STRUCTURE OF ATOM 29

UNIT 2

STRUCTURE OF
ATOM

The rich diversity of chemical behaviour of different

Objectives elements can be traced to the differences in the internal
structure of atoms of these elements.

After studying this unit you will be

able to

 know about the discovery of

The existence of atoms has been proposed since the
electron, proton and neutron and
time of early Indian and Greek philosophers (400 B.C.)
their characteristics;
who were of the view that atoms are the fundamental
 describe Thomson, Rutherford building blocks of matter. According to them, the
and Bohr atomic models; continued subdivisions of matter would ultimately yield
 understand the important atoms which would not be further divisible. The word
features of the quantum ‘atom’ has been derived from the Greek word ‘a-tomio’
mechanical model of atom; which means ‘uncut-able’ or ‘non-divisible’. These
earlier ideas were mere speculations and there was no
 understand natur e way to test them experimentally. These ideas remained
of
electromagnetic radiation and dormant for a very long time and were revived again by
Planck’s quantum theory; scientists in the nineteenth century.
 explain the photoelectric effect The atomic theory of matter was first proposed on a
and describe features of atomic firm scientific basis by John Dalton, a British school
spectra; teacher in 1808. His theory, called Dalton’s atomic
theory, regarded the atom as the ultimate particle of
 state the de Broglie relation and
matter (Unit 1). Dalton’s atomic theory was able to
Heisenberg uncertainty
explain the law of conservation of mass, law of
principle;
constant composition and law of multiple
 define an atomic orbital in terms proportion very successfully. However, it failed to
of quantum numbers; explain the results of many experiments, for example,
 state aufbau principle, Pauli
it was known that substances like glass or ebonite
exclusion principle and Hund’s
when rubbed with silk or fur get electrically charged.
rule of maximum multiplicity; In this unit we start with the experimental
and observations made by scientists towards the end of
nineteenth and beginning of twentieth century. These
 write the electronic established that atoms are made of sub-atomic
configurations of atoms. particles, i.e., electrons, protons and neutrons — a
concept very different from that of Dalton.

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30 CHEMISTRY

1. DISCOVERY OF SUB-ATOMIC
PARTICLES
An insight into the structure of atom was
obtained from the experiments on electrical
discharge through gases. Before we discuss
these results we need to keep in mind a
basic rule regarding the behaviour of
charged particles : “Like charges repel each
other and unlike charges attract each Fig. 2.1(a) A cathode ray discharge tube
other”.
1. Discovery of Electron
In 1830, Michael Faraday showed that if
electricity is passed through a solution of an
electrolyte, chemical reactions occurred at
the electrodes, which resulted in the
liberation and deposition of matter at the
electrodes. He formulated certain laws which
you will study in class XII. These results Fig. 2.1(b) A cathode ray discharge tube with
suggested the particulate nature of perforated anode
electricity.
In mid 1850s many scientists mainly The results of these experiments are
Faraday began to study electrical summarised below.
discharge in partially evacuated tubes, (i) The cathode rays start from cathode
known as cathode ray discharge tubes. and move towards the anode.
It is depicted in Fig. 2.1. A cathode ray These rays themselves are not visible but
(ii)
tube is made of glass containing two thin their behaviour can be observed with
pieces of metal, called electrodes, sealed in the help of certain kind of
it. The electrical discharge through the materials (fluorescent or
gases could be observed only at very low phosphorescent) which glow when hit
pressures and at very high voltages. The by them. Television picture tubes are
pressure of different gases could be cathode ray tubes and television
adjusted by evacuation of the glass tubes. pictures result due to fluorescence
When sufficiently high voltage is applied on the television screen coated with
certain fluorescent or
across the electrodes, current starts
(iii) phosphorescent materials.
flowing through a stream of particles
In the absence of electrical or magnetic
moving in the tube from the negative
field, these rays travel in straight lines
electrode (cathode) to the positive electrode
(anode). These were called cathode rays or (iv) (Fig. 2.2).
In the presence of electrical or magnetic
cathode ray particles. The flow of
field, the behaviour of cathode rays are
current from cathode to anode was
similar to that expected from negatively
further checked by making a hole in the charged particles, suggesting that the
anode and coating the tube behind anode cathode rays consist of negatively
with phosphorescent material zinc charged particles, called electrons.
sulphide. When these rays, after passing (v) The characteristics of cathode rays
through anode, strike the zinc sulphide (electrons) do not depend upon the
coating, a bright spot is developed on the
coating [Fig. 2.1(b)].

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STRUCTURE OF ATOM 31

material of electrodes and the nature of (iii) the strength of the electrical or magnetic
the gas present in the cathode ray tube. field — the deflection of electrons from
Thus, we can conclude that electrons are its original path increases with the
basic constituent of all the atoms. increase in the voltage across the
electrodes, or the strength of the
2.1.2 Charge to Mass Ratio of Electron magnetic field.
In 1897, British physicist J.J. Thomson By carrying out accurate measurements
measured the ratio of electrical charge (e) to on
the mass of electron (me ) by using cathode the amount of deflections observed by
ray tube and applying electrical and the electrons on the electric field strength
magnetic field perpendicular to each other or magnetic field strength, Thomson was
as well as to the path of electrons (Fig. 2.2). able to determine the11value –1of e/me as:
When only electric field is applied, the m e = 1.758820 × 10 C kg
(2.1)
e
electrons deviate from their path and hit the Where me is the mass of the electron in kg
cathode ray tube at point A (Fig. 2.2). and
e is the magnitude of the charge on the
Similarly when only magnetic field is electron
applied, electron strikes the cathode ray tube in coulomb (C). Since electrons are
at point C. By carefully balancing the negatively charged, the charge on electron is
electrical and magnetic field strength, it is –e.
possible to bring back the electron to the
2.1.3 Charge on the Electron
path which is followed in the absence of
electric or magnetic field and they hit the R.A. Millikan (1868-1953) devised a method
screen at point B. Thomson argued that known as oil drop experiment (1906-14), to
the amount of deviation of the particles from determine the charge on the electrons. He
found the charge on the electron
their
(i) thepath in the of
magnitude presence of electrical
the negative charge on or
to be
magnetic field depends
the particle, upon:
greater the magnitude of – 1.6 × 10–19 C. The present accepted value of
the charge on the particle, greater is electrical charge is – 1.602176 × 10–19 C. The
the interaction with the electric or mass of the electron (me) was determined by
magnetic field and thus greater is the
combining these results with Thomson’s
(ii) deflection. value of e/me ratio.
the mass of the particle — lighter the = 9.1094×10–31 kg
particle, greater the deflection. (2.2)

Fig. 2.2 The apparatus to determine the charge to the mass ratio of electron

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32 CHEMISTRY

2.1.4 Discovery of Protons and Neutrons

Millikan’s Oil Drop Method
Electrical discharge carried out in the
In this method, oil droplets in the form of
modified cathode ray tube led to the
mist, produced by the atomiser, were
discovery of canal rays carrying positively allowed to enter through a tiny hole in the
charged particles. The characteristics of upper plate of electrical condenser. The
these positively charged particles are listed downward motion of these droplets was
below.
(i) Unlike cathode rays, mass of positively viewed through the telescope, equipped
charged particles depends upon the with a micrometer eye piece. By measuring
nature of gas present in the cathode ray the rate of fall of these droplets, Millikan
tube. These are simply the positively was able to measure the mass of oil
charged gaseous ions. droplets. The air inside the chamber was
ionized by passing a beam of X-rays
The
(ii) charge to mass ratio of the particles through it. The electrical charge on these
depends on the gas from which these oil droplets was acquired by collisions with
originate. gaseous ions. The fall of these charged oil
Some
(iii) of the positively charged particles droplets can be retarded, accelerated or
carry a multiple of the fundamental made stationary depending upon the
unit of electrical charge. charge on the droplets and the polarity and
The
(iv) behaviour of these particles in the strength of the voltage applied to the plate.
By carefully measuring the effects of
magnetic or electrical field is opposite to
electrical field strength on the motion of
that observed for electron or cathode oil droplets, Millikan concluded that the
rays. magnitude of electrical charge, q, on the
The smallest and lightest positive ion was droplets is always an integral multiple of
obtained from hydrogen and was called the electrical charge, e, that is, q = n e,
proton. This positively charged particle was where n = 1, 2, 3... .
characterised in 1919. Later, a need was felt
for the presence of electrically neutral
particle as one of the constituent of atom.
These particles were discovered by
Chadwick (1932) by bombarding a thin
sheet of beryllium by
-particles. When electrically neutral
protons
particles were emitted.
having a mass He slightly
named greater
these
particles
than that of as neutrons . The important
properties of all these fundamental particles
are given in Table 2.1.
2.2 ATOMIC MODELS
Observations obtained from the experiments
mentioned in the previous sections have Fig. 2.3 The Millikan oil drop apparatus for
suggested that Dalton’s indivisible atom is measuring charge ‘e’. In chamber, the
composed of sub-atomic particles carrying forces acting on oil drop are:
positive and negative charges. The major gravitational, electrostatic due to
problems before the scientists after the electrical
 to explain thefield and a viscous
formation drag
of different
discovery of sub-atomic particles were: force when the oil drop is moving.
kinds of molecules by the combination of
 to account for the stability of atom, different atoms and,
 to compare the behaviour of elements in  to understand the origin and nature of
terms of both physical and chemical the characteristics of electromagnetic
properties, radiation absorbed or emitted by atoms.

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STRUCTURE OF ATOM 33

Table 2.1 Properties of Fundamental Particles

Name Symbol Absolute Relative Mass/kg Mass/u Approx.

charge/C charge
mass/u

Electron e –1.602176×10–19 –1 9.109382×10–31 0.00054 0

Proton p +1.602176×10–19 +1 1.6726216×10–27 1.00727 1
Neutron n 0 0 1.674927×10–27 1.00867 1

Different atomic models were proposed to

explain the distributions of these charged In the later half of the nineteenth
particles in an atom. Although some of these century different kinds of rays were
models were not able to explain the stability discovered, besides those mentioned
of atoms, two of these models, one proposed earlier. Wilhalm Röentgen (1845-1923)
by in 1895 showed that when electrons
J.J. Thomson and the other proposed strike a material in the cathode ray
by Ernest Rutherford are discussed below. tubes, produce rays which can cause
2.2.1 Thomson Model of Atom fluorescence in the fluorescent
materials placed outside the cathode
J. J. Thomson, in 1898, proposed that an ray tubes. Since Röentgen did not know
atom possesses a spherical shape
the nature of the radiation, he named
(radius approximately 10–10 m) in which the
them X-rays and the name is still
positive charge is uniformly distributed. The
carried on. It was noticed that X-rays
electrons are embedded into it in such a
are produced effectively when electrons
manner as to give the most stable
strike the dense metal anode, called
electrostatic arrangement (Fig. 2.4). Many
different names are given to this model, for targets. These are not deflected by the
example, plum pudding, raisin pudding or electric and magnetic fields and have a
watermelon. This model can be very high penetrating power through
the matter and that is the reason that
these rays are used to study the
interior of the objects. These rays are
of very short wavelengths (0.1 nm)
and possess electro-magnetic character
(Section 2.3.1).
Fig.2.4 Thomson model of atom Henri Becqueral (1852-1908)
visualised as a pudding or watermelon of observed that there are certain elements
positive charge with plums or seeds which emit radiation on their own and
(electrons) embedded into it. An important named this phenomenon as
feature of this model is that the mass of the radioactivity and the elements known
atom is assumed to be uniformly distributed as radioactive elements. This field
over the atom. Although this model was was developed by Marie Curie, Piere
able to explain the overall neutrality of the Curie, Rutherford and Fredrick Soddy.
atom, but was not consistent with the It was observed that three kinds of rays
results of later experiments. Thomson was i.e., ,
awarded Nobel Prize for physics in 1906, for - and -rays are emitted.
his theoretical and experimental Rutherford found that -rays consists
investigations on the conduction of of high energy particles carrying two
electricity by gases. units of positive charge and four unit
of atomic mass. He concluded that -
particles are helium

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34 CHEMISTRY

nuclei as when - particles combined represented in Fig. 2.5. A stream of high

with two electrons yielded helium gas. energy
-rays are negatively charged particles –particles from a radioactive source was
similar to electrons. The -rays are directed at a thin foil (thickness  100 nm)
high energy radiations like X-rays, are of gold metal. The thin gold foil had a
neutral in nature and do not consist of circular fluorescent zinc sulphide screen
around it. Whenever –particles struck the
particles. As regards penetrating power,
screen, a tiny flash of light was produced at
-particles are the least, followed by -
that point.
rays (100 times that of –particles) and
-rays (1000 times of that -particles). The results of scattering experiment were
quite unexpected. According to Thomson
model of atom, the mass of each gold atom
2.2.2 Rutherford’s Nuclear Model of
in the foil should have been spread evenly
Atom
over the entire atom, and – particles had
Rutherford and his students (Hans Geiger enough energy to pass directly through such
and Ernest Marsden) bombarded very thin a uniform distribution of mass. It was
gold foil with –particles. Rutherford’s expected that the particles would slow
famous down and change directions
–particle scattering experiment is (i) most of the –particles passedonly by a
through
smalltheangles as they passed
gold foil undeflected. through the foil.
It was observed that:
(ii) small fraction of the –particles was
a
deflected by small angles.
a very few –particles (1 in 20,000)
(iii)
bounced back, that is, were deflected
by nearly 180°.
On the basis of the observations,
A. Rutherford’s scattering Rutherford drew the following conclusions
experiment regarding the structure of atom:
(i) Most of the space in the atom is empty
as most of the –particles passed
through the foil undeflected.
(ii) few positively charged –particles were
A
deflected. The deflection must be due to
enormous repulsive force showing that
the positive charge of the atom is not
spread throughout the atom as
Thomson had presumed. The positive
charge has to be concentrated in a very
small volume that repelled and
deflected the positively charged –

B. Schematic molecular view of the gold (iii) particles.

foil Calculations by Rutherford showed that the
Fig. 2.5 Schematic view of Rutherford’s volume occupied by the nucleus is
scattering experiment. When a beam negligibly small as compared to the
of alpha () particles is “shot” at a thin total volume of the atom. The radius of
gold foil, most of them pass through the atom is about 10 –10 m, while that
without much effect. Some, however, of nucleus is 10–15 m. One can
are deflected. appreciate this difference in size by
realising that if

