CHAPTER #1

The Structure of The Atom and The Periodic Table

ATOMIC THEORY
Introduction
In fifth century, the Greek philosopher Democritus expressed that all matter consists of very
small, indivisible particles, named as ‘atomos’ (means uncuttable or indivisible), but his idea was
not accepted. Experimental evidence from early scientific investigations provides support for the
‘atomism’ and gradually gave the modern definitions of elements and compounds. It was in
1808, English scientist John Dalton, formulated a precise definition of the indivisible building
blocks of matter that we call atoms.
Dalton’s Atomic Theory ( DAT)
John Dalton was the first to put forward an atomic theory on physical and chemical properties of
the atom.
Atomic theory is the study of the nature of the atoms and forces which hold them together.
During the Dalton’s time many scientists did not fully accept the idea that matter was made up
of atoms. The Atomic theory proposed by Dalton represented a major breakthrough in the
development of chemistry

There are five basic postulates of the Dalton’s atomic theory

1. All substances consist of very small particles called atoms

2. Atoms are indivisible
3. All the atoms of the same element are exactly alike and have same mass and properties
4. Atoms of one element are different from atoms of any other element
5. When atoms combine to form a compounds they do so in a small whole numbers.

Note: although Dalton’s atomic theory is considered the cornerstone of modern chemistry, it had
to be modified over the years as a result of new discoveries.

The Short Coming of Dalton’s Atomic Theory Were

1. Atoms are indivisible. But they can be broken down into sub-atomic particles
2. All atoms of same element are exactly alike. But atoms of same element may not have
same properties ( e.g. isotopes)

Modern Atomic Theory ( MAT)

1. Each substance is made up atoms

2. Atoms are built up from smaller particles called, protons, electrons, and neutrons.
3. All atoms of any element have same number of protons and electrons , but may have
different number of neutrons.

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 4. Atoms of different elements are different
5. Atoms of different elements combine in small whole numbers to from compounds
6. In chemical reactions, atoms are not made, destroyed, or changed.

The structure of the Atom

On the basis of Dalton’s atomic theory, we can define an atom as the basic unit of an element
that can enter into chemical combination.
Dalton imagined an atom that was both extremely small and indivisible. However, a series of
investigations, clearly demonstrated that, atoms actually posses internal structures; that is, they
are made up of even smaller particles, which are called subatomic particles.
This research discovered the three such particles, named as electrons, protons and neutrons.
Discovery of the subatomic particles
Discovery of the Electrons
Electron was discovered by J. J. Thomson in 1897 when he was studying the properties of
cathode ray.
J. J. Thomson constructed a glass tube which was partially evacuated i.e. much of the air was
pumped out of the tube. Then he applied a high electrical voltage between two electrodes at
either end of the tube. He detected that a stream of particle (ray) was coming out from the
negatively charged electrode (cathode) to positively charged electrode (anode). This ray is called
cathode ray and the whole construction is called cathode ray tube. The schematic of a cathode
ray tube is given in the figure below

An electron:
is the fundamental particle which carries one unit negative charge
it is mass is almost zero or negligible
it can be found somewhere outside the nucleus
Discovery of Proton
In 1909, Rutherford discovered proton in his famous gold foil experiment.
In his gold foil experiment, Rutherford bombarded a beam of alpha particles on an
ultrathin gold foil and then detected the scattered alpha particles in zinc sulfide (ZnS)
screen
Results
1. Most of the particles pass through the foil without any deflection.
2. Some of the alpha particles deflect at small angle.
3. Very few even bounce back (1 in 20,000).

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Conclusion
Based on his observations, Rutherford proposed the following structural features of an
atom:
1. Most of the atom’s mass and its entire positive charge are confined in a small core, called
nucleus. The positively charged particle is called proton.
2. Most of the volume of an atom is empty space.
3. The number of negatively charged electrons dispersed outside the nucleus is same as number
of positively charge in the nucleus.
A proton

Is the fundamental particle which carries one unit positive charge

It has a mass nearly equally to that of hydrogen or 1 amu
It can be found inside the nucleus of the atom

Discovery of Neutron
From the previous discussion, we can see that the gold foil experiment gave a clear picture of the
structure of an atom which consists of protons (nucleus) and same number of electrons outside of
the nucleus
In 1932, James Chadwick discovered the existence of neutrons by radiation of beryllium
atoms experiment.
They have no charge and are neutral
He observed that the mass of the neutron is approximately equal to that of proton.
He also proposed that the neutron was a constituent of all nuclei
Atomic number and Mass number
Atomic number
The atomic number (Z) is the number of protons in the nucleus of each atom of an element.

