250 3,360 554,660 6,990 8,500
6
1
Cl 1,251 2,297 3,820 5,160 6,540 9,300
7
1
Ar 1,521 2,666 3,900 5,770 7,240 8,800
8
Although the general trend in the periodic table is for first ionization energies to increase from
left to right, some irregularities do exist. The first exception occurs between Group 2 and 3
elements in the same period (for example, between Be and B and between Mg and Al). The
Group 13 elements have lower first ionization energies than 2 elements because they all have
a single electron in the outermost p subshell (ns2np 1), which is well shielded by the inner
electrons and the ns 2 electrons. Therefore, less energy is needed to remove a single p electron
than to remove an s electron from the same principal energy level. The second irregularity
occurs between Groups 15 and 16 (for example, between N and O and between P and S). In
the Group 15 elements (ns2np3), the p electrons are in three separate orbitals according to
Hund’s rule. In Group 16 ( ns2np 4 ), the additional electron must be paired with one of the
three p electrons. The proximity of two electrons in the same orbital results in greater
electrostatic repulsion, which makes it easier to ionize an atom of the Group 16 element, even
though the nuclear charge has increased by one unit. Thus, the ionization energies for Group
16 elements are lower than those for Group 15 elements in the same period.

56
Factors affecting the value of ionization potential : In general, the ionization potential depends
upon the following factors :
(i) Size of the atom : The larger the distance of the electron from the nucleus. weaker will be the
forces of attraction and thus, less will be the amount of energy required to remove the electron. In
other words, larger the size of the atom, weaker will be the ionization potential.
(ii) The charge on the nucleus: The higher the charge on the nucleus, the greater will be the force of
attraction and thus, it will be more difficult to remove an electron. Hence, higher will be the value of
ionization potential.
(iii) Electrons in the inner shells : The electrons in the inner shells produce a screening effect on the
nucleus. The electrons of the outermost shell are, therefore, attracted with less force and hence it is
easier to remove the valency electrons. Thus larger the number of electrons in the inner shells, lesser
will be the value of ionization potential.
(iv) Completed shells, completed or half completed subshells: The atoms having such type of
electronic structures are relatively more stable. Therefore, more energy is required to remove
electrons in such cases. Hence, ionization potential will be high.
(v) Shape of orbital: The shape of the orbitals also affects ionization potential. s-orbital is more close
to the nucleus than the p-orbital of the same orbit. Thus, it is easier to remove electrons from a p-
orbital as compared to s-orbital. In general, for the same orbit, ionization potential decreases in the
order
s>p>d>f.
Variation of ionization potential in a group: In general, the ionization
potential decreases in a group as the atomic number increases. This is because in
a group, atomic size increases. On account of this, the outer electrons are
attracted less and less strongly by the nucleus.
Variation of ionization potential in a period: In general, the ionization
potential increases in a period as the atomic number increases. This is, because in
a period the nuclear charge increases and the atomic size decreases. On account
of this, the electrons are attracted more and more strongly by the nucleus.

Application in explaining the chemical behaviour:

(i) The elements having lower value of ionization potential e.g. alkali and
alkaline earth metals are more reactive, strong reducing agents and are
basic in nature.
(ii) The elements having higher value of ionization potential are less
reactive, strong oxidizing agents and are acidic in nature (except inert
elements).
(iii) The relative value of ionization potential and electron affinity of two

57
elements gives an idea about the nature of bonds formed between two
elements. If the difference between both the values is greater, the bond
will be more ionic and if the difference is less, the bond will be more
covalent.
(iv) The value of ionization potential gives an evidence about the number of
valency electrons in the atom. For example, in the case of sodium, the
second ionization potential (47.3 e.v.) is too much higher than the first
ionization potential (5.1 e.v.). This indicates the presence of one electron
in the valency shell of sodium.

Electron affinity
Electron affinity reflects the ability of an atom to accept an electron. It is the energy given off
when a neutral atom in the gas phase gains an electron to form a negatively charged ion.

X(g)+ e- X-(g)

For example gaseous fluorine accepts an electron to form fluoride ion.

