System of classifications :

Atomic structure :
Dalton in 1808-1810, Dalton proposed the theory known as "Daltons atomic theory" which can
postulates as

1. All matter is made up of extremely small, invisible particles called atoms.

2. Atoms do not undergo subdivision during chemical reactions.
3. Atoms cannot be created or destroyed by any chemical process.
4. Atoms of the same elements are identical in all respects.
5. Atoms of different elements have different masses and different properties.
6. Combination between two or more atoms takes place in small whole numbers resulting in
formation of Compound atoms.
7. The compound atoms of a compound are identical in all aspects.
8. The combining weight of elements represents the combining weights of the atoms.

The researches done by various eminent scientists like J. J. Thompsons, Goldstein, Rutherford,
Chadwick, Bohr and others in the latter half of the 19th century and in the beginning of the 20th
century have established, beyond doubt, that atom was not the smallest indivisible particle but
had a complex structure of its own and was made up of still smaller particles like electrons,
proton and neutrons etc.

Sub atomic particles :

There are three subatomic particles of matter namely electrons, protons and neutrons.

Electrons :
In 1879, William Crookes, studied the conduction of electricity through gases at low pressure.
He took a discharge tube which was a long glass tube, about 60 cm long, sealed at both the end
and fitted with two metal electrodes. It has a side a side tube fitted with a stopcock. This tube is
connected to a vacuum pump and pressure inside the discharge tube is reduced to as low as 0.01
mm. Now when a high voltage (nearly 10,000 volts) is applied between the two electrodes, it is
found that some invisible rays are emitted from the cathode. The presence of these rays is
detected from the fact that the glass wall of the discharge tube opposite to the cathode begins to
glow with a faint greenish light. Obviously this must be due to the bombardment of the walls by
some rays emitted from the cathode. These rays were called cathode rays.

Sir J.J Thomson in 1897 studied the deflection of cathode rays by electric and magnetic field and
concluded that cathode rays consists of stream of negatively charged minute particles and
named these particles known as electrons denoted by e -.

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 Discharge tube experiment -production of cathode rays

Protons :
Since the atom as a whole is electrically neutral and the presence of negatively charged particles
is in it was established, therefore it was thought that the some positively charged particles must
also be present in the atom. For this purpose, Goldstein in 1886, performed a discharge tube
experiments in which he took perforated cathode and a gas at low pressure was kept inside the
tube, as shown in figure. On passing high voltage between the electrodes, it was found that some
rays were coming from the side of the anode which passed through the holes in the cathode and
produced green fluorescence on the opposite glass wall coated with zinc sulphide.

Production of anode rays or positive rays

These rays were called anode rays or canal rays or positive rays. These rays are believed to be
produced as a result of the knock of electrons from the gaseous atom by the bombardment of
high speed electrons of cathode rays on them. Thus the anode rays are not emitted from the
anode but the produced in the space between the anode and the cathode. Hence proton may be
defined as that fundamental particle which carries one unit positive charge and has a mass nearly
equal to that of hydrogen atom.

Neutrons :
In 1930, Bothe and Baker observed very penetrating radiations when they bombarded certain
light elements like Lithium, Beryllium and Boron with α-particles. In 1932, Chadwick showed
that these radiations definitely consist of neutral particles having a mass almost equal to that of
protons and named them neutrons. Neutrons are uncharged particles and therefore, not deflected
in electric or magnetic field. It has mass of 1.00871 atomic mass unit which is slightly greater

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than that of proton. It is represented by symbol 'n'. A neutron is unstable particle and undergoes
spontaneous disintegration to form a proton and an electron.

Thomson's atomic model :

On the basis of his experiments with the electric discharge in gases Sir J .J. Thomson concluded
in 1891 the presence of electrons and protons in an atom. He was first to propose that the
electrically neutral atom be considered a sphere of positive electricity in which negative
electrons are embedded like seeds in a watermelon. Unfortunately only a few properties of an
atom can be understood from this model alone.

