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Mohammad Akter Hossain

Dept. of MNS

(Definition of atom, Significance of Studying atom)

What is an atom?
Atom is the smallest part of an element that can take part in a
chemical reaction.
Significance of Studying Atom
The fundamental unit of all matter is the atom and so the structure
of matter can be adequately explained only in terms of the
constituent atoms.

The physical and chemical properties of matter are

basically function of their constituent atoms. So, in order
to understand these properties, it is important to
understand the the atom its make-up and properties.

It is impossible to understand the chemistry involved in a

study of actual pharmaceutical problems without a
thorough knowledge of the molecule and properties. In
turn, to understand the molecule, it is of fundamental
importance to understand the atom.

Atomic Theory)


The idea that matter is constructed of ultimately indivisible particles is

as old as science itself. The Greek Philosopher, Democritus (460-370
BC) is attributed to have originated the atomic concept of matter.
Daltons Atomic Theory
It was in 1803 that John Dalton, an English Chemist, came up with his
atomic theory. The postulates of this theory can be stated as follows:

All Elements consist of tiny particles called atoms.

All atoms of an element are identical and they have the
same mass.
Atoms are indivisible and unchanging. (Greek: atom =
cannot be cut, i.e. indivisible).
Atoms of each element are different from one another and
they have different masses.
Compounds consist of atoms of different elements
combined together and they have constant composition
because they contain constituent atoms in a fixed ratio.
Chemical reactions involve the rearrangement of
combinations of constituent atoms of compounds.

(Limitations of Daltons Atomic Theory, Subatomic Particles)

Limitation of Daltons Atomic Theory

Daltons theory states that atoms are indivisible, but the subsequent
works of various scientists proved that atoms consist of various
subatomic particles, mainly electron, proton and neutron.
Daltons theory states that atoms are unchanging, but subsequent
experiments of scientists proved that one atom can be converted to
another atom.

Subatomic Particles
After proposition of Daltons atomic theory, experiments of
various scientists proved that the atom is essentially built
of three principal fundamental particles:
Proton &
The proton & neutron constitutes the nucleus of the of the
atom around which the electrons move in circular paths.

J.J. Thomson 1856-1940

What particle did
Thomson discover? J.J.
Thomson discovered that
atoms are made of
smaller negativelycharged particles called
Thomsons discovery was
the result of doing
experiments with cathode
ray tubes

Thomsons Cathode Ray

Stream of electrons is attracted to positively
charged plate here.

"What are these particles?

are they atoms, or
molecules, or matter in a still
finer state of subdivision? quote by Thomson

Thomsons Cathode Ray


(Subatomic Particles [Continued])
Electron (e)
An electron is a subatomic particle which bears a charge of
1.60 x 1019 coulombs (or 1 unit ve charge) and has a mass of
9.1 x 1028g (or 1/1835 amu).

Sir J.J. (Joseph John) Thomson, an English Physicist, discovered

electron in 1897 as the constituent of cathode rays by the study of
electric discharge in discharge tube. The name was given by the
Dutch Physicist H.A.(Hendrik Antoon ) Lorentz.

The Plum Pudding Model

Thomson did not know how the
electrons in an atom were
arranged. He believed they were
mixed throughout an atom.
He proposed that the atom was a
sphere of positively charged
material. Spread throughout the
atom were the negatively charged
electrons similar to plums in a
pudding or chocolate chips in
ice cream.

Proton (p)
A proton is a subatomic particle which carries a charge of
+1.60 x 1019 coulombs (or 1 unit +ve charge) and a
mass of 1.672 x 1024g (or 1 amu).
E. (Eugen) Goldstein, a German Physicist, discovered
anode ray in a discharge tube containing hydrogen. It was
J.J. Thomson who later established that these rays
consisted of positively charged particles. The particles
were assigned the name proton by Lord Ernest Rutherford,
an New Zealander-English Physicist.

