ATOMIC STRUCTURE
Chemistry has been defined as the study of matter in terms of its structure, composition and the
properties. As you are aware, matter is made up of atoms, and therefore an understanding of the
structure of atom is very important. You have studied in your earlier classes that the earliest concept of
atom (smallest indivisible part of matter) was given by ancient (600-400 BC) Indian and Greek
philosophers. At that time there was no experimental evidence.
The origin of the concept of atom was based on their thoughts on ‘What would happen if we
continuously keep dividing matter’. John Dalton revived the concept of atom in the beginning of
nineteenth century in terms of his atomic theory this successfully explained the laws of chemical
combination. Later experiments showed that the atom is not indivisible but has an internal structure.
In this lesson you will learn about the internal structure of an atom which will help you to understand
the correlations between its structure and properties.
After reading this you will be able to:
i. Discuss Bohr’s atomic model and explain his postulates
ii. Angular momentum, centrifugal force and coulombic attraction
iii. Express the P.E & K.E. of an orbiting electron (ET = K.E. + P.E.)
iv. Express energy in terms of the principal quantum number
v. Relate Rydberg constant and energy transitions (E = RH(1/n2f – 1/n2i)
vi. Relate energy transitions to frequency & wavelength (E = hc/λ)
Bohr’s atomic model
In 1913, Niels Bohr (1885-1962) proposed model of the atom where electrons move around the
nucleus in circular paths. Bohr’s atomic model is built upon a set of postulates, which are as follows:
1. The electrons move in definite circular paths around the nucleus. He called these circular paths as
orbits and postulated that as long as the electron is in a given orbit its energy does not change (or energy
remains fixed) (Fig. 1). These orbits were therefore referred to as stationary orbits or stationary states
or non radiating orbits.
Fig. 1: Bohr’s model
2. The electron can change its orbit by absorbing or releasing energy. An electron at a lower
(initial) state of energy, Ei can go to a (final) higher state of energy, Ef by absorbing a single photon of
energy given by E = hv = Ef - Ei Similarly, when electron changes its orbit from a higher initial state of
energy Ei to a lower final state of energy Ef , a single photon of energy hν is released (Fig. 2).
Fig. 2: Absorption and emission of photon causes the electron to change its energy level.
3. The angular momentum of an electron of mass me moving in a circular orbit of radius r and
velocity υ is an integral multiple of h/2π.
Where n is a positive integer, known as the principal quantum number.
Bohr obtained the following expressions for the energy of an electron in stationary states of
hydrogen atom by using his postulates:
Energy of the orbit,
Bohr could correlate RH to other properties as,
Where,
m = mass of the electron h = Planck’s constant
z = nuclear charge Ɛ20 = permittivity of the medium
e = electronic charge
The negative sign in the energy expression means that the there is an attractive interaction between
the nucleus and the electron. This means that certain amount of energy (called ionization energy) would
be required to remove the electron from the influence of the nucleus in the atom. You may note here that
the energies of the Bohr orbits are inversely proportional to the square of the quantum number n. As n
increases the value of the energy increases (becomes lesser negative or more positive). It means that as
we go farther from the nucleus the energy of the orbit goes on increasing.
Wave - Particle Duality
As you are aware that some of the properties of light e.g., diffraction and interference can be
explained on the basis of its wave nature. On the other hand some other properties like photoelectric
effect and scattering of light can be explained only on the basis of particle nature of light. Thus light has
a dual nature possessing the properties of both a wave and a particle, i.e., light could under some
conditions behave like a particle and other conditions behave as a wave.
In 1923 French physicist, Louis de Broglie, argued that if light can show wave as well as particle nature,
why should particles of matter (e.g., electron) not possess wave like characteristics? He proposed that
matter particles should indeed have a wave nature and said that a particle of mass m moving with a velocity υ
has an associated wavelength, λ (sometimes called de Broglie wavelength) given by the formula;
Where p (= mv) is the momentum of the particle. The de Broglie wavelength of a body is inversely
proportional to its momentum. Since the magnitude of h is very small, the wavelength of the objects of
our everyday world would be too small to be observed. Let us make a calculation to see this.
Example: Calculate the de Broglie wavelength associated with a cricket ball weighing 380 g thrown
at a speed of 140 km per hour.
Solution: Mass of the cricket ball = 380 g = 380 x 10-3 kg = 0.38 kg Speed or Velocity = 140 km/hr
= (140 x 1000)/3600 = 38.89 m s-1
The wavelength associated with the cricket ball will be
If the electrons show wave nature then a beam of these electrons is expected to show diffraction
which is a property of waves. In 1927 G.P. Thomson and C.J. Davisson demonstrated the diffraction of
electron waves by the crystal lattice of nickel (Fig. 3). Thus electrons also show a dual nature. That is,
sometimes these show particle nature while at some other times they show wave nature.