F(g)+ e- F-(g) DH=-328 kJ/m

As you move down the group, electron affinity decreases while you move across the period
electron affinity increases. Experimentally, electron affinity is determined by removing the
additional electron from an anion. The electron affinities of metals are generally lower than
those of non-metals. The values vary little within a given group. The halogens (Group 17)
have the highest electron affinity values. A table showing some ionization energy is shown
below.

1 2 13 14 15 16 17 18
H He
73 ,0
Li Be B C N O F Ne
60 #0 27 122 0 141 328 ,0
Na Mg Al Si P S Cl Ar
53 #0 44 134 72 200 349 ,0
K Ca Ga Ge As Se Br Kr
48 2.4 29 118 77 195 325 ,0
Rb Sr In Sn Sb Te I Xe
47 4.7 29 121 101 190 295 ,0
Cs Ba Tl Pb Bi Po At Rn

58
 45 14 30 110 110 ? ? ,0

Although electron affinity increases across the period, there are some irregularities. The
electron affinity of a Group 2 element is lower than that for the corresponding Group 1 element,
and the electron affinity of a Group 15 element is lower than that for the corresponding Group1
4 element. These exceptions are due to the valence electron configurations of the elements
involved. An electron added to a Group 2 element must end up in a higher-energy np orbital,
where it is effectively shielded by the ns2 electrons and therefore experiences a weaker
attraction to the nucleus. Therefore, it has a lower electron affinity than the corresponding
Group 1 element. Likewise, it is harder to add an electron to a Group 15 element (ns2 np3) than
to the corresponding Group 14 element ( ns2 np2 ) because the electron added to the Group 15
element must be placed in a np orbital that already contains an electron and will therefore
experience a greater electrostatic repulsion. Finally, in spite of the fact that noble gases have
high effective nuclear charge, they have extremely low electron affinities (zero or negative
values). The reason is that an electron added to an atom with an ns2np6 configuration has to
enter an (n + 1) s orbital, where it is well shielded by the core electrons and will only be very
weakly attracted by the nucleus. This analysis also explains why species with complete valence
shells tend to be chemically stable.

Factors affecting the value of electron affinity : In general, electron

affinity depends upon the following factors :
(i) Size of the atom : The larger iE> the size of the atom, smaller will be the
forces of attraction between the nucleus and additional electron. Consequently,
electron affinity will be low. Thus, bigger is the size of the atom, smaller will be
the electron affinity.
(ii) Charge on the nucleus: The higher is the charge on the nucleus, the
greater will be the forces of attraction between the nucleus and additional
electron, consequently electron affinity will be high.
(iii) Electronic configuration : The atoms having stable electronic
configuration, e.g., completed shells, completed or half completed subshells do not
have a tendency to accept additional electron. Such atoms have either zero or very
low electron affinity.

Variation of electron affinity in a group : In general, the electron

affinity decreases in a group as the atomic number increases. This is because the

59
atomic size increases and, therefore, effective nuclear attraction for the electron
decreases.

Variation of electron affinity in a period: In general, electron affinity

increases in a period as the atomic number increases. In a period, the nuclear
charge increases and the atomic size decreases. Therefore, the tendency of the
atom to attract additional electron increases and hence electron affinity increases
in a period.

Electronegativity
Electronegativity is a measure of the tendency of an atom to attract a bonding pair of electrons.
The positively charged protons in the nucleus attract the negatively charged electrons. An
atom's electronegativity is affected by both its atomic number and the distance that its valence
electrons reside from the charged nucleus. As the number of protons in the nucleus increases
the electronegativity or attraction will increase. Therefore electronegativity increases from left
to right in a row in the periodic table. Electronegativity decreases on going down the group.
The overall trend for electronegativity in the periodic table is diagonal from the lower left
corner to the upper right corner. Since the electronegativity of some of the important elements
cannot be determined by these trends. The order of electronegativity for some of the common
elements is given below.