(Subatomic Particles [Continued])
Neutron (n)
A neutron is a subatomic particle which has a mass almost equal to
that of proton (1.674x 1024g or 1 amu) and has no charge.

Sir James Chadwick, an English Physicist, discovered neutron in

1932 by bombarding light nuclei like Li and Be with -particles
(dipositive helium ions, He2+ or 42 He). He named these particles
as neutrons on account of their neutral nature.

Other Subatomic Particles

Nearly all the ordinary chemical properties of matter can be
examined in terms of the three-particle (electron, proton and
neutron) of atoms.
But many other subatomic particles have so far been
discovered including: mesons, positrons, neutrinos and

A great deal of recent research is producing a long list of

still other subatomic particles named quarks, pions and

STRUCTURE OF ATOM (Rutherfords Atomic Model)

Rutherfords Atomic Model

Having known that atom contains electrons and a positive ion,
Rutherford proceeded to perform experiments to know about how
and where these were located.
In 1909 Ernest Rutherford and Ernest Marsden (a 20 yr old
undergraduate student working in Ernest Rutherford's laboratory)
performed their historic Alpha particle-scattering experiment (by
thin metal foils), and based on the observations of this experiment
proposed a model of the atom which is named after him as
Rutherfords Atomic Model. This is also called the Nuclear Atom
or Rutherfords Solar System Atom Model.
The postulates of this model are as follows:

Atom has a tiny dense central core or the NUCLEUS

which contains practically the entire mass of the atom,
leaving the rest of the atom almost empty.

The entire positive charge of the atom is located on the

nucleus, where electrons are distributed in vacant space
around it.

The electrons are moving in orbits or closed circular paths

around the nucleus like planets around the sun.

STRUCTURE OF ATOM (Rutherfords Atomic

Model [Continued])

Figure: Rutherfords Atom Model Electrons orbiting around nucleus

STRUCTURE OF ATOM (Limitations of

Rutherfords Atomic Model)

Limitations of Rutherford Atomic Model

The assumption that electrons move in orbits around the nucleus

like planets around the sun does not hold good because electrons
are negatively charged bodies which in an atom repel one another,
whereas planets are neutral bodies which attract each other by
gravitational forces. Besides there is electrostatic attraction in a
nuclear atom model.

According to Maxwells electromagnetic theory, if a

charged body rotates in an orbit around another oppositely
charged body, the former must radiate energy continuously
and thereby lose kinetic energy (getting slower in speed).
So the electrons must gradually go in spiral motion and
finally fall into the nucleus. But practically it does not
happen because then the atom would be unstable which it
is not.

Since the process of radiating energy would go on

continuously, the atomic spectra should also be continuous
and should not give sharp and well-defined lines as
practically found.

(Limitations of Rutherford Atomic Model [Continued])

Figure: Orbiting electrons would radiate energy and spiral into the nucleus

STRUCTURE OF ATOM (Some Definitions)

Avogadros Number (N): Avogadros number is the number of
molecules in a gram atom or the number of atoms in a gram
atom of any substance. It is represented by the symbol N. The
usually accepted value for N is 6.023 x 1023.
Atomic Number (Z): The atomic number of an element is the
number of protons in the nucleus of the atom of that element. It
is represented by Z. Since atom as a whole is electrically
neutral, the atomic number is also equal to the number of
extraneuclear electrons.
Atomic Number (Z) = Number of protons
(also = Number of electrons)

(Some Definitions [Continued])

Mass Number (A): The mass number of an atom is the total

number of protons and neutrons in the nucleus of an atom.
Mass Number (A) = Number of protons + Number of neutrons
In situations where it is unnecessary to differentiate between
protons and neutrons, these elementary particles are collectively
referred to nucleons.
The number of neutrons can be determined by subtracting
atomic number (Z) from the mass number (A).
Isotopes: If an element can exist in more than one form with
the same atomic number but different mass number, then these
forms are known as isotopes.
Examples: 8O16 (99.757%), 8O17 (0.039%), 8O18 (0.204%)

STRUCTURE OF ATOM (Origin of Spectral Lines)

SPECTRUM: A spectrum is an array of waves or particles arranged according to
the increasing or decreasing of some property such as wavelength or frequency.