Rutherford atomic model of atom :

Rutherford's α-scattering experiments

In 1911, Ernest Rutherford performed a series of experiments; he shot a thin stream of newly
discovered high speed α- particles from radioactive polonium through a thin foil made up of gold
which may be considered equivalent to athin layer of gold atoms. The fate of every α- particle
was determined by observing with microscope the tiny flash of light which was produced by the
impact of the α- particles on a zinc sulphide fluorescent screen as shown in figure.

From these experiments he made the following experiments,

1. Most of the α- particles (99.9%) passed through the foil without undergoing any
deflection.
2. Few α- particles underwent deflection through small angles.
3. Very few (once in 1, 00,000 times) were deflected back.
From these observations, Rutherford drew the following conclusions.

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 1. Atom is mostly empty because of almost all (99.9%) α- particles passed through it.
2. The mass of atom is concentrated in very small volume within the atom called
nucleus. The diameter of the nucleus of an atom was estimated to be of the order of
10-13 cm while the atoms have diameter of the order of 10 -8 cm.
3. All the protons are enclosed in this dense nucleus and large deflections are caused of
electrostatic repulsive force when α- particles pass very near to this positively
charged nucleus.
The atom as a whole is electrically neutral, Rutherford assume that to counter balance
the positive charge just enough electrons occupy the empty space. To convey stability
of the nuclear model of the atom, the electrons were assumed to be revolving around
the nucleus balancing by the centrifugal force with electrostatic force of attraction of
the nucleus.
Hence, the Rutherford model of the atom consists of a small, positively charged
nucleus surrounded by the fast moving electrons in a large space.
Rutherford proposed his model of the atom in 1911 while the neutrons discovered in 1930. The
nucleus of atom consists of protons and neutrons are known as nucleons.

Drawbacks of Rutherford's atomic model :

Drawbacks of Rutherford's atomic model are as belows.
1. According to classical theory of electrodynamics, when charged particles like electrons
are accelerated, it will lose energy by emitting radiation. In Rutherford's atomic model,
the atom continuously accelerated towards the centre of the orbit and consequently loses
energy by emitting radiation drop to nucleus and collapse the atom which is not possible.

Electron falling into the nucleus

2. This atomic model could not account for the discontinuous spectral lines of Hydrogen
and Hydrogen like atoms.

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 Bohr's Model of the atom :
To overcome the drawbacks of Rutherford's model of atom and to explain the line
spectrum of Hydrogen, Neil Bohr, in 1913 proposed a new model of atom based upon
Planck's quantum theory which is called Bohr's model of atom.

Postulates of Bohr's model of atom :

1. The electrons revolve around the nucleus in a fixed circular path, called an orbit. The
electrons in a particular orbit or shell have a fixed amount of energy called stationary
state or energy levels.

Circular orbits (energy levels/stationary states around the nucleus

2. Only limited number of orbits are possible in which the electron has a angular
momentum of an integral multiple of h/2 π .
i.e. mvr = nh
2π

Where, m= mass of electron

v= velocity of electron
r= radius of atom
h= Planck's constant (6.62×10-27ergs sec)
n= number representing the orbit called principal quantum numbers in whole number
3. Electron moving in an orbit cannot lose or gained energy continuously but in discrete
units of hυ, known as quantum.
i.e E= hυ
where ,h= Planck's constant (6.62×10-27ergs sec) and υ=is the frequency of the radiations.

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4. Radiations is emitted or absorbed only when an electrons jumps from one stationary orbit
(ground state or lower state) to another (excited or higher state). The energy emitted or
absorbed depends upon the energy difference in the two energy levels.
i.e. ΔE= E2-E1= hυ
or, ΔE= E2-E1= hc
λ
Where, ΔE= change in energy
E2 = Higher energy level (excited state)
E1= lower energy level (ground state)
h= Planck's constant (6.62×10-27ergs sec)
υ=is the frequency of the radiations.
c= velocity of light
λ= wavelength of radiation

Atomic spectrum of Hydrogen on the basis of Bohr's atomic model :

When hydrogen gas at low pressure is taken in the discharge tube and the light emitted on
passing electric discharge is examined with the spectroscope, the spectrum obtained is
called the atomic spectrum of hydrogen. It is found to consist of a large number of lines
which are grouped under different series named behind the discoveries. The name and
regions are as shown in figure given below.