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STRUCTURE OF ATOM 35

a cricket ball represents a nucleus, The total number of nucleons is termed as

then the radius of atom would be mass number (A) of the atom.
about 5 km. mass number (A) = number of protons (Z )
On the basis of above observations and + number of
conclusions, Rutherford proposed the neutrons (n)
nuclear
(i) model of atom. According to this
The positive charge and most of the
model: (2.4)
mass of the atom was densely
concentrated in extremely small
2.2.4 Isobars and Isotopes
region. This very small portion of the
atom was called nucleus by The composition of any atom can be
Rutherford. represented by using the normal element
(ii)
symbol (X) with super-script on the left
The nucleus is surrounded by electrons that
hand
numberside
(i.e.,asZA X).
the atomic mass number (A)
move around the nucleus with a very
and subscript (ZIsobars ) on the
areleft
thehand side
atoms as
with
high speed in circular paths called
orbits. Thus, Rutherford’s model of the atomic same mass
atom resembles the solar system in example,146C and number
14
N. On but different
the other hand,atomic
7
which the nucleus plays the role of sun atoms number
with identical atomic number but different for

(iii) and the electrons that of revolving atomic mass number are known as
planets. Isotopes. In other words (according to
Electrons and the nucleus are held equation 2.4), it is evident that difference
together by electrostatic forces of between the isotopes is due to the presence
2.2.3 Atomic Number and Mass Number of different number of neutrons present in
attraction.
The presence of positive charge on the the nucleus. For example, considering of
nucleus is due to the protons in the hydrogen atom again, 99.985% of hydrogen
nucleus. As established earlier, the charge atoms
This contain
isotope only one
is called proton.
protium ( 1H). Rest of
1
on the proton is equal but opposite to the
percentage of hydrogen atom
that of electron. The number of protons contains two other
present in the nucleus is equal to atomic
isotopes,
neutron is thecalled
one containing
deuterium1 ( 21D, 0.015%)
number (Z ). For example, the number of proton
protons in the hydrogen nucleus is 1, in and theand
other1 one possessing 1
proton
neutronsandis 2called tritium ( 13 T ). The latter
sodium atom it is 11, therefore their atomic
numbers are 1 and 11 respectively. In order isotope is found in trace amounts on the
to keep the electrical neutrality, the number earth.
of electrons in an atom is equal to the Other examples of commonly occuring
number of protons (atomic number, Z ). isotopes are: carbon atoms containing 6, 7
8 neutrons besides 6 protons ( 12 C, 613 C, 614 C );6
For example, number of electrons in and
chlorine atoms containing 18 and 20
hydrogen atom and sodium atom are 1 and neutrons
besides 17 protons ( 3517Cl, 37 Cl17).
11 respectively. Lastly an important point to mention
Atomic number (Z) = number of protons regarding isotopes is that chemical
in properties of atoms are controlled by the
the nucleus of an atom number of electrons, which are
= number of electrons determined by the number of protons in
in a nuetral atom (2.3) the nucleus. Number of neutrons present in
While the positive charge of the nucleus the nucleus have very little effect on the
is due to protons, the mass of the nucleus, chemical properties of an element. Therefore,
due to protons and neutrons. As discussed all the isotopes of a given element show
earlier protons and neutrons present in the same chemical behaviour.
nucleus are collectively known as nucleons.

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36 CHEMISTRY

massive sun and the electrons being similar

Problem 2.1
to the lighter planets. When classical
Calculate the number of protons, mechanics* is applied to the solar system, it
neutrons and electrons in 80
Br35. shows that the planets describe well-defined
Solution orbits around the sun. The gravitational
force between the planets is given by the
Br , Z = 35, A = 80, species
80 35
In this case,
is neutral expression
 m1m 2 
Number of protons = number of  G.  where m and m are the masses,
r
electrons  2
r  1 2

= Z = 35 is the distance of separation of the masses

Number of neutrons = 80 – 35 = 45, and G is the gravitational constant. The
(equation 2.4) theory can also calculate precisely the
planetary orbits and these are in agreement
Problem 2.2 with the experimental measurements.
The number of electrons, protons and The similarity between the solar system
neutrons in a species are equal to 18, and nuclear model suggests that electrons
16 and 16 respectively. Assign the should move around the nucleus in well
proper symbol to the species. defined orbits. Further, the coulomb force
Solution (kq1q2/r2 where q1 and q2 are the charges, r is
The atomic number is equal to the distance of separation of the charges and
number of protons = 16. The element is k is the proportionality constant) between
sulphur (S). electron and the nucleus is mathematically
similar to the gravitational force. However,
Atomic mass number = number of
when a body is moving in an orbit, it
protons + number of neutrons
undergoes acceleration even if it is moving
= 16 + 16 = 32 with a constant speed in an orbit because
Species is not neutral as the number of changing direction. So an electron in
of protons is not equal to electrons. It the nuclear model describing planet like
is anion (negatively charged) with orbits is under acceleration. According
charge equal
Symbol is 16
32
S2–to. excess electrons = 18 to the electromagnetic theory of Maxwell,
– 16 = 2. charged particles when accelerated
Note : Before using the notation ZA X, find
should emit electromagnetic radiation
out whether the species is a neutral
(This feature does not exist for planets since
atom, a cation or an anion. If it is a
they are uncharged). Therefore, an electron
neutral atom,
in an orbit will emit radiation, the energy
equation (2.3) is valid, i.e., number of carried by radiation comes from electronic
protons = number of electrons = atomic motion. The orbit will thus continue to
number. If the species is an ion, shrink. Calculations show that it should
determine whether the number of take an electron only 10–8 s to spiral into the
protons are larger nucleus. But this does not happen. Thus,
(cation, positive ion) or smaller (anion, the Rutherford model cannot explain
negative ion) than the number of the stability of an atom. If the motion of
electrons. an electron is described on the basis of the
2.2.5 Drawbacks
Number of neutronsof Rutherford
is always Model
given by classical mechanics and
A–Z, whether the species is
As you have learnt above, Rutherford neutral or electromagnetic theory, you may ask that
ion.
nuclear model of an atom is like a small since the motion of electrons in orbits is
scale solar system with the nucleus playing leading to the instability of the atom, then
the role of the why not consider electrons as stationary
* Classical mechanics is a theoretical science based on Newton’s laws of motion. It specifies the laws of motion
of
macroscopic objects.

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STRUCTURE OF ATOM 37

around the nucleus. If the electrons were in the early 1870’s by James Clerk Maxwell,
stationary, electrostatic attraction between which was experimentally confirmed later by
the dense nucleus and the electrons would Heinrich Hertz. Here, we will learn some
pull the electrons toward the nucleus to facts about electromagnetic radiations.
form a miniature version of Thomson’s James Maxwell (1870) was the first to
model of atom. give a comprehensive explanation about
Another serious drawback of the the interaction between the charged bodies
Rutherford model is that it says nothing and the behaviour of electrical and magnetic
about distribution of the electrons around fields on macroscopic level. He suggested
the nucleus and the energies of these that when electrically charged particle
electrons. moves under accelaration, alternating
electrical and magnetic fields are produced
2.3 DEVELOPMENTS LEADING TO THE
and transmitted. These fields are
BOHR’S MODEL OF ATOM
transmitted in the forms of waves called
Historically, results observed from the electromagnetic waves or
studies of interactions of radiations with electromagnetic radiation.
matter have provided immense information
Light is the form of radiation known
regarding the structure of atoms and
from early days and speculation about its
molecules. Neils Bohr utilised these results
nature dates back to remote ancient times.
to improve upon the model proposed by
In earlier days (Newton) light was supposed
Rutherford. Two developments played a
to be made of particles (corpuscules). It was
major role in the formulation of Bohr’s
only in the 19th century when wave nature
model of atom. These were:
of light was established.
(i) Dual character of the electromagnetic
Maxwell was again the first to reveal that
radiation which means that radiations
light waves are associated with oscillating
possess both wave like and particle like
electric and magnetic character (Fig. 2.6).
properties, and
(ii)Experimental results regarding atomic
spectra.
First, we will discuss about the duel
nature of electromagnetic radiations.
Experimental results regarding atomic
spectra will be discussed in Section 2.4.
2.3.1 Wave Nature of Electromagnetic
Radiation
In the mid-nineteenth century, physicists
actively studied absorption and emission of Fig.2.6 The electric and magnetic field
radiation by heated objects. These are called components of an electromagnetic wave.
thermal radiations. They tried to find out of These components have the same
what the thermal radiation is made. It is wavelength, frequency, speed and
now a well-known fact that thermal amplitude, but they vibrate in two
radiations consist of electromagnetic waves mutually perpendicular planes.
of various frequencies or wavelengths. It is
based on a number of modern concepts, Although electromagnetic wave motion is
which were unknown in the mid-nineteenth complex in nature, we will consider here
century. First active study of thermal only a few simple properties.
radiation laws occured in the 1850’s and the (i) The oscillating electric and magnetic
theory of electromagnetic waves and the fields produced by oscillating charged
emission of such waves by accelerating particles
charged particles was developed

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38 CHEMISTRY

are perpendicular to each other and (iv) Different kinds of units are used to
both are perpendicular to the represent electromagnetic radiation.
direction of propagation of the wave.
These radiations are characterised by the
Simplified picture of electromagnetic
wave is shown in Fig. 2.6. properties, namely, frequency (  )
and wavelength ().
(ii) Unlike sound waves or waves produced
in water, electromagnetic waves do not The SI unit for frequency (  ) is
require medium and can move in hertz (Hz, s–1), after Heinrich Hertz. It is
vacuum. defined as the number of waves that pass a
(iii) It is now well established that there are given point in one second.
many types of electromagnetic Wavelength should have the units of
radiations, which differ from one length and as you know that the SI units of
another in wavelength (or length is meter (m). Since electromagnetic
frequency). These constitute what is
radiation consists of different kinds of
called electromagnetic spectrum (Fig.
waves of much smaller wavelengths, smaller
2.7). Different regions of the spectrum
are identified by different names. units are used. Fig.2.7 shows various
Some examples are: radio types of electro- magnetic radiations
frequency region around 106 Hz, used which differ from one another in
for broadcasting; microwave region wavelengths and frequencies.
around 1010 Hz used for radar; infrared In vaccum all types of electromagnetic
region around 10 1 3 Hz used for radiations, regardless of wavelength, travel
heating; ultraviolet region around
at the same speed, i.e., 3.0 × 108 m s–1
10 1 6 Hz a component of sun’s radiation.
(2.997925
The small portion around 10 1 5 Hz, is
what is ordinarily called visible light. × 108 m s–1 , to be precise). This is called
It is only this part which our eyes can speed
see (or detect). Special instruments are of light and is given the symbol ‘c‘. The
required to detect non-visible radiation. frequency ( ), wavelength () and velocity of
light
(c) are related by the equation (2.5). 
(a) c =  

(2.5)

(b)

Fig. 2.7 (a) The spectrum of electromagnetic radiation. (b) Visible spectrum. The visible region is
only a small part of the entire spectrum.

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STRUCTURE OF ATOM 39

The other commonly used quantity

specially in spectroscopy, is the Frequency of red light
wavenumber ( ). It is defined as the number
of wavelengths per unit length. Its units are = = 4.00 × 1014 Hz
reciprocal of wavelength unit, i.e., m–1. The range of visible spectrum is from
However commonly used unit is cm–1 (not SI 4.0 × 1014 to 7.5 × 1014 Hz in terms of
unit). frequency units.
Problem 2.3
The Vividh Bharati station of All India Problem 2.5
Radio, Delhi, broadcasts on a frequency Calculate (a) wavenumber and (b)
of 1,368 kHz (kilo hertz). Calculate the frequency of yellow radiation having
wavelength of the electromagnetic wavelength 5800 Å.
radiation emitted by transmitter. Which Solution
part of the electromagnetic spectrum (a) Calculation of wavenumber ( )
does it belong to? =5800Å = 5800 × 10–8 cm
Solution = 5800 × 10–10 m
The wavelength, , is equal to c/,
where c is the speed of electromagnetic
radiation in vacuum and  is the
frequency. Substituting the given
values, we have
c

v (b) Calculation of the
frequency ( )

2.3.2 Particle Nature of Electromagnetic

Radiation: Planck’s Quantum
Theory
Some of the experimental phenomenon such
This is a characteristic radiowave as diffraction* and interference** can be
wavelength. explained by the wave nature of the
electromagnetic radiation. However, following
Problem 2.4
are some of the observations which could
The wavelength range of the visible not be explained with the help of even
spectrum extends from violet (400 nm) the electromagentic theory of 19th
to red (750 nm). Express these century physics (known as classical
wavelengths in frequencies (Hz). (1nm = physics):
10–9 m) (i) the nature of emission of radiation from
hot bodies (black -body radiation)
Solution
(ii)
ejection of electrons from metal surface
Using equation 2.5, frequency of violet
when radiation strikes it (photoelectric
light
effect)
(iii)
variation of heat capacity of solids as a
function of temperature
= 7.50 × 1014 Hz
* Diffraction is the bending of wave around an obstacle.
** Interference is the combination of two waves of the same or different frequencies to give a wave whose distribution at
each point in space is the algebraic or vector sum of disturbances at that point resulting from each interfering wave.