Atomic Emission Spectrum: When an element in the vapor or

gaseous state is heated in a flame or a discharge tube, the atoms are
excited (energized) and emit light radiations of a characteristic color
When this emitted light is passed through a spectroscope (a device in
which a beam of light is passed through a prism and received on a
photograph), a spectrum of bright lines is obtained, each of which
represents a specific wavelength. This type of spectrum obtained
from the light emitted from an atom is known as Atomic Emission
Spectrum or Line Spectrum of the element, and an individual line

Atomic Absorption Spectrum: When white light,

composed of all visible wavelengths, is passed through the
cool vapor of an element, certain wavelengths may be
absorbed, and thus these wavelengths are found missing in
the transmitted light.
Therefore, when the transmitted light is passed through a
spectroscope, the spectrum obtained consists of a series of
dark lines.
This type of spectrum is known as the Atomic Absorption
Spectrum or simply Absorption Spectrum.
The wavelengths of the dark lines are exactly the same as
those of bright lines in the emission spectrum. Thus the
absorption spectrum of an element is the reverse of the
emission spectrum of the element.

STRUCTURE OF ATOM (Atomic Spectrum of Hydrogen)

The emission line spectrum of hydrogen can be obtained by
passing electric discharge through the gas contained in a
discharge tube at low pressure. The emitted light radiation is then
passed through a spectroscope to get the spectrum.

Figure: The emission spectrum of hydrogen atom obtained on passing light

emitted from a discharge tube (containing hydrogen) through a prism


Spectrum of Hydrogen [Continued])

In 11884, J.J. Balmer observed there are four prominent colored

lines in the visible hydrogen spectrum:
A red line with a wavelength of 6563
A blue-green line with a wavelength 4861
A blue line with wavelength 4340
A violet line with wavelength 4102 .
These four lines in the visible spectrum of hydrogen were named after
him as the Balmer Series.

Figure: Balmer Series in the Hydrogen Spectrum


Spectrum of Hydrogen

In addition to Balmer series four other spectral series were

discovered in the UV and IR regions of the hydrogen spectrum,
which also have been named after their discovers. Thus, in all,
we have five spectral series in the atomic spectrum of hydrogen.
Sl. No.



Lyman Series


Balmer Series


Paschen Series


Brackett Series


Pfund Series


STRUCTURE OF ATOM (Plancks Quantum Theory

of Radiation)

Plancks Quantum Theory of Radiation

In 1900, Max Planck studied the spectral lines obtained from hot
body radiations at different temperatures and put forward a theory
which, after his name, is known as Plancks Quantum Theory of
Radiation. The postulates of this theory, in its present form, are as

1. When atoms or molecules absorb or emit radiant energy, they

do so in discrete (separate) units of waves called quanta or

2. The energy, E, of a quantum or photon is given by the

relation: E=h (where, h is the Plancks constant with
the value of 6.62 x 1027 erg sec and is the frequency
of the emitted radiation.)

Now, since c = (where c and are velocity and

wavelength of radiation), we can write: E = hc / .

This means that the magnitude of a quantum of energy

is directly proportional to the frequency of the radiant
energy and inversely proportional to its wavelength.


The energy emitted or absorbed by an atom or molecule

can be either one quantum of energy (h ) or an integral
multiple of it.