Different series in the hydrogen spectrum

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 Rydberg formula :
Rydberg in 1890 gave a very simple theoretical equation for the calculation of the wavelengths
of these lines is as,

Where, R= Rydberg constant (109,677cm-1)

The spectral lines are Lyman series, Balmer series, Paschen series, Bracket series, P-Fund
series lies in the hydrogen and hydrogen like atom which is successfully explained by Bohr's
model of atom.

Mass number (Z) :

The sum of the number of protons and neutrons present in the nucleus is called mass number
denoted by 'A' and its value is very close to atomic mass although not equal to it. For example
Na atom has 11 protons and 12 neutrons in its nucleus and its mass number is 23.

Atomic number (A) :

The number of proton present in the nucleus is called atomic number of that atom and denoted
by 'A'. For example Chlorine has 17 protons in its nucleus and the atomic number of Chlorine is
17.

Arrangement of electrons( Bohr-Bury Scheme of distribution of electrons) :

Bohr and Bury in 1921 proposed a scheme for distribution of electrons in different orbits. The
main points of this scheme are as,
1. The maximum number of electrons that can be present in an orbit or energy level is 2n 2,
where n is the number of the orbit.
2. The outermost orbit cannot have more than eight electrons and next to the outermost
cannot have more than 18 electrons. The electrons in the outermost orbit are called
valence electrons.
3. It is not necessary for an orbit to be completed before another begins to be formed.

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 According to Bohr-Bury rule the electronic configuration of noble gases are as follows,

Concept of Shell and sub-shell :

An electron shell may be thought of as an orbit followed by electrons around an atom's nucleus.
The electron shells are labeled as K, L, M, N, O, P and Q; or 1,2,3,4,5,6 and 7, going from
innermost shell to outwards. Each shell can contain only a fixed number of electrons, the n shell
to can hold upto 2n2 electrons. The electrons in outer shell have higher average energy and travel
farther from nucleus than those in inner shells. The electrons of outer shells are more important
for reactivity.

Shell designation in an atom

Sub-shell :
Each shell consists of one or more atomic orbitals. There are four types of subshells. These
various subshells are denoted by s, p, d and f.

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Shell name Subshell name Maximum electrons Maximum electrons
in subshell in shell
K 1s 2 2
L 2s 2 2+6=8
2p 6
M 3s 2 2+6+10=18
3p 6
3d 10
N 4s 2 2+6+10+14=32
4p 6
4d 10
4f 14

For example, The copper atom has 29 atomic number as structure is as,

Electronic configuration of Copper atom

The sub shell bearing energy levels are as,

s<p<d<f

Shape of orbitals :
As already defined an orbital is the region of space around the nucleus within which the
probability of findings an electron of given energy is maximum (90-95%). The shape of the
electron cloud thus obtained gives the shape of the orbital.The shape of s and p orbitals are
briefly described below:
1. Shapes of s-orbital :
The probability of finding the electron belonging to s-orbitals of any main shell is found
to be identical in all directions at a given distance from the nucleus. Hence s-orbital is
spherical in shape which is symmetrical around the nucleus. For s-orbital, azimuthal

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 quantum number l = 0. Hence magnetic quantum number m is equal to '0'(i.e. has only
one value).Thus s-orbital has only one value). Thus s-orbital has only one orientation.
The only shape having one orientation is a sphere. Hence s-orbital is in spherical shape.