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In a neutral atom the number of protons is equal to the number of electrons, so the atomic
number also indicates the number of electrons present in the atom. For example, the atomic
number of nitrogen is 7. This means that each neutral nitrogen atom has 7 protons and 7
electrons.
Mass number
The mass number (A) is the total number of protons and neutrons present in the nucleus of an
atom of an element. Except for the most common form of hydrogen, which has one proton and
no neutron, all atomic nuclei contain both protons and neutrons. In general the mass number is
given by,
Mass number = No. of protons + No. of neutrons
= Atomic number + No. of neutrons
The number of neutrons in an atom is equal to the difference between the mass number and the
atomic number, (A-Z). For example, the mass number of
fluorine is 19 and the atomic number is 9 (indicate 9 protons in the nucleus). Thus the number of
neutrons in an atom of fluorine is 19-9=10. The atomic number, number of neutrons and mass
number all must be positive integer (whole numbers).
The accepted way to denote the atomic number and mass number of an atom of an element is
represented as ZXA, A is mass number and Z is an atomic number.
atomic masses and Isotopes
Atomic mass ( Relative Atomic Mass )
The Atomic mass of an element is the number of times an atom of that element is heavier than
carbon -12 isotope.
the atomic masses on the atomic mass scale are expressed in terms of atomic mass unit( amu)
Isotopes: are atoms of same element having same atomic number but different mass number.
The word isotope is of Greek origin that consist of two words iso means same and tope means
place.Most of the elements have two or more isotopes; For example, there are three isotopes of
hydrogen. One, simply known as hydrogen, has one proton and no neutrons. The deuterium
isotope contains one proton and one neutron, and tritium has one proton and two neutrons.
Thus, for the isotope of hydrogen, we write 1H1 (hydrogen), 1H2 (deuterium) and 1H3
(tritium). As another example, consider two common isotopes of uranium with mass numbers of
235 and 238, respectively: 92U235, 92U238.
Example
Chlorine has two isotopes Cl-35 and Cl-37. Cl-35 has relative isotopic mass of 34.97 amu and
Cl-37 has 36.97. the relative abundance of Cl-35 and Cl-37 are 75.77% and 24.23% respectively.
Calculate the relative atomic mass of chlorine.
Quantum Numbers
In quantum mechanics, three quantum numbers are required to describe the distribution of
electrons in atoms. These numbers are derived from the mathematical solution of the
Schrodinger equation for the hydrogen atom. They are called the
principal quantum number (n)
the angular momentum quantum number (l)
and the magnetic quantum number (ml).
These quantum numbers will be used to describe atomic orbitals and label the electrons.
A fourth quantum number, spin quantum number describes the behavior of specific electron.

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 1. Principal quantum number (n)
The principal quantum number (n) can have integer values 1,2,3,……… The value of n
determines the energy of an orbital. In the case of hydrogen atom or single electron atomic ions,
such as Li2+ and Be3+, the energy of these determined by their principal quantum number.
For other atoms, the energy also depends on the angular momentum quantum number (l).
The size of an atom also depends on the value of n. The orbitals of the same quantum state “n”
are said to belong to the same shell. Shells are designates by the following letters,

2. Angular momentum or Azimuthal quantum number ( l)

This quantum number distinguishes the orbitals of a given “n” having different shapes. The
values of l depends on the value of principal quantum number, it can have any integer value from
0 to n- 1. With each shell of quantum number, n, there are n different kinds of orbitals, each
with a different shape denoted by an “l” quantum number.
For example,
If, n = 1 has only one value i.e., l = 0
n = 2 has two l values i.e., l = 0, 1
n = 3 has three l values i.e., l = 0,1,2
n = 4 has four l values i.e., l = 0,1,2,3
An electron has a n value is 3, the possible value for l are 0,1 and 2. Thus, with in the M shell
(n=3), there are three kinds of orbitals, each having different shape.

3. Magnetic quantum number( ml)

The magnetic quantum number (ml) describes the orientation of the orbital in space. Within a
sub-shell, the value of ml depends on the value of the angular
momentum quantum number, l.