2020-21
40 CHEMISTRY

(iv) Line spectra of atoms with special of radiant energy. Furthermore, a black body
reference to hydrogen. is in thermal equilibrium with its
These phenomena indicate that the surroundings. It radiates same amount of
system can take energy only in discrete energy per unit area as it absorbs from its
amounts. All possible energies cannot be surrounding in any given time. The amount
taken up or radiated. of light emitted (intensity of radiation) from a
It is noteworthy that the first concrete black body and its spectral distribution
explanation for the phenomenon of the depends only on its temperature. At a given
black body radiation mentioned above was temperature, intensity of radiation emitted
given by Max Planck in 1900. Let us first increases with the increase of
try to understand this phenomenon, which wavelength, reaches a maximum value at a
is given below: given wavelength and then starts decreasing
Hot objects emit electromagnetic with further increase of wavelength, as
radiations shown in Fig. 2.8. Also, as the temperature
over a wide range of wavelengths. At increases, maxima of the curve shifts to
high temperatures, an appreciable short wavelength. Several attempts were
proportion of radiation is in the visible made to predict the intensity of radiation
region of the spectrum. As the as a function of wavelength.
temperature is raised, a higher proportion But the results of the above experiment
of short wavelength (blue light) is generated. could not be explained satisfactorily on the
For example, when an iron rod is heated in basis of the wave theory of light. Max Planck
a furnace, it first turns to dull red and then
progressively becomes more and more red as
the temperature increases. As this is heated
further, the radiation emitted becomes white
and then becomes blue as the
temperature becomes very high. This means
that red radiation is most intense at a
particular temperature and the blue
radiation is more intense at another
temperature. This means intensities of
radiations of different wavelengths emitted
by hot body depend upon its
temperature. By late 1850’s it was known
that objects made of different material and
kept at different temperatures emit different
amount of radiation. Also, when the surface Fig. 2.8 Wavelength-intensity relationship
of an object is irradiated with light
(electromagnetic radiation), a part of radiant
energy is generally reflected as such, a part
is absorbed and a part of it is transmitted.
The reason for incomplete absorption is
that ordinary objects are as a rule imperfect
absorbers of radiation. An ideal body, which
emits and absorbs radiations of all
frequencies uniformly, is called a black body
and the radiation emitted by such a body is
called black body radiation. In practice, no
such body exists. Carbon black approximates
fairly closely to black body. A good physical
approximation to a black body is a cavity Fig. 2.8(a) Black body
with a tiny hole, which has no other opening.
Any ray entering the hole will be reflected by
the cavity walls and will be eventually
absorbed by the walls. A black body is also a
perfect radiator 2020-21
STRUCTURE OF ATOM 41

arrived at a satisfactory relationship by

Max Planck
making an assumption that absorption and
(1858 – 1947)
emmission of radiation arises from oscillator
Max Planck, a German
i.e., atoms in the wall of black body. Their
frequency of oscillation is changed by physicist, received his Ph.D in
interaction with oscilators of electromagnetic theoretical physics from the
radiation. Planck assumed that radiation University of Munich in 1879.
could be sub-divided into discrete chunks of In 1888, he was appointed
energy. He suggested that atoms and Director of the Institute
molecules could emit or absorb energy only of Theoretical Physics at the
in discrete quantities and not in a University of Berlin. Planck was awarded the
continuous manner. He gave the name Nobel Prize in Physics in 1918 for his quantum
quantum to the smallest quantity of theory. Planck also made significant
energy that can be emitted or absorbed contributions in thermodynamics and other
in the form of electromagnetic radiation. Photoelectric Effect
areas of physics.
The energy (E ) of a quantum of radiation In 1887, H. Hertz performed a very
is proportional to its frequency ( ) and interesting experiment in which electrons
is expressed by equation (2.6). (or electric current) were ejected when
E = h certain metals (for example potassium,
rubidium, caesium etc.) were exposed to a
(2.6) beam of light as shown in Fig.2.9. The
The proportionality constant, ‘h’ is known phenomenon is called Photoelectric
as Planck’s constant and has the value effect. The results observed in this
6.626×10–34 J s. experiment were:
(i) The electrons are ejected from the metal
With this theory, Planck was able to surface as soon as the beam of light
explain the distribution of intensity in the strikes the surface, i.e., there is no
radiation from black body as a function of time lag between the striking of light
frequency or wavelength at different beam and the ejection of electrons from
temperatures. (ii) the metal surface.
Quantisation has been compared to The number of electrons ejected is
standing on a staircase. A person can stand proportional to the intensity or
on any step of a staircase, but it is not (iii) brightness of light.
possible for him/her to stand in between the minimum there is a characteristic
metal, frequency,
For each 0 (also known as
two steps. The energy can take any one of threshold frequency) below which
the values from the following set, but photoelectric effect is not observed. At a
cannot take on any values between them. frequency  > 0, the ejected electrons
E = 0, h, 2h, 3h....nh..... come out with certain kinetic energy.
The kinetic energies of these electrons
increase with the increase of frequency
of the light used.
All the above results could not be
explained on the basis of laws of classical
physics. According to latter, the energy
content of the beam of light depends upon
the brightness of the light. In other words,
Fig.2.9 Equipment for studying the photoelectric number of electrons ejected and kinetic
effect. Light of a particular frequency
strikes a clean metal surface inside a energy associated with them should depend
vacuum chamber. Electrons are ejected on the brightness of light. It has been
from the metal and are counted by a observed that though the number of
detector that measures their kinetic
energy.
electrons ejected does depend upon the
brightness of light, the kinetic energy of the

2020-21
 42 CHEMISTRY

Table 2.2 Values of Work Function (W0) for a Few Metals

Metal Li Na K Mg Cu Ag

W0 /eV 2.42 2.3 2.25 3.7 4.8 4.3

ejected electrons does not. For example, red minimum energy required to eject the
light [ = (4.3 to 4.6) × 1014 Hz] of any is h (also called work function, W ; Table
electron
0
brightness (intensity) may shine on a piece of 2.2),
then the difference in
0
energy
potassium metal for hours but no (h – h0 ) is transferred as the kinetic energy
photoelectrons are ejected. But, as soon as of photoelectron. Following the conservation
the
even a very weak yellow light ( = 5.1–5.2 × of energy principle, the kinetic energy of the
1014 Hz) shines on the potassium metal, the ejected electron is given by the equation 2.7.
photoelectric effect is observed. The
threshold frequency (0) for potassium (2.7)
metal is 5.0×10 Hz.
14

Einstein (1905) was able to explain the where me is the mass of the electron and v is
photoelectric effect using Planck’s quantum the velocity associated with the ejected
theory of electromagnetic radiation as a electron. Lastly, a more intense beam of
starting point.
Albert Einstein, a German light consists of larger number of photons,
born American physicist, is consequently the number of electrons
regarded by many as one of ejected is also larger as compared to that in
the two great physicists the an experiment in which a beam of weaker
world has known (the other intensity of light is employed.
is Isaac Newton). His three
research papers (on special Dual Behaviour of Electromagnetic
relativity, Brownian motion Radiation
and the photoelectric effect) Albert Einstein
(1879-1955) The particle nature of light posed a dilemma
which he published in 1905,
for scientists. On the one hand, it could
wh ile he was emplo ye d as a te ch n ica l
assistant in a Swiss patent office in Berne explain the black body radiation and
have profoundly influenced the development photoelectric effect satisfactorily but on the
of physics. He received the Nobel Prize in other hand, it was not consistent with the
Physics in 1921 for his explanation of the known wave behaviour of light which could
photoelectric effect. account for the phenomena of interference
and diffraction. The only way to resolve the
Shining a beam of light on to a metal dilemma was to accept the idea that light
surface can, therefore, be viewed as shooting possesses both particle and wave-like
a beam of particles, the photons. When a
properties, i.e., light has dual behaviour.
photon of sufficient energy strikes an
Depending on the experiment, we find that
electron in the atom of the metal, it
light behaves either as a wave or as a
transfers its energy instantaneously to the
stream of particles. Whenever radiation
electron during the collision and the
electron is ejected without any time lag or interacts with matter, it displays particle like
delay. Greater the energy possessed by the properties in contrast to the wavelike
photon, greater will be transfer of energy properties (interference and diffraction),
to the electron and greater the kinetic which it exhibits when it propagates. This
energy of the ejected electron. In other concept was totally alien to the way the
words, kinetic energy of the ejected scientists thought about matter and
electron is proportional to the frequency of radiation and it took them a long time to
the electromagnetic radiation. Since the become convinced of its validity. It turns
striking photon has energy equal to h out, as you shall see later, that some
and the microscopic particles like electrons also
exhibit this wave-particle duality.
C:\Chemistry XI\Unit-2\Unit-2(2)-Lay-3(reprint).pmd 27.7.6, 16.10.6 (Reprint)

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STRUCTURE OF ATOM 43

Problem 2.6 Solution

The energy (E) of a 300 nm photon is
Calculate energy of one mole of photons
given by
of radiation whose frequency is 5 1014
Hz.
Solution
Energy (E) of one photon is given by the
expression = 6.626  10-19 J
E = h The energy of one mole of photons
h = 6.626 ×10–34 J s = 6.626 10–19 J  6.022 1023 mol–1
 = 5×1014 s–1 (given) = 3.99  105 J mol–1
E = (6.626 ×10–34 J s) × (5 ×1014 s–1) The minimum energy needed to remove
= 3.313 ×10–19 J one mole of electrons from sodium
Energy of one mole of photons = (3.99 –1.68) 105 J mol–1
= (3.313 ×10–19 J) × (6.022 × 1023 mol–1) = 2.31  105 J mol–1
= 199.51 kJ mol–1 The minimum energy for one electron
Problem 2.7
A 100 watt bulb emits monochromatic
light of wavelength 400 nm. Calculate
the number of photons emitted per This corresponds to the wavelength
second by the bulb.
Solution hc
=
Power of the bulb = 100 watt E
34
= 100 J s–1 8
6.626 10 J s  3.0  10
1

Energy of one photon E = h = hc/ =

ms
6.626 10 34 J s  3  108 m s1 3.84  10 19 J
= = 517 nm
400  10 9 m
(This corresponds to green light)
= 4.969  10-19 J The threshold frequency 0 for a metal is
Number of photons emitted Problem
7.0 10142.9s–1. Calculate the kinetic
energy of an electron emitted when
100 J s1 radiation of frequency  =1.0 1015 s–1
 2.012  1020 s 1
4.969  10  19
J hits the metal.
Solution
Problem 2.8
According
Kinetic to Einstein’s
energy equation
= ½ m v2=h( – )
When electromagnetic radiation of e
0
wavelength 300 nm falls on the surface
of sodium, electrons are emitted with a = (6.626 10–34 J
kinetic energy of 1.68 105 J mol–1. s) (1.0  1015 s–1 –
What is the minimum energy needed to 7.0
remove an electron from sodium? What 1014 s–1)
is the maximum wavelength that will = (6.626 10–34 J
cause a photoelectron to be emitted? s) (10.0 1014 s–1 –
7.0
1014 s–1)
= (6.626 10–34 J s)  (3.0 1014 s–1)
= 1.988 10–19 J

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44 CHEMISTRY

2.3.3 Evidence for the quantized* spectrum. A continuum of radiation is

Electronic Energy Levels: Atomic passed through a sample which absorbs
spectra radiation of certain wavelengths. The
missing wavelength which corresponds to
The speed of light depends upon the nature
the radiation absorbed by the matter, leave
of the medium through which it passes. As a
dark spaces in the bright continuous
result, the beam of light is deviated or
spectrum.
refracted from its original path as it passes The study of emission or absorption
from one medium to another. It is observed spectra is referred to as spectroscopy. The
that when a ray of white light is passed spectrum of the visible light, as discussed
through a prism, the wave with shorter above, was continuous as all wavelengths
wavelength bends more than the one with a (red to violet) of the visible light are
longer wavelength. Since ordinary white represented in the spectra. The emission
light consists of waves with all the spectra of atoms in the gas phase, on the
wavelengths in the visible range, a ray of other hand, do not show a continuous
white light is spread out into a series of spread of wavelength from red to violet,
coloured bands called spectrum. The light of rather they emit light only at specific
red colour which has longest wavelength is wavelengths with dark spaces between
deviated the least while the violet light, them. Such spectra are called line spectra
which has shortest wavelength is deviated or atomic spectra because the emitted
the most. The spectrum of white light, that radiation is identified by the appearance of
we can see, ranges from violet at 7.50  1014 bright lines in the spectra (Fig. 2.10 page
Hz to red at 410 1 4 Hz. Such a spectrum 45).
is called continuous spectrum. Line emission spectra are of great
Continuous because violet merges into blue, interest in the study of electronic structure.
blue into green and so on. A similar Each element has a unique line emission
spectrum is produced when a rainbow spectrum. The characteristic lines in atomic
forms in the sky. Remember that visible spectra can be used in chemical analysis to
identify unknown atoms in the same way as
light is just a small portion of the
fingerprints are used to identify people. The
electromagnetic radiation (Fig.2.7). When
exact matching of lines of the emission
electromagnetic radiation interacts with
spectrum of the atoms of a known element
matter, atoms and molecules may absorb with the lines from an unknown sample
energy and reach to a higher energy state. quickly establishes the identity of the latter,
With higher energy, these are in an unstable German chemist, Robert Bunsen (1811-
state. For returning to their normal (more 1899) was one of the first investigators to
stable, lower energy states) energy state, the use line spectra to identify elements.
atoms and molecules emit radiations in Elements like rubidium (Rb), caesium
various regions of the electromagnetic (Cs) thallium (Tl), indium (In), gallium (Ga)
spectrum. and scandium (Sc) were discovered when
Emission and Absorption Spectra their minerals were analysed by
The spectrum of radiation emitted by a spectroscopic methods. The element
substance that has absorbed energy is called helium (He) was
an emission spectrum. Atoms, molecules discovered in the sun by spectroscopic
or ions that have absorbed radiation are method.
said to be “excited”. To produce an Line Spectrum of Hydrogen
emission spectrum, energy is supplied to a When an electric discharge is passed
sample by heating it or irradiating it and the through gaseous hydrogen, the H2 molecules
wavelength (or frequency) of the radiation
emitted, as the sample gives up the dissociate and the energetically excited
absorbed energy, is recorded. hydrogen atoms produced emit
* The restriction of any property to discrete values is called electromagnetic radiation of
quantization. discrete
An absorption spectrum is like the
photographic negative of an emission frequencies. The hydrogen spectrum
consists of several series of lines named
after their discoverers. Balmer showed in
1885 on the basis of experimental
observations that if
2020-21
STRUCTURE OF ATOM 45

(a)

(b)

Fig. 2.10 (a) Atomic emission. The light emitted by a sample of excited hydrogen atoms (or any other
element) can be passed through a prism and separated into certain discrete wavelengths. Thus an
emission spectrum, which is a photographic recording of the separated wavelengths is called as line
spectrum. Any sample of reasonable size contains an enormous number of atoms. Although a single
atom can be in only one excited state at a time, the collection of atoms contains all possible excited
states. The light emitted as these atoms fall to lower energy states is responsible for the spectrum. (b)
Atomic absorption. When white light is passed through unexcited atomic hydrogen and then through
a slit and prism, the transmitted light is lacking in intensity at the same wavelengths as are emitted
in
(a) The recorded absorption spectrum is also a line spectrum and the photographic negative of the
emission spectrum.

spectral lines are expressed in terms of The value 109,677 cm –1 is called the
wavenumber ( ), then the visible lines of the Rydberg constant for hydrogen. The first
hydrogen spectrum obey the following five series of lines that correspond to n1 = 1,
formula: 2, 3, 4, 5 are known as Lyman, Balmer,
(2.8) Paschen, Bracket and Pfund series,
respectively, Table 2.3 shows these series
where n is an integer equal to or greater of transitions in the hydrogen spectrum. Fig
than 3 (i.e., n = 3,4,5,....) 2.11 (page, 46) shows the Lyman, Balmer
The series of lines described by this and Paschen series of transitions for
formula are called the Balmer series. The hydrogen atom.
Balmer series of lines are the only lines in Of all the elements, hydrogen atom has
the hydrogen spectrum which appear in the the simplest line spectrum. Line spectrum
visible region of the electromagnetic becomes
spectrum. The Swedish
Table 2.3 The Spectral Lines for Atomic
spectroscopist, Johannes Rydberg, noted
Hydrogen
that all series of lines in the hydrogen
spectrum could be described by the
following expression :
(2.9)

where n1=1,2........
n2 = n1 + 1, n1 + 2......