spherical shape of s-orbitals

2. Shape of p-orbitals :
On the basis of probability calculations, it is found that the probability of finding the p-
electrons is maximium in two lobes on the opposite sides of the nucleus. This gives rise
to a dumbbell shape for p-orbital. However it may be noted that the probability of finding
a particular p-electron is equal in both the lobes. Further, there is a plane passing through
the nucleus on which the probability of finding the electron is almost zero. This is called
a nodal plane.

shape of px-orbitals shape of py-orbitals shape of p z-orbitals

Representation of shapes of p-orbitals

3. Shape of d-orbitals :
Angular probability distribution of d-orbitals is as shown in figure below.

Representation of shapes of d-orbitals

In d-orbitals ,five in number ,are designated as dxy , dyz, dxz , dx2-y2, dz2. dx2-y2 orbitals lie in the xy
plane with its four lobes coinciding the x- and y-axes. The dz2 has a shape somewhat different

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from the other four, most of its desity around the z-axis. dxy , dyz, dxz all have their lobes of
electron density situated between the axes i.e. directed in between the three mutually
perpendicular axes. Except dz2 orbital, all other d-orbitals are double dumbbell in shape.

4. Shape of f-orbitals :

Quantum numbers :
Quantum numbers may be defined as a set of four numbers which give complete
information about the electrons in an atom i.e. energy, orbital occupied, size, shape and
orientation of that orbital and direction of electron spin. There are four quantum numbers
namely principal Quantum numbers, azimuthal Quantum numbers, magnetic Quantum
numbers and spin Quantum numbers on the basis of energy, orbital occupied, size, shape
and orientation of that orbital and direction of electron spin.
1. Principal Quantum numbers

Principal quantum numbers are denoted by the symbol ‘n’. They designate the principal
electron shell of the atom. Since the most probable distance between the nucleus and the
electrons is described by it, a larger value of the principal quantum number implies a
greater distance between the electron and the nucleus (which, in turn, implies a greater
atomic size).The value of the principal quantum number can be any integer with a
positive value that is equal to or greater than one. The value n=1 denotes the innermost
electron shell of an atom, which corresponds to the lowest energy state (or the ground
state) of an electron. Thus, it can be understood that the principal quantum number, n,
cannot have a negative value or be equal to zero because it is not possible for an atom to
have a negative value or no value for a principal shell. When a given electron is infused
with energy (excited state), it can be observed that the electron jumps from one principle
shell to a higher shell, causing an increase in the value of n. Similarly, when electrons
lose energy, they jump back into lower shells and the value of n also decreases. The

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increase in the value of n for an electron is called absorption, emphasizing the photons or
energy being absorbed by the electron. Similarly, the decrease in the value of n for an
electron is called emission, where the electrons emit their energy.

2. Azimuthal Quantum numbers :

The azimuthal (or orbital angular momentum) quantum number describes the shape
of a given orbital. It is denoted by the symbol ‘l’ and its value is equal to the total
number of angular nodes in the orbital.A value of the azimuthal quantum
number can indicate either an s, p, d, or f subshell which vary in shapes. This value
depends on (and is capped by) the value of the principal quantum number, i.e. the
value of the azimuthal quantum number ranges between 0 and (n-1).For example, if n
=3, the azimuthal quantum number can take on the following values – 0,1, and 2.
When l=0, the resulting subshell is an ‘s’ subshell. Similarly, when l=1 and l=2, the
resulting subshells are ‘p’ and ‘d’ subshells (respectively). Therefore, when n=3, the
three possible subshells are 3s, 3p, and 3d.In another example where the value of n is
5, the possible values of l are 0, 1, 2, 3, and 4. If l = 3, then there are a total of three
angular nodes in the atom.

Combinations of the Principal and Azimuthal Quantum Numbers

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The allowed subshells under different combinations of ‘n’ and ‘l’ are listed above. It can be
understood that the ‘2d’ orbital cannot exist since the value of ‘l’ is always less than that of ‘n’

3. Magnetic Quantum numbers:

The total number of orbitals in a subshell and the orientation of these orbitals are
determined by the magnetic quantum number. It is denoted by the symbol ‘ml’. This
number yields the projection of the angular momentum corresponding to the orbital
along a given axis.