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The allowed values are the integers as follows: -l,….. ,0,……+l (or) –l,(-l+1),…,0,---. (+l-1),+l
For l = 0 (s sub-shell), the allowed ml quantum number is 0 only; there is only one orbital in the
s sub-shell. For l =1 (p sub-shell), ml = -1,0 and +1; there are 3 different orbital in the p sub-
shell. The orbitals have the same sub-shell, but it has different orientation in space (as in px, py
and pz). if, n=2, ml = -2,-1,0,+1,+2 has five orientation: dxy, dyz, dxz, dx2 – y 2, dz2.
if, n=3, ml=-3,-2,-1,0,+1,+2,+3 has seven orbital orientations. But the orientation of ‘f’ orbital
is difficult to suggest. In addition each orbital of a given sub-shell has the same energy.
4. Spin quantum number
According to electromagnetic theory, a spinning charge generates a magnetic field, and it is this
motion that causes an electron to behave like a magnet.
It has two possible spinning motions of an electron, one clockwise and the other counter
clockwise.
It is also , called the electron spin quantum number (ms), which has a
value of +1/2( )or –1/2. ( )

Electron Configuration
the quantum mechanical description for the arrangement of electrons about the nucleus of an
atom is called electron configuration.
The electron configuration of an atom is the particular description of the electrons among
available sub-shells. Its described by a notation that lists the sub-shell symbols one after another.
It is used to show the positions of the electrons in an atom.

Pauli Exclusion Principle: states that no two electrons in one atom can have the same four
quantum numbers. Another statement of this principle is : if two electrons occupy the same
orbital, they must have different values of ms ( opposite spins). It means you cannot place two
electrons in a same direction or spin. Example for helium atom e.g.
He, 2S
Hund’s Rule: sates that “ every orbital in the subshell is occupied by a single electron before
any orbital is doubly occupied”.
According to Hund’s rule, when electrons fill a sub-shell, every orbital in the sub-shell is
occupied by a single electron before any orbital is doubly occupied. ( parallel spins ).
For example, the electron configuration of carbon (Z=6) is 1s2 2s2 2p2.
The orbital diagram representation of this is:

The Building-Up Principle

This process is based on the Aufbau principle (The German word “Aufbau” means “building up”).
The Aufbau principle states that as protons are added one to the nucleus to build up the elements,

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electrons are similarly added to the atomic orbitals. In short, the filling of energy sublevels in the
order of increasing energy.

Methods of writing electronic configuration: orbital method and Box method

Electronic configuration is expressed by indicating the principal quantum number and its
representative sub-shell along with number of electrons present in it. For example, in ground
state hydrogen atom must be in the 1s orbital, so its electron configuration is 1s1.
orbital method
The electronic configurations of the first eighteen elements can be shown with the orbital method
as follows:

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Box method( arraw and Box method
The arrow and box method represents each orbital as a box and each electron as an arrow. The
direction of spin is shown by the orientation of the arrow.

Paramagnetism and Diamagnatism

If the two electrons in the 1s orbital of a helium atom had the same, or parallel spins their net
magnetic fields would reinforce each other. Such an arrangement would make the helium atom is
paramagnetic one.
Paramagnetic substances are those that are attracted by a magnet.
On the other hand, if the electron spins are paired or antiparallel to each other, the magnetic
effects cancel out and the atom is diamagnetic.
Diamagnetic substances are slightly repelled by a magnet. Also by experimentally we
confirmed that the helium atom is diamagnetic in the ground state. Thus, an odd number of
electrons must be paramagnetic and atoms containing an even number of electrons may be either
diamagnetic or paramagnetic. If, consider the lithium atom (Z=3) which has three electrons, third
electron has the parallel spin (unpaired electron) compare with first electron of this atom and is
therefore paramagnetic.
The modern periodic table
Introduction
Only few elements were known before 18 century. Therefore it was very easy to remember and
study the properties of these elements and their compounds individually. But at present as many
as 118 elements are known and many more may be discovered in the future. Therefore it is very
difficult to study individually the properties of these elements and millions of their compounds.
Hence there is a great need of some simple method to simplify the study of these elements and
their compounds. This necessity led to the classification of various elements into groups based
on their properties. This arrangement of elements is called is called classification of elements in
the form of table known as periodic table.