2020-21
46 CHEMISTRY

rationalize many points in the atomic

structure and spectra. Bohr’s model for
hydrogen atom is based on the following
postulates:
i) The electron in the hydrogen atom can
move around the nucleus in a circular
path of fixed radius and energy. These
paths are called orbits, stationary
states or allowed energy states. These
orbits are arranged concentrically
around the nucleus.
ii) The energy of an electron in the orbit
does not change with time. However,
the electron will move from a lower
stationary state to a higher stationary
state when required amount of energy
is absorbed by the electron or energy is
emitted when electron moves from
higher stationary state to lower
stationary state (equation 2.16). The
energy change
Angulardoes not take place in a
Momentum
continuous manner.
Just as linear momentum is the product
of mass (m) and linear velocity (v),
angular momentum is the product of
Fig. 2.11 Transitions of the electron in the moment of inertia (I ) and angular
hydrogen atom (The diagram shows velocity (). For an electron of mass me,
the Lyman, Balmer and Paschen
series of transitions) moving in a circular path of radius r
around the nucleus,
more and more complex for heavier atom. angular momentum = I  
There are, however, certain features which
Since I = mer2, and  = v/r where v is the
are common to all line spectra, i.e., (i) line
spectrum of element is unique and (ii) there linear velocity,
is regularity in the line spectrum of each angular momentum = mer2  v/r = mevr
element. The questions which arise are: iii) The frequency of radiation absorbed or
What are the reasons for these similarities? emitted when transition occurs
Is it something to do with the electronic between two stationary states that
structure of atoms? These are the questions differ in energy by E, is given by:
need to be answered. We shall find later
that the answers to these questions provide E E 2  E1 (2.10)
ν  
the key in understanding electronic h E 1 andh E 2 are the energies of the
Where
structure of these elements.
lower and higher allowed energy states
2.4 BOHR’S MODEL FOR HYDROGEN respectively. This expression is
ATOM commonly known as Bohr’s frequency
Neils Bohr (1913) was the first to explain rule.
quantitatively the general features of the iv) The angular momentum of an electron
structure of hydrogen atom and its is
spectrum. He used Planck’s concept of quantised. In a given
h stationary state it can
quantisation of energy. Though the theory be e r 
mexpressed
v n. asn = equation
in 1,2,3..... (2.11) (2.11)
is not the modern quantum mechanics, it
can still be used to 2

2020-21
STRUCTURE OF ATOM 47

Where me is the mass of electron, v is the

Niels Bohr
velocity and r is the radius of the orbit in (1885–1962)
which electron is moving.
Thus an electron can move only in those N i e l s B o h r, a D a n i s h
orbits for which its angular momentum is physicist received his
integral multiple of h/2 That means Ph.D. from the
angular momentum is quantised. Radiation University of
is emitted or obsorbed only when transition Copenhagen in 1911. He
of electron then spent a year with J.J.
takes place from one quantised value of Thomson and Ernest Rutherford in England.
angular momentum to another. Therefore, In 1913, he returned to Copenhagen where
Maxwell’s electromagnetic theory does not he remained for the rest of his life. In 1920
apply here that is why only certain fixed he was named Director of the Institute of
orbits are allowed. theoretical Physics. After first World War,
The details regarding the derivation of Bohr worked energetically for peaceful uses
energies of the stationary states used by of atomic energy. He received the first Atoms
Bohr, for Peace award in 1957. Bohr was
awarded the Nobel Prize in Physics in
a) areThe quite complicated
stationary states for and will are
electron be
discussed in higher classes. However, Fig. 2.11 depicts the energies of different
1922.
numbered n = 1,2,3.......... These stationary states or energy levels of hydrogen
according
integralto Bohr’s
numberstheory for 2.6.2)
(Section hydrogenare atom. This representation is called an
atom:known as Principal quantum energy level diagram.
numbers.
When the electron is free from the
b) The radii of the stationary states are influence of nucleus, the energy is taken as
rexpressed
= n2 a0 as:
n
zero. The electron in this situation is
(2.12) associated with the stationary state of
where a0 =stationary
the first 52.9 pm. Thus thecalled
state, radiustheof Principal Quantum number
Bohr orbit, is 52.9 pm. Normally the = n =  and is called as ionized hydrogen
electron in the hydrogen atom is found atom. When the electron is attracted by the
in this orbit (that is n=1). As n nucleus and is present in orbit n, the energy
increases the value of r will increase. In What does the negative electronic
is emitted
other words the electron will be present energy (En) for hydrogen atom mean?
away from the nucleus. The energy of the electron in a
c) The most important property associated hydrogen atom has a negative sign for
with the electron, is the energy of its all possible orbits (eq. 2.13). What does
stationary state. It is given by the this negative sign convey? This negative
expression. sign means that the energy of the
 1 n = 1,2,3.... (2.13) electron in the atom is lower than the
En   R H  2
n energy of a free electron at rest. A free
where RH is called Rydberg constant and its electron at rest is an electron that is
 infinitely far away from the nucleus and
value is 2.1810–18 J. The energy of the
is assigned the energy value of zero.
state, also called as the ground state, is
lowest
Mathematically, this corresponds to
1 setting n equal to infinity in the equation
E 1 = –2.1810 –18
( 2 1) = –2.1810 –18 J. The (2.13) so that E=0. As the electron getsn
becomes larger
closer to the in absolute
nucleus value and
(as n decreases), E
energy of the stationary state for n = more and more negative. The most
2, will negative energy value is given by n=1
1 which corresponds to the most stable
be : E2 = –2.1810–18J ( 22 )= – orbit. We call this the ground state.
0.54510–18 J.

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48 CHEMISTRY

and its energy is lowered. That is the reason  R   R 

for the presence of negative sign in equation  E    H2    H2  (where n and n
i f
(2.13) and depicts its stability relative to the
 n  ni 
f

reference state of zero energy and n = .  orbit and final

stand for initial
d) Bohr’s theory can also be applied to the orbits)
ions containing only one electron,  1 1  1 1
E  R  ni2  n f2   2.18  10 J  n2i  n f2 
H 18
similar to that present in hydrogen
atom. For example, He+ Li2+, Be3+ and so  
on. The energies of the stationary states (2,17)
associated with these kinds of ions (also The frequency ( ) associated with the
known as hydrogen like species) are absorption and emission of the photon can
given by the expression. be evaluated by using equation (2.18)

E n   2.18  18  Z 2  ν   E  RH  1  1 
 n 2  J (2.14) h h  ni2 n f2 
10
and radii by the expression
 2.18  1034 J  12  12 
18
52.9(n 2 ) (2.18)
rn  6.626  10 J s  ni nf 
Z pm (2.15)
where Z is the atomic number and has  1 1
values 2,3 for the helium and lithium  3.29  1015 n2  n 2  Hz (2.19)
i f
atoms respectively. From the above 
and in terms of wavenumbers
equations, it is evident that the value of
( )
energy becomes more negative and that of
ν RH  1 1
radius becomes smaller with increase of Z . ν  c  hc  n2  n 2  (2.20)
This means that electron will be tightly i f

bound toItthe
e) is nucleus.
also possible to calculate the
= 3.29 10 s 1  1  1 
15
velocities of electrons moving in these
orbits. Although the precise equation is 3  108 m s  s  2i n f2 
not given here, qualitatively the n
magnitude of velocity of electron = 1.09677 107  12  12  m (2.21)
increases with increase of positive  1
ni nf 
charge on the nucleus and decreases
with increase of principal quantum In case of absorption spectrum, nf > ni
number. and the term in the parenthesis is positive
2.4.1 Explanation of Line Spectrum of and energy is absorbed. On the other hand
Hydrogen in case of emission spectrum ni > nf ,  E is
Line spectrum observed in case of hydrogen negative and energy is released.
atom, as mentioned in section 2.3.3, can be The expression (2.17) is similar to that
explained quantitatively using Bohr’s model. used by Rydberg (2.9) derived empirically
According to assumption 2, radiation using the experimental data available at that
(energy) is absorbed if the electron moves time. Further, each spectral line, whether in
from the orbit of smaller Principal quantum absorption or emission spectrum, can be
number to the orbit of higher Principal associated to the particular transition in
quantum number, whereas the radiation hydrogen atom. In case of large number of
(energy) is emitted if the electron moves from hydrogen atoms, different possible transitions
higher orbit to lower orbit. The energy gap can be observed and thus leading to large
between the two orbits is given by equation number of spectral lines. The brightness or
(2.16) intensity of spectral lines depends upon the
E = E – E
f i
(2.16) number of photons of same wavelength or
Combining equations (2.13) and (2.16) frequency absorbed or emitted.

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STRUCTURE OF ATOM 49

Problem 2.10 2.4.2 Limitations of Bohr’s Model

What are the frequency and wavelength Bohr’s model of the hydrogen atom was no
of a photon emitted during a transition doubt an improvement over Rutherford’s
from n = 5 state to the n = 2 state in the nuclear model, as it could account for the
hydrogen atom? stability and line spectra of hydrogen atom
and hydrogen like ions (for example, He+,
Solution Li2+, Be3+, and so on). However, Bohr’s model
Since ni = 5 and nf = 2, this transition was too simple to account for the following
gives rise to a spectral line in the points.
i) It fails to account for the finer details
visible region of the Balmer series. (doublet, that is two closely spaced lines)
From equation (2.17) of the hydrogen atom spectrum observed
1
E = 2.18  1018 J  2  2 by using sophisticated spectroscopic
5 2  techniques. This model is also unable to
1 =  4.58  1019 J
explain the spectrum of atoms other
It is an emission energy than hydrogen, for example, helium
atom which possesses only two
The frequency of the photon (taking electrons. Further, Bohr’s theory was
energy in terms of magnitude) is given
also unable to explain the splitting of
by
spectral lines in the presence of magnetic
field (Zeeman effect) or an electric field
E (Stark effect).
ν =
h ii) It could not explain the ability of atoms
to form molecules by chemical bonds.
= 6.91×1014 Hz In other
points words,above,
mentioned taking into
one account
needs the
a better
theory which can explain the salient
features of the structure of complex atoms.

Problem 2.11 2.5 TOWARDS QUANTUM MECHANICAL

MODEL OF THE ATOM
Calculate the energy associated with the
first orbit of He+. What is the radius of In view of the shortcoming of the Bohr’s
this orbit? model, attempts were made to develop a
more suitable and general model for atoms.
Solution
Two important developments which
(2.18  10 18 J)Z 2 contributed significantly in the formulation
En   atom–1
n2 of such a model were :
For He+, n = 1, Z = 2 1. Dual behaviour of matter,
2. Heisenberg uncertainty principle.
(2.18  1018 J)(22 )
E1   12  8.72  1018 J 2.5.1 Dual Behaviour of Matter
The radius of the orbit is given by The French physicist, de Broglie, in 1924
equation (2.15) proposed that matter, like radiation, should
also exhibit dual behaviour i.e., both particle
(0.0529 nm)n 2
rn  and wavelike properties. This means that
Z just as the photon has momentum as well
Since n = 1, and Z = 2 as wavelength, electrons should also
have momentum as well as wavelength, de
(0.0529 nm)12
rn   0.02645 nm Broglie, from this analogy, gave the
2 following relation between wavelength ()
and momentum (p) of a material particle.

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50 CHEMISTRY

Louis de Broglie (1892 – 1987) Solution

Louis de Broglie, a French
According to de Brogile equation
physicist, studied history as an
(2.22)
h (6.626  1034
undergraduate in the early  
Js) (0.1kg)(10 m
mv
1910’s. His interest turned to
s 1 ) × 10–34 m (J = kg m2 s–2)
= 6.626
science as a result of his
assignment to radio Problem 2.13
communications in World War
The mass of an electron is 9.110–31 kg.
I.
If its K.E. is 3.010 – 2 5 J, calculate its
He received his Dr. Sc. from the University of
wavelength.
Paris in 1924. He was professor of theoretical
physics at the University of Paris from 1932 Solution
untill Since K. E. = ½ mv2
his retirement in 1962. He was awarded the 1/ 2

Nobel Prize in Physics in 1929.  2  3.0  10 25 kg m2 s 2 

v =  2K.E.
1/ 2
h h (2.22) = 
  mv  p m  9.1  10 31 kg
 
= 812 m s–1 
where m is the mass of the particle, v its
velocity and p its momentum. de Broglie’s
prediction was confirmed experimentally 6.626  1034 Js
when it was found that an electron beam   mhv
undergoes diffraction, a phenomenon  –10  10
(9.1 31 kg)(812 m s 1 )
= 8967 × 10 m = 896.7 nm
characteristic of waves. This fact has been
put to use in making an electron Problem 2.14
microscope, which is based on the wavelike Calculate the mass of a photon with
behaviour of electrons just as an ordinary wavelength 3.6 Å.
microscope utilises the wave nature of Solution
light. An electron microscope is a powerful  = 3.6 Å = 3.6 × 10–10 m
tool in modern scientific research Velocity of photon = velocity of light
because it achieves a magnification of
about 15 million times.
It needs to be noted that according to de
Broglie, every object in motion has a wave
character. The wavelengths associated with = 6.135 × 10–29 kg
ordinary objects are so short (because of
their large masses) that their wave properties 2.5.2 Heisenberg’s Uncertainty Principle
cannot be detected. The wavelengths Werner Heisenberg a German physicist in
associated with electrons and other
1927, stated uncertainty principle which is
subatomic particles (with very small mass)
the consequence of dual behaviour of matter
can however be detected experimentally.
Results obtained from the following and radiation. It states that it is
problems prove these points impossible to determine
Problem 2.12
qualitatively. simultaneously, the exact position and
What will be the wavelength of a ball of exact momentum (or velocity) of an
mass 0.1 kg moving with a velocity of electron.
10 m s–1 ? Mathematically, it can be given as in
equation (2.23).

