ATOMIC STRUCTURE

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 Dalton’s Atomic Theory
English physicist and chemist
John Dalton in 1808, stated
that all substances made up
of small sized indivisible
particles called atom.

Postulates
• All substances are made up of tiny, indivisible particles called atom.
• Atoms can neither be created nor destroyed but can be transformed from one form to
another.
• All atoms of a specific element are identical in mass, size, and other properties.
• Atoms of different elements exhibit different properties and vary in mass and size.
• Atoms of different elements can combine with each other in fixed whole-number
ratios to form compounds.
• Atoms undergo rearrangement during a chemical reaction.
 Limitations of Dalton’s Atomic Theory
• Constituent particles of a matter can be atoms, molecules or
ions.
• An atom can be divided into its subatomic particles like
electrons, protons, and neutrons.
• Isotopes of an element have the same atomic number but
different atomic masses.
● Isobars of two elements are the atoms with different atomic
numbers but same atomic masses and they exhibit different
properties. E.g.

● Non-stoichiometric compounds are solid inorganic compounds have elemental

composition whose proportions cannot be represented by a fixed whole
number ratio such as Fe0.93O, Ni0.98O etc.
 Fundamental Particles
● An atom is the smallest particle of an element having its own chemical
identity and property. But according to various experiments, atoms can
be subdivided into smaller subatomic particles known as fundamental
particles. Electron, proton, and neutron are fundamental particles.
 Discovery of Subatomic particles
Electron Discovery
J.J. Thomson in 1897 by Cathode Ray experiment discovered
electron.
Proton Discovery
Goldstein, one of the students of Rutherford, in 1886, after
carrying out Anode Ray experiment, concluded that in addition to
the electrons, or cathode rays, that travel from the negatively
charged cathode toward the positively charged anode, there is
another ray that travels in the opposite direction, from the anode
toward the cathode.
Neutron Discovery
In 1932, Chadwick discovered neutron.
 Rutherford’s Atom Model
Rutherford’s Alpha Scattering Experiment
Having known that atom contains electrons and a positive ion, Rutherford proceeded to
perform experiments to know as to how and where these were located in the atom. In
1909 Rutherford and Marsden performed their historic Alpha Particle-Scattering
Experiment.
▪ They directed a stream of very highly energetic α-particles from a radioactive source
against a thin gold foil provided with a circular fluorescent zinc sulphide screen around
it. Whenever an α-particle struck the screen, a tiny flash of light was produced at that
point.
Rutherford and Marsden noticed that
✓ most of the α-particles passed straight through the gold foil and
thus produced a flash on the screen behind it
✓ This indicated that gold atoms had a structure with plenty of
empty space.
✓ Tiny flashes were also seen on other portions of the screen,
some time in front of the gold foil
✓ This showed that gold atoms deflected or ‘scattered’ α-particles
through large angles so much so that some of these bounced
back to the source

Based on these observations, Rutherford proposed a model of the

atom which is named after him. This is also called the Nuclear
Atom.
 Postulates of Rutherford’s Atomic Model
► Two parts of an atom are i) nucleus and ii) extra nuclear part. Nucleus is a
minute, massively positively charged body at the centre of the atom. All
the positive charges and almost total mass of the atom are present in the
nucleus. The volume of the nucleus is very small compared to that of the
atom as a whole.
► Atom is electrically neutral. So, a number of electrons equal to positive
charges of the nucleus are present in an atom. Electrons are in constant
motion around the nucleus in different circular orbits like the planets in a
solar system.
► Due to the constant motion of the electrons around the nucleus, outward
centrifugal force is exactly counter-balanced by the inward electrostatic
attraction between electrons and nucleus i.e. centripetal force.
Since Rutherford’s atom model resembles the solar system, it is also known as
solar system atom model. Again, since the concept of nucleus was first
introduced in this atom model, it is also known as nuclear model of atom.
 Some aspects of Rutherford’s Observation

● Major part of an atom is empty. Electrons may be present in this space.

Due to their negligible masses compared to alpha particle, they can not
deflect the high speedy alpha particles.
● Since a few alpha particles (positively charged) are deflected through
some angles and a few alpha particles turn back on their opposite paths,
atoms would have positively charged bodies which repel positively
charged alpha particles. Rutherford named this positively charged body
as nucleus of atoms.
● Returning back of alpha particles in opposite direction suggests that the
nucleus is heavy where all masses and positive charges are concentrated
centrally in a small region.
● From the number of alpha particles deviated from their paths,
Rutherford calculated the size of the nucleus and found that the
diameter of an atom is about 105 times greater than that of the
nucleus. This proves that major part of the atom is empty.