F > O > Cl > N > Br > I > S > C > H > metals

60
Figure 23 variation of paulis electronegativities

Factors affecting the value of electronegativity: In general, electronegativity depends upon the
following factors :
(i) Size of the atom : Smaller is the size of the atom, greater will be its tendency to attract shared pairs
of electrons towards itself and hence has greater electronegativity. Thus, electronegativity decreases
with the increase in the size of the atom.
(ii) Effective nuclear charge : Higher is the effective nuclear charge, greater will be its tendency to
attract shared pairs of electrons towards itself and hence has greater electronegativity.
(iii) Oxidation state : Higher is the oxidation state of an atom, greater is its electronegativity. For
example, electronegativity of Fe3+ (1.96) is greater than that of Fe2+ (1.83).
(iv) State of hybridization: The electronegativity of an atom is also affected by the state of
hybridization. Greater is the s-character in a hybrid orbital, more will be its electronegativity.

v) Nature of other atoms with which the atom is bonded: Electronegativity is not the property of
isolated atom. It depends upon the number and nature of atoms to which it is bonded. Thus,
electronegativity is not
constant. For example, electronegativity of phosphorus in PF3 is 2.44 and in PCl3 it is 2.24, whereas
its accepted value is 2.15

Variation of electronegativity in a group: In general, the electronegativity decreases in a group as

the atomic number increases

Variation of electronegativity in a period. In general, the electronegativity increases in a period

with the increase of atomic number.

Application in explaining the chemical behaviour:

(i) Metallic and non-metallic character of elements : The element having smaller value of
electronegativity will be a metal whereas an element having higher value of electronegativity will be a
non-metal.
(ii) Diagonal relationship: The diagonally placed elements of second and third period of the periodic
table show many similar properties due to almost same electronegativity of the elements.
(iii) Nature of bond: With the help of electronegativity value, it is possible to predict the nature of
the bond formed between two atoms. If there is a large difference between the electronegativity of the
two atoms, the bond formed will be ionic or polar in character. On the other hand, if the difference is
small, the bond formed will be covalent or non-polar in character.

61
(iv) Stability of bond: The greater is the difference in the electronegativity of two atoms, more stable
will be the bond.

(v) Acid Base character of the oxides of the elements of the same period: The electronegativity
difference between an element and oxygen predicts the nature of oxide formed by the element. If the
difference of electronegativity between the two is large, the oxide is basic and if the said difference is
small, the oxide will be acidic.

Diagonal relationships

62
The atomic radius, and hence some chemical properties, of some Period 2 elements is similar to that
of the element to their lower right in the periodic table. The element at the head of each group also
commonly possesses a diagonal relationship with the element to its lower right. Diagonal
relationships arise because the atomic radii, charge densities, electronegativities, and hence many of
the chemical properties, of the two elements are similar. The most striking diagonal relationships are
those between Li and Mg. For example, whereas
the Group 1 elements form compounds that are
essentially ionic in nature, Li and Mg salts have
some degree of covalent character in their
bonding. There is a strong diagonal relationship
between Be and Al: both elements form covalent
hydrides, halides, and oxides; the analogous
compounds of Group 2 are predominantly ionic.
The diagonal relationship between B and Si is
illustrated by the fact that both elements form
flammable, gaseous hydrides whereas aluminium
hydride is a solid.

Figure 24 The diagonal relationship between (a) atomic radii (in picometres) and (b) Pauling electronegativity in Periods
2 and 3.

63
Molecules and ions

A molecule is an aggregate of at least two atoms in a definite arrangement held together by chemical
forces (also called chemical bonds). A molecule may contain atoms of the same element or atoms of
two or more elements joined in a fixed ratio, in accordance with the law of definite proportions. We
have diatomic and poly atomic molecules.

An ion is an atom or a group of atoms that has a net positive or negative charge. The number of
positively charged protons in the nucleus of an atom remains the same during ordinary chemical
changes (called chemical reactions), but negatively charged electrons may be lost or gained. The loss
of one or more electrons from a neutral atom results in a cation, an ion with a net positive charge. For
example, a sodium atom (Na) can readily lose an electron to become a sodium cation, which is
represented by Na+.
On the other hand, an anion is an ion whose net charge is negative due to an increase in the number
of electrons. A chlorine atom (Cl), for instance, can gain an electron to become the chloride ion Cl-

Chemical formulas

Chemists use chemical formulas to express the composition of molecules and ionic compounds in
terms of chemical symbols.

A molecular formula shows the exact number of atoms of each element in the smallest unit of a
substance. H2O, O3, O2, NH3

Empirical formula tells us which elements are present and the simplest whole-number ratio of their
atoms, but not necessarily the actual number of atoms in a given molecule.