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STRUCTURE OF ATOM 51

(2.23) h

momentum photons of such light p= 

would change the energy of electrons by
collisions. In this process we, no doubt,
would be able to calculate the position of the
electron, but we would know very little
where x is the uncertainty in position and x about the velocity of the electron after
p
(or vx) is the uncertainty in momentum (or the collision.
velocity) of the particle. If the position of the
electron is known with high degree of Significance of Uncertainty Principle
accuracy (x is small), then the velocity of One of the important implications of the
the electron will be uncertain [(vx) is large]. Heisenberg Uncertainty Principle is that it
On the other hand, if the velocity of the rules out existence of definite paths or
precisely
electron is((v trajectories of electrons and other
x ) is small), then the position of
known
the electron will be uncertain similar particles. The trajectory of an
(x will be large). Thus, if we carry out some object is determined by its location and
physical measurements on the electron’s velocity at various moments. If we know
where a body is at a particular instant and
position or velocity, the outcome will always
if we also know its velocity and the forces
depict a fuzzy or blur picture.
acting on it at that instant, we can tell
The uncertainty principle can be best where the body would be sometime later.
understood with the help of an example. We, therefore, conclude that the position of
Suppose you are asked to measure the an object and its velocity fix its trajectory.
thickness of a sheet of paper with an Since for a sub-atomic object such as an
unmarked metrestick. Obviously, the results electron, it is not possible simultaneously to
obtained would be extremely inaccurate determine the position and velocity at any
and meaningless, In order to obtain any given instant to an arbitrary degree of
accuracy, you should use an instrument precision, it is not possible to talk of the
graduated in units smaller than the trajectory of an electron.
thickness of a sheet of the paper. The effect of Heisenberg Uncertainty
Analogously, in order to determine the Principle is significant only for motion of
position of an electron, we must use a microscopic objects and is negligible
meterstick calibrated in units of smaller for that of macroscopic objects. This can
than the dimensions of electron (keep in be seen from the following examples.
If uncertainty principle is applied to
mind that an electron is considered as a
an
point charge and is therefore,
object of mass, say about a milligram
dimensionless). To observe an electron, we
(10 kg), then
–6
can illuminate it with “light” or
electromagnetic radiation. The “light” used
must have a wavelength smaller than the
dimensions of an electron. The high
Werner Heisenberg (1901 – 1976) Werner Heisenberg (1901 – 1976) received his Ph.D.
in physics from the University of Munich in 1923. He then spent a year working with
Max Born at Gottingen and three years with Niels Bohr in Copenhagen. He was
professor of physics at the University of Leipzig from 1927 to 1941. During World War
II, Heisenberg was in charge of German research on the atomic bomb. After the war he
was named director of Max Planck Institute for physics in Gottingen. He was also
accomplished mountain climber. Heisenberg was awarded the Nobel Prize in Physics
in 1932.

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52 CHEMISTRY

The value of vx obtained is extremely

small and is insignificant. Therefore, one
may say that in dealing with milligram-
sized or heavier objects, the
associated uncertainties are hardly
of any real consequence.
In the case of a microscopic object like = 0.579×107 m s–1 (1J = 1 kg m2 s–2)
an electron on the other hand. v.x = 5.79×106 m s–1
obtained is much larger and such
uncertainties are of real consequence. For Problem 2.16
example, for an electron whose mass is A golf ball has a mass of 40g, and a
9.11×10–31 kg., according to Heisenberg speed of 45 m/s. If the speed can be
uncertainty principle measured within accuracy of 2%,
calculate the uncertainty in the
position.
Solution
The uncertainty in the speed is 2%, i.e.,

It, therefore, means that if one tries to Using the equation (2.22)
find the exact location of the electron, say
to an uncertainty of only 10–8 m, then the
uncertainty
v in velocity would be
104 m2s1  104
1
108 m ms
= 1.46×10–33 m
which is so large that the classical picture of
electrons moving in Bohr’s orbits (fixed) This is nearly ~ 1018 times smaller than
the diameter of a typical atomic
cannot hold good. It, therefore, means
nucleus. As mentioned earlier for large
that the precise statements of the
particles, the uncertainty principle sets
position and momentum of electrons
no meaningful limit to the precision of
have to be replaced by the statements measurements.
of probability, that the electron has at a Reasons for the Failure of the Bohr
given position and momentum. This is Model
what happens in the quantum One can now understand the reasons for the
mechanical model of atom. failure of the Bohr model. In Bohr model,
Problem 2.15 an electron is regarded as a charged
particle moving in well defined circular
A microscope using suitable photons is
orbits about the nucleus. The wave
employed to locate an electron in an
character of the electron is not considered in
atom within a distance of 0.1 Å. What
Bohr model. Further, an orbit is a clearly
is the uncertainty involved in the
defined path and this path can completely
measurement of its velocity?
be defined only if both the position and the
Solution velocity of the electron are known exactly at
h the same time. This is not possible
x
h
p = or x m v = according to the Heisenberg uncertainty
principle. Bohr model of the hydrogen
4
atom, therefore, not only ignores dual
4 behaviour of matter but also contradicts
Heisenberg uncertainty principle. In view of

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STRUCTURE OF ATOM 53

properties. It specifies the laws of motion

Erwin Schrödinger, an
that these objects obey. When quantum
Austrian physicist
mechanics is applied to macroscopic objects
received his Ph.D. in (for which wave like properties are
theoretical physics from insignificant) the results are the same as
the University of Vienna those from the classical mechanics.
in 1910. In 1927
Quantum mechanics was developed
Schrödinger succeeded independently in 1926 by Werner
Max Planck at the Heisenberg and Erwin Schrödinger. Here,
University of Berlin at however, we shall be discussing the
Planck’s request. In Erwin Schrödinger quantum mechanics which is based on the
(1887-1961)
1933, Schrödinger left ideas of wave motion. The fundamental
Berlin
because of his opposition to Hitler and Nazi equation of quantum mechanics was
policies and returned to Austria in 1936. After developed by Schrödinger and it won him
the invasion of Austria by Germany, the Nobel Prize in Physics in 1933. This
Schrödinger was forcibly removed from his equation which incorporates wave-
professorship. He then moved to Dublin, particle duality of matter as proposed by de
Ireland where he remained for seventeen Broglie is quite complex and knowledge of
years. Schrödinger shared the Nobel Prize
higher mathematics is needed to solve it.
for Physics with P.A.M. Dirac in 1933.
You will learn its solutions for different
systems in higher classes.
these inherent weaknesses in the Bohr
For a system (such as an atom or a
model, there was no point in extending
molecule whose energy does not change
Bohr model to other atoms. In fact an
with time) the Schrödinger
where equation is
is a mathematical
insight into the structure of the atom was
writtenHamiltonian.
called asoperator Schrödinger gave a
needed which could account for wave-
of constructing this operator from the
recipe
particle duality of matter and be consistent
expression for the total energy of the
with Heisenberg uncertainty principle.
system. The total energy of the system
This came with the advent of quantum
takes into account the kinetic energies of
mechanics.
all the sub- atomic particles (electrons,
2.6 QUANTUM MECHANICAL MODEL OF nuclei), attractive potential between the
ATOM electrons and nuclei and repulsive potential
Classical mechanics, based on Newton’s laws among the electrons and nuclei
of motion, successfully describes the individually. Solution of this equation gives
motion of all macroscopic objects such as a E and .
falling stone, orbiting planets etc., which Hydrogen Atom and the Schrödinger
have essentially a particle-like behaviour as Equation
shown in the previous section. However it When Schrödinger equation is solved for
fails when applied to microscopic objects hydrogen atom, the solution gives the
like electrons, atoms, molecules etc. This is possible energy levels the electron can
mainly because of the fact that classical occupy and the corresponding wave
mechanics ignores the concept of dual function(s) () of the electron associated
behaviour of matter especially for sub- with each energy level. These quantized
atomic particles and the uncertainty energy states and corresponding wave
principle. The branch of science that takes functions which are characterized by a
into account this dual behaviour of matter is set of three quantum numbers (principal
called quantum mechanics. quantum number n, azimuthal
Quantum mechanics is a theoretical quantum number l and magnetic
science that deals with the study of the quantum number m l ) arise as a natural
motions of the microscopic objects that consequence in the solution of the
have both observable wave like and Schrödinger equation. When an electron is
particle like in

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54 CHEMISTRY

any energy state, the wave function 2. The existence of quantized electronic
corresponding to that energy state contains energy levels is a direct result of the wave
all information about the electron. The like properties of electrons and are
wave function is a mathematical function allowed solutions of Schrödinger wave
whose value depends upon the coordinates equation.
of the electron in the atom and does not 3. Both the exact position and exact velocity
carry any physical meaning. Such wave of an electron in an atom cannot be
functions of hydrogen or hydrogen like determined simultaneously (Heisenberg
uncertainty principle). The path of an
species with one electron are called atomic
electron in an atom therefore, can never
orbitals. Such wave functions pertaining to be determined or known accurately.
one-electron species are called one- That is why, as you shall see later on,
electron systems. The probability of one talks of only probability of finding
finding an electron at a point within an the electron at different points in
atom is proportional to the ||2 at that an atom.
point. The quantum mechanical results of 4. An atomic orbital is the wave function
the hydrogen atom successfully predict all  for an electron in an atom.
aspects of the hydrogen atom spectrum Whenever an electron is described by a
including some phenomena that could not wave function, we say that the electron
be explained by the Bohr model. occupies that orbital. Since many such
wave functions are possible for an
Application of Schrödinger equation to electron, there are many atomic orbitals
multi-electron atoms presents a difficulty: in an atom. These “one electron orbital
the Schrödinger equation cannot be solved wave functions” or orbitals form the
exactly for a multi-electron atom. This basis of the electronic structure of
difficulty can be overcome by using atoms. In each orbital, the electron
approximate methods. Such calculations has a definite energy. An orbital
with the aid of modern computers show cannot contain more than two
electrons. In a multi-electron atom, the
that orbitals in atoms other than hydrogen
electrons are filled in various orbitals in
do not differ in any radical way from the
the order of increasing energy. For
hydrogen orbitals discussed above. The each electron of a multi-electron
principal difference lies in the consequence of atom, there shall, therefore, be an
increased nuclear charge. Because of this orbital wave function characteristic of
all the orbitals are somewhat contracted. the orbital it occupies. All the
Further, as you shall see later (in information about the electron in an
subsections atom is stored in its orbital wave
2.6.3 and 2.6.4), unlike orbitals of function  and quantum mechanics
hydrogen makes it possible to extract this
information out of .
or hydrogen like species, whose
Important
energies dependFeatures
only on theof quantum
the 5. The probability of finding an electron at
Quantum Mechanical Model
number n, the energies of the orbitals of in a point within an atom is proportional
Atom to the square of the orbital wave
multi-electron atoms depend on quantum
Quantum function i.e., ||2 at that point. ||2
numbers nmechanical
and l. model of atom is the
is known as probability density and
picture of the structure of the atom, which
emerges from the application of the is always positive. From the value of
Schrödinger equation to atoms. The | |2 at different points within an
following are the important features of the atom, it is possible to predict the
region around the nucleus where
quantum-mechanical model of atom:
electron will most probably be
1. The energy of electrons in atoms is found.
quantized (i.e., can only have certain 2.6.1 Orbitals and Quantum Numbers
specific values), for example when A large number of orbitals are possible in an
electrons are bound to the nucleus in atom. Qualitatively these orbitals can be
atoms.

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STRUCTURE OF ATOM 55

distinguished by their size, shape and For example in the first shell (n = 1), there is
orientation. An orbital of smaller size means only one sub-shell which corresponds to l =
there is more chance of finding the electron 0. There are two sub-shells (l = 0, 1) in the
near the nucleus. Similarly shape and second shell (n = 2), three (l = 0, 1, 2) in
orientation mean that there is more third shell (n = 3) and so on. Each sub-shell
probability of finding the electron along is assigned an azimuthal quantum number
certain directions than along others. (l ). Sub-shells corresponding to different
Atomic orbitals are precisely distinguished values of l are represented by the following
by what are known as quantum numbers. symbols.
Each orbital is designated by three Value for l : 0 1 2 3 4 5 ............
quantum numbers labelled as n, l and ml. notation for s p d f g
The principal quantum number ‘n’ is h ............ sub-shell
a positive integer with value of n = 1,2,3....... Table 2.4 shows the permissible values
The principal quantum number determines of ‘l ’ for a given principal quantum number
the size and to large extent the energy of and the corresponding sub-shell notation.
the orbital. For hydrogen atom and Table 2.4 Subshell Notations
hydrogen like species (He+, Li2+, .... etc.)
energy and size of the orbital depends only
on ‘n’.
The principal quantum number also
identifies the shell. With the increase in the
value of ‘n’, the number of allowed orbital
increases and are given by ‘n2’ All the
orbitals of a given value of ‘n’ constitute
a single shell of atom and are represented
by the following letters
n = 1 2 3 4 ............
Shell = K L M N ............
Size of an orbital increases with increase
of principal quantum number ‘n’. In other
words the electron will be located away
from the nucleus. Since energy is required
in shifting away the negatively charged
electron from the positively charged nucleus,
the energy of the orbital will increase with
increase of n. Magnetic orbital quantum number. ‘ml
Azimuthal quantum number. ‘l’ is also gives’ information about the spatial
known as orbital angular momentum or orientation of the orbital with respect to
subsidiary quantum number. It defines the standard set of co-ordinate axis. For any
three-dimensional shape of the orbital. For sub-shell (defined by ‘l’ value) 2l+1 values
a given value of n, l can have n values of m are possible and these values are given
ranging from 0 to n – 1, that is, for a given by :
value of n, the possible value of l are : l = 0, ml = – l, – (l –1), – (l – 2)... 0,1... (l – 2), (l –
1, 2, .......... (n–1) 1), lThus for l = 0, the only permitted value
For example, when n = 1, value of l is of ml = 0, [2(0)+1 = 1, one s orbital]. For l =
only 1, ml can be –1, 0 and +1 [2(1)+1 = 3,
0. For n = 2, the possible value of l can orbitals].
three p For l = 2, m l = –2, –1, 0, +1 and +2,
be 0 [2(2)+1 = 5, five d orbitals]. It should be
and 1. For n = 3, the possible l values noted
are 0, 1
and 2.
Each shell consists of one or more sub-
shells or sub-levels. The number of sub-
shells in a principal shell is equal to the 2020-21
value of n.
56 CHEMISTRY