Fig. 3: Electron diffraction pattern from nickel crystal
Heisenberg’s Uncertainty Principle
An important consequence of the wave-particle duality of matter and radiation was
discovered by Werner Heisenberg in 1927 and is called the uncertainty principle. According to this
principle it is not possible to simultaneously measure both the position and momentum (or velocity) of an
electron accurately. In simple words we may state that more accurately you measure a particle’s position,
the less accurately you’re able to measure its momentum, and vice versa. Mathematically, the Heisenberg
principle can be expressed in terms of an inequality
Where Δx and Δp are the uncertainties in the measurements of position and momentum
respectively. If the position of an object is known exactly (i.e., Δx = 0), then the uncertainty
in the momentum must be infinite, meaning that we cannot say anything about the velocity.
Similarly, if the velocity is known exactly, then the position would be entirely uncertain and
the particle could be anywhere.
It means that we cannot say anything about the position of the particle. In actual practice none of
the two properties can be measured with certainty. Due to the small value of the Planck’s constant , h (
6.626 x 10-34 Js) this principle is not relevant while making measurements of large objects like car, bus
or aero plane etc.. It is relevant, only when you are making measurements on very small objects such
as electrons.
Heisenberg’s principle questioned the validity of Bohr’s model. It is so because according to Bohr’s
model we can precisely calculate the radius of the orbit (i.e., the position of the electron) and the velocity
of electron in it. But it is not possible according to Heisenberg’s principle. It motivated many scientists to
develop newer models of the atom using the dual nature of the electron. This resulted into the
development of a Quantum mechanical or Wave Mechanical Model.
Electromagnetic Radiation
Electromagnetic radiation is a kind of energy, which is transmitted through space in the form of
electric and magnetic fields. These do not require any medium to propagate. Visible light, radiant heat,
radio waves, X-rays and gamma radiation are some of the examples of electromagnetic radiations.
According to the Maxwell’s theory, an electromagnetic radiation can be visualized as oscillating electric
and magnetic fields. These travel as waves in the planes perpendicular to each other and also to the
direction of propagation (Fig. 4 (a)). These radiations travel with the velocity of light (3.0 x108 ms-1).
Fig. 4 (a) An electromagnetic wave showing electric and magnetic fields travelling in planes perpendicular to each other and also to
the direction of propagation (b) Characteristics of electromagnetic wave
Characteristic Parameters of Electromagnetic Radiations
The electromagnetic radiations are characterized by a number of parameters. These are:-
Amplitude: This refers to the maximum height to which the wave oscillates. It equals the height
of the crests or depth of the troughs.
Wavelength: It is the linear distance between two consecutive wave-crests or wave- troughs as
shown in Fig. 4(b). It is represented by a Greek letter lambda (and is expressed in terms of m, cm, nm
or Angstrom (1Å = 10-10 m).
Frequency: It is defined as the number of wave crests or wave troughs that pass through a given
point per second. It is represented by a Greek letter nu () and is expressed in terms of s-1 (second
inverse or per second). It is also called as Hz (Hertz).
Wave number: It equals the number of waves per unit length. It is denoted as v (nu bar) and is
equal to the reciprocal of the wavelength. The SI unit of v is m–1 (meter inverse). However, sometimes it
is also expressed as cm–1 (centimeter inverse).
Velocity: it is defined as the linear distance travelled by the wave in one second.
The velocity in meters per second can be obtained by multiplying frequency in Hertz
(s-1) with wavelength in meters.
The velocity of a radiation depends on the medium. In vacuum the velocity is equal to
3.00 x 108 m s-1.
The electromagnetic radiations also show the characteristics of particles. These are called
as quanta. These quanta are actually bundles of energy. A quantum of visible light is called a photon. The
energy of the quantum (or photon) is proportional to the frequency of the radiation. The two are related as
The energy of the quantum can also be related to the wavelength or wave number as
the energy of photon can be readily calculated from these equations if we know the
frequency, wavelength or wave number.
Example: A microwave radiation has a frequency of 12 gigahertz. Calculate the energy of the
photon corresponding to this radiation. (h = 6.626 10–34 J s and 1 gigahertz = 109 Hz.).
The energy is given by the expression, E = hv
Solution: Substituting the values we get,
E = 6.626 10–34 Js 1.2 1010s-1 = 7.95 10–24 J