● From the amount of deviation of alpha particles, Rutherford further

showed that the amount of positive charge on an atomic nucleus is
equal to the atomic number of that element. Rutherford knew that the
mass of an alpha particle is 7000 times heavier than the mass of an
electron and it is doubly positive charged.
Main Drawbacks of Rutherford Model
2. The Rutherford’s atom model has been compared with the solar
system. The rotating electrons are negatively charged and repel
each other while the rotating planets are neutral and have force of
gravitation acting between them. On the other hand, the force
between nucleus and electron is electrostatic. So, here comparison
between gravitational force and electrostatic force is not correct.
3. The model can’t give any explanation of the atomic spectra.
4. Don’t give idea about shape and size of the orbits of electrons in
which electron move around the nucleus.
5. No explanation about the rotation of many electrons in an orbit.
Bohr’s Atom Model
Neils Bohr, a brilliant Danish Physicist, pointed out that the old laws of physics just did not
work in the submicroscopic world of the atom. He closely studied the behavior of electrons,
radiations and atomic spectra.

In 1913 Bohr proposed a new model of the atom based on the modern Quantum theory of
energy. With his theoretical model he was able to explain as to why an orbiting electron did
not collapse into the nucleus and how the atomic spectra were caused by the radiations
emitted when electrons moved from one orbit to the other.
Drawbacks of Bohr’s Atomic Model
▪ No explanation for the value of angular momentum:
Calculation of radius of orbits

According to one of the postulates of Bohr’s theory:

Radius of orbit:
Energy of electron in each orbit
Bohr’s Explanation of Hydrogen Spectrum
 WAVE MECHANICAL CONCEPT OF ATOM
The new theory rejects the view that electrons move in closed orbits, as was
visualised by Bohr. The Wave mechanical theory gave a major breakthrough by
suggesting that the electron motion is of a complex nature best described by its
wave properties and probabilities.
HEISENBERG’S UNCERTAINTY PRINCIPLE

One of the most important consequences of the dual nature of matter is the uncertainty
principle developed by Werner Heisenberg in 1927.
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 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:
The uncertainty product is negligible in case of large objects.
But for an electron of mass m = 9.109 × 10– 28 g, the product of the
uncertainty of measurements is quite large as:

This value is large enough in comparison with the size of the electron and is
thus in no way negligible. If position is known quite accurately i.e., Δx is very
small, the uncertainty regarding velocity Δv becomes immensely large and vice
versa. It is therefore very clear that the uncertainty principle is only important
in considering measurements of small particles comprising an atomic system.

It appears clear that the Bohr’s picture of an electron as moving in an orbit with
fixed velocity (or energy) is completely untenable.
 ħ = h/2ᴨ

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 favor of the probability approach.
SCHRÖDINGER’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.

ORBITALS
The three-dimensional region within which there is higher probability that an electron having a
certain energy will be found, is called an orbital.

QUANTUM NUMBERS
Principal Quantum Number ‘n’
This quantum number denotes the principal shell to which the electron belongs. This is also
referred to as major energy level. It represents the average size of the electron cloud i.e., the
average distance of the electron from the nucleus. This is, therefore, the main factor that
determines the values of nucleus-electron attraction, or the energy of the electron.
Azimuthal Quantum number ‘l ’

This is also called secondary or subsidiary quantum number. It defines the spatial distribution of
the electron cloud about the nucleus and describes the angular momentum of the electron. In
other words, the quantum number l defines the shape of the orbital occupied by the electron
and the angular momentum of the electron. It is for this reason that ‘l’ is sometimes referred to
as orbital or angular quantum number. For any given value of the principal quantum number n,
the azimuthal quantum number l may have all integral values from 0 to n – 1, each of which
refers to an Energy sublevel or Sub-shell.
These sub levels are also symbolised by
letters s, p, d, f etc.
Magnetic Quantum Number ‘m’
This is also called Orientation Quantum Number because it gives the
orientation or distribution of the electron cloud. For each value of the
azimuthal quantum number ‘l’, the magnetic quantum number m, may
assume all the integral values between + l to – l through zero i.e., + l, (+ l
– l),... 0..., (– l + 1), – l. Therefore for each value of l there will be (2l + 1)
values of m .

Thus when l = 0, m = 0 and no other value. This means that for each value
of principal quantum number ‘n’, there is only one orientation for l = 0 (s
orbital) or there is only one s orbital. For s orbital, there being only one
orientation, it must be spherically symmetrical about the nucleus.

For l = 1 (p orbital), the magnetic quantum number m will have three

values : + 1, 0 and – 1; so there are three orientations for p orbitals.
These three types of p orbitals differ only in the value of magnetic
quantum number and are designated as px , py , pz depending upon the
axis of orientation. The subscripts x, y and z refer to the coordinate axes.
In the absence of a magnetic field, these three p orbitals are equivalent in
energy and are said to be three-fold degenerate or triply degenerate.
PAULI’S EXCLUSION PRINCIPLE

No two electrons in an atom can have the same set of four identical quantum
numbers.
Pauli’s exclusion principle is of immense value in telling the maximum number of
electrons accommodated in any shell.

DISTRIBUTION OF ELECTRONS IN ORBITALS

Hund’s Rule of Maximum Multiplicity

Electrons are distributed among the orbitals of a subshell in such a way as to give
the maximum number of unpaired electrons and have the same direction of spin.

Aufbau Principle
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.
GROUND-STATE ELECTRON CONFIGURATION OF ELEMENTS