STRUCTURE OF ATOM (Bohrs Atomic Model)

Bohrs Atomic Model
Rutherfords nuclear atomic model simply stated the atom had a
nucleus and electrons were present outside the nucleus.
It did not say anything about how and where the electrons are
arranged. It also could not explain why electrons did not fall into the

In 1913, Neils Bohr proposed a new model of the atom which

explained some of these things and also the emission spectrum of
Bohrs theory was based on Plancks quantum theory and was
built on the following postulates:

1. Electrons revolve round the nucleus in specific concentric

circular orbits situated at definite (i.e. fixed) distance from
the nucleus and with a definite velocity.
2. As long as an electron remains in its specific orbit, it neither emits
(i.e. radiates or loses) nor absorbs (i.e. gains) energy.
Therefore, in a specific orbit the energy of a revolving electron
remains constant or stationary. Hence, the specific orbits available
to the electron in an atom are referred to as Stationary energy
levels or simply Energy levels.
The energy associated with a certain energy level increases with the
increase of its distance from the nucleus.


Model [Continued])


Model [Continued])

3. An electron can move from one energy level to another by absorbing or

emitting energy, but the absorption or emission of energy can take place only
in form of discrete quanta or photons.

When an electron resides in the lowest energy level the energy level 1
(i..e. the orbit closest to the nucleus), it is said to be in the ground state.
Now, if energy is supplied to the electron residing in the energy level 1, it
will absorb the supplied energy in the form of quanta or photons and hence
will jump to the higher energy levels 2, 3, 4 --------etc. depending on the
amount of energy absorbed by the electron. The electron then is said to be
in an excited state.
The quanta or photons of energy emitted or absorbed is the difference
between the lower and higher energy levels of atom, i.e.,E = Ehigh Elow


The angular momentum (mvr) of an electron orbiting around

the nucleus is an integral multiple of Plancks constant
divided by 2.

Angular momentum = mvr

= n. h/2

Where, m = mass of electron; v = velocity of the electron; r = radius of

the orbit; n = 1, 2, 3, etc., and h = Plancks constant.

Thus, according to this postulate, the angular momentum of a

moving electron is quantized. The integer n in the above
equation can be used to designate an orbit and its
corresponding energy level, and it is called the atoms
principal quantum number.


Model [Continued])


Model [Continued])

Limitations of Bohrs Atomic Model

1. Bohrs theory has successfully explained the origin of the
spectrum of hydrogen, but it cannot explain the origin of atoms
containing more than one electron.

2. If the hydrogen spectrum is observed by means of a spectroscope

of high resolving power, the individual spectral lines are found to
consist of multiple very fine lines lying close together. Bohrs
model cannot explain this fine structure of spectral lines in the
hydrogen spectrum.

3. Appearance of several lines in a single spectral line

suggests that in a given orbit (or shell or energy level)
there are several sub-orbits (or sub-shells or sub-energy
levels) which are slightly different in energies. This
necessitates additional quantum numbers for a given
principal quantum number (n) to quantize the angular
momentum of an orbiting electron.


Model [Continued])

4. It has been found that the spectral lines are further split up into a
number of still thinner lines when the excited atom is placed in a
magnetic field (Zeeman effect) or an electric field (Stark
effect). Bohrs model can explain none of these effects.

5. According to Bohrs model, the electrons move in definite

circular orbits round the nucleus, but the modern researches have
shown that the motion of electrons takes place in threedimensional space rather than a single plane.

6. Bohrs model assumes that an electron

moves round the nucleus at a fixed distance
with a fixed velocity. But, Heisenberg
showed later that both the position and the
velocity of an electron cannot be accurately
determined simultaneously (Heisenbergs
uncertainty principle).


of Electrons in Orbits)

Bohr-Bury Scheme of Distribution of Electrons in Orbits

In 1921, Bohr and Bury independently put forward two identical
schemes for the distribution of electrons in orbits. This scheme is
now called Bohr-Bury Scheme. According to this scheme:

1. The maximum number of electrons that an orbit can contain is 2 x

n2, where n is the number of the orbit.
Thus, the first orbit can contain 2 x 12 = 2; second 2 x 22 = 8; third
2 x 32 = 18; fourth 2 x 42 and so on.