Shapes of Orbitals (as per the corresponding Quantum Numbers)

The value of the magnetic quantum number is dependant on the value of the azimuthal (or orbital
angular momentum) quantum number. For a given value of l, the value of ml ranges between the
interval -l to +l. Therefore, it indirectly depends on the value of n.
For example, if n = 4 and l = 3 in an atom, the possible values of the magnetic quantum number
are -3, -2, -1, 0, +1, +2, and +3.

Azimuthal Quantum Number Corresponding Number of

Possible Values of ml
Value Orbitals (2l + 1)

0 (‘s’ subshell) 2*0 + 1 = 1 0

1 (‘p’ subshell) 2*1 + 1 = 3 -1, 0, and 1

2 (‘d’ subshell) 2*2 + 1 = 5 -2, -1, 0, 1, and 2

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3 (‘f’ subshell) 2*3 + 1 = 7 -3, -2, -1, 0, 1, 2, and 3

The total number of orbitals in a given subshell is a function of the ‘l’ value of that orbital. It is
given by the formula (2l + 1). For example, the ‘3d’ subshell (n=3, l=2) contains 5 orbitals (2×2
+ 1). Each orbital can accommodate 2 electrons. Therefore, the 3d subshell can hold a total of 10
electrons.

4. Spin Quantum numbers :

The electron spin quantum number is independent of the values of n, l, and m l. The value of this
number gives insight into the direction in which the electron is spinning, and is denoted by the
symbol ms. The value of ms offers insight into the direction in which the electron is spinning.
The possible values of the electron spin quantum number are +½ and -½.The positive value of
ms implies an upward spin on the electron which is also called ‘spin up’ and is denoted by the
symbol ↑. If ms has a negative value, the electron in question is said to have a downward spin, or
a ‘spin down’, which is given by the symbol ↓.The value of the electron spin quantum number
determines whether the atom in question has the ability to produce a magnetic field. The value of
ms can be generalized to ±½.

In order to simplify the details of the four different quantum numbers that are related to atomic
physics, a tabular column detailing their names, symbols, meanings, and possible values is
provided below.

Name and Symbol Meaning and Possible Values

Principal quantum number, n Electron shell, n ≥ 1

Azimuthal quantum number, l Subshells (s=0, p=1, etc.) , (n-1) ≥ l ≥ 0

Magnetic quantum number, ml Total number and orientation of orbitals, l≥ml≥-l

Electron spin quantum number, ms The direction of electron spin, ms = ±½

It is important to note that it is impossible for two electrons of the same atom to have exactly the
same quantum state or exactly the same values of the set of quantum numbers, as per Hund’s
rules.

Filling of orbitals in atom:

1. Aufbau principle :
Aufbau principle is also known as the building up principle. According to principle ,"the
electrons in an atom are so arranged that they occupy the orbitals in the order of their increasing

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energy." Thus the orbital with the lowest energy will filled first, then the next higher in energy
and so on.

The correct sequence of energy levels can be derived on the basis of the following to rules:
1. The orbitals having the lowest value of ( n+ l ) are occupied by first.
2. When two orbitals have the same values of ( n+ l ), the orbital having the lower
value of 'n' is filled first.
The sequence followed in the filling up of some of the energy levels is derived in
the following table.
Orbitals Principal Azimuthal (n+l)
quqntum quqntum
number(n) number(l)
1s 1 0 1
2s 2 0 2
2p 2 1 3
3s 3 0 3
3p 3 1 4
4s 4 0 4
4p 4 1 5
……….. ……….. ……….. ………..
……….. ……….. ……….. ………..
It obvious that the electron will first accommodated by 1s. when 1s is completely filled ,the
electrons will accommodated to 2s orbitalin preference to 2p orbitaltill becomes it completely
saturated.In case of 2p and 3s orbitals have same(n+l) value.Therefore according to rule 2 2p
orbital having lower value of n,will be first filled. The order to be followed in the filling up of
other orbitals can similarly be deduced.The order of filling atomic orbitals is shown in figure
below.