Reading assignment: IUPAC naming of inorganic compounds, acids and bases

Stoichiometry
Atomic mass
The most accurate method currently available for comparing the masses of atoms involves the use of
the mass spectrometer. Atomic mass (sometimes called atomic weight) is the mass of the atom in
atomic mass units (amu). One atomic mass unit is defined as a mass exactly equal to one-twelfth the
mass of one carbon-12 atom. Carbon-12 is the carbon isotope that has six protons and six neutrons.
Setting the atomic mass of carbon-12 at 12 amu provides the standard for measuring the atomic mass
of the other elements. , a hydrogen atom is only 8.400 percent as massive as the carbon-12 atom.
Thus, if the mass of one carbon- 12 atom is exactly 12 amu, the atomic mass of hydrogen must be
0.084 3 12.00 amu or 1.008 amu. Mole

The mole

Define the mole (abbreviated mol) as the number equal to the number of carbon atoms in exactly 12
grams of pure 12C. Modern techniques that allow us to count atoms very precisely have been
used to determine this number as 6.022137 x 1023 the number is called Avogadro’s number.

Thus the mole is defined such that a sample of a natural element with a mass equal to the element’s
atomic mass expressed in grams contains 1 mole of atoms.

64
Molecular Mass
If we know the atomic masses of the component atoms, we can calculate the mass of
a molecule. The molecular mass (sometimes called molecular weight) is the sum of the
atomic masses (in amu) in the molecule. For example, the molecular mass of H2O is Percent
composition of compounds

2(atomic mass of H) 1 atomic mass of O

Exercise

Calculate the molecular masses (in amu) of the following compounds: (a) sulfur dioxide
(SO2) and (b) caffeine (C8H10N4O2).

Percent Composition of Compounds

The percent composition by mass is the percent by mass of each element in a compound.
Percent composition is obtained by dividing the mass of each element in 1 mole of the
compound by the molar mass of the compound and multiplying by 100 percent.
Mathematically, the percent composition of an element in a compound is expressed as:

where n is the number of moles of the element in 1 mole of the compound. For example, in 1
mole of hydrogen peroxide (H2O2) there are 2 moles of H atoms and 2 moles of O atoms.
The molar masses of H2O2, H, and O are 34.02 g, 1.008 g, and 16.00 g, respectively.
Therefore, the percent composition of H2O2 is calculated as follows:

Exercise

1. Phosphoric acid (H3PO4) is a colorless, syrupy liquid used in detergents, fertilizers,

toothpastes, and in carbonated beverages for a “tangy” fl avor. Calculate the percent
composition by mass of H, P, and O in this compound.
2. Chalcopyrite (CuFeS2) is a principal mineral of copper. Calculate the number of
kilograms of Cu in 3.71 3 103 kg of chalcopyrite.

DETERMINING THE FORMULA OF A COMPOUND

Chemical Equations and Chemical Analysis

Analytical chemists use a variety of approaches to identify substances as well as to measure the
quantities of components of mixtures. Analytical chemistry is often done now using instrumental
methods but classical chemical reactions and stoichiometry still play a central role.

65
Quantitative Analysis of a Mixture
Quantitative chemical analysis generally depends on one of the following basic ideas:
• A substance, present in unknown amount, can be allowed to react with a known quantity of another
substance. If the stoichiometric ratio for their
reaction is known, the unknown amount can be determined.
• A material of unknown composition can be converted to one or more substances of known
composition. Those substances can be identified, their amounts determined, and these amounts related
to the amount of the original, unknown substance.

Determining the Formula of a Compound by Combustion

The empirical formula of a compound can be determined if the percent composition of the compound
is known. But where do the percent composition data come from? One chemical method that works
well for compounds that burn in oxygen is analysis by combustion. In this technique, each element in
the compound combines with oxygen to produce the appropriate oxide.