2. The maximum number of electrons in the outermost orbit is

8 and next-to-the outermost 18.
3. It is not necessary for an orbit to be completed before
another begins to be formed. In fact, a new orbit begins
when the outermost orbit attains 8 electrons.
4. The outermost orbit cannot have more than 2 electrons and
next-to-the outermost cannot have more than 9 as long
as the next inner orbit, in each case, has not received the
maximum electrons as required by the rule (1).


of Electrons in Orbits)
Electronic Configuration of Inert Gases
According to the Bohr-Bury scheme, the electronic configuration of
inert gases is given in the table below:

STRUCTURE OF ATOM (Quantum Numbers)

The position, energy and spinning direction of an electron in an
atom can be completely described or defined by a set of four
(identification) numbers. These numbers are known as quantum
numbers. (These four quantum numbers altogether precisely
specify the energy level in which the electron resides.)
The four quantum numbers required to completely describe an
electron are as follows:
Principal Quantum Number (n)
Azimuthal or Subsidiary Quantum Number (l)
Magnetic Quantum Number (m) &
Spin Quantum Number (s)

STRUCTURE OF ATOM (Quantum Numbers [Continued])

Principal Quantum Number (n)

The principal quantum number denotes the distance of the electron

orbit from the nucleus. In other words, it represents the size of the
electron orbit. It is expressed by the letter designation n.

Theoretically, the principal quantum number can have non-zero,

positive, integral values up to infinity, i.e. n = 1, 2, 3,
... But practically only values 1 to 7 have so far been
established for the atoms of the known elements.

In a polyelectron atom or ion, the electron that has a higher principal

quantum number is at a higher energy level.

The letters K, L, M, N, O, P and Q are also used to designate the energy

levels or shells of electrons with an n value of 1, 2, 3, 4, 5, 6, 7 respectively

(1st Shell)

(2nd Shell)

(3rd Shell) (4th Shell)

STRUCTURE OF ATOM (Quantum Numbers [Continued])


Fig.: Principal Quantum Number

STRUCTURE OF ATOM (Quantum Numbers [Continued])

Azimuthal or Subsidiary Quantum Number (l)
The subsidiary quantum number (l) is used to represent the subshells
of which a given shell (represented by a particular value of the
principal quantum number, n) is composed.

The value of l depends on the value of n. For a given value of n, l

can have the values from 0 to (n1), i.e.
l = 0, 1, 2, 3, (n2), (n1)
Thus, l can have n values.

The subshells represented by the l values 0, 1, 2, 3, . are designated by

small letters s, p, d, f respectively.

Value of l

Designation of sub-shell

Each sub-shell represented by an l value has a definite shape.

For example, the

s sub-shell has spherical shape, p sub-shell has dumbbell shape, d sub-shell has a shape resembling four pears with their stems
pointed towards the nucleus.

Subshells with higher l values have more complex shapes. So, it can be said
that: the values of l define the shape of the sub-shell.

STRUCTURE OF ATOM (Quantum Numbers [Continued])

Magnetic Quantum Number (m or ml)

When an atom is placed in a strong magnetic field, each sub-shell
(represented by l values) is further sub-divided into sub-shells called
These orbitals actually represent the different three dimensional
space orientations that a particular sub-shell can assume.
The magnetic quantum number (m) is used to represent the orbitals
of which a given sub-shell is composed.

The value of m depends on the value of l. For a

given value of m, l can assume all the integral
values between +l and l including zero.

i.e. m = +l, (+l-1), ..0.., (l+1), l.

Thus, m can have (2l+1) values.

The maxim number of electrons that can be
present in an orbital is 2.
This means that an orbital can have none, one or
two electrons, but never more than two.

STRUCTURE OF ATOM (Quantum Numbers [Continued])

Spin Quantum Number (s or ms)

An electron, while moving in an orbit round the nucleus, also
rotates or spins about its own axis (self-rotation) either in a
clockwise direction or in an anticlockwise direction. The spin
quantum number (s) represents the direction of the spin or selfrotation of an electron about its own axis.

Since an electron can spin in either of the two directions, the spin
quantum number (s) can have two values, viz. + and . By
convention, s= + is used to indicate clockwise direction and s =
to indicate anticlockwise direction.

The clockwise and anticlockwise directions are

represented by and respectively. When there are two
electrons in an orbital, they spin in opposite directions and
thus an electron pair in an orbital is represented as .
Two electrons with the same sign of the spin quantum
numbers are said to have parallel spins. In contrast, two
electrons with opposite signs of the spin quantum numbers
are said to have opposite spins, antiparallel spins or
paired-up spin.

STRUCTURE OF ATOM (Quantum Numbers [Continued])

Physical significance of Quantum

Size of the electron orbit




of the electron orbit

electron orbit in space
of spin of
electron in the orbit


STRUCTURE OF ATOM (Paulis Exclusion Principle)

Paulis Exclusion Principle
In 1925, Wolfgang Pauli, put forward an ingenious principle
regarding the assignment of the four quantum numbers to an
This principle imposes some restrictions as regards assigning the
quantum numbers to the electrons of an atom and hence the name
Puaulis exclusion principle. This principle can be stated as:
No two electrons in an atom can have the same set of
four identical quantum numbers.

This means that two electrons of an atom may

have, at the most, three same quantum
numbers, but the fourth one must be
This follows that --- Every electron in an atom is different in total energy from every
other electron and so there can be as many electrons in a shell as
there are possible arrangements of different quantum numbers.
An orbital can not accommodate more than two electrons.

STRUCTURE OF ATOM (Paulis Exclusion Principle [Continued])

Illustration of the Principle
We know, the 1st shell of an atom has only one orbital --- 1s that
contains two electrons. These two electrons will have the same set
of the first three quantum numbers, i.e. n=1, l=0 and m=0, but the
fourth quantum number will be different, i.e., either + or .

1st Electron

2nd Electron

Let us suppose that the 1s orbital have three

electrons so that:

1st Electron

2nd Electron

3rd Electron


It is clear from the above illustration that the 3 rd electron cannot be

accommodated in the 1s orbital, because there are only two possible
values of the spin quantum number --- + and .


Hunds Rule (of Maximum Multiplicity)
This is an empirical rule which states that: Electrons are
distributed among the degenerate orbitals of a sub-shell
(orbitals of equivalent energy such as 2px, 2py and 2pz) in such a
way as to give maximum number of unpaired electrons with
the same direction of spin.
Thus the orbitals available to a sub-shell are first filled singly with
parallel spin before they begin to pair.
The following illustration (next page) shows the order of filling of
electrons in the orbitals of n=1 and n=2 shells. (The orbirals are
shown in circles and the electrons entering them by numbers 1, 2,
3 .. according to their order of entering.)

STRUCTURE OF ATOM (Aufbau Process)

Aufbau Process
Aufbau process or Aufbau principle is an empirical rule that
governs the order of filling or building up of energy sub-shells of
an atom with electrons (Aufbau is a German expression meaning
building up or construction). This rule states that:

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.

The following figure shows the energy level

schemes of the commonly encountered
energy sub-shells and their sequence of




Fig.: Sequence of filling of atomic sub-shells

STRUCTURE OF ATOM (Aufbau Process [continued])

There are quite a few elements which show slight deviations
from the standard pattern dictated by Aufbau principle. The
deviations involve placing of one or two electrons from ns
orbitals to (n1)d orbitals.
Actually, there is little energy difference between such s and d
orbitals and the deviations occur when the d level orbitals are
either almost full (e.g. in Cu, Pd, Ag, Pt , and Au) or half-full (Cr
and Mo).
The probable underlying reason of such deviations is the fact that
a completely filled (e.g. d10) or half-filled (e.g. d5) orbital is more
stable than a nearly filled or nearly half-filled orbital (e.g. d9, d8
or d4).

Bahl and Tuli (Physical)
General ChemistryEbbing