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Modern periodic Law
According to Henry’s Mosely, Mendeleev’s periodic law was modified. This is known as the
modern periodic law and can be stated as: The physical and chemical properties of the
elements are periodic functions of their atomic numbers.
Modern periodic table ( Long form of periodic table)
Many different forms of a periodic classification of the elements have appeared since the 1871
periodic table by Mendeleev. Some forms emphasize chemical reactions and valence, whereas
others stress the electronic configuration of elements. A modern version, the so-called “Long
form” of the periodic table , is the most convenient and widely used. The horizontal rows
(series)of periodic table are called periods and the vertical columns called groups.
Elements having similar chemical properties, and are arranged in 1-18 horizontal rows referred
to as groups or families.
The inert gases are placed at the extreme right of the table, reflecting the completion of the s and
p sub-shells of their outer or valence shell.
There are seven horizontal rows, called periods. The period number corresponds to the highest
principal quantum number (n) of the elements in the period.
The first period contains 2 elements, the second and third containing 8 elements, the fourth
and fifth periods containing 18 elements, and the sixth and seventh periods containing 32
elements. This gives a total of 118 elements.
In this form of the periodic table, 14 elements of both sixth and seventh periods (lanthanides and
actinides, respectively) are placed at the main body of the periodic table.
Each set of elements appearing in the vertical column of a periodic table is called a Group and
represents a family of elements that have similar physical and chemical properties.
Group IA is the alkali family;
Group IIA is the alkaline earth family;
Group VIA is the Oxygen family;
Group VIIA is the halogen family.
Group VIIIA is the inert gases or group zero
Classification of elements : Based on electronic configuration
s – Block elements.
Group 1 (IA) and group 2 (IIA) which have ns1 and ns2 outermost electronic configuration
belongs to the s-block elements. They are all reactive metals with low ionization energies,
readily forms +1 and +2 ion respectively.
Because of high reactivity they are never found pure form in nature.
The elements in the first two groups of the periodic table are characterized as “s-block” elements
because of their outer shell having one or two electrons in an s-orbital..
p - block elements
The p-block elements comprise those belonging to group 13-18 and these together with the s-
block elements (except noble gases) are called representative or main group elements .
The outer most electronic configuration varies from ns1 np1 to ns2 np6 in each period. At the end
of each period placed a noble gas element. Proceeding the noble gas family are two chemically
important groups of non-metals. They are the halogens group 17) and the chalcogens (group 16).
d – block elements
These are the elements of group 3 - 12 in the centre of the periodic table.
They are all metals. Transition metals form a bridge between the chemically active
metals of s-block elements and the less active elements of groups 13 - 14.

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f - block elements
The two rows of elements at the bottom of the periodic table, called lanthanides (58Ce – 71Lu)
and actinides (90Th – 103Lr).
These two series of elements are hence called the inner transition elements (f-block elements).
They are also metals. Actinide elements are radioactive.
Many of the actinide elements have been made only in nanogram or even less by nuclear
reactions and their chemistry is not fully explored.
Periodic properties in the periodic table
The properties of the elements show periodicity. Periodicity means: repetition of the similar
properties of the elements placed in a group and separated by definite gaps and atomic number.
Periodic property: is any physical and chemical property which changes periodically with
increasing atomic number.
Some of the important periodic properties are
I. Atomic radius
II. Ionization energy
III. Electronegativity

I. Atomic radius
The atomic radius can be defined as the distance from the centre of the nucleus to the
outer most shell containing the electrons in an isolated atom.
The atomic radius of the elements increases from top to bottom in a group.
Reason: the increase in atomic radius in group from to bottom is due to the addition
of a new shell. i.e. number of shells goes on increasing.
The atomic radius of elements decreases from left to right in a period.
Reason: this is due to the increase of effective nuclear charge from left to right. The
electrons are also getting attracted by the nucleus more and more. As a result, the atomic
size of elements decreases across a period.
II. Ionization energy ( Ionization potential)
The minimum amount of energy required to remove the most loosely bound electron
from an isolated gaseous atom to form a cation is called Ionization Energy.
e.g. M(g) + I.E M+(g) + e-
In general, I.E decreases from to bottom in a group.
Reason: as we move down the group, distance of valence electrons increases with
increase in the number of shells. Hence, removal of electron becomes easy due to less
attraction between the nucleus.
I.E increases from left to right along a period with increase in atomic number.
Reason: this is due to increase in atomic size. Force of attraction between valence
electrons and nucleus increases. As a result, removal of electron becomes difficult and
hence I.E increases.
III. electro negativity
The electro negativity of an atom is the ability of an atom to attract the electrons to it
when it is in a molecule.
Down a group, atomic radius increases and ability to attract bonded electrons reduced,
electro negativty therefore decreases down the same group.
Across a same period, effective nuclear charge increases. When atoms are bonded to
other atoms, their nuclei become nearer to the electrons to attract them.

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