that the values of ml are derived from l and electron has, besides charge and mass,
the value of l are derived from n.
that intrinsic spin angular quantum number.
Each orbital in an atom, therefore, is Spin angular momentum of the electron — a
defined by a set of values for n, l and m l. An vector quantity, can have two orientations
orbital described by the quantum numbers relative to the chosen axis. These two
n = 2, l = 1, m = 0 is an orbital in the p sub- orientations are distinguished by the spin
l
of the second shell. The following chart gives
shell quantum numbers ms which can take the
the relation between the subshell and the values of +½ or –½. These are called the
number of orbitals associated with it. two spin states of the electron and are
normally represented by two arrows,  (spin
Value of l 0 1 2 3 4 5 up) and  (spin down). Two electrons that
Subshell notation s p d f g h have different ms values (one +½ and the
number of orbitals 1 3 5 7 9 11 other –½) are said to have opposite spins.
An orbital cannot hold more than two
Electron spin ‘s’ : The three quantum electrons and these two electrons should
numbers labelling an atomic orbital can be have opposite spins.
used equally well to define its energy, shape To sum up, the four quantum numbers
and orientation. But all these quantum provide
i) the following
n defines information
the shell, determines: the size
numbers are not enough to explain the line of the orbital and also to a large extent
spectra observed in the case of multi- the energy of the orbital.
electron atoms, that is, some of the lines
actually occur in doublets (two lines closely ii) There are n subshells in the nth shell. l
spaced), triplets (three lines, closely spaced) identifies the subshell and determines
etc. This suggests the presence of a few the shape of the orbital (see section
more energy levels than predicted by the 2.6.2). There are (2l+1) orbitals of each
three quantum numbers. type in a subshell, that is, one s orbital
(l = 0), three p orbitals (l = 1) and five d
In 1925, George Uhlenbeck and Samuel
orbitals (l = 2) per subshell. To some
Goudsmit proposed the presence of the
extent l also determines the energy of
fourthquantum
spin quantum number
number (m sknown as the
). An electron
the orbital in a multi-electron atom.
electron
spins around its own axis, much in a similar
way as earth spins around its own axis iii) m designates the orientation of the
orbital.
while revolving around the sun. In other l
For a given value of l, m has (2l+1)
words, an values,
l
Orbit, orbital and its importance
Orbit and orbital are not synonymous. An orbit, as proposed by Bohr, is a circular path
around the nucleus in which an electron moves. A precise description of this path of the
electron is impossible according to Heisenberg uncertainty principle. Bohr orbits, therefore,
have no real meaning and their existence can never be demonstrated experimentally. An
atomic orbital, on the other hand, is a quantum mechanical concept and refers to the one
electron wave function  in an atom. It is characterized by three quantum numbers (n, l and
ml) and its value depends upon the coordinates of the electron.  has, by itself, no physical
meaning. It is the square of the wave function i.e., ||2 which has a physical meaning. ||2
at any point in an atom gives the value of probability density at that point. Probability density
(||2) is the probability per unit volume and the product of ||2 and a small volume (called a
volume element) yields the probability of finding the electron in that volume (the reason for
specifying a small volume element is that ||2 varies from one region to another in space but
its value can be assumed to be constant within a small volume element). The total probability
of finding the electron in a given volume can then be calculated by the sum of all the products
of ||2 and the corresponding volume elements. It is thus possible to get the probable
distribution of an electron in an orbital.

2020-21
STRUCTURE OF ATOM 57

the same as the number of orbitals per

subshell. It means that the number of
orbitals is equal to the number of ways
in which they are oriented.
iv) ms refers to orientation of the spin of the
electron.

Problem 2.17
What is the total number of orbitals
associated with the principal quantum
number n = 3 ?
Solution
For n = 3, the possible values of l are 0,
1 and 2. Thus there is one 3s
(n = 3, l = 0 and m
orbital l
= 0); there are three
3p
orbitals (n = 3, l = 1 and m l = –1, 0, +1);
there are five 3d orbitals (n = 3, l = 2 Fig. 2.12 The plots of (a) the orbital wave
and
function  (r ) ; (b) the variation of
ml = –2, –1, 0, +1+, +2).
probability density  2(r) as a function
Therefore, the total number of orbitals
is 1+3+5 = 9 of distance r of the electron from the
nucleus for 1s and 2s orbitals.
The same value can also be obtained by
using the relation; number of orbitals According to the German physicist, Max
= n2, i.e. 32 = 9. Born, the square of the wave function
(i.e., 2) at a point gives the probability
Problem 2.18 density of the electron at that point. The
Using s, p, d, f notations, describe the variation of
orbital with the following quantum  2 as a function of r for 1s and 2s
numbers orbitals is given in Fig. 2.12(b). Here again,
(a) n = 2, l = 1, (b) n = 4, l = 0, (c) n = 5, you may note that the curves for 1s and 2s
l = 3, (d) n = 3, l = 2 orbitals are different.
It may be noted that for 1s orbital the
Solution n l orbital
probability density is maximum at the
a) 2 1 2p nucleus and it decreases sharply as we move
b) 4 0 4s away from it. On the other hand, for 2s
c) 5 3 5f orbital the probability density first
d) 3 2 3d decreases sharply to zero and again starts
increasing. After reaching a small maxima it
2.6.2 Shapes of Atomic Orbitals decreases again and approaches zero as
The orbital wave function or  for an the value of r increases further. The region
electron in an atom has no physical where this probability density function
meaning. It is simply a mathematical reduces to zero is called nodal surfaces or
simply nodes. In general, it has been found
function of the coordinates of the
that ns-orbital has (n – 1) nodes, that is,
electron. However, for different orbitals the
number of nodes increases with increase of
plots of corresponding wave functions as a
principal quantum number n. In other
function of r (the distance from the nucleus)
words, number of nodes for 2s orbital is
are different. Fig. 2.12(a), gives such plots
one, two for 3s and so on.
for 1s (n = 1, l = 0) and 2s (n = 2, l = 0)
orbitals. These probability density variation can
be visualised in terms of charge cloud
diagrams [Fig. 2.13(a)]. In these diagrams,
the density
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58 CHEMISTRY

of the dots in a region represents electron

probability density in that region.
Boundary surface diagrams of constant
probability density for different orbitals give
a fairly good representation of the shapes of
the orbitals. In this representation, a
boundary surface or contour surface is
drawn in space for an orbital on which the
value of probability density ||2 is constant.
In principle many such boundary surfaces
may be possible. However, for a given
orbital, only that boundary surface
diagram of constant probability density*
is taken to be good representation of the
shape of the orbital which encloses a region Fig. 2.13 (a) Probability density plots of 1s and
or volume in which the probability of 2s atomic orbitals. The density of the
dots represents the probability
finding the electron is very high, say, 90%.
density of finding the electron in that
The boundary surface diagram for 1s and 2s region. (b) Boundary surface diagram
orbitals are given in Fig. 2.13(b). One may for 1s and 2s orbitals.
ask a question : Why do we not draw a
boundary surface diagram, which bounds a
region in which the probability of finding the
electron is, 100 %? The answer to this
question is that the probability density ||2
has always some value, howsoever small it
may be, at any finite distance from the
nucleus. It is therefore, not possible to draw
a boundary surface diagram of a rigid size
in which the probability of finding the
electron is 100%. Boundary surface
diagram for a s orbital is actually a sphere
centred on the nucleus. In two
dimensions, this sphere looks like a circle. It
encloses a region in which probability of
finding the electron is about 90%.
Thus, we see that 1s and 2s orbitals are
spherical in shape. In reality all the s-orbitals
are spherically symmetric, that is, the Fig. 2.14 Boundary surface diagrams of the
probability of finding the electron at a given three 2p orbitals.
distance is equal in all the directions. It is diagrams are not spherical. Instead each
also observed that the size of the s orbital p orbital consists of two sections called lobes
increases with increase in n, that is, 4s > 3s that are on either side of the plane that
> 2s > 1s and the electron is located further passes through the nucleus. The probability
away from the nucleus as the principal density function is zero on the plane where
quantum number increases. the two lobes touch each other. The size,
Boundary surface diagrams for three 2p shape and
* If probability
orbitals 1) are|
(l = density |2 is constant
shown in Fig.on 2.14. surface, || is also constant over the surface. The boundary
a given In
these diagrams, the nucleus is at the origin.
surface for || and || are identical.
2
Here, unlike s-orbitals, the boundary
surface

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STRUCTURE OF ATOM 59

energy of the three orbitals are identical. there are, therefore, three p orbitals whose
They differ however, in the way the lobes axes are mutually perpendicular. Like s
are oriented. Since the lobes may be orbitals, p orbitals increase in size and
considered to lie along the x, y or z axis, energy with increase in the principal
they are given2p
designations the
x
, 2p y, and 2p .z It should be quantum number and hence the order of
understood, however, that there is no simple the energy and size of various p orbitals is
relation between the values of m l (–1, 0 and 4p > 3p > 2p. Further, like s orbitals, the
+1) and the x, y and z directions. For our probability density functions for p-orbital
purpose, it is sufficient to remember that, also pass through value zero, besides at zero
because there are three possible values of l and infinite distance, as the distance from
m, the nucleus increases. The number of nodes
are given by the n –2, that is number of
radial node is 1 for 3p orbital, two for 4p
orbital and so on.
For l = 2, the orbital is known as d-
orbital and the minimum value of principal
quantum
be number
greater than n–1. (n) hasare
There to five
be m
3.
l
as the
values
value
2,
(– –1, of
0,l +1
cannot
and +2) for l = 2 and thus there
are five d orbitals. The boundary surface
diagram of d orbitals are shown in Fig. 2.15.
The five d-orbitals are designated as dxy,
dyz, dxz, dx2–y2 and dz2. The shapes of the first
four d- orbitals are similar to each other,
where as that of the fifth one, dz2, is different
from others, but all five 3d orbitals are
equivalent in energy. The d orbitals for
which n is greater than 3 (4d, 5d...) also
have shapes similar to 3d orbital, but differ
in energy and size.
Besides the radial nodes (i.e., probability
density function is zero), the probability
density functions for the np and nd orbitals
are zero at the plane (s), passing through the
nucleus (origin). For example, in case of pz
orbital, xy-plane is a nodal plane, in case of
dxy orbital, there are two nodal planes
passing through the origin and bisecting the
xy plane containing z-axis. These are called
angular nodes and number of angular
nodes are given by ‘l’, i.e., one angular node
for p orbitals, two angular nodes for ‘d’
orbitals and so on. The total number of
nodes are given by (n–1), i.e., sum of l
angular nodes and (n – l – 1) radial nodes.

Fig. 2.15 Boundary surface diagrams of the five 2.6.3 Energies of Orbitals
3d orbitals. The energy of an electron in a hydrogen
atom is determined solely by the principal
quantum

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60 CHEMISTRY

number. Thus the energy of the orbitals in The energy of an electron in a multi-
hydrogen atom increases as follows : electron atom, unlike that of the hydrogen
1s < 2s = 2p < 3s = 3p = 3d <4s = 4p = 4d atom, depends not only on its principal
= 4f < quantum number (shell), but also on its
(2.23) azimuthal quantum number (subshell). That
and is depicted in Fig. 2.16. Although the is, for a given principal quantum number, s,
shapes of 2s and 2p orbitals are different, p, d, f ... all have different energies. Within a
an electron has the same energy when it is given principal quantum number, the
energy of orbitals increases in the order
in the 2s orbital as when it is present in 2p
s<p<d<f. For higher energy levels, these
orbital. The orbitals
degenerate. The 1s having
orbital the same
in a energy
hydrogen
differences are sufficiently pronounced and
are called
atom, as said earlier, corresponds to the straggering of orbital energy may result,
most stable condition and is called the e.g., 4s<3d and
ground state and an electron residing in 6s<5d ; 4f<6p. The main reason for having
different energies of the subshells is the
this orbital is most strongly held by the repulsion among the electrons in multi-
mutual
nucleus. An electron in the 2s, 2p or higher electron atoms. The only electrical
orbitals in a hydrogen atom is in excited interaction present in hydrogen atom is the
state. attraction between the negatively charged
electron and the positively charged
nucleus. In multi- electron atoms,
besides the presence of attraction
between the electron and nucleus, there
are repulsion terms between every
electron and other electrons present in the
atom. Thus the stability of an electron in a
multi-electron atom is because total
attractive interactions are more than the
repulsive interactions. In general, the
repulsive interaction of the electrons in
the outer shell with the electrons in the
inner shell are more important. On the
other hand, the attractive interactions of an
electron increases with increase of positive
charge (Ze) on the nucleus. Due to the
presence of electrons in the inner shells,
the electron in the outer shell will not
experience the full positive charge of the
nucleus (Ze). The effect will be lowered due
to the partial screening of positive charge on
Fig. 2.16 Energy level diagrams for the few the nucleus by the inner shell electrons.
electronic shells of (a) hydrogen atom This is known as the shielding of the
and (b) multi-electronic atoms. Note outer shell electrons from the nucleus by
that orbitals for the same value of the inner nuclear
shell electrons,
as effective charge (Z and the net
eff e). Despite
principal quantum number, have positive charge experienced by the outer
the same energies even for different the shielding of the outer
electrons is known
from the
azimuthal quantum number for
hydrogen atom. In case of multi- nucleus by the inner shell electrons, the
electron atoms, orbitals with same attractive force experienced by the outer
principal quantum number possess shell electrons increases with increase of
different energies for different nuclear charge. In other words, the
azimuthal quantum numbers. energy of interaction between, the nucleus
and electron