Sequence of filling up of the atomic orbital .

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2. Pauli exclusion Principle :
In 1925, Wolfgang Pauli discovered the principle which is very useful in constructing
the electronic configuration of atoms. According to this principle, "no two electrons
in an atom can have the same values of four quantum numbers."For example, in 1s
orbital of Helium atom there are two electrons. According to this concept of quantum
numbers and Pauli's exclusion principle, their quantum numbers are,

The electrons particular orbital have same values of quantum number (n),azimuthal
quantum number (l),magnetic quantum number (m). For example, all the electrons in
3s orbital have n=3,l=0 and m=0. Therefore in order to have unique sets of quantum
numbers, they must have different values of spin quantum number (s) only two
values+1/2 or - 1/2. Hence in an orbital only two electrons can be accommodated on
spinning clockwise (s= +1/2) and other spinning anticlockwise(s= -1/2). From above
discussions it follows that,
s-sub-shell (containing only one orbital) can have maximum of 2 electrons.
p-sub-shell (containing three orbitals ) can have maximum of 6 electrons.
d-sub-shell (containing five orbitals ) can have maximum of 10 electrons.
f-sub-shell (containing seven orbitals) can have maximum of 14 electrons.

3. Hund's rule :
It states that "When more than one orbitals with equal energies are available, then the
electrons tends to first occupy these orbitals separately with parallel spins, and the
pairing of electron will start only after all orbitals of a given sub-level are singly
occupied."
Two electrons with parallel spins, tends to be as far apart as possible in order to
minimize the electrostatic repulsion. Therefore, the electrons prefer to occupy the
orbitals singly as far as possible. When all the orbitals get singly occupied, then the
incoming electron has two choices; either to pair up with the order electron, or to go
to next higher orbital. When a higher orbital of suitable energy is available, then the
incoming electron will have no choice except to pair up.
In writing the electronic configuration s according to Hund's rule generally boxes are
used for orbitals. The electronic configuration of carbon (1s2 2s2 2p2) filled as below.

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 electronic configuration of carbon filling of electrons according to Hund's rule

Electronic configuration of first 30 elements with atomic numbers:

Atomic number Name of elements Symbol Electronic configuration
1 Hydrogen H 1s1
2 Helium He 1s2
3 Lithium Li [He] 2s1
4 Berylium Be [He] 2s2
5 Boron B [He] 2s2 2p1
6 Carbon C [He] 2s2 2p2
7 Nitrogen N [He] 2s2 2p3
8 Oxygen O [He] 2s2 2p4
9 Fluorine F [He] 2s2 2p5
10 Neon Ne [He] 2s2 2p6
11 Sodium Na [Ne] 3s1
12 Magnesium Mg [Ne] 3s2
13 Aluminum Al [Ne] 3s2 3p1
14 Silicon Si [Ne] 3s2 3p2
15 Phosphorous P [Ne] 3s2 3p3
16 Sulphur S [Ne] 3s2 3p4
17 Chlorine Cl [Ne] 3s2 3p5
18 Argon Ar [Ne] 3s2 3p6

17
19 Potassium K [Ar] 4s1
20 Calcium Ca [Ar] 4s2
21 Scandium Sc [Ar] 3d14s2
22 Titanium Ti [Ar] 3d24s2
23 Vanadium V [Ar] 3d34s2
24 * Chromium Cr [Ar] 3d54s1
25 Manganese Mn [Ar] 3d54s2
26 Iron Fe [Ar] 3d64s2
27 Cobalt Co [Ar] 3d74s2
28 Nickel Ni [Ar] 3d84s2
29* Copper Cu [Ar] 3d104s1
30 Zinc Zn [Ar] 3d104s2

Note: * indicated that the filling of electrons in unusual way (exception ) with aufbau's principle.

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