Consider the compound ethanol. When ethanol is burned in an apparatus such as that shown in Figure
below carbon dioxide (CO2) and water (H2O) are given off. Because neither carbon nor hydrogen
was in the inlet gas, we can conclude that both carbon (C) and hydrogen (H) were present in ethanol
and that oxygen (O) may also be present. (Molecular oxygen was added in the combustion process,
but some of the oxygen may also have come from the original ethanol sample.) The masses of CO2
and of H2O produced can be determined by measuring the increase in mass of the CO2 and H2O
absorbers, respectively. Suppose that in one experiment the combustion of 11.5 g of ethanol produced
22.0 g of CO2 and 13.5 g of H2O. We can calculate the mass of carbon and hydrogen in the original
11.5-g sample of ethanol as follows:

66
Thus, 11.5 g of ethanol contains 6.00 g of carbon and 1.51 g of hydrogen. The remainder must be
oxygen, whose mass is

The number of moles of each element present in 11.5 g of ethanol is

The formula of ethanol is therefore C0.50H1.5O0.25 (we round off the number of moles to two significant figures).
Because the number of atoms must be an integer, we divide the subscripts by 0.25, the smallest subscript, and
obtain for the empirical formula C2H6O.

Empirical formula represents the simplest whole-number ratio of the various types of atoms in a
compound. It is found by finding the smallest whole-number ratio of atoms in this compound
by dividing each of the mole values by the smallest of them.

Determination of the Empirical Formula

1 Since mass percent gives the number of grams of a particular element per 100 grams of compound,
base the calculation on 100 grams of compound. Each percent will then represent the mass in grams
of that element present in the compound.
2 Determine the number of moles of each element present in 100 grams of compound using the
atomic weights (masses) of the elements present.
3 Divide each value of the number of moles by the smallest of the values. If each resulting number is
a whole number (after appropriate rounding), these numbers represent the subscripts of the elements
in the empirical formula.
4 If the numbers obtained in the previous step are not whole numbers, multiply each number by an
integer so that the results are all whole numbers.

Determination of Molecular Formulas

The formula calculated from percent composition by mass is always the empirical formula because
the subscripts in the formula are always reduced to the smallest whole numbers. To calculate the
actual, molecular formula we must know the approximate molar mass of the compound in addition to

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its empirical formula. Knowing that the molar mass of a compound must be an integral multiple of the
molar mass of its empirical formula, we can use the molar mass to find the molecular formula.

Determination of the Molecular Formula

Method 1
• Obtain the empirical formula.
• Compute the empirical formula mass.
• Calculate the ratio

• The integer from the previous step represents the number of empirical formula units in one
molecule. When the empirical formula subscripts are multiplied by this integer, we obtain the
molecular formula.
Method 2
• Using the mass percents and the molar mass, determine the mass of each element present in 1 mole
of compound.
• Determine the number of moles of each element present in 1 mole of compound.
• The integers from the previous step represent the subscripts in the molecular formula.

Example:
A sample of a compound contains 1.52 g of nitrogen (N) and 3.47 g of oxygen (O). The molar mass of
this compound is between 90 g and 95 g. Determine the molecular formula and the accurate molar
mass of the compound.

Soln

We are given grams of N and O. Use molar mass as a conversion factor to convert grams to moles of
each element. Let n represent the number of moles of each element. We write

Thus, we arrive at the formula N0.108O0.217, which gives the identity and the ratios of atoms
present. However, chemical formulas are written with whole numbers. Try to convert to whole
numbers by dividing the subscripts by the smaller subscript (0.108). After rounding off, we obtain
NO2 as the empirical formula.

The molecular formula might be the same as the empirical formula or some integral multiple of it (for
example, two, three, four, or more times the empirical formula). Comparing the ratio of the molar
mass to the molar mass of the empirical formula will show the integral relationship between the
empirical and molecular formulas. The molar mass of the empirical formula NO2 is

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Next, we determine the ratio between the molar mass and the empirical molar mass

The molar mass is twice the empirical molar mass. This means that there are two NO2 units in each
molecule of the compound, and the molecular formula is (NO2)2 or N2O4. The actual molar mass of
the compound is two times the empirical molar mass, that is, 2(46.01 g) or 92.02 g, which is between
90 g and 95 g.

Reading assignments

Read more about

Writing chemical reactions

Reactants and products

Balanced reactions

Limiting reagents

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A Lewis structure is a representation of covalent bonding in which shared electron pairs are
shown either as lines or as pairs of dots between two atoms, and lone pairs are shown as
pairs of dots on individual atoms. Only valence electrons are shown in a Lewis structure.

The valence electrons in the outermost energy level of an atom are responsible for the
electron activity that occurs to form chemical bonds. The Lewis structure of an atom is a
representation that shows the valence electrons for that atom. American chemist Gilbert N.
Lewis (1875–1946) proposed using the symbol for the element and dots for electrons. The
number of dots placed around the symbol equals the number of s and p electrons in the
outermost energy level of the atom. Paired dots represent paired electrons;
unpaired dots represent unpaired electrons. For example, H. is the Lewis symbol
for a hydrogen atom, is the Lewis symbol for a boron atom, With valence electrons 2s2
2p1. In the case of boron, the symbol represents the boron nucleus and the electrons; the dots
represent only the electrons.

Lewis structure for some elements.

Steps of writng Lewis structures

Step 1 Determine the total number of valence electrons for the molecule or polyatomic ion. (Remember
that the number of valence electrons for a representative element is equal to its group number,
using the A-group convention for numbering groups. For example, chlorine, Cl, is in group
7A, so it has seven valence electrons. Hydrogen has one valence electron.)
For uncharged molecules, the total number of valence electrons is the sum of the valence
electrons of each atom.
For polyatomic cations, the total number of valence electrons is the sum of the valence
electrons for each atom minus the charge.

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For polyatomic anions, the total number of valence electrons is the sum of the valence electrons
for each atom plus the charge.

Step 2 Draw a reasonable skeletal structure, using single bonds to join all the atoms. One or more of
the following guidelines might help with this step. (They are clarified in the examples that
follow.)
Try to arrange the atoms to yield the most typical number of bonds for each atom.
Apply the following guidelines in deciding what element belongs in the center of your
structure.
Hydrogen and fluorine atoms are never in the center.
Oxygen atoms are rarely in the center.
The element with the fewest atoms in the formula is often in the center.
The atom that is capable of making the most bonds is often in the center.
Oxygen atoms rarely bond to other oxygen atoms.
The molecular formula often reflects the molecular structure.
Carbon atoms commonly bond to other carbon atoms.

Step 3 Subtract two electrons from the total for each of the single bonds (lines) described in Step
2 above. This tells us the number of electrons that still need to be distributed.

Step 4 Try to distribute the remaining electrons as lone pairs to obtain a total of eight electrons
around each atom except hydrogen and boron. The following are some helpful observations
pertaining to octets.
• In a reasonable Lewis structure, carbon, nitrogen, oxygen, and fluorine always have eight
electrons around them.
• Hydrogen will always have a total of two electrons from its one bond.
• Boron can have fewer than eight electrons but never more than eight.
• The nonmetallic elements in periods beyond the second period (P, S, Cl, Se, Br, and I)
usually have eight electrons around them, but they can have more. (In this text, they will
always have eight electrons around them, but if you go on to take other chemistry courses,
it will be useful to know that they can have more.)
• The bonding properties of the metalloids arsenic, As, and tellurium, Te, are similar to those
of phosphorus, P, and sulfur, S, so they usually have eight electrons around them but can
have more.

Step 5 Do one of the following.

If in Step 4 you were able to obtain an octet of electrons around each atom other than
hydrogen and boron, and if you used all of the remaining valence electrons, go to step 6.
If you have electrons remaining after each of the atoms other than hydrogen and boron have
their octet, you can put more than eight electrons around elements in periods beyond the
second period
If you do not have enough electrons to obtain octets of electrons around each atom (other
than hydrogen and boron), convert one lone pair into a multiple bond for each two
electrons that you are short.
If you would need two more electrons to get octets, convert one lone pair in your
structure to a second bond between two atoms.
If you would need four more electrons to get octets, convert two lone pairs into bonds.
This could mean creating a second bond in two different places or creating a triple bond
in one place.
If you would need six more electrons to get octets, convert three lone pairs into bonds.
Etc.

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Step 6 Check your structure to see if all of the atoms have their most common bonding pattern.
If each atom has its most common bonding pattern, your structure is a reasonable structure.
Skip Step 7.
If one or more atoms are without their most common bonding pattern, continue to Step 7.

Step 7 If necessary, try to rearrange your structure to give each atom its most common bonding
pattern. One way to do this is to return to Step 2 and try another skeleton.

Lewis structure procedure

Formaldehyde, CH2O, has many uses, including the preservation of biological specimens.
Draw a reasonable Lewis structure for formaldehyde.

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The cyanide polyatomic ion, CN− is similar in structure to carbon monoxide, CO. Although
they work by different mechanisms, they are both poisons that can disrupt the use of oxygen,
O2, in organisms. Draw a reasonable Lewis structure for the cyanide ion.

Examples

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Exceptions to the octet rule
There are inevitably, cases arise where the importance of an octet of electrons is called into
question, i.e the octet rules are not obeyed.
Exceptions to the octet rule fall into three categories characterized by an incomplete octet, an
odd number of electrons, or more than eight valence electrons around the central atom.

The Incomplete Octet

In some compounds, the number of electrons surrounding the central atom in a stable
molecule is fewer than eight. Consider, for example, beryllium, which is a Group 2A (and a
second-period) element. The electron confi guration of beryllium is 1s22s2; it has two
valence electrons in the 2s orbital. In the gas phase, beryllium hydride (BeH2) exists as
discrete molecules. The Lewis structure of BeH2 is:

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Only four electrons surround the Be atom, and there is no way to satisfy the octet rule for
beryllium in this molecule.
Boron and aluminum, also tend to form compounds in which they are surrounded by fewer
than eight electrons. Take boron as an example. Because its electron configuration is
1s22s22p1, it has a total of three valence electrons. Boron reacts with the halogens to form a
class of compounds having the general formula BX3, where X is a halogen atom. Thus, in
boron trifluoride there are only six electrons around the boron atom:

Odd-Electron Molecules
Some molecules contain an odd number of electrons. Among them are nitric oxide (NO) and
nitrogen dioxide (NO2):

Because we need an even number of electrons for complete pairing (to reach eight), the octet
rule clearly cannot be satisfied for all the atoms in any of these molecules. Odd-electron
molecules are sometimes called radicals. Many radicals are highly reactive. The reason is
that there is a tendency for the unpaired electron to form a covalent bond with an unpaired
electron on another molecule. For example, when two nitrogen dioxide molecules collide,
they form dinitrogen tetroxide in which the octet rule is satisfied for both the N and O atoms:

The Expanded Octet

Atoms of the second-period elements cannot have more than eight valence electrons around
the central atom, but atoms of elements in and beyond the third period of the periodic table
form some compounds in which more than eight electrons surround the central atom. In
addition to the 3s and 3p orbitals, elements in the third period also have 3d orbitals that can
be used in bonding. These orbitals enable an atom to form an expanded octet. One compound
in which there is an expanded octet is sulfur hexafluoride, a very stable compound. The
electron configuration of sulfur is [Ne]3s23p4. In SF6, each of sulfur’s six valence electrons
forms a covalent bond with a fluorine atom, so there are 12 electrons around the central sulfur
atom:

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Draw the Lewis structure of the following; H2SO4, XeF4, SF4 ClF3 , XeO3 , RnCl2 , BeCl2 , ICl4
Formal charge and Lewis structures
An atom’s formal charge is the electrical charge difference between the valence electrons in
an isolated atom and the number of electrons assigned to that atom in a Lewis structure.
Rules for Determining Formal Charge
1. Start with normal # of valence e- for atom.
2. Subtract number of nonbonding e- surrounding atom.
3. Subtract ½ number of bonding electrons surrounding atom.

The formal charge on each atom in O3 can now be calculated according to the following scheme:

When you write formal charges, these rules are helpful:

1. For molecules, the sum of the charges must add up to zero because molecules are
electrically neutral species. (This rule applies, for example, to the O3 molecule.)
2. For cations, the sum of formal charges must equal the positive charge. For anions, the sum
of formal charges must equal the negative charge.

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Resonance structures
Sometimes more than one valid Lewis structure is possible for a given molecule. For
example, consider the Lewis structure for the nitrate ion (NO3-), which has 24 valence
electrons. So that an octet of electrons surrounds each atom, a structure like the following is
required:

The nitrate ion does not exist as any of the three extreme forms indicated by the individual
Lewis structures but instead exists as an average of all three. Resonance is invoked when
more than one valid Lewis structure can be written for a particular molecule. The resulting
electron structure of the molecule is given by the average of these resonance structures.
This situation is usually represented by double-headed arrows as follows:

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Note that in all these resonance structures the arrangement of the nuclei is the same.
Only the placement of the electrons differs. The arrows do not indicate that the molecule
“flips” from one resonance structure to another. They simply show that the actual structure
is an average of the three resonance structures.

A resonance structure, is one of two or more Lewis structures for a single molecule that
cannot be represented accurately by only one Lewis structure. The double-headed arrow
indicates that the structures shown are resonance structures.
The term resonance itself means the use of two or more Lewis structures to represent a
particular molecule.

Resonance hybrid A structure that represents the average of the resonance structures for a
molecule or polyatomic ion.

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Give possible Lewis structures for XeO3, an explosive compound of xenon. Determine the
formal charges of each atom in the various Lewis structures.

Lewis dot symbols

A Lewis dot symbol consists of the symbol of an element and one dot for each
valence electron in an atom of the element. To represent a Lewis symbol for an element, write
down the symbol of the element and surround the symbol with a number of dots (or crosses)
equal to the number of valence electrons. The Lewis symbols for hydrogen, chlorine, oxygen
and sulphur may be written as:

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The structural formulae of compounds built by union of Lewis symbols for the component
atoms, are referred to as Electron-dot formulas, or Electron-dot structures or Lewis
structures.

Electronic theory of valence

In chemical bond formation, atoms interact by losing, gaining, or sharing of electrons so
as to acquire a stable noble gas configuration. While atoms of noble gases possess a stable
outer shell of eight electrons or octet, atoms of most other elements have incomplete octets.
They may have less than 8 electrons or in excess. Thus, the electronic theory or valence could
well be named as the Octet theory of Valence. It may be stated as: Atoms interact by
electron-transfer or electron-sharing, so as to achieve the stable outer shell of eight
electrons. The tendency for atoms to have eight electrons in the outer shell is also known as
the Octet Rule or the Rule of Eight.
i. Exhibit isomerism

Coordinate bond
A coordinate bond is a type of covalent bond in which the shared pair of electrons is provided
by only one of the bonded atoms. One atom is the donor while the other is the acceptor.
Coordinate bond is also called dative covalent bond. The molecule that contain the lone pair of
electrons is called a ligand.

The concept of resonance

The bonding in some molecules cannot be adequately described by a single Lewis structure.
Consider the Lewis structure of ozone (O3)

Each of the structure is correct. This has been experimentally proved because the bond
lengths between oxygen are equal. However we expect the O=O to be shorter but that is not
the case. Each of the structure is called resonance structure. Resonance structure, then, is
one of two or more Lewis structures for a single molecule that cannot be represented

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accurately by only one Lewis structure. The double-headed arrow indicates that the structures
shown are resonance structures.
The carbonate ion provides another example of resonance:

According to experimental evidence, all carbon-to-oxygen bonds in CO3-2 are equivalent.

Therefore, the properties of the carbonate ion are best explained by considering its resonance
structures together.
Exceptions of the octet rule
Atoms in some molecules cannot obey the octet rule because they are either too few or too
many electrons. This often happens when atoms more than four bonds e.g. PCl5, SF6 in which
there are five P-Cl bonds and six S-F bonds respectively. The sulfur and phosphorous must
exceed the octet rule. Exceptions to the octet rule fall into three categories characterized by
an incomplete octet, an odd number of electrons, or more than eight valence electrons around
the central atom.
Exercise
Write the Lewis structures for the following;
SO2, HClO3, SO42-, SO3, SF4, PCl3, PCl5, N2O, BF3 BF2
Molecular geometry
Molecular geometry is the three dimensional arrangement of atoms in a molecule. The three
dimensional shapes of molecules can be predicted if we assume that the electron pair in the
valence shells of atoms stay as far as possible. The shapes of molecules are very important
because many of their physical and chemical properties depend upon them. Quantum
mechanics is used for theoretical explanation of molecular shapes. To study molecular
geometry, the valence-shell electron-pair repulsion (VSEPR) model, because it accounts for
the geometric arrangements of electron pairs around a central atom in terms of the
electrostatic repulsion between electron pairs is employed. Arrangement of electron pairs

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