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STRUCTURE OF ATOM 61

(that is orbital energy) decreases (that is Table 2.5 Arrangement of Orbitals with
more negative) with the increase of atomic Increasing Energy on the Basis of
number (Z ). (n+l ) Rule
Both the attractive and repulsive
interactions depend upon the shell and
shape of the orbital in which the electron is
present. For example electrons present in
spherical shaped, s orbital shields the outer
electrons from the nucleus more effectively
as compared to electrons present in p
orbital. Similarly electrons present in p
orbitals shield the outer electrons from the
nucleus more than the electrons present in
d orbitals, even though all these orbitals are
present in the same shell. Further within a
shell, due to spherical shape of s orbital, the
s orbital electron spends more time close to
the nucleus in comparison to p orbital
electron which spends more time in the
vicinity of nucleus in comparison to d orbital
electron. Inquantum
(principal other words, for a given
number), the shell
Z
experienced by the electron decreases witheff
increase of azimuthal quantum number (l),
that is, the s orbital electron will be more
tightly bound to the nucleus than p orbital
electron which in turn will be better tightly
bound than the d orbital electron. The energy
of electrons
in s orbital will be lower (more negative) than
that of p orbital electron which will have less
energy than that of d orbital electron and so
on. Since the extent of shielding from the the same energy. Lastly it may be mentioned
nucleus is different for electrons in different here that energies of the orbitals in the
orbitals, it leads to the splitting of energy same subshell decrease with increase in
levels within the same shell (or same the atomic number (Zeff). For example,
principal quantum number), that is, energy energy of 2s orbital of hydrogen atom is
of electron in an orbital, as mentioned greater than that of 2s orbital of lithium
earlier, depends upon the values of n and l. and that of lithium is greater than that of
Mathematically, the dependence of energies sodium and so on, that is, E2s(H) > E2s(Li) >
of the orbitals on n and l are quite E2s(Na) > E2s(K).
complicated but one simple rule is that, the
lower the value of (n + l) for an orbital, 2.6.4 Filling of Orbitals in Atom
the lower is its energy. If two orbitals The filling of electrons into the orbitals of
have the same value of (n + l), the orbital different atoms takes place according to the
with lower value of n will have the lower aufbau principle which is based on the
energy. The Table 2.5 illustrates the (n Pauli’s exclusion principle, the Hund’s
+ l ) rule and Fig. 2.16 depicts the energy rule of maximum multiplicity and the
levels of multi-electrons atoms. It may be relative energies of the orbitals.
noted that different subshells of a particular Aufbau Principle
shell have different energies in case of
multi–electrons atoms. However, in The word ‘aufbau’ in German means
hydrogen atom, these have ‘building up’. The building up of orbitals
means the

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62 CHEMISTRY

filling up of orbitals with electrons. The the top, the direction of the arrows gives the
principle states : In the ground state of the order of filling of orbitals, that is starting
atoms, the orbitals are filled in order of from right top to bottom left. With respect
their increasing energies. In other words, to placement of outermost valence electrons,
electrons first occupy the lowest energy it is remarkably accurate for all atoms.
orbital available to them and enter into For example, valence electron in potassium
higher energy orbitals only after the lower must choose between 3d and 4s orbitals
energy orbitals are filled. As you have learnt and as predicted by this sequence, it is
above, energy of a given orbital depends found in 4s orbital. The above order should
upon effective nuclear charge and different be assumed to be a rough guide to the filling
type of orbitals are affected to different of energy levels. In many cases, the orbitals
extent. Thus, there is no single ordering of are similar in energy and small changes
energies of orbitals which will be universally in atomic structure may bring about a
correct for all atoms. change in the order of filling. Even then, the
However, following order of energies of above series is a useful guide to the building
the orbitals is extremely useful: of the electronic structure of an atom
provided that it is remembered that
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p,
exceptions may occur.
4f, 5d, 6p, 7s...
The order may be remembered by using Pauli Exclusion Principle
the method given in Fig. 2.17. Starting from The number of electrons to be filled in
various orbitals is restricted by the exclusion
principle, given by the Austrian scientist
Wolfgang Pauli (1926). According to this
principle : No two electrons in an atom
can have the same set of four quantum
numbers. Pauli exclusion principle can
also be stated as : “Only two electrons may
exist in the same orbital and these
electrons must have opposite spin.” This
means
n, l andthat the must
m l , but two electrons
have the can havespin
opposite the
same value
quantum of threeThe
number. quantum numbers
restriction imposed by
Pauli’s exclusion principle on the number of
electrons in an orbital helps in calculating
the capacity of electrons to be present in
any subshell. For example, subshell 1s
comprises one orbital and thus the
maximum number of electrons present in 1s
subshell can be two, in p and d subshells,
the maximum number of electrons can be 6
and 10 and so on. This can be summed up
as : the maximum number of electrons
in the shell with principal quantum
number n is equal to 2n2.
Hund’s Rule of Maximum Multiplicity
This rule deals with the filling of electrons
Fig.2.17 Order of filling of orbitals into the orbitals belonging to the same
subshell (that is, orbitals of equal
energy, called

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STRUCTURE OF ATOM 63

degenerate orbitals). It states : pairing of also occupy the 1s orbital. Its configuration
electrons in the orbitals belonging to the is, therefore, 1s2. As mentioned above, the
same subshell (p, d or f) does not take two electrons differ from each other with
place until each orbital belonging to opposite spin, as can be seen from the
that subshell has got one electron each orbital diagram.
i.e., it is singly occupied.
Since there are three p, five d and seven The third electron of lithium (Li) is not
f orbitals, therefore, the pairing of electrons allowed in the 1s orbital because of Pauli
will start in the p, d and f orbitals with the exclusion principle. It, therefore, takes the
entry of 4th, 6th and 8th electron, next available choice, namely the 2s orbital.
respectively. It has been observed that half The electronic configuration of Li is 1s22s1.
filled and fully filled degenerate set of The 2s orbital can accommodate one more
orbitals acquire extra stability due to their electron. The configuration of beryllium (Be)
symmetry (see Section, 2.6.7). atom is, therefore, 1s2 2s2 (see Table 2.6,
2.6.5 Electronic Configuration of page 66 for the electronic configurations of
Atoms elements).
The distribution of electrons into orbitals In the next six elements—boron
of an atom is called its electronic (B, 1s22s22p1), carbon (C, 1s22s22p2), nitrogen
configuration. If one keeps in mind the (N, 1s22s22p3), oxygen (O, 1s22s22p4),
basic rules which govern the filling of fluorine (F, 1s22s22p5) and neon (Ne,
different atomic orbitals, the electronic 1s 2s 2p ), the 2p orbitals get progressively
2 2 6

configurations of different atoms can be filled. This process is completed with the
written very easily. neon atom. The orbital picture of these
elements can be represented as follows :
(i) The
sa pbelectronic configuration of different
d c ...... notation
atoms can be represented in two ways. For
(ii) Orbital diagram
example :
s p
d In the first notation, the subshell is
represented by the respective letter symbol
and the number of electrons present in the
subshell is depicted, as the super script, like
a, b, c, ... etc. The similar subshell
represented for different shells is
differentiated by writing the principal
quantum number before the respective
subshell. In the second notation each
orbital of the subshell is represented by a
box and the electron is represented by an
arrow () a positive spin or an arrow () a The electronic configuration of the
negative spin. The advantage of second elements sodium (Na, 1s 2 2 s 2 2 p 6 3 s 1 )
notation over the first is that it represents all to argon (Ar,1s22s22p63s23p6), follow
the four quantum numbers. exactly the
pattern as same
the elements from lithium to
The hydrogen atom has only one electron neon with the difference that the 3s and 3p
energy,
which goes namely 1 s. The
in the orbital with electronic
the lowest orbitals are getting filled now. This process
configuration of the hydrogen atom is 1s1 can be simplified if we represent the total
meaning that it has one electron in the 1s number of electrons in the first two shells
orbital. The second electron in helium (He) by the name of element neon (Ne). The
can electronic configuration

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64 CHEMISTRY

of the elements from sodium to argon can be filling of 6p, then 7s and finally 5f and 6d
written as (Na, [Ne]3s1) to (Ar, [Ne] 3s23p6). orbitals takes place. The elements after
The electrons in the completely filled shells uranium (U) are all short-lived and all of
are known as core electrons and the them are produced artificially. The
electrons that are added to the electronic electronic configurations of the known
shell with the highest principal quantum elements (as determined by spectroscopic
number are called valence electrons. For methods) are tabulated in Table 2.6 (page
example, the electrons in Ne are the core 66).
electrons and the electrons from Na to Ar One may ask what is the utility of
are the valence electrons. In potassium (K) knowing the electron configuration? The
and calcium (Ca), the 4s orbital, being lower modern approach to the chemistry, infact,
in energy than the 3d orbitals, is occupied depends almost entirely on electronic
by one and two electrons respectively. distribution to understand and explain
A new pattern is followed beginning with chemical behaviour. For example, questions
scandium (Sc). The 3d orbital, being lower in like why two or more atoms combine to
energy than the 4p orbital, is filled first. form molecules, why some elements are
Consequently, in the next ten elements, metals while others are non- metals, why
scandium (Sc), titanium (Ti), vanadium (V), elements like helium and argon are not
chromium (Cr), manganese (Mn), iron (Fe), reactive but elements like the halogens are
cobalt (Co), nickel (Ni), copper (Cu) and zinc reactive, find simple explanation from the
(Zn), the five 3d orbitals are progressively electronic configuration. These questions
occupied. We may be puzzled by the fact have no answer in the Daltonian model of
that chromium and copper have five and atom. A detailed understanding of the
ten electrons in 3d orbitals rather than four electronic structure of atom is, therefore,
and nine as their position would have very essential for getting an insight into the
indicated with two-electrons in the 4s various aspects of modern chemical
orbital. The reason is that fully filled knowledge.
orbitals and half-filled orbitals have extra
stability (that is, lower energy). Thus p3, p6, 2.6.6 Stability of Completely Filled and
d5, d10,f 7, f14 etc. configurations, which are Half Filled Subshells
either half-filled or fully filled, are more The ground state electronic configuration of
stable. Chromium and copper therefore the atom of an element always corresponds
adopt the d 5 and d 1 0 configuration to the state of the lowest total electronic
(Section 2.6.7)[caution: exceptions do energy. The electronic configurations of
exist] most of the atoms follow the basic rules
With the saturation of the 3d orbitals, given in Section 2.6.5. However, in certain
the filling of the 4p orbital starts at gallium elements such as Cu, or Cr, where the two
(Ga) and is complete at krypton (Kr). In the subshells (4s and 3d) differ slightly in their
next eighteen elements from rubidium (Rb) to energies, an electron shifts from a subshell of
xenon (Xe), the pattern of filling the 5s, 4d lower energy (4s) to a subshell of higher
and 5p orbitals are similar to that of 4s, 3d energy (3d), provided such a shift results
and 4p orbitals as discussed above. Then in all orbitals of the subshell of higher
comes the turn of the 6s orbital. In caesium energy getting either completely filled or half
(Cs) and the barium (Ba), this orbital filled. The valence electronic configurations
contains one and two electrons, respectively. of Cr and Cu, therefore, are 3d5 4s1 and 3d10
Then from lanthanum (La) to mercury (Hg), 4s1 respectively and not 3d4 4s2 and 3d9 4s2.
the filling up of electrons takes place in 4f It has been found that there is extra
and 5d orbitals. After this, stability associated with these electronic
configurations.

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STRUCTURE OF ATOM 65

Causes of Stability of Completely Filled and Half-filled

Subshells
The completely filled and completely
half-filled subshells are stable due to
the following reasons:
1.Symmetrical distribution of
electrons: It is well known that
symmetry leads to stability. The
completely filled or half filled subshells
have symmetrical distribution of
electrons in them and are therefore
more stable. Electrons in the same
subshell (here 3d) have equal energy
but dif ferent spatial distribution.
Consequently, their shielding of one-
another is relatively small and the
electrons are more strongly attracted by
the nucleus.
2.Exchange Energy : The stabilizing
effect arises whenever two or more
electrons with the same spin are
present in the degenerate orbitals of a
subshell. These electrons tend to
exchange their positions and the energy
released due to this exchange is called
exchange energy. The number of
exchanges that can take place is
maximum when the subshell is either
half filled or completely filled (Fig.
2.18). As a result the exchange energy is
maximum and so is the stability.
You may note that the exchange
energy is at the basis of Hund’s rule
that electrons which enter orbitals of
equal energy have parallel spins as
far as possible. In other words, the
extra stability of half-filled and
completely filled subshell is due to: (i)
relatively small shielding, (ii) smaller Fig. 2.18 Possible exchange for a d5
coulombic repulsion energy, and (iii) configuration
larger exchange energy. Details about
the exchange energy will be dealt with
in higher classes.

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66 CHEMISTRY

Table 2.6 Electronic Configurations of the Elements

* Elements with exceptional electronic configurations

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STRUCTURE OF ATOM 67

** Elements with atomic number 112 and above have been reported but not yet fully authenticated and named.

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68 CHEMISTRY

SUMMARY

Atoms are the building blocks of elements. They are the smallest parts of an element
that chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded
atom as the ultimate indivisible particle of matter. Towards the end of the nineteenth
century, it was proved experimentally that atoms are divisible and consist of three
fundamental particles: electrons, protons and neutrons. The discovery of sub-atomic
particles led to the proposal of various atomic models to explain the structure of atom.
Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity
with electrons embedded into it. This model in which mass of the atom is considered to be
evenly spread over the atom was proved wrong by Rutherford’s famous alpha-particle
scattering experiment in 1909. Rutherford concluded that atom is made of a tiny
positively charged nucleus, at its centre with electrons revolving around it in
circular orbits. Rutherford model, which resembles the solar system, was no doubt an
improvement over Thomson model but it could not account for the stability of the atom
i.e., why the electron does not fall into the nucleus. Further, it was also silent about the
electronic structure of atoms i.e., about the distribution and relative energies of
electrons around the nucleus. The difficulties of the Rutherford model were overcome by
Niels Bohr in 1913 in his model of the hydrogen atom. Bohr postulated that electron
moves around the nucleus in circular orbits. Only certain orbits can exist and each orbit
corresponds to a specific energy. Bohr calculated the energy of electron in various orbits
and for each orbit predicted the distance between the electron and nucleus. Bohr
model, though offering a satisfactory model for explaining the spectra of the hydrogen
atom, could not explain the spectra of multi-electron atoms. The reason for this was soon
discovered. In Bohr model, an electron is regarded as a charged particle moving in a
well defined circular orbit about the nucleus. The wave character of the electron is
ignored in Bohr’s theory. An orbit is a clearly defined path and this path can completely
be defined only if both the exact position and the exact velocity of the electron at the
same time are known. This is not possible according to the Heisenberg uncertainty
principle. Bohr model of the hydrogen atom, therefore, not only ignores the
dual behaviour of electron but also contradicts Heisenberg uncertainty principle.
Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to
describe the electron distributions in space and the allowed energy levels in atoms. This
equation incorporates de Broglie’s concept of wave-particle duality and is consistent with
Heisenberg uncertainty principle. When Schrödinger equation is solved for the electron in
a hydrogen atom, the solution gives the possible energy states the electron can occupy
[and the corresponding wave function(s) () (which in fact are the mathematical
functions) of the electron associated with each energy state]. These quantized energy states
and corresponding wave functions which are characterized by a set of three quantum
numbers (principal quantum number n, azimuthal quantum number l and magnetic
quantum number ml) arise as a natural consequence in the solution of the Schrödinger
equation. The restrictions on the values of these three quantum numbers also come
naturally from this solution. The quantum mechanical model of the hydrogen atom
successfully predicts all aspects of the hydrogen atom spectrum including some
phenomena that could not be explained by the Bohr model.
According to the quantum mechanical model of the atom, the electron distribution of an
atom containing a number of electrons is divided into shells. The shells, in turn, are
thought to consist of one or more subshells and subshells are assumed to be composed of
one or more orbitals, which the electrons occupy. While for hydrogen and hydrogen like
systems (such as He+, Li2+ etc.) all the orbitals within a given shell have same energy, the
energy of the orbitals in a multi-electron atom depends upon the values of n and l: The
lower the value of (n + l ) for an orbital, the lower is its energy. If two orbitals have the
same (n + l ) value, the orbital with lower value of n has the lower energy. In an atom
many such orbitals are possible and electrons are filled in those orbitals in order of
increasing energy in

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STRUCTURE OF ATOM 69

accordance with Pauli exclusion principle (no two electrons in an atom can have the
same set of four quantum numbers) and Hund’s rule of maximum multiplicity (pairing
of electrons in the orbitals belonging to the same subshell does not take place until
each orbital belonging to that subshell has got one electron each, i.e., is singly occupied).
This forms the basis of the electronic structure of atoms.

EXERCISES

2.1 (i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
2.2 (iii) Calculate the total number of electrons present in one mole of methane.
(iv) Find (a) the total number and (b) the total mass of neutrons in 7 mg of 14C.
(Assume that mass of a neutron = 1.675  10–27 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH3
at
STP.
2.3 How Will
manytheneutrons
answer change if the are
and protons temperature and following
there in the pressure nuclei
are changed
? ?
13
6 C, 168O, 12
24
Mg, 26
56
Fe, 88
Sr
38

2.4 Write the complete symbol for the atom with the given atomic number (Z) and
atomic mass (A)
(i) Z = 17 ,
A = 35. (ii) Z = 92 ,
A = 233.
2.5 (iii) Z = 4 , A = 9.
Yellow light emitted from a sodium lamp has a wavelength () of 580 nm.

2.6 Calculate the frequency () and wavenumber ( ν ) of the yellow light.
Find energy of each of the photons which
(i) correspond to light of frequency 3×1015 Hz.
2.7 (ii) have wavelength of 0.50 Å.
Calculate the wavelength, frequency and wavenumber of a light wave whose
2.8
period is 2.0 × 10–10 s.
What is the number of photons of light with a wavelength of 4000 pm that provide
2.9
1J of energy?
A photon of wavelength 4  10–7 m strikes on metal surface, the work function of
the metal being 2.13 eV. Calculate (i) the energy of the photon (eV), (ii) the kinetic
energy of the emission, and (iii) the velocity of the photoelectron
(1 eV= 1.6020 × 10–19 J).
10. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionise the
sodium atom. Calculate the ionisation energy of sodium in kJ mol–1.
11. A 25 watt bulb emits monochromatic yellow light of wavelength of 0.57m.
Calculate the rate of emission of quanta per second.
12. Electrons are emitted with zero velocity from a metal surface when it is exposed
to radiation of wavelength 6800 Å. Calculate threshold frequency (0 ) and work
function (W0 ) of the metal.
13. What is the wavelength of light emitted when the electron in a hydrogen atom
undergoes transition from an energy level with n = 4 to an energy level with n = 2?

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70 CHEMISTRY

14. How much energy is required to ionise a H atom if the electron occupies n = 5
orbit? Compare your answer with the ionization enthalpy of H atom ( energy
required to remove the electron from n =1 orbit).
15. What is the maximum number of emission lines when the excited electron of a
H atom in n = 6 drops to the ground state?
16. (i) The energy associated with the first orbit in the hydrogen atom is
–2.18 × 10–18 J atom–1. What is the energy associated with the fifth orbit?
(ii) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.
17. Calculate the wavenumber for the longest wavelength transition in the Balmer
series of atomic hydrogen.
18. What is the energy in joules, required to shift the electron of the hydrogen atom
from the first Bohr orbit to the fifth Bohr orbit and what is the wavelength of the
light emitted when the electron returns to the ground state? The ground state
electron energy is –2.18  10–11 ergs.
2.19 The electron energy in hydrogen atom is given by nE = (–2.18  10–18 )/n2 J.
Calculatethe energy required to remove an electron completely from the n = 2 orbit. What is
the longest wavelength of light in cm that can be used to cause this transition?
20. Calculate the wavelength of an electron moving with a velocity of 2.05  107 m s–1.
21. The mass of an electron is 9.1  10–31 kg. If its K.E. is 3.0  10–25 J, calculate its
wavelength.
22. Which of the following are isoelectronic species i.e., those having the same
number of electrons?
Na+, K+, Mg2+, Ca2+, S2–, Ar.
23. (i) Write the electronic configurations of the following ions: (a) H – (b) Na+
(c) O 2–

(d) F–
(ii) What are the atomic numbers of elements whose outermost electrons are
represented by (a) 3s1 (b) 2p3 and (c) 3p5 ?
(iii) Which atoms are indicated by the following configurations ?
(a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1.
24. What is the lowest value of n that allows g orbitals to exist?
l
25. thiselectron
An electron.
is in one of the 3d orbitals. Give the possible values
26. of
An atom of anforelement contains 29 electrons and 35 neutrons. Deduce (i) the
n, l and m
number of protons and (ii) the electronic configuration of the element.
27. Give the number of electrons in the species
28. (i) An atomic orbital has n = 3. What are the possible values of l and
l
m ?
(ii) List the quantum numbers (m l and l ) of electrons for 3d orbital.
(iii) Which of the following orbitals are possible?
1p, 2s, 2p and 3f
29. Using s, p, d notations, describe the orbital with the following quantum numbers.
(a) n=1, l=0; (b) n = 3; l=1 (c) n = 4; l =2; (d) n=4; l=3.
30. Explain, giving reasons, which of the following sets of quantum numbers are not
possible.
(a) n = 0, l = 0, ml = 0, ms = + ½
(b) n = 1, l = 0, ml = 0, ms = – ½
(c) n = 1, l = 1, ml = 0, ms = + ½
(d) n = 2, l = 1,
ml = 0, ms = – ½

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(e) n = 3, l = 3, ml = –3, ms = + ½
(f) n = 3, l = 1, ml = 0, ms = + ½
31. How many electrons in an atom may have the following quantum numbers?
(a) n = 4, ms = – ½ (b) n = 3, l = 0
32. Show that the circumference of the Bohr orbit for the hydrogen atom is an
integral multiple of the de Broglie wavelength associated with the electron
revolving around the orbit.
33. What transition in the hydrogen spectrum would have the same wavelength as
the Balmer transition n = 4 to n = 2 of He+ spectrum ?
34. Calculate the energy required for the process
He+ (g) * He2+ (g) + e–
The ionization energy for the H atom in the
ground state is 2.18  10–18 J atom–1
35. If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon
atoms which can be placed side by side in a straight line across length of scale of
length 20 cm long.
36. 2 ×108 atoms of carbon are arranged side by side. Calculate the radius of carbon
atom if the length of this arrangement is 2.4 cm.
37. The diameter of zinc atom is 2.6 Å.Calculate (a) radius of zinc atom in pm and (b)
number of atoms present in a length of 1.6 cm if the zinc atoms are arranged side
by side lengthwise.
38. A certain particle carries 2.5 × 10–16C of static electric charge. Calculate the
number of electrons present in it.
39. In Milikan’s experiment, static electric charge on the oil drops has been obtained
by shining X-rays. If the static electric charge on the oil drop is –1.282 × 10–18C,
calculate the number of electrons present on it.
40. In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold,
platinum etc. have been used to be bombarded by the -particles. If the thin foil
of light atoms like aluminium etc. is used, what difference would be observed
from the 79
above results
79
? 35 35
2.41 Symbols 35 Br and Br can be written, whereas symbols 79
Br
and Br are not
acceptable. Answer briefly.
42. An element with mass number 81 contains 31.7% more neutrons as compared to
protons. Assign the atomic symbol.
43. An ion with mass number 37 possesses one unit of negative charge. If the ion
conatins 11.1% more neutrons than the electrons, find the symbol of the ion.
44. An ion with mass number 56 contains 3 units of positive charge and 30.4% more
neutrons than electrons. Assign the symbol to this ion.
45. Arrange the following type of radiations in increasing order of frequency: (a)
radiation from microwave oven (b) amber light from traffic signal (c) radiation
from FM radio
(d) cosmic rays from outer space and (e) X-rays.
46. Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of
photons emitted is 5.6 × 1024, calculate the power of this laser.
47. Neon gas is generally used in the sign boards. If it emits strongly at 616 nm,
calculate (a) the frequency of emission, (b) distance traveled by this radiation in
30 s (c) energy of quantum and (d) number of quanta present if it produces 2 J of
energy.

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48. In astronomical observations, signals observed from the distant stars are
generally weak. If the photon detector receives a total of 3.15 × 10–18 J from the
radiations of 600 nm, calculate the number of photons received by the detector.
49. Lifetimes of the molecules in the excited states are often measured by using
pulsed radiation source of duration nearly in the nano second range. If the
radiation source has the duration of 2 ns and the number of photons emitted
during the pulse source is 2.5 × 1015, calculate the energy of the source.
50. The longest wavelength doublet absorption transition is observed at 589 and
589.6 nm. Calcualte the frequency of each transition and energy difference
between two excited states.
51. The work function for caesium atom is 1.9 eV. Calculate (a) the threshold
wavelength and (b) the threshold frequency of the radiation. If the caesium
element is irradiated with a wavelength 500 nm, calculate the kinetic energy
and the velocity of the ejected photoelectron.
52. Following results are observed when sodium metal is irradiated with different
wavelengths. Calculate (a) threshold wavelength and, (b) Planck’s constant.
 (nm) 500 450 400
v × 10–5 (cm s–1) 2.55 4.35 5.35
2.53 The ejection of the photoelectron from the silver metal in the photoelectric effect
experiment can be stopped by applying the voltage of 0.35 V when the radiation
256.7 nm is used. Calculate the work function for silver metal.
54. If the photon of the wavelength 150 pm strikes an atom and one of tis inner
bound electrons is ejected out with a velocity of 1.5 × 107 m s–1, calculate the
energy with which it is bound to the nucleus.
55. Emission transitions in the Paschen series end at orbit n = 3 and start from orbit
n and can be represeted as v = 3.29 × 1015 (Hz) [ 1/32 – 1/n2]
Calculate the value of n if the transition is observed at 1285 nm. Find the region
of the spectrum.
56. Calculate the wavelength for the emission transition if it starts from the orbit
having radius 1.3225 nm and ends at 211.6 pm. Name the series to which this
transition belongs and the region of the spectrum.
57. Dual behaviour of matter proposed by de Broglie led to the discovery of electron
microscope often used for the highly magnified images of biological molecules and
other type of material. If the velocity of the electron in this microscope is 1.6 × 106
ms–1, calculate de Broglie wavelength associated with this electron.
58. Similar to electron diffraction, neutron diffraction microscope is also used for the
determination of the structure of molecules. If the wavelength used here is 800
pm, calculate the characteristic velocity associated with the neutron.
59. If the velocity of the electron in Bohr’s first orbit is 2.19 × 106 ms–1, calculate the
de Broglie wavelength associated with it.
60. The velocity associated with a proton moving in a potential difference of 1000 V is
4.37 × 105 ms–1. If the hockey ball of mass 0.1 kg is moving with this velocity,
calcualte the wavelength associated with this velocity.
61. If the position of the electron is measured within an accuracy of + 0.002 nm,
calculate the uncertainty in the momentum of the electron. Suppose the
momentum of the electron is h/4m × 0.05 nm, is there any problem in defining
this value.
62. The quantum numbers of six electrons are given below. Arrange them in order of
1. n = 4, lenergies.
increasing = 2, ml = –2
If ,any
m s =of–1/2
these combination(s) has/have the same energy
lists:n = 3, l = 2, ml = 1 , ms = +1/2
2.

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3. n = 4, l = 1, ml = 0 , m s = +1/2
4. n = 3, l = 2, ml = –2 , m s = –1/2
5. n = 3, l = 1, ml = –1 , m s = +1/2
6. n = 4, l = 1, ml = 0 , m s = +1/2
63. The bromine atom possesses 35 electrons. It contains 6 electrons in 2p orbital,
6 electrons in 3p orbital and 5 electron in 4p orbital. Which of these electron
experiences the lowest effective nuclear charge ?
64. Among the following pairs of orbitals which orbital will experience the larger
effective nuclear charge? (i) 2s and 3s, (ii) 4d and 4f, (iii) 3d and 3p.
65. The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will
experience more effective nuclear charge from the nucleus ?
66. Indicate the number of unpaired electrons in : (a) P, (b) Si, (c) Cr, (d) Fe and (e) Kr.
67. (a) How many subshells are associated with n = 4 ? (b) How many electrons will
be present in the subshells having ms value of –1/2 for n = 